JP2682571B2 - Siloxane-containing cellulose derivative and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a siloxane-containing cellulose derivative, and more particularly to a stable siloxane-containing cellulose derivative which has both properties of cellulose and silicone, and which has not been described in the literature.

[0002]

2. Description of the Related Art There have been numerous reports on attempts to react a cellulose derivative with an organosilicon compound to obtain a composition which makes the best use of the characteristics of both, but the reaction efficiency of the organosilicon compound has been reported. However, cellulose containing an organic silicon compound such as trimethylsilyl cellulose has the disadvantage that it is unstable to water, and furthermore, it does not exhibit the expected performance. There was a problem in practical application.

[0003]

For this siloxane-containing cellulose derivative, however, a method for obtaining a siloxane-containing cellulose derivative by reacting an allyl cellulose derivative with an organosilicon compound having an ≡Si—H bond is also known. However, it is difficult to prepare the allyl cellulose derivative as a raw material by this method, and when unreacted allyl groups remain, the allyl groups are cross-linked during storage. Therefore, there is a drawback that the solubility in a solvent is lost due to the loss.

[0004]

The present invention relates to a novel siloxane-containing cellulose derivative, which has not been described in the literature, and a method for producing the same, which solves such disadvantages. The siloxane-containing cellulose derivative is represented by the general formula (1).

Embedded image [Where Cell- is a glucose residue of cellulose or a cellulose derivative, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, R ² ,
R ³ and R ⁴ are monovalent organic groups having 1 to 8 carbon atoms or a siloxy group represented by -OSiR ⁵ R ⁶ R ⁷ (R ⁵ , R ⁶ and R ⁷ are monovalent organic groups having 1 to 8 carbon atoms) , N is an integer of 1 to 10, a is 0, 1 or 2,
x / y is y / x of 0.1 or more], and the degree of polymerization is 50 to 50.
There are 4,000 substituted silylalkylcarbamic acid cellulose derivatives, which are produced by A) a cellulose derivative having a hydroxyl group and B) a general formula (2).

Embedded image [Here, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, R ² , R ³ and R ⁴ are monovalent organic groups having 1 to 8 carbon atoms or a siloxy group represented by -OSiR ⁵ R ⁶ R ⁷ ( R ^5, R ^6, R ⁷ is a monovalent organic group having 1 to 8 carbon atoms), n is an integer of from 1 to 10, a is reacting the isocyanate group-containing organopolysiloxane represented by 0, 1 or 2] It is characterized by that.

That is, the present inventors have conducted various studies to develop a siloxane-containing cellulose derivative having both properties of a cellulose derivative and a silicone, and as a result, the cellulose derivative containing a hydroxyl group and the above-mentioned general formula (2) are shown. When the isocyanate group-containing organopolysiloxane is reacted with the isocyanate group-containing organopolysiloxane, the isocyanate group of the isocyanate group-containing organopolysiloxane is highly reactive. It was found that the substituted silylalkylcarbamic acid cellulose derivative represented by (1) can be easily obtained, and the thus-obtained substituted silylalkylcarbamic acid cellulose derivative is a novel one not yet published in the literature. Characteristics of film forming and toughness Since it has characteristics such as elasticity and gas permeability that organic silicon compounds have and dissolves in various organic solvents, it is useful as a gas separation membrane, cosmetic material, adhesive, fiber treatment agent, etc. The present invention has been completed after confirming that This will be described in more detail below.

[0006]

The present invention relates to a siloxane-containing cellulose derivative and a method for producing the same. The siloxane-containing cellulose derivative is represented by the above-mentioned general formula (1). B) It is characterized by reacting with the isocyanate group-containing organopolysiloxane represented by the above general formula (2), and the siloxane-containing cellulose derivative is stable and has the properties of both a cellulose derivative and a silicone. It has the characteristics of film-forming property and toughness of cellulose derivatives, elasticity of organic silicon compounds, gas permeability, etc., and it dissolves in various organic solvents. It is useful as a film, cosmetic material, adhesive, fiber treatment agent, etc.

The siloxane-containing cellulose derivative of the present invention is a substituted silylalkylcarbamic acid cellulose derivative obtained by reacting A) a hydroxyl group-containing cellulose derivative with B) an isocyanate group-containing organopolysiloxane represented by the general formula (2). However, as the cellulose derivative having a hydroxyl group used here, methyl cellulose,
Examples include cellulose derivatives such as ethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, and hydroxyethyl cellulose, and cellulose ester derivatives such as cellulose acetate and cellulose acetate butyrate. Since the amount of the isocyanate group-containing organopolysiloxane that reacts with is reduced and the characteristics of elasticity and gas permeability, which are the characteristics of the organosilicon compound, cannot be exhibited, it should have at least 0.1 hydroxyl groups per glucose unit. Is good. The degree of polymerization may be in the range of ordinary cellulose derivatives, preferably 50 to 4,000.

The isocyanate group-containing organopolysiloxane used here is represented by the above-mentioned general formula (2). This R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
Examples of the monovalent organic group having 1 to 8 carbon atoms represented by R ⁷ include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryls such as phenyl group Group, aralkyl group such as benzyl group, alkenyl group such as vinyl group and allyl group, chloromethyl group, substituted hydrocarbon group such as 3,3,3-trifluoropropyl group, and the like.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ may be the same or different, but most preferably all are methyl groups. Further, the R ^2, R ^3, R ⁴ may be a siloxy group represented by -OSiR ⁵ R ⁶ R ^7, but trimethylsiloxy groups as this siloxy group, ethyl dimethylsiloxy group, phenyl dimethylsiloxy group, Examples thereof include a vinyldimethylsiloxy group, a chloromethyldimethylsiloxy group and a 3,3,3-trifluoropropyldimethylsiloxy group.

This isocyanate group-containing organopolysiloxane has the following formula

Embedded image As shown in, phosgene is allowed to act on the primary amino group-containing organopolysiloxane to induce an isocyanate group, or

Embedded image As shown in (1), a primary amino group-containing organopolysiloxane is reacted with a chloroformate to give a carbamate, which is thermally decomposed (alcohol elimination) to be converted into an isocyanate group.

Examples of the chloroformate used here include alkyl esters such as methyl chloroformate and ethyl chloroformate, aryl esters such as phenyl chloroformate, halogenated alkyl esters such as chloromethyl chloroformate and trichloromethyl chloroformate, and the like. As an example, this method is known as a method that does not use phosgene, which is a poison gas.

[0011] manufacturing method of a siloxane-containing cellulose derivative of the present invention, since it is due to the urethane bond forming reaction between a hydroxyl group and an isocyanate group of the isocyanate group-containing organopolysiloxane of cellulose derivatives containing a hydroxyl group in the molecule, specially It is not necessary to use various reaction conditions or reaction equipment, but it is desirable to use a solvent for the mixing of this cellulose derivative and the isocyanate group-containing organopolysiloxane, reaction efficiency, and reaction control. , Esters such as ethyl acetate, butyl acetate and isobutyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, diethyl ether, dibutyl Ether, tetrahydrofuran and ethers such as dioxane are exemplified, it may be used in either singly or in combination.

The reaction conditions for this reaction differ depending on the type of cellulose derivative and solvent used here, but it is usually 20 to 150 ° C. for 2 to 10 hours. In this case, pyridine as a base catalyst is used. May be added in a small amount. After completion of the reaction, the target siloxane-containing cellulose derivative can be obtained by washing and then drying.

The production of the siloxane-containing cellulose derivative according to the present invention is carried out by the reaction of the hydroxyl group-containing cellulose derivative with the isocyanate group-containing organopolysiloxane as described above. The isocyanate group-containing organopolysiloxane is particularly tristrimethyl. Siloxysilylpropyl isocyanate (hereinafter TM
Abbreviated as SI), and hydroxypropylmethylcellulose, ethylcellulose, and acetylcellulose are specified as this cellulose derivative, and
Is reacted with MSI tris trimethylsiloxy silyl propyl carbamic acid hydroxypropylmethylcellulose, tris trimethylsiloxy silyl propyl carbamic acid ethyl cellulose, it is possible to obtain a tris trimethylsiloxy silyl propyl carbamic acid acetate Chi le cellulose, both of which documents Not Are new, these are the formulas

Embedded image It is shown by.

In this case, the amount of TMSI used here varies depending on the amount of hydroxyl groups per glucose unit contained in the cellulose derivative, but if TMSI is larger than the equivalent of hydroxyl groups, TMSI is not only wasted but also produced. Since it is difficult to purify the siloxane-containing cellulose derivative, it is preferable that the amount is not more than 0.1 mol per glucose unit and not more than 0.1 mol per glucose unit of the cellulose derivative.

[0015]

Next, examples of the present invention will be described. Example 1 The hydroxyl group per glucose unit is 1.12 and the methoxyl group is 1.
88, hydroxypropylmethylcellulose having a hydroxypropoxy group of 0.26, dried at 105 ° C. for 2 hours, and dissolved in 10 g of 100 g of dimethylformamide,
While stirring, the temperature was raised to 80 ° C, 14 g of TMSI was added, and the reaction was completed by stirring and reacting at 105-118 ° C for 2 hours. The reaction solution was poured into 200 ml of water with stirring, and the resulting precipitate was collected. After being filtered off, washed repeatedly with water, and dried,
23 g of product was obtained.

Then, the product was subjected to elemental analysis, IR qualitative analysis and substance identification by ¹³ C- NMR. As a result, the results shown in Tables 1, 2 and 3 described later were obtained. From this, it was confirmed that this was also hydroxypropylmethylcellulose tristrimethylsiloxysilylpropylcarbamate. Next, this product is dissolved in butyl acetate and the thickness is 20μ by casting method.
When a film of m is produced, a tough and elastic film is obtained, which also has an oxygen permeability coefficient of 3.3 × 10 ^-8 cm.
^{Since it is 3} (STP) cm / cm ² · sec · cm Hg, it has been proved to be useful for applications such as gas separation membranes.

Example 2 0.71 hydroxyl group and 2. ethoxyl group per glucose unit.
Ethyl cellulose 29, which was dried at 105 ° C for 2 hours, was dissolved in 100 ml of ethylene glycol dimethyl ether, and the temperature was raised to 80 ° C with stirring.
The same procedure as in Example 1 was carried out except that 7 g was added to obtain 14 g of a product.

Then, the product was subjected to elemental analysis, IR qualitative analysis and substance identification by ¹³ C- NMR. As a result, the results shown in Tables 1, 2 and 3 described later were obtained. From this, it was confirmed that this was also hydroxypropylmethylcellulose tristrimethylsiloxysilylpropylcarbamate. Next, a film was formed by the same method as in Example 1, which was tough and elastic, and had an oxygen permeability coefficient of 6.0 × 10 ⁻⁹ cm ³ (STP) cm / cm ² ·. It was sec · cmHg.

Example 3 Instead of hydroxypropyl cellulose in Example 1, 10 g of acetyl cellulose having 0.96 hydroxyl groups per glucose unit and 2.04 acetyl groups was used.
When 21 g of the product was obtained by the same treatment as in Example 1 except that 13 g of SI was used, the elemental analysis and IR qualitative analysis of this product and the substance identification by ¹³ C- NMR were carried out. Since the results shown in Tables 1, 2, and 3 were obtained, it was confirmed that this was acetyl cellulose tristrimethylsiloxysilylpropylcarbamate. Regarding this, a film was prepared in the same manner as in Example 1. As a result, this film was tough and rich in elasticity, and the oxygen permeability coefficient of this film was 2.1 × 10 ⁻⁸ cm ³ (STP) cm / It was cm ² · sec · cmHg.

[0020]

[Table 1]

[Table 2]

[Table 3]

[0021]

INDUSTRIAL APPLICABILITY The present invention relates to a siloxane-containing cellulose derivative and a method for producing the same. As described above, the siloxane-containing cellulose derivative is a substituted silylalkylcarbamic acid cellulose derivative represented by the general formula (1), particularly tris. Trimethylsiloxysilylpropylcarbamate hydroxypropylmethylcellulose, tristrimethylsiloxysilylpropylcarbamate ethylcellulose, tristrimethylsiloxysilylpropylcarbamate acetylcellulose. Substituted silylalkylcarbamic acid cellulose derivatives, especially tristris, by reacting with trimethylsiloxysilylpropyl isocyanate. It is characterized in that to produce a chill siloxy silyl propyl carbamic acid cellulose derivatives.

Thus, the siloxane-containing cellulose derivatives thus produced are all novel substances which have not been published in the literature, and they are both stable and have the properties of both cellulose and silicone, and are gas separated. film, cosmetics materials, adhesives, which are useful as paints, since the isocyanate group of the isocyanate group-containing organopolysiloxane used herein according to the manufacturing method described above is of high reactivity, This gives an advantage that the desired siloxane-containing cellulose derivative can be easily and efficiently obtained by reacting with the hydroxyl group of the cellulose derivative.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of tristrimethylsiloxysilylpropylcarbamate hydroxypropylmethylcellulose obtained in Example 1 of the present invention.

FIG. 2 shows an IR spectrum of tristrimethylsiloxysilylpropyl carbamic acid ethyl cellulose obtained in Example 2 of the present invention.

FIG. 3 shows an IR spectrum of tristrimethylsiloxysilylpropylcarbamate acetylcellulose obtained in Example 3 of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuyoshi Oshima 28-1 Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (72) Inventor Shoji Ichinohe Matsui Usui-gun Gunma Prefecture Tamachi Daiji Hitomi 1-10 Shin-Etsu Chemical Co., Ltd. Silicon Silicon Electronic Materials Research Laboratory (72) Inventor Toshio Yamazaki Matsuida-cho, Gunma Prefecture Usida Gun Daiji Hitomi 10 Shin-Etsu Chemical Industrial Silicon Silicon Electronic Materials Research Laboratory

Claims (7)

(57) [Claims] 1. A compound of the general formula [Where Cell- is a glucose residue of cellulose or a cellulose derivative, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, R ² ,
R ³ and R ⁴ are monovalent organic groups having 1 to 8 carbon atoms or a siloxy group represented by -OSiR ⁵ R ⁶ R ⁷ (R ⁵ , R ⁶ and R ⁷ are monovalent organic groups having 1 to 8 carbon atoms) , N is an integer of 1 to 10, a is 0, 1 or 2,
x / y is y / x of 0.1 or more], and the degree of polymerization is 50 to 50.
4,000 substituted silylalkylcarbamic acid cellulose derivatives. 2. A substituted silylalkylcarbamic acid cellulose derivative according to claim 1, wherein n = 3, R ² , R ³ and R ⁴ are methyl groups and a = 0. 3. The tristrimethylsiloxysilylpropylcarbamic acid cellulose derivative according to claim 2, wherein the cellulose derivative is hydroxypropylmethylcellulose. 4. The tristrimethylsiloxysilylpropyl carbamic acid cellulose derivative according to claim 2, wherein the cellulose derivative is ethyl cellulose. 5. The tristrimethylsiloxysilylpropylcarbamic acid cellulose derivative according to claim 2, wherein the cellulose derivative is acetylcellulose. 6. A) a cellulose derivative having a hydroxyl group and B) a general formula: [Here, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, R ² , R ³ and R ⁴ are monovalent organic groups having 1 to 8 carbon atoms or a siloxy group represented by -OSiR ⁵ R ⁶ R ⁷ ( R ^5, R ^6, R ⁷ is a monovalent organic group having 1 to 8 carbon atoms), n is an integer of from 1 to 10, a is reacting the isocyanate group-containing organopolysiloxane represented by 0, 1 or 2] A method for producing a substituted silylalkylcarbamic acid cellulose derivative, which comprises: 7. A method for producing a trimethylsiloxysilylpropylcarbamic acid cellulose derivative, wherein the isocyanate group-containing organopolysiloxane of claim 6 is tristrimethylsiloxysilylpropyl isocyanate.