POLYALKYLENE OXIDE COMPOSITION

Abstract

An aqueous solution and an aqueous dispersion of a composition that contains a polyalkylene oxide, a phenolic antioxidant and a sulfur-containing amine compound are less likely to impair the stability of the polyalkylene oxide even in the case of containing an alkali. In the above composition, the content of each of the phenolic antioxidant and the sulfur-containing amine compound is preferably set to 0.001 to 5 pasts by mass based on 100 parts by mass of the polyalkylene oxide, and the ratio of the sulfur-containing amine compound relative to 100 parts by mass of the phenolic antioxidant is preferably set to 20 to 200 pasts by mass.

Claims

1. A polyalkylene oxide aqueous liquid which is either a solution or dispersion comprising a polyalkylene oxide composition, wherein the polyalkylene oxide cc position comprises: a polyalkylene oxide; a phenolic antioxidant; and a sulfur-containing amine compound.

2. The polyalkylene oxide aqueous liquid according to claim 1, wherein the sulfur-containing amine compound is at least one selected from the group consisting of mercaptobenzimidazoles, thioureas, thiurams, dithiocarbamates, and thiazoles.

3. The polyalkylene oxide aqueous liquid according to claim 1, wherein a content of the phenolic antioxidant in the composition is 0.001 to 5 parts by mass based on 100 parts by mass of the polyalkylene oxide.

4. The polyalkylene oxide aqueous liquid according to claim 1, wherein a content of the sulfur-containing amine compound in the composition is 0.001 to 5 parts by mass based on 100 parts by mass of the polyalkylene oxide.

5. The polyalkylene oxide aqueous liquid according to claim 1, wherein a ratio of the sulfur-containing amine compound relative to 100 parts by mass of the phenolic antioxidant in the composition is 20 to 200 parts by mass.

6. The polyalkylene oxide aqueous liquid according to claim 1, further comprising an alkali.

Description

EXAMPLES

[0041] Hereinafter, the present invention will be specifically described by way of examples, comparative examples, and reference examples, but the present invention is not limited to the examples.

Example 1

[0042] 29.94 parts by mass of a polyethylene oxide having a viscosity--average molecular weight of 800,000, 0.03 parts by mass of dibutylhydrozytoluene (BHT), and 0.03 parts by mass of 2-mercaptobenzimidazole (manufactured by Kawaguchi Chemical Industry Co., Ltd.) were dry-blended to produce a polyalkylene oxide composition (1).

[0043] 970 parts by mass of a 3% sodium hydrogen carbonate aqueous solution was placed in a 1,000-mL plastic beaker, and stirring was started at a tip peripheral speed of 1.0 m/s using a flat plate (width: 80 mm, length: 25 mm). 30 parts by mass of the resulting polyalkylene oxide composition (1) was charged thereto, and stirring was continued for 3 hours while the same conditions were maintained to produce an alkali-containing aqueous solution.

Example 2

[0044] 29.94 parts by mass of a polyethylene oxide having a viscosity-average molecular weight of 800,000, 0.03 parts by mass of dibutylhydroxytoluene (BHT), and 0.03 parts by mass of 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were dry blended to produce a polyalkylene oxide composition (2). An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (2) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Example 3

[0045] 29.94 parts by mass of a polyethylene oxide having a viscosity-average molecular weight of 800,000, 0.03 parts by mass of dibutylhydroxytoluene (BHT), and 0.03 parts by mass of ethylenethiourea (manufactured by Tokyo Chemical Industry Co., Ltd.) were dry-blended to produce a polyalkylene oxide composition (3). An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (3) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Example 4

[0046] 29.94 parts by mass of a polyethylene oxide having a viscosity-average molecular weight of 800,000, 0.03 parts by mass of dibutylhydroxytoluene (BHT), and 0.03 parts by mass of tetraethylthiuram disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) were dry-blended to produce a polyalkylene oxide composition (4). An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (4) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Example 5

[0047] 29.94 parts by mass of a polyethylene oxide having a viscosity-average molecular weight of 800,000, 0.03 parts by mass of dibutylhydroxytoluene (BHT), and 0.03 parts by mass of zinc dimethyldithiocarbamate (manufactured by Kawaguchi Chemical Industry Co., Ltd.) were dry-blended to produce a polyalkylene oxide composition (5). An alkali-containing aqueous solution was produced in the same manner as in Example l except that 30 parts by mass of the resulting polyalkylene oxide composition (5) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Example 6

[0048] 29.94 parts by mass of a polyethylene oxide having a viscosity-average molecular weight of 800,000, 0.03 parts by mass of dibutylhydroxytoluene (BHT), and 0.03 parts by mass of zinc diethyldithiocarbamate (manufactured by Kawaguchi Chemical Industry Co., Ltd.) were dry-blended to produce a polyalkylene oxide composition (6). An alkali containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (6) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Example 7

[0049] 29.94 parts by mass of a polyethylene oxide having a viscosity-average molecular weight of 800,000, 0.03 parts by mass of dibutylhydroxytoluene (BHT), and 0.03 parts by mass of sodium N,N-diethyldithiocarbamate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were dry-blended to produce a polyalkylene oxide composition (7). An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (7) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Example 8

[0050] 29.955 parts by mass of a polyethylene oxide having a viscosity-average molecular weight of 800,000, 0.03 parts by mass of dibutylhydroxytoluene (BHT), and 0.015 parts by mass of 2-mercaptobenzimidazole (manufactured by Kawaguchi Chemical Industry Co., Ltd.) were dry-blended to produce a polyalkylene oxide composition (8). An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (8) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Example 9

[0051] 29.82 parts by mass of a polyethylene oxide having a viscosity-average molecular weight of 800,000, 0.03 parts by mass of dibutylhydroxytoluene (BET), and 0.15 parts by mass of tetraethylthiuram disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) were dry-blended to produce a polyalkylene oxide composition (9). An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (9) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Example 10

[0052] 29.67 parts by mass of a polyethylene oxide having a viscosity-average molecular weight of 800,000, 0.03 parts by mass of dibutylhydroxytoluene (BHT), and 0.3 parts by mass of tetraethylthiuram disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) were dry-blended to produce a polyalkylene oxide composition (10). An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (10) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Comparative Example 1

[0053] A polyalkylene oxide composition (11) was produced in the same manner as in Example 1 except that 2-mercaptobenzimidazole was not used. An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (11) was used in place of 30 Parts by mass of the polyalkylene oxide composition (1).

Comparative Example 2

[0054] A polyalkylene oxide composition (12) was produced in the same manner as in Example 1 except that 0.03 parts by mass of 2,4,6-tris(3′,5′-di-tert-butyl-4′-hydroxybenzyl mesitylene (manufactured by BASF) was used in place of 0.03 parts by mass of 2-mercaptobenzimidazole. An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (12) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Comparative Example 3

[0055] A polyalkylene oxide composition (13) was produced in the same manner as in Example 1 except that 0.03 parts by mass of hexamethylenetetramine (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.) was used in place of 0.03 parts by mass of 2-mercaptobenzimidazole. An alkali-containing aqueous solution was produced in the same manner as in Example 1 except that 30 parts by mass of the resulting polyalkylene oxide composition (13) was used in place of 30 parts by mass of the polyalkylene oxide composition (1).

Reference Example 1

[0056] A polyalkylene oxide composition (14) corresponding to the polyalkylene oxide composition (11) produced in Comparative Example 1 was produced.

[0057] 970 parts by mass of water was placed in a 1,000-mL plastic beaker, and stirring was started at a tip peripheral speed of 1.0 m/s using a flat plate (width: 80 mm, length: 25 m). 30 parts by mass of the resulting Polyalkylene oxide composition (14) was charged thereto, and stirring was continued for 3 hours while the same conditions were maintained, to produce an aqueous solution.

Stability Evaluation

[0058] Each of the alkali-containing aqueous solutions produced in Examples 1 to 10 and Comparative Examples 1 to 3 and the aqueous solution produced in Reference Example 1 were separately placed in a polyethylene container having a volume of 500 mL, and the stability immediately after the production and temporal stability of each of the aqueous solutions were evaluated based on the measurement results of viscosities. The sealed polyethylene container was kept in a thermo-hygrostat (model number: “PR-2ST” manufactured by ESPEC) adjusted to an environment of 40° C. and 75% RH, and the temporal stability was evaluated at each of time points after 7 days, 13 days, 21 days, 28 days, 60 days, and 75 days from the production.

[0059] In the viscosity measurement of each of the alkali aqueous solutions and aqueous solution, the polyethylene container was immersed in a constant temperature bath at 25° C. for about 30 minutes. The viscosity was then measured at 25° C. for 3 minutes by using a B type rotary viscometer (“Rotor No. 2” manufactured by TOKIMEC) with a rotation speed adjusted to 12 rpm.

[0060] The results are shown in Table 1. In Table 1, a viscosity retention rate is determined by the following formula. A higher viscosity retention rate represents higher temporal stability.

Viscosity retention rate (%)={viscosity at each time point [mPa.Math.s]/viscosity immediately after production [mPa.Math.s]}×100   [Expression 1]

TABLE-US-00001 TABLE 1 Immediately after After After After After After After production 7 days 13 days 21 days 28 days 60 days 75 days Example 1 Viscosity [mPa .Math. s] 266 222 235 219 216 221 219 Viscosity retention 100 83 88 82 81 83 82 rate [%] pH 8.86 — 8.80 — 8.92 9.22 9.06 Example 2 Viscosity [mPa .Math. s] 240 225 225 210 210 210 205 Viscosity retention 100 94 94 88 88 88 85 rate [%] pH 9.01 9.03 9.06 8.98 9.11 8.99 9.22 Example 3 Viscosity [mPa .Math. s] 235 210 215 215 210 210 210 Viscosity retention 100 89 91 91 89 89 89 rate [%] pH 9.01 9.04 9.10 8.99 9.12 8.98 9.25 Example 4 Viscosity [mPa .Math. s] 360 200 200 185 185 185 170 Viscosity retention 100 56 56 51 51 51 47 rate [%] pH 9.00 9.04 9.04 8.96 9.11 8.98 9.24 Example 5 Viscosity [mPa .Math. s] 240 215 190 160 135 130 110 Viscosity retention 100 90 79 67 56 54 46 rate [%] pH 9.02 9.05 9.11 8.97 9.08 8.93 9.22 Example 6 Viscosity [mPa .Math. s] 235 215 210 195 190 170 160 Viscosity retention 100 91 89 83 81 72 68 rate [%] pH 9.00 9.03 9.08 8.97 9.08 8.97 9.19 Example 7 Viscosity [mPa .Math. s] 235 220 210 195 190 170 160 Viscosity retention 100 94 89 83 81 72 68 rate [%] pH 9.00 9.05 9.09 8.97 9.10 8.98 9.25 Example 8 Viscosity [mPa .Math. s] 240 210 230 210 215 220 210 Viscosity retention 100 83 96 88 90 92 88 rate [%] pH 9.00 9.07 8.97 9.01 9.16 9.08 9.18 Example 9 Viscosity [mPa .Math. s] 350 210 195 195 205 170 170 Viscosity retention 100 60 56 56 59 49 49 rate [%] pH 8.98 9.04 8.93 8.96 9.12 8.98 9.05 Example 10 Viscosity [mPa .Math. s] 355 210 185 200 195 210 170 Viscosity retention 100 59 52 56 55 59 48 rate [%] pH 9.01 9.04 8.92 8.98 9.11 8.96 9.05 Comparative Viscosity [mPa .Math. s] 354 132 39 19 13 5 6 Example 1 Viscosity retention 100 37 11 5 4 1 2 rate [%] pH 8.84 — 8.83 — 8.86 9.08 8.96 Comparative Viscosity [mPa .Math. s] 341 101 36 21 14 6 10 Example 2 Viscosity retention 100 30 11 6 4 2 3 rate [%] pH 8.82 — 8.85 — 8.85 9.08 8.93 Comparative Viscosity [mPa .Math. s] 345 162 59 32 13 10 12 Example 3 Viscosity retention 100 47 17 9 4 3 3 rate [%] pH 8.84 — 8.82 — 8.88 9.17 8.96 Reference Viscosity [mPa .Math. s] 396 309 283 283 266 241 239 Example 1 Viscosity retention 100 78 71 71 67 61 60 rate [%] pH 7.23 — 7.12 — 7.87 6.76 7.04