JPS61171702A - Fluorine-containing cellulose ether derivative - Google Patents

Abstract

PURPOSE:The titled novel derivative useful as a molded article, semipermeable membrane, coating agent, gas separating membrane, medical high polymer material, etc., having solvent solubility, and improved practical properties such as molding properties, film-forming properties, spinnability, etc. CONSTITUTION:For example, a cellulose derivative having 2.0-2.9 degree of substitution of OH groups in per anhydrous glucose unit of cellulose replaced with OR group (R is alkyl or aryl wherein one of CN, OH, and aryl may be replaced) is reacted with a hexafluoropropylene oxide or its oligomer as a fluorine-introducing agent, to give a novel derivative shown by the formula I (x is 1.5-2.95; y is 0.05-1.5; p is 0-3; n is 10-2,000) or formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a novel fluorine-containing cellulose ether derivative, and particularly to a solvent-soluble fluorine-containing cellulose ether conductor.

Among the cellulose ether rust conductors, those that are soluble in solvents are
It has many practical properties such as moldability, film-forming properties, and spinnability, so it can be used for molded products, films, semipermeable membranes,
They are used in applications such as coating films that take advantage of the physical properties unique to each derivative.

However, these cellulose ether conductors have the disadvantage that they are too hydrophilic for certain applications. For example, cyanoethylcellulose is a thermoplastic polymer with a particularly high dielectric constant and is used in electroluminescent display cells (EL display cells) and capacitor films, but it has hydrophilic properties especially when used in light emitters such as EL display cells. Due to its large size, it has the disadvantage of having a short lifespan as a light emitter.

The most effective means of increasing the hydrophobicity of a substance is to combine the substance with a fluorine atom or a compound containing a fluorine atom. Furthermore, by introducing fluorine atoms, new functions such as greatly changing the permeability of substances such as gases (eg, oxygen) can be expected. However, fluorine-introducing reagents are generally too reactive and difficult to handle, and it is not easy to introduce fluorine without losing the properties of the starting material.

Recently, hexafluoropropylene oxide (HFP)
It has been found that HFPO (hereinafter abbreviated as HFPO oligomer) and its oligomer (hereinafter abbreviated as HFPO oligomer) are effective fluorine-introducing reagents for organic compounds. The above HFPO and HF
PO oligomers are relatively easy to handle compounds and are strong electrophiles. When these compounds were applied to cellulose ether conductors, they reacted with the hydroxyl groups to form ester bonds, and through this reaction, it was possible to introduce fluorine into the cellulose crocodile conductors.

That is, the inventors of the present invention synthesized a hydrophobic fluorine-containing cellulose ether that has moldability, film-forming properties, and solvent solubility by reacting a cellulose ether having an unsubstituted hydroxy group with the above-mentioned HFPO or HFPO oligomer. This invention was successfully achieved.

Thus, the present invention relates to the general formula: (wherein R is a lower alkyl group or an aryl group which may be tr-treated with any one of a cyano group, a hydroxy group, or an aryl group; X is 1.5 to 2.95 Near is 0.05
~1.5: P is 0,1,2° or 3; n is 10-2
000) A fluorine-containing cellulose ether derivative represented by
1. ) Ah,. Korumei's fluorine-containing cellulose ether derivative is a novel compound that differs from the above-mentioned fluorine-containing cellulose in chemical structure and physical properties.

The cellulose ether used in this invention is suitably one that is soluble in a low boiling point organic solvent such as acetonitrile, methylene chloride, toluene, alcohol, etc., and has an unsubstituted hydroxy group, and has anhydroglucose units in cellulose. The degree of conversion by 10R groups (where R is the same as defined above) of the hydroxy group is preferably 1.5 or more and 2.95 or less, more preferably 2.0 or more and 2.9 or less.

Examples of cellulose ether derivatives used in this invention include ethyl cellulose, n-propyl cellulose, benzyl cellulose, and cyanoethyl cellulose, and some of the substituents may be mixed ethers in place of other substituents.

The fluorine-containing cellulose derivative of this invention is synthesized by dissolving the cellulose ether derivative as the starting material in a solvent such as 7-setone, and converting it into HFPO or HF in the presence of a reaction catalyst.
PO oligomers may be introduced into the solution.

For example, when HFPO is reacted with cellulose ether as described above, ethylcellulose is dissolved in fermented ethyl acetate, cyanoethylcellulose is dissolved in acetonate, benzylcellulose is dissolved in benzene or toluene, triethylamine is added, and HFPO is introduced. H
FPO isomerizes in the presence of triethylamine and reacts with unsubstituted hydroxy groups of cellulose ether to form pentafluoropropionyl ester.

The reaction format is thought to follow the following formula.

However, R is the same as defined above and Ce11 represents a cellulose residue.

In this reaction, triethylamine acts as an isomerization catalyst as well as a scavenger for hydrogen fluoride produced as a by-product during the reaction. Also, trimethylamine is substituted for triethylamine,
Amines such as tripropylamine, pyridine, picoline may also be used.

The HFPO oligomer is separated into oligomers having a single degree of polymerization by distillation, taking advantage of the fact that HFPO oligomers prepared in advance have different boiling points depending on their degree of polymerization, and are used as a fluorine-introducing reagent. For example, HFPO dimer is a liquid with a boiling point of 52 to 56°C (HFPO oligomer is insoluble in common organic solvents) and reacts immediately when cellulose nitrate triethylamine is dissolved and introduced into a solvent.

HFPO oligomers used in this invention include the following.

Boiling point trimer 113-114℃ tetramer
158-166℃ Pentamer 13
The reaction for producing oligomers by isomerizing HFPO at 5° C./9 times is given by the following equation.

'J (dimer) CFs0 σ, 0F30 (tri ζ-1) CF3CF30 Also cellulose ether,! The reaction of HFPO oligomer is expressed by the following formula.

CF3CF', 0 + These fluorine-introducing reagents are used in an amount t of 'C118' relative to the unsubstituted '*yM' number of cellulose ether. In order to obtain a fluorine-containing cellulose-conductor with a low degree of w resistance due to the fluorine-introducing reagent for unsubstituted hydroxyl groups, for example, one with the degree of substitution of 0.05, approximately 1.2 times the mole of 0.0
A small excess of fluoridation reagent, such as 6 moles, is used, whereas a large excess (2 to 6 times per liter) is used to obtain a high conversion. Further, the above reaction is generally carried out at 0 to 60°C for 1 to 16 hours. The reaction products obtained in these reactions were subjected to elemental analysis and infrared absorption spectra F, and the results showed that a new ester bond was formed with the hydroxyl group of the t=II cellulo% reaction as described above. This was sufficient to prove that the fluorine-containing cellulose ether conductor is a conductor. It is expected to be used as a film, semipermeable membrane, fiber, etc. for gas separation membranes, coating agents, modifiers, binders, medical polymer materials, etc.0 The above-mentioned cellulose ether used in this invention is Fluorine atoms can be easily introduced into cellulose ether ester or cellulose mixed ether by reacting with a carbon-introducing reagent using a known method.

Next, the present invention will be explained by giving examples.

Example 1 Ethyl cellulose 0.2765 t (= 1.2 m
mol glucose unit = 0.72 mmol OH group)
was dissolved in ethyl acetate (dehydrated and purified in advance) 20-, and dehydrated triethylamine 1-1 was added.

Carefully add this solution to HFPO)limer-1,8F(=
3.61 mmol = 5 eqOH groups) were added and stirred for 6 hours under 7 lux conditions. After the reaction was completed, it was cooled and added to a large excess of methanol (approximately 10,011 tons) to precipitate the product. 20
sd, and the solution was poured into methanol for reprecipitation. The obtained precipitate was separated from F, thoroughly washed with water and methanol, and then dried under reduced pressure to obtain a flaky white substance.

The physical and chemical properties of the obtained product were determined as follows: ILF band → 1) Solubility: The product was dissolved in a solvent such as chloroform. It was also found that the film has the property of repelling water droplets.

H) Infrared absorption spectrum The spectrum measured for a film obtained by casting a chloroform solution on glass and subjected to a vacuum converter is shown in Figure 1 K.
Figure 2 shows the spectrum of the raw material ethyl cellulose. In Figure 1, the absorption of 750crR-1 is 10F-
The absorption of C-e-F of the CF3 atomic group, the absorption at 1340 cm-' is the absorption of C-F, and the absorption at 17905+-' is CF.
Each belongs to νC=0 of the -C-0- atomic group.

On the other hand, the absorption of νOH at 3 450 cptt-' observed in the spectrum of ethylcellulose almost disappears in FIG.

I) Elemental analysis CIHN analysis was performed using Yanagimoto CHN coder MT-2 model. As a result, C=40.08%.

The degree of substitution of this numerical value (FiHFPO) remer is approximately 0.
He became a monk at the age of 45.

In summary, the product of Example 1 is an unreacted hydroxyl tea scoop of ethyl cellulose with a degree of acetyl substitution of about 2.5.
Approximately 0.45 of this is thought to be ester bonded to the HFPO (HFPO) trimer.

Example 2 (1) Production of raw material cyanoethyl cellulose 150 f of rayon fibers were immersed overnight in 1500 tons of 4% caustic soda aqueous solution and then compressed to remove liquid. The weight of the drained product is 387
It was t.

This drained product was charged into a kneader, and acrylonitrile 18
0 f and acetone 120 f were mixed and added, and the mixture was reacted at 50° C. for 30 minutes.

Furthermore, acrylonitrile i s o t, acetone 12
Add 0′ and 50℃″C″. It took me 7 minutes to react! 1
3,259 tons of acrylonitrile and 285 tons of acetone were added to the mixture, and the reaction was carried out at 50°C for 2 hours.The reaction product was cooled, neutralized with acetic acid, and then poured into water to precipitate. This deliquified product was dissolved in acetone, poured into water to precipitate vk1F, washed with water, and deliquified repeatedly, and dried to obtain flaky white cyanoethylcellulose.The acetone solution was poured onto a glass plate. Figure 3 shows the infrared absorption spectrum measured for the film obtained by casting and drying in vacuum.Also, the result of nitrogen analysis using a CHN coder was N=11.86%.

This indicates that the degree of substitution of the cyanethyl group is 2.5.

(2) Fluoroesterification of cyanoethylcellulose The cyanethylcellulose 0.54f (=1.8mm
1 glucose unit = 0.9 mmol OH group) was dissolved in acetone 20, which had been purified with water. After adding dehydrated and purified triethylamine 1-, add HFPO die beak-1,5f (=4.6 faces 1=s) while stirring.
eqOH) was added. The mixture was stirred and reacted for 6 hours under reflux of acetone. The reaction solution was added to a large excess of water (approximately 100,117 ml), and the precipitate was taken from house to house. It was redissolved in the obtained precipitate, and then reprecipitated in water. After being taken from house to house, it was thoroughly washed with water, methanol, and ether. After that, the mixture was dried under reduced pressure to obtain a flaky white substance.

The physical and chemical properties of the product are shown below.

1) Solubility The product was dissolved in a solvent such as acetone, pyridine, dimethylacetamide, etc. It was also found that the film had the property of repelling water droplets.

I) Hygroscopicity In order to compare the moisture absorption of the above-mentioned fluorine-containing cyan ethyl cellulose and cyano ethyl cellulose, the powders of both were placed in a desiccator containing a saturated aqueous solution of nitric acid and left at 23°C for 8 days. Equilibrium moisture was measured. The raw material cyan ethyl cellulose had a content of 2.70%, while the fluorinated sample had a content of 1.10%.
It can be seen that it has been made hydrophobic.

■)ll Train and Tanδ The above fluorine-containing cyanoethyl cellulose and Hisyano W 4
+Jl+Jp j++ PI 94〒+ L yWg
A film of m l mW l /0, 3 W I was prepared, and the dependence of the dielectric constant and tan δ on the same wave number was measured. The results are shown in FIGS. 5 and 6. The dielectric constant of the above fluorine-containing cyanoethyl cellulose is slightly lower than that of cyanoethyl cellulose, but shows a high dielectric constant.

~) Infrared absorption spectrum Figure 4 shows the infrared absorption spectrum measured for a film obtained by casting the acetone solution of the fluorine-containing cyanoethyl cellulose on glass and drying it under vacuum.

In Figure 4, the absorption of 750eff1-' is -0F-C
F.

Absorption of atomic group VC-F, absorption of 1330a*-' is absorption of C-F, absorption of 1790m-1 is CF-C-0
-The absorption of 227-Ots-' belongs to the absorption of shiC-O of the atomic group, and the absorption of 227-Ots-' belongs to the absorption of shiC-N, respectively. On the other hand, the absorption of 3 450 an-' νOH seen in the spectrum C of cyanoethyl cellulose (Fig. 3) almost disappears in Fig. 4.

V) Elemental Analysis CHN analysis was performed using Yanagimoto CHN Coder Model MT-2. As a result, C46.14%, H4.27chi, N
8.77%, which corresponds to a Ds of about 0.36 as the degree of substitution of the HFPO dimer.

Taking all the above into consideration, the product of Example 2 was obtained from unreacted hydroxyl cellulose with a degree of cyanoethyl substitution of about 2.5.
．． Approximately 0.4 of the 5 is considered to be ester bonded to the HFPO dimer.

Example 3 Cyanoethyl cellulose produced in the same manner as in Example 2 (1) was prepared using HFPO instead of HFPO dimer.
) A fluorine-containing cyanoethyl cellulose was produced by reacting the remer.

Cyanoethyl cellulose 0.45? (1.5 mmo
Acetone 20#I/1 glucose unit) dehydrated and purified
#NL*o **ffli! L*) II-'? #
7571m/.

After adding HFPO) Limer-1,85f while stirring
(3.72 mmol) was added. Under refluxing acetone (6
The mixture was stirred and reacted at 0°C for 5 hours. The reaction solution was poured into a large excess of water, and the precipitate was separated by F. After washing the precipitate with methanol and ether, it was redissolved in acetone and reprecipitated in water. After separating F, the residue was thoroughly washed with water, methanol, and ether, and then dried under reduced pressure to obtain a flaky white substance.

The physical and chemical properties of the product were as follows.

1) Solubility: It dissolves in solvents such as acetone, pyridine, dimethylacetamide, etc., and its film has the property of repelling water droplets.

I) Hygroscopicity The equilibrium moisture content of the above product was determined as in Example 2 and was found to be 1.27%. It can be seen that it is hydrophobicized compared to 2.7% of the raw material cyanoethyl cellulose.

l) Infrared absorption spectrum The infrared absorption spectrum of a vacuum-dried film obtained by casting a 77 ton solution of the above product on glass is shown in FIG.

ku e A-1/ 1171 rs
X4 n * ts -----1/ ,,
7+I vxll 790cm-' (νc=o of ester group), 2270e! 11-' (C-N) IV) Elemental analysis The elemental analysis of the above product was measured using a CHN coder, showing that C = 4SL 34%, N = 7.67%,
This value corresponds to a degree of substitution (DS) of the UHFPO remer of approximately 0.39 (based on carbon based analysis) (0.34° based on nitrogen analysis).

Taking all the above into account, the product of Example 3 has a degree of cyanethylation of 2
．． Approximately 0.4 out of 0.5 of the unreacted hydroxyl cyanoethyl cellulose in No. 5 is considered to have ester bonds with the HFPO) trimer.

Example 4 Cyanoethyl cellulose produced in the same manner as in Example 2 (1) was treated with HFPO dimer (1 containing HFPO).
Fluorine-containing cyanethylcellulose was produced by reacting tetramers.

Cyanoeterse, A10-su 0.53 t (1,79
mmol) was dissolved in dehydrated and purified acetone 20-.

After adding dehydrated and purified triethylamine 1-, HFPO tetramer 2.97 f (448 mm
ol) was added. The mixture was stirred and reacted for 8 hours under refluxing acetone (60°C). The reaction solution was added to a large excess of water, and the precipitate was dissolved in F.
Separated. After washing the precipitate with methanol and ether, it was redissolved in acetone and further precipitated again in water. After F separation, Wednesday.
After thorough washing with methanol and ether, the mixture was dried under reduced pressure to obtain a flaky white substance.

The obtained product has the following physical properties.

l) Soluble Soluble in acetone Soluble in pyridine and DMF W! The film obtained by dissolving in aqueous acetone, rolling, and drying has water-repellent properties.

I) Infrared absorption spectrum The absorption spectrum of the above product obtained by the KBr tablet method is shown in FIG.

750ts-' (vc-F), 1340am-'
(C-F).

1790 cm-'(νC=O of z stell group)-, 227
0 cmg-' (vC-N) tv) Elemental analysis Elemental analysis of the above product was performed using a CHN coder and the results showed C=48.33%, N=9.651,
The numerical value is 0, which corresponds to about 0.11 as the degree of substitution (DS) of HFPO tetra i-.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of the fluorine-containing ethyl cellulose produced in Example 1, Figure 2 shows the infrared absorption spectrum of the raw material ethyl cellulose used in Example 1, and Figure 3 shows the cyanoethyl cell produced in Example 2. Figure 4 shows the infrared absorption spectrum of the fluorine-containing cyanoethylcellulose prepared in Example 2, and Figures 5 and 6 show the infrared absorption spectrum of the attached cellulose.
The figures are the cyanoethyl cellulose of Example 2 and 11iF)4g8:'l'7/"2p""-!"oi*
Figure 7 shows the infrared absorption spectrum of the fluorine-containing cyanoethylcellulose produced in Example 3. Figure 8 shows the infrared rays of the fluorine-containing cyanoethylcellulose produced in Example 4. This is an absorption spectrum.

Claims (1)

[Claims] 1. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is any one of a cyano group, a hydroxy group, or an aryl group) Lower alkyl group or aryl group which may be substituted with; x is 1.5 to 2.95; y is 0.05
~1.5; p is 0, 1, 2, or 3; n is 10-2
000) A fluorine-containing cellulose ether derivative represented by: