JPH0321602A - Sulfinylethyl pullulan and its production method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a novel pullulan derivative that has never been described in the literature, particularly as a thickener, a binder, a protective colloid agent, and as a selective material for sulfur dioxide, etc. This article relates to sulfinylethyl bullulane, which is useful as a permeable membrane material, and a method for producing the same.

(Prior art) Bullulan is a linear polymer in which maltotriose, which is a trimer of glucose, is repeatedly bonded to each other through α-1,6 bonds. By culturing the bacterial strain, it can be isolated and collected as extracellular mucilage. Unlike starch, which consists of the same glucose unit, it is soluble in both cold and hot water, has a relatively low aqueous solution viscosity, and has excellent manufacturing properties.
It has characteristics such as excellent hygroscopicity and caking property.

(Problems to be Solved by the Invention) Conventionally, pullulan derivatives obtained by subjecting pullulan and a vinyl compound to a Michael addition reaction in the presence of an alkali catalyst include cyanoethyl pullulan obtained by reacting pullulan with allylonitrile. is only known.

The present inventors have arrived at the present invention as a result of various studies on novel derivatives of bullulan.

(Means for Solving the Problems) The present inventors have developed pullulan and the formula: R S C H = C H 2 .
・(1) ↓ ○ (here R represents an alkyl group having 1 to 6 carbon atoms), or an alkyl vinyl sulfoxide represented by the formula: CsH, SCH=C}l2−・− (It)↓ O When the represented phenylvinyl sulfoxide is reacted in the presence of an alkali catalyst, the general formula [wherein each X is a hydrogen atom, formula: RSCH20H. 1...(1■)↓ An alkylsulfinylethyl group represented by O (where R represents an alkyl group having 1 to 6 carbon atoms), or the formula: C, HSSCH2CH. phenylsulfinylethyl group represented by 1・−=−<■)↓ O , the average degree of substitution of the alkylsulfinylethyl group and phenylsulfinylethyl group per glucose unit is at least 0.05, and n is the number of glucose units It was discovered that sulfinylethyl pullulan, such as alkylsulfinylethyl pullulan and phenylsulfinylethyl pullulan, which are new compounds represented by the following integer representing the number of repetitions can be obtained, and the present invention was completed.

The present invention will be explained in detail below.

In the sulfinylethyl pullulan of the present invention, the above (
In the alkylsulfinylethyl group represented by the formula III), R represents an alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, proyl, butyl, bentyl and hexyl groups.

The average degree of substitution (average number of sulfinylethyl groups present per glucose unit) by sulfinylethyl groups of formula (m), (Vl) per each glucose unit (i.e., each anhydroglucose ring) is at least 0.05. I need. This is because if the average degree of substitution is less than this, the properties based on the sulfinylethyl group, such as selective permselectivity for sulfur dioxide, will be insufficient.

As mentioned above, the sulfinylethyl pullulan of the present invention is produced by reacting pullulan with an alkyl vinyl sulfoxide represented by the above formula (1) or a phenyl vinyl sulfoxide represented by the above formula (n) in the presence of an alkali catalyst. This can be obtained by doing so.

The alkyl vinyl sulfoxide used here can be synthesized, for example, through a reaction process shown by the following formula.

R S H + C2H, ONa- + R S Na + C2H
50HR S Na+ C Ic H2C H. ○I1
→R S C H 2C H 20 H 1N a C
1? OH RSCH2CH, OH ■ → RSCH=CH, +H20 [
In each of the above formulas, R is the same as the formula (tU)] That is, alkyl mer butane is reacted with sodium ethoxide in ethanol at room temperature, and the resulting sodium thiolate is reacted with ethylene chlorohydrin to form hydroxyethyl alkyl sulfide. Synthesize. Next, this hydroxyethyl alkyl sulfide is subjected to a dehydration reaction in an aqueous potassium hydroxide solution to form a vinyl alkyl sulfide, which is then oxidized in an aqueous sodium metaperiodate solution to synthesize an alkyl vinyl sulfoxide.

Phenylvinyl sulfoxide can also be synthesized in the same manner as above using mercabutane as a starting material, but commercially available products can also be used.

Examples of the alkali catalyst used in the above production method include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, but sodium hydroxide is usually economically advantageous. The above production method is generally carried out in an aqueous solution containing an alkali catalyst at a concentration of 0.5 to 10% at 10 to 90° C. by reacting a portion of both reactions with stirring. Generally, 1 to 20 moles of vinyl sulfoxide are reacted with 1 mole of glucose units in pullulan so as to obtain sulfinylethyl pullulan having a desired degree of substitution. After the reaction, acetic acid is added to stop the reaction, and the reaction solution is poured into a mixed solvent of acetone/methanol (2/3 volume ratio) to precipitate the product, which is dissolved in water or dimethyl sulfoxide and then mixed with acetone/methanol. Purification can be achieved by repeating the operation of reprecipitating with a methanol mixed solvent or the like two or three times.

The sulfinylethyl pullulan of the present invention is a derivative with a structure in which a part of the hydrogen atoms of the hydroxyl group on the right side of pullulan is substituted with an alkylsulfinylethyl group or a phenylsulfinylethyl group. Water that is (D) (hereinafter referred to as "heavy water")
Alternatively, when dissolved in dimethyl sulfoxide (hereinafter referred to as "heavy DMSOJ") and subjected to proton nuclear magnetic resonance (1H-NMR) spectrum analysis, in addition to the absorption of pullulan used as a starting material (see Figure 1, 270Mt in heavy water
lz), a new alkylsulfinylethyl group,
In particular, a characteristic absorption of hydrogen bonded to the carbon adjacent to the SO group is observed (see Q) and m) in Figures 2 to 4).

In addition, in the case of phenylsulfinylethyl pullulan, the absorption of protons of the phenyl group is 7.5 pp. It is observed near m (see m in Figure 5).

On the other hand, no proton signal of the vinyl group of the starting material vinyl sulfoxide was observed (see Figures 2 to 5).
.

These facts indicate that the hydroxyl group of pullulan undergoes an addition reaction with the vinyl group of vinyl sulfoxide to introduce a sulfinylethyl group, and that sulfinylethyl pullulan having the above-mentioned structure is obtained.

"H-N" of sulfinylethyl pullulan of the present invention
The spectroscopic characteristics shown by MR spectrum analysis are as follows.

Alkylsulfinylethyl pullulan: 1H-NMR (
Heavy water) δppm, 2.9-3.2ppm (m, 10C
H,C2%SR) ↓ ○ →See Q) in Figures 2 to 4 1.3 to 3.0 ppm (s.m, -0CH,
CH2S R) ↓ ○ → Refer to m) in Figures 2 to 4 Phenylsulfinylethyl pullulan: "H-NMR (
Heavy DMS○) δppm. 3, Oppm (m, -oCH
2CH S C,}I,)↓ ○ →Q in Figure 5. ) Reference 7.5-7.7ppm (m, -ocH2ct+2sc
tr ) ↓ O → See m) in Figure 5 (Example) Hereinafter, specific aspects of the present invention will be explained using Examples.
The invention is not limited to this example.

Example f~3. After adding and dissolving 1.0 g of pullulan (trade name: PI-20, manufactured by Ichibayashibara) in 20 parts of water, add methyl vinyl sulfoxide (MVSO in the table) per glucose unit shown in Table 1. of pullulan (in the table, referred to as PL). Next, 1% by weight of sodium hydroxide based on the total system was added, and the mixture was allowed to react at 60°C for 5 hours with stirring, and the resulting reaction product was neutralized with acetic acid. Next, this was poured into a mixed solvent of acetone/methanol (volume ratio 2/3) to precipitate the reaction product. The precipitate was purified by repeating three times the operation of dissolving the precipitate in water and reprecipitating it with acetone/methanol.

The average degree of substitution of the obtained methylsulfinyl ethyl pullulan was determined from H-NMR measurement. These results are also listed in Table 1. The 'H-NMR spectrum of ethyl pullulan (measured in heavy water, D.S. 1.68, 270In) is shown in FIG.

Table 1 (DMSO: dimethyl sulfoxide in the table) Examples 4 to 8. The same operation as in the previous example was carried out except that ethyl vinyl sulfoxide (referred to as EVSO in the table) was used instead of methyl vinyl sulfoxide and the reaction conditions shown in Table 2 were used. These results are also listed in Table 2. In addition, 'H-N of ethylsulfinyl ethyl pullulan obtained in Example 8
MR spectrum (in heavy water, D.S. 1.37,270
MHz) is shown in FIG.

Table 2 It is shown in Figure 4.

Table 3 Examples 9-11. The same operations as in Examples 1 to 3 were carried out, except that tert-butyl vinyl sulfoxide (referred to as BVSO in the table) was used in the molar ratio shown in Table 3 instead of methyl vinyl sulfoxide. These results are also listed in Table 3. In addition, 'H-NMR spectrum of tart-butylsulfinylethyl pullulan obtained in Example 11 (
In heavy water, D. S, 1.15, measured at 270MIIz)
Examples 12 to 14. The same operations as in Examples 1 to 3 were carried out, except that phenyl vinyl sulfoxide (referred to as pvso in the table) was used in place of methyl vinyl sulfoxide at the molar ratio shown in Table 4. These results are also listed in Table 4. Further, 'H-NMR spectrum of phenylsulfinylethyl pullulan obtained in Example 14 (in heavy DMSO.
D. S. 1.69, measured with 270 old 1z) is shown in Figure 5.

Table 4 (Effects of the Invention) Since the sulfinylethyl cellulose of the present invention is soluble in water or dimethyl sulfoxide, it is useful as a thickener, a binder, a protective colloid agent, etc. The material can be expected to be used as a permselective membrane material for sulfur dioxide.

[Brief explanation of drawings]

In the figure, the lower figure is the 1H-NMR spectrum of pullulan, which is the starting material for the sulfinylethyl pullulan of the present invention. Figure 2 and the following are related to the present invention; Figure 2 is the 18-NMR spectrum of methylsulfinylethyl pullulan obtained in Example 3, and Figure 3 is the 1H-NMR spectrum of ethylsulfinylethyl pullulan obtained in Example 8. Spectrum, FIG. 4 is the "H-NMR spectrum of tert-butylsulfinylethyl pullulan obtained in Example 11, and FIG. 5 is the 11-I-NMR spectrum of phenylsulfinylethyl pullulan obtained in Example 14. are shown respectively. Fig. 2 b ko 4 j 2 0 Fig. 3

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, each X is a hydrogen atom, ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (Here, R is the number of carbon atoms 1 ~ 6 alkyl groups), or phenylsulfinylethyl groups represented by ▲ ▲ There are mathematical formulas, chemical formulas, tables, etc. Sulfinylethyl pullulan whose average degree of substitution of the groups is at least 0.05, n being an integer representing the number of repeating glucose units. 2. Pullulan, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R represents an alkyl group having 1 to 6 carbon atoms) Alkylvinyl sulfoxide, or ▲ Numerical formulas, chemical formulas, tables, etc. The method for producing sulfinylethyl pullulan according to claim 1, characterized in that the phenylvinyl sulfoxide represented by ▼ is reacted in the presence of an alkali catalyst.