Polyfluoroalkyl phosphoric acid ester or salt thereof, and mold-releasing agent comprising the same as an active ingredient

Abstract

A polyfluoroalkyl phosphoric acid ester represented by the general formula [C.sub.nF.sub.2n+1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cO].sub.mP(O)(OH).sub.3m [I] n: 1 to 6, a: 1 to 4, b: 1 to 3, c: 1 to 3, m: 1 to 3) or a salt thereof. The polyfluoroalkyl phosphoric acid ester represented by the general formula [I] is produced by subjecting a polyfluoroalkyl alcohol represented by the general formula C.sub.nF.sub.2n+1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cOH [II] (n: 1 to 6, a: 1 to 4, b: 1 to 3, c: 1 to 3) to a dehydration condensation reaction with phosphoric acid. The polyfluoroalkyl phosphoric acid ester can be easily synthesized without passing through dialkyl ester as in the case of phosphonic acid, and used for a mold-releasing agent comprising the same or a salt thereof as an active ingredient.

Claims

1. A polyfluoroalkyl phosphoric acid ester represented by the general formula:
[C.sub.nF.sub.2n+1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cO].sub.mP(O)(OH).sub.3m [I] wherein n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, c is an integer of 1 to 3, and m is an integer of 1 to 3, or a salt thereof.

2. The polyfluoroalkyl phosphoric acid ester or a salt thereof according to claim 1, which is a mixture of monoester of the general formula [I]wherein m is 1, and diester of the general formula [I] wherein m is 2.

3. A method for producing the polyfluoroalkyl phosphoric acid ester according to claim 1, comprising subjecting a polyfluoroalkyl alcohol represented by the general formula:
C.sub.nF.sub.2n1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cOH [II] wherein n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3; to a dehydration condensation reaction with phosphoric acid.

4. A mold-releasing agent comprising the polyfluoroalkyl phosphoric acid ester or a salt according to claim 1 as an active ingredient.

5. A method for producing the polyfluoroalkyl phosphoric acid ester according to claim 2, comprising subjecting a polyfluoroalkyl alcohol represented by the general formula:
C.sub.nF.sub.2n+1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cOH [II] wherein n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3; to a dehydration condensation reaction with phosphoric acid.

6. A mold-releasing agent comprising the polyfluoroalkyl phosphoric acid ester or a salt according to claim 2 as an active ingredient.

Description

EXAMPLES

(1) The following describes the present invention with reference to Examples.

Example 1

(2) 100 g (0.23 mol) of the compound:
CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)OH (95.4 GC%)
obtained in Example 1 of Patent Document 8 and 26.5 g (0.23 mol) of phosphoric acid (about 85%) were charged in a 300-ml four-necked flask equipped with a thermometer, a condenser, and a Dean-Stark apparatus. After stirring at an internal temperature of 110 C. for 24 hours, 110 g of solid matters were collected. The solid matters were dried by heating under reduced pressure, thereby obtaining 106.8 g (yield: 91.4%) of product.

(3) From the results of .sup.1H-NMR and .sup.19F-NMR, it was confirmed that the product was mixture of compounds represented by the following formulae:
CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)OP(O)(OH).sub.2 [Ia]
[CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)O].sub.2P(O)(OH) [Ib]

(4) .sup.1H-NMR(acetone-d6, TMS): 3.56(CH.sub.2CF.sub.2)
2.68(CF.sub.2CH.sub.2CH.sub.2)
4.33(CF.sub.2CH.sub.2CH.sub.2)

(5) .sup.19F-NMR(acetone-d6, C.sub.6F.sub.6): 80.2(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2)
124.9(CF.sub.3CF.sub.3CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2)
120 to 123(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2)
112.3(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2)
109.5(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2)
120 to 123(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2)
110.3(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2-)
Moreover, it was confirmed that the mixing ratio of the compounds [Ia] and [Ib] was 7:3 with respect to the molar ratio by means of a titration method.

Example 2

(6) 100 g (0.19 mol) of the compound:
CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2).sub.2(CH.sub.2CH.sub.2)OH (95.3 GC%)
obtained in Example 2 of Patent Document 8 and 21.9 g (0.19 mol) of phosphoric acid (about 85%) were charged in the four-necked flask used in Example 1. The subsequent procedure was the same as in Example 1, thereby obtaining 113 g of solid matters and 107.5 g (yield: 93.6%) of product.
CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2).sub.2(CH.sub.2CH.sub.2)OP(O)(OH).sub.2 [Ic]
[CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF)(CF.sub.2CF.sub.2).sub.2(CH.sub.2CH.sub.2)O].sub.2P(O)(OH) [Id]

(7) .sup.1H-NMR(acetone-d6, TMS): 3.56(CH.sub.2CF.sub.2)
2.68(CF.sub.2CH.sub.2CH.sub.2)
4.33(CF.sub.2CH.sub.2CH.sub.2)

(8) .sup.19F-NMR(acetone-d6, C.sub.6F.sub.6): 80.2(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2)
124.9(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2)
120 to 123(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2)
112.3(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2)
110.3(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2)
120 to 123(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2)
120 to 123(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2)
120 to 123(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2)
110.3(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2)
Moreover, it was confirmed that the mixing ratio of the compounds [Ic] and [Id] was 7:3 with respect to the molar ratio by means of a titration method.

Example 3

(9) 100 g (0.19 mol) of the compound:
CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)OH (95.5 GC%)
obtained in Reference Example 6 of Patent Document 9 and 21.9 g (0.19 mol) of phosphoric acid (about 85%) were charged in the four-necked flask used in Example 1. The subsequent procedure was the same as in Example 1, thereby obtaining 114 g of solid matters and 101.4 g (yield: 91.3%) of product.
CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)OP(O)(OH).sub.2 [Ie]
[CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)O].sub.2P(O)(OH) [If]

(10) .sup.1H-NMR(acetone-d6, TMS):
2.84(CH.sub.2CF.sub.2CH.sub.2CF.sub.2)
2.89(CH.sub.2CF.sub.2CH.sub.2CF.sub.2)
2.75(CF.sub.2CH.sub.2CH.sub.2)
4.21(CF.sub.2CH.sub.2CH.sub.2)
.sup.19F-NMR(acetone-d6, C.sub.6F.sub.6):
81.9(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
125.5(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
122 to 125(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
113.0(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
112.2(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
111.5(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
122 to 125(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
111.5(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
Moreover, it was confirmed that the mixing ratio of the compounds [Ie] and [If] was 4:1 with respect to the molar ratio by means of a titration method.

Example 4

(11) 100 g (0.24 mol) of the compound:
CF.sub.3(CF.sub.2)(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)OH (95.0 GC%)
obtained in Reference Example 8 of Patent Document 9 and 27.7 g (0.24 mol) of phosphoric acid (about 85%) were charged in the four-necked flask used in Example 1. The subsequent procedure was the same as in Example 1, thereby obtaining 112.9 g of solid matters and 101.8 g (yield: 89.1%) of product.
CF.sub.3(CF.sub.2)(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)OP(O)(OH).sub.2 [Ig]
[CF.sub.3(CF.sub.2)(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)O].sub.P(O)(OH) [Ih]

(12) .sup.1H-NMR(acetone-d6, TMS):
2.82(CH.sub.2CF.sub.2CH.sub.2CF.sub.2)
2.85(CH.sub.2CF.sub.2CH.sub.2CF.sub.2)
2.75(CF.sub.2CH.sub.2CH.sub.2)
4.25(CF.sub.2CH.sub.2CH.sub.2)

(13) .sup.19F-NMR(acetone-d6, C.sub.6F.sub.6):
87.3(CF.sub.3CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
116.5(CF.sub.3CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
112.1(CF.sub.3CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
113.2(CF.sub.3CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
124.0(CF.sub.3CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
112.6(CF.sub.3CF.sub.2CH.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2)
Moreover, it was confirmed that the mixing ratio of the compounds [Ig] and [Ih] was 4:1 with respect to the molar ratio by means of a titration method.

Example 5

(14) After 50 parts (by weight; hereinafter the same) of isopropanol was added to 20 parts of the product (polyfluoroalkyl phosphoric acid ester mixture) obtained in Example 2, 26 parts of ion-exchanged water was added, and neutralization was performed with 4 parts of triethylamine. The resultant was diluted with water to prepare an aqueous solution having a solid matters content of 0.1 wt. %, thereby preparing a mold-releasing agent.

(15) Using this mold-releasing agent, a mold release test during urethane rubber molding was performed in the following manner:

(16) A SUS cup (diameter: 45 mm, depth: 50 mm) was used as a mold. After the mold was heated to 80 C., the mold-releasing agent was applied to the cup surface, and dried at 120 C. 10 g of a mixture of 100 parts of polyurethane prepolymer (Coronate 4090, produced by Nippon Polyurethane Industry Co., Ltd.) heated to 85 C. and 14.5 parts of methylene-bis-o-chloroaniline curing agent (Iharacuamine MT, produced by Ihara Chemical Industry Co., Ltd.) heated to 120 C. was injected into the mold coated with the mold-releasing agent, and cured by heating at 120 C. for 1.5 hours.

(17) Before heat curing, a hook for taking out a cured molded product was placed in the center of the injection part. After curing, the hook was pulled to take out the molded product, and the load was calculated with a spring balance positioned above. The resulting value was 18 N (mold release performance).

Comparative Example 1

(18) In Example 5, when the mold release test was performed without applying the mold-releasing agent to the SUS cup, the rubber stuck to the SUS cup and the mold release could not be done.

Comparative Example 2

(19) In Example 5, when the mold release performance was determined using the polyfluoroalkyl phosphonic acid diethyl ester:

(20) CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2).sub.2(CH.sub.2CH.sub.2)P(O)(OCH.sub.2CH.sub.3).sub.2 (96 GC%) obtained in Example 1 of Patent Document 7, in place of the product (polyfluoroalkyl phosphoric acid ester) obtained in Example 2, the resulting value was 34 N.