JPS6411201B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing a substituted silylpropyl group-containing cellulose derivative by reacting allylcellulose or a derivative thereof (hereinafter simply referred to as allylcellulose derivative) with an organosilicon compound. (Objective of the invention) Gas separation membranes, adhesives, and paints that combine the film-forming properties, toughness, and other properties of conventional cellulose derivatives with the gas permeability, electrical properties, and other properties of organosilicon compounds. The purpose of the present invention is to provide cellulose derivatives that are useful as fiber treatment agents. (Structure of the Invention) The present inventors have discovered that an allyl cellulose derivative and ≡Si−
The present invention was completed by discovering that an organosilicon compound having an H bond undergoes a quantitative addition reaction and that a cellulose derivative into which the organosilicon compound is chemically introduced can be easily obtained. The present invention applies the general formula having at least one ≡Si-H bond per minute to allylcellulose or its derivatives, which have an average of 0.1 or more allyloxy groups per glucose unit of cellulose or cellulose derivatives. (R ¹ , R ² , R ³ in the formula each has 1 carbon atom
a group selected from ~8 monovalent hydrocarbon groups or halogenated monovalent hydrocarbon groups, alkoxy groups having 1 to 4 carbon atoms, organosiloxy groups, or R ¹
- A method for producing a substituted silylpropyl group-containing cellulose derivative, which is characterized by carrying out an addition reaction with an organosilicon compound represented by (a cyclic organosiloxy group formed by two of ^R3 ) It is something. The present invention will be explained in detail below. The allyl cellulose derivative used in the present invention has an allyloxy group (-
OCH ₂ CH=CH ₂ ), and examples thereof include allyl cellulose, allyl methyl cellulose, allyl ethyl cellulose, allyl methylhydroxypropyl cellulose, and allyl acetyl cellulose. These allylcellulose derivatives must have an average degree of substitution (DS) of the allyloxy group of 0.1 or more, and if the degree of substitution is less than 0.1, the reaction rate of the organosilicon compound described later will be reduced. It becomes relatively small, and the introduction of the characteristics of the organosilicon compound becomes insufficient. On the other hand, the organosilicon compound having a ≡Si-H bond in the molecule to be reacted with the above allylcellulose derivative has the general formula In the formula, R ¹ , R ² , R ³ are each individually,
An organosilane compound which is a group selected from a monovalent hydrocarbon group having 1 to 8 carbon atoms, a halogenated monovalent hydrocarbon group, and an alkoxy group having 1 to 4 carbon atoms, and their R ¹ to ^{R 3} At least one of them is an organosiloxy group, or
It is widely selected from organopolysiloxane compounds in which two of R ¹ to ^{R 3} are taken together to form a cyclic organosiloxy group. Specific examples of the above-mentioned organosilane compounds include the following. However, in the following description, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, and Ph represents a phenyl group. H-Si(Me) ₃ , H-Si(Et) ₃ , H-Si(Pr) ₃ , H-Si(Ph) ₃ , H-Si(Me) ₂ (Ph), H-Si(Et) ₂ (Ph), H-Si(Me) ₂ (CH ₂ CH ₂ CF ₃ ), H-Si(Me)
(Ph) ₂ , H-Si(Ph) ₂ ( _{CH2CH2CF3 )} , H-Si(OMe) ₃ , H-Si(OEt) ₃ , H-Si(Me)(OMe) _{2 ,} H- Si(Me)(OEt) ₂ , H-Si(Et)(OEt) ₂ , H-Si(Et)(OMe) ₂ , H-Si(Ph)(OMe) ₂ , H-Si(Ph)(OEt ) ₂ , and as organopolysiloxane compounds,
The organic group (organic group bonded to a silicon atom) in each of these organopolysiloxane compounds includes linear structures, branched structures, and cyclic structures.
is selected from a monovalent hydrocarbon group having 1 to 8 carbon atoms or a halogenated monovalent hydrocarbon group, and an alkoxy group having 1 to 4 carbon atoms. Specific examples are as follows.

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The organosilicon compounds having a ≡Si-H bond exemplified above are not limited to one type, and two or more types thereof may be used in combination. The method of the present invention obtains the desired substituted silylpropyl group-containing cellulose derivative by subjecting the allylcellulose derivative to an addition reaction with an organosilicon compound having a ≡Si-H bond.This reaction will be specifically explained. Then, the following is true. First, allylcellulose derivative is mixed with benzene,
It is dissolved or dispersed in an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as chloroform or dichloroethane, or a solvent such as tetrahydrofuran, and an organosilicon compound having a ≡Si-H bond is added to this system. By heating above ℃, preferably 80 to 150℃, an addition reaction proceeds between ≡Si-H in the organosilicon compound and the allyl group in the cellulose derivative to obtain the desired substituted silylpropyl group-containing cellulose derivative. . In the above reaction, as a catalyst to promote the reaction, chloroplatinic acid, a complex of chloroplatinic acid and olefin, a reaction product of chloroplatinic acid and a vinyl group-containing organosilicon compound, or a rhodium-based catalyst is used as a reaction system. By adding and reacting an organosilicon compound while heating to 40° C. or higher, a substituted silylpropyl group-containing cellulose derivative can be quantitatively obtained. In addition, since allylcellulose derivatives and organosilicon compounds containing ≡Si-H bonds react quantitatively, in the normal case, the total number of moles of allyl groups in the cellulose derivative and the number of ≡Si-H bonds in the organosilicon compound react with each other quantitatively. It is preferable to carry out the reaction in such a manner that the total number of moles becomes equivalent to the same mole. Of course, by introducing an insufficient number of moles of either, allyl group or ≡Si-H
The bond can remain in the product molecule. Another way to carry out the reaction is to dissolve the allyl cellulose derivative and an organosilicon compound having a ≡Si-H bond in a predetermined ratio in a solvent such as toluene, xylene, or tetrahydrofuran, and then use a catalyst such as chloroplatinic acid In addition, plate-like, film-like,
A molded object can be obtained by molding into a filament, hollow fiber, etc., and heat-treating it during or after molding to cause an addition reaction between the two. The substituted silylpropyl group-containing cellulose derivative obtained by the method of the present invention has both the properties of cellulose derivatives, such as film-forming properties and toughness, and the properties of organosilicon compounds, such as gas permeability and electrical properties. gas separation membranes, adhesives, paints,
It is said to be useful as a fiber treatment agent. Next, specific examples will be given. Examples 1 to 4 Allyl cellulose (DS of allyl group = 2.0) 5 g
was dissolved in 100 ml of tetrahydrofuran, and 0.01 ml of 2% chloroplatinic acid-n-butanol solution was added.
The temperature was raised to 66°C, and 0.042 mol of the organosilicon compounds shown in Table 1 were added dropwise to react. The reaction solution was stirred and poured into a large amount of water-methanol (1:1 volume ratio), and the resulting precipitate was separated, washed repeatedly with water, and then dried. The yields were as shown in Table 1. Next, each product was dissolved in toluene to make a film with a thickness of 10 μm using the casting method, and examined by infrared absorption spectroscopy ^.
The absorptions at 1645cm ^-1 , 995cm ^-1 and 910cm ^-1 have completely disappeared, and are replaced by the absorption of methylene groups at 1450cm ^-1 and the absorption of methylsiloxane at 1260cm ^-1 , 840cm ^-1 and 780cm -1 .
cm ^-1 was newly large. From these results, it was confirmed that the organosilicon compound ≡Si-H was quantitatively added to the allyl group of allylcellulose to produce substituted silylpropylcellulose. On the other hand, the tensile strength and gas permeability coefficient of each of the above films were measured. The results are shown in Table 1. As is clear from the results shown in Table 1, substituted silylpropylcellulose has both the membrane strength of cellulose and the gas permeability of silicon compounds, making it particularly useful for gas separation membranes. It is something that will be done.

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[Table] Examples 5 to 7 Allyl acetyl cellulose (DS of allyl group =
0.5, DS of acetyl group = 2.5) was dissolved in 100 ml of tetrahydrofuran, 0.01 ml of 2% chloroplatinic acid-butanol solution was added, and then the organosilicon compounds shown in Table 2 were added in the amounts shown in the same table. reaction temperature 66
A dropwise reaction was carried out at ℃. After the reaction was completed, tetrahydrofuran was distilled off under reduced pressure, and the reaction products were obtained in the yields shown in Table 2. As a result of examining each reaction product by infrared absorption spectroscopy in the same manner as in the previous example, it was confirmed that it was substituted silylpropylacetylcellulose. The substituted silylpropyl acetylcellulose obtained in this way has a silyl group substituted with an alkoxyl group, so it easily hydrolyzes with moisture in the air and becomes a three-dimensional polymer, which can be used as a strong adhesive or paint. It is said to be useful for applications such as

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[Table] Example 8 Allyl ethyl cellulose (DS of allyl group =
0.2, DS of ethyl group = 2.5) 5g was dissolved in 100ml of toluene, and the following formula After adding and dissolving 3 g of organopolysiloxane, the reaction product of chloroplatinic acid and tetravinyltetramethyltetracyclohexane was expressed as the amount of Pt.
It was added in an amount of 2×10 ^-4 g and mixed uniformly.
A film with a thickness of 10 μm was made from this solution by casting, and after heating to 130°C for 2 hours,
As a result of infrared absorption spectrometry analysis, it was confirmed that it was a cellulose derivative containing substituted silylpropyl groups. The tensile strength of this film is 435Kg/cm ² and the oxygen permeability coefficient is PO ₂ = 7.4×10 ^-9 cm ² (STP).
It has an excellent value of cm/cm ²・sec・cmHg and is considered useful as a gas separation membrane.

Claims (1)

[Scope of Claims] 1 Allylcellulose or a derivative thereof having an average of 0.1 or more allyloxy groups per glucose unit of cellulose or cellulose derivative, 1
General formula with at least one ≡Si-H bond in the molecule (R ¹ , R ² , R ³ in the formula each has 1 carbon atom
a group selected from ~8 monovalent hydrocarbon groups or halogenated monovalent hydrocarbon groups, alkoxy groups having 1 to 4 carbon atoms, organosiloxy groups, or R ¹
A method for producing a substituted silylpropyl group-containing cellulose derivative, which comprises carrying out an addition reaction with an organosilicon compound represented by (a cyclic organosiloxy group formed by two of ^R3 ). 2. The method for producing a substituted silylpropyl group-containing cellulose derivative according to claim 1, wherein the organosilicon compound is an organosilane compound. 3. The method for producing a substituted silylpropyl group-containing cellulose derivative according to claim 1, wherein the organosilicon compound is an organopolysiloxane compound.