Poly(oxyalkylene)urethanes as a solubilizer and stabilizer in active ingredient formulations

Abstract

Poly(oxyalkylene)urethane surfactants of the formula (I)
R.sup.2XOCHN[R.sup.1NHCOO[(CH.sub.2).sub.qO].sub.xCONH].sub.nR.sup.1NHCOXR.sup.2(I)
in which R.sup.1: an alkylene radical, a cycloalkylene radical or an arylene radical; X: O or NH; R.sup.2: a linear or branched (C.sub.1-C.sub.4)-alkyl radical, monosubstituted by a group selected from: sulfo, carboxyl and [N,N-di-(C.sub.1-C.sub.4)-alkyl]amino, or disubstituted by: carboxyl; carboxyl and hydroxyl; carboxyl and mercapto; or, if X=O, R.sup.2 may also be defined as [R.sup.3OCONHR.sup.1NHCOO].sub.mR.sup.4 in which R.sup.3: a linear or branched (C.sub.1-C.sub.4)-alkylene radical, monosubstituted by COOH, especially a CH.sub.2[C(COOH)(CH.sub.3)]CH.sub.2 radical, R.sup.1 is as defined above, and R.sup.4: C.sub.2-C.sub.22-alkyl or a CH.sub.2[C(COOH)(CH.sub.3)]CH.sub.2OH radical, and m=an integer from 1 to 10; n=an integer from 1 to 7; q=an integer from 3 to 5; and x=an integer from 10 to 70;
and the water-soluble or water-dispersible salts thereof are described as a solubilizer and stabilizer in active ingredient formulations.

Claims

1. A poly(oxyalkylene)urethane surfactant of the formula (I)
R.sup.2XOCHN[R.sup.1NHCOO[(CH.sub.2).sub.qO].sub.xCONH].sub.nR.sup.1NHCOXR.sup.2(I) in which R.sup.1: an alkylene radical, a cycloalkylene radical or an arylene radical; X: O or NH; R.sup.2: a linear or branched (C.sub.1-C.sub.4)-alkyl radical, monosubstituted by a group selected from: sulfo, carboxyl and [N,N-di-(C.sub.1-C.sub.4)-alkyl]amino, or disubstituted by: carboxyl; carboxyl and hydroxyl; carboxyl and mercapto; or, if X=O, R.sup.2 may also be defined as [R.sup.3OCONHR.sup.1NHCOO].sub.mR.sup.4 in which R.sup.3: a linear or branched (C.sub.1-C.sub.4)-alkylene radical, monosubstituted by COOH, R.sup.1 is as defined above, and R.sup.4 : C.sub.2-C.sub.22-alkyl or a CH.sub.2[C(COOH)(CH.sub.3)]CH.sub.2OH radical, and m=an integer from 1 to 10; n=an integer from 1 to 7; q=an integer from 3 to 5; and x=an integer from 10 to 70; or a water-soluble or water-dispersible salt thereof.

2. The poly(oxyalkylene)urethane surfactant of claim 1, wherein, in the formula (I), q=4 and R.sup.1 is an alkylene having 4 to 12 carbon atoms or a cycloalkylene having 6 to 12 carbon atoms.

3. The poly(oxyalkylene)urethane surfactant of claim 1, wherein R.sup.1 is isophoronediyl.

4. The poly(oxyalkylene)urethane surfactant claim 1, wherein R.sup.2 is a linear or branched (C.sub.1-C.sub.4)-alkyl radical, which is monosubstituted by a group selected from the group consisting of sulfo, carboxyl and [N,N-di-(C.sub.1-C.sub.2)-alkyl]amino, or which is disubstituted by carboxyl.

5. The poly(oxyalkylene)urethane surfactant of claim 1, wherein R.sup.2 is a linear or branched (C.sub.2-C.sub.4)-alkyl radical which is monosubstituted by carboxyl or N,N-di(methyl)amino, or which is disubstituted by: carboxyl, carboxyl and hydroxyl; or, if X=O, R.sup.2=[R.sup.3OCONHR.sup.1NHCOO].sub.mR.sup.4 in which R.sup.3: CH.sub.2[C(COOH)(CH.sub.3)]CH.sub.2, R.sup.4: C.sub.2 to C.sub.22-alkyl or a CH.sub.2[C(COOH)(CH.sub.3)]CH.sub.2OH radical, and m=1 to 5.

6. A process for preparing the poly(oxyalkylene)urethane surfactant of formula (I) of claim 1, comprising a) reacting at least one diisocyanate OCNR.sup.1 NCO with at least one polyetherdiol HO[(CH.sub.2).sub.qO].sub.xH in a polar aprotic solvent to give a polyurethane; and b1) reacting the polyurethane obtained with an optionally terminally functionalized amine or alcohol of the formula NH.sub.2R.sup.2 or HOR.sup.2, and b2) optionally, if the alkyl radical R.sup.2 of the alcohol HOR.sup.2 is a di-carboxyl- and -hydroxyl-substituted (C.sub.1-C.sub.4)-alkyl radical, reacting the functionalized polyurethane with further diisocyanate OCNR.sup.1NCO and an alkyl alcohol.

7. The process of claim 6, wherein the polar aprotic solvent used is a polar aprotic oil of a fatty acid ester or fatty acid amide of saturated fatty acids.

8. A composition comprising the poly(oxyalkylene)urethane surfactant of claim 1 and a sparingly water-soluble active ingredient having a water-solubility of at most 10 g/l at 20 C.

9. The composition of claim 8 comprising: i) 0.1 to 25% by weight of the poly(oxyalkylene)urethane surfactant, ii) 0.01 to 20% by weight of the sparingly water-soluble active ingredient having a water-solubility of at most 10 g/l at 20 C., iii) 0 to 30% by weight of at least one water-insoluble oil and iv) 40 to 99% by weight of water.

10. The composition of claim 8 comprising: i) 0.1 to 25% by weight of the poly(oxyalkylene)urethane surfactant ii) 1 to 50% by weight of the sparingly water-soluble active ingredient having a water-solubility of at most 10 g/l at 20 C., iii) 40 to 98% by weight of at least one water-insoluble oil, and iv) 0 to 10% by weight of water.

11. A method for controlling phytopathogenic fungi, unwanted vegetation, or unwanted insect or mite infestation or for regulating growth of plants comprising allowing a formulation comprising the poly(oxyalkylene)urethane surfactant of claim 1 to act on the insect or mite or the surroundings thereof on plants to be protected from the fungi, insect or mite or the soil surroundings.

12. A seed treated with a composition comprising the poly(oxyalkylene)urethane surfactant of claim 1.

13. The poly(oxyalkylene)urethane surfactant of claim 4, wherein X=NH, q=4, R.sup.1=isophoronediyl, n=1 to 7, x=13 to 28 and R.sup.2 is one of the following moieties: sulfonato-2-ethyl, carboxymethyl, carboxylatomethyl, 1,2-dicarboxylatoethyl, N,N-dimethyl-2-aminoethyl and the ammonium ion thereof.

14. The poly(oxyalkylene)urethane surfactant of claim 5, wherein q=4, R.sup.1=isophoronediyl, n=1 to 7, x=13 to 28, XO, R.sup.2 is CH.sub.2[C(COOH)(CH.sub.3)]CH.sub.2OH or [R.sup.3OCONHR.sup.1NHCOO].sub.mR.sup.4 in which m=1 to 3, R.sup.4=C.sub.12-C.sub.22-alkyl or a CH.sub.2[C(COOH)(CH.sub.3)]CH.sub.2OH radical and R.sup.3is a linear or branched (C.sub.1-C.sub.4)-alkylene radical, monosubstituted by COOH.

15. The seed of claim 12, wherein, in the formula (I), q=4 and R.sup.1 is an alkylene having 4 to 12 carbon atoms or a cycloalkylene having 6 to 12 carbon atoms.

16. The seed of claim 12, wherein, R.sup.1 is isophoronediyl.

17. The method of claim 11, wherein, in the formula (I), q=4 and R.sup.1 is an alkylene having 4 to 12 carbon atoms or a cycloalkylene having 6 to 12 carbon atoms.

18. The method of claim 11, wherein, R.sup.1 is isophoronediyl.

19. The method of claim 11, wherein, R.sup.2 is a linear or branched (C.sub.1-C.sub.4)-alkyl radical, which is monosubstituted by a group selected from the group consisting of sulfo, carboxyl and [N,N-di-(C.sub.1-C.sub.2)-alkyl]amino, or which is disubstituted by carboxyl.

20. The method of claim 11, wherein, R.sup.2 is a linear or branched (C.sub.2-C.sub.4)-alkyl radical which is monosubstituted by carboxyl or N,N-di(methyl)amino, or which is disubstituted by: carboxyl, carboxyl and hydroxyl; or, if X=O, R.sup.2=[R.sup.3OCONHR.sup.1NHCOO].sub.mR.sup.4 in which R.sup.3: CH.sub.2[C(COOH)(CH.sub.3)]CH.sub.2, R.sup.4: C.sub.2 to C.sub.22-alkyl or a CH.sub.2[C(COOH)(CH.sub.3)]CH.sub.2OH radical, and m=1 to 5.

Description

EXAMPLES

(1) Reagents used: PolyTHF1000 is a commercial product from BASF (Ludwigshafen, Germany). Agnique AMD 12 is a commercial product from BASF.

Example 1

(2) Batch in methyl ethyl ketone (MEK) with solids content 300 g:

(3) 75 g of MEK, 0.19 g of DABCO (1,4-diazabicyclo[2.2.2]octane; catalyst) and 234.77 g (0.23 mol) of PolyTHF 1000 are initially charged in a 3-neck flask and heated to 70 C. Using a dropping funnel, 65.23 g (0.29 mol) of isophorone diisocyanate (IPDI) are added while stirring within 25 minutes. Thereafter, the mixture is heated to 80 C. and polymerized for 2 hours.

(4) The NCO value is then checked (via titration: admix with defined amount of base - back-titration with an acid). If the NCO value is too high, another 0.19 g of DABCO is added and the NCO value is determined regularly until the theoretical value has been attained.

(5) Subsequently, 225 g of MEK are added and the mixture is cooled to 40 C.

(6) Thereafter, 46.42 g of 30% sodium taurinate solution (corresponding to 0.12 mol of taurinate) are added and the mixture is stirred at 40 C. for another hour.

(7) After MEK has been removed by rotary evaporation, the inventive poly(THF)urethane surfactant is dispersed in water, so as to obtain a 30% dispersion in water.

Examples 2 to 6

(8) Examples 2 to 6 were prepared according to example 1, except that the proportions of PTHF and IPDI (examples 2 to 4) or the functionalized amine (examples 5 and 6) were varied according to table 1.

Example 7

(9) Batch in Agnique AMD 12 with solids content 300 g:

(10) 75 g of Agnique AMD 12, 0.19 g of DABCO and 175.00 g (0.18 mol) of PolyTHF1000 were initially charged in a 3-neck flask and heated to 70 C. Using a dropping funnel, 48.62 g (0.22 mol) of IPDI are added while stirring within 25 minutes. Thereafter, the mixture is heated to 80 C. and polymerized for 2 hours. The NCO value is checked and, if necessary, a further 0.19 g of DABCO is added and the mixture is stirred until the theoretical NCO value is attained.

(11) Subsequently, the mixture is cooled to 70 C., 15.65 g (0.12 mol) of dimethylolpropionic acid (DMPA), 31.56 g (0.12 mol) of stearyl alcohol and 0.19 g of DABCO are added, and a dropping funnel is used to add 29.17 g (0.13 mol) of IPDI dropwise over the course of 25 minutes. Thereafter, the mixture is stirred again at 80 C. for a further 2 to 5 h, until no NCO is present any longer. Subsequently, 225 g of Agnique AMD 12 are added. This gives a solution of the inventive poly(THF)urethane surfactant.

Example 8

(12) Batch in Agnique AMD 12 with solids content 300 g:

(13) 75 g of Agnique AMD 12, 0.19 g of DABCO and 184.80 g (0.18 mol) of PolyTHF1000 are initially charged in a 3-neck flask and heated to 70 C. Using a dropping funnel, 51.35 g (0.23 mol) of IPDI are added while stirring within 25 minutes. Thereafter, the mixture is heated to 80 C. and polymerized for 2 hours.

(14) The NCO value is checked and, if necessary, a further 0.19 g of DABCO is added and the mixture is stirred until the theoretical NCO value is attained.

(15) Subsequently, the mixture is cooled to 70 C., 33.05 g (0.25 mol) of dimethylolpropionic acid (DMPA) and 0.19 g of DABCO are added, and a dropping funnel is used to add 30.81 g (0.14 mol) of IPDI dropwise over the course of 25 minutes. Thereafter, the mixture is stirred again at 80 C. for a further 2 to 5 h, until no NCO is present any longer.

(16) Subsequently, 225 g of Agnique AMD 12 are added. This gives a solution of the inventive poly(THF)urethane surfactant.

(17) The inventive poly(oxyalkylene)urethane surfactants of the formula (I) tested are summarized in table 1.

(18) NL=neutralization level

(19) TABLE-US-00001 TABLE 1 Solubility NH.sub.2R.sup.2 Solubility in Agnique Polyurethane or Neutralizing in water AMD 12 Example block HOR.sup.2 agent (NL 100%) (NL 100%) 1 4 mol PTHF Na taurinate dispersed (1000 g/mol); 5 mol IPDI 2 2 mol PTHF Na taurinate dispersed (2000 g/mol); 3 mol IPDI 3 3 mol PTHF Na taurinate dispersed (1000 g/mol); 4 mol IPDI 4 5 mol PTHF Na taurinate dispersed (1000 g/mol); 6 mol IPDI 5 4 mol PTHF Na glycinate dispersed soluble (1000 g/mol); 5 mol IPDI 6 4 mol PTHF N,N- lactic acid dispersed soluble (1000 g/mol); dimethylethylene- or HCl 5 mol IPDI diamine 7 4 mol PTHF DMPA, stearyl AMP dispersed soluble (1000 g/mol); alcohol 5 mol IPDI 8 4 mol PTHF DMPA AMP dispersed soluble (1000 g/mol); 5 mol IPDI

(20) The inventive neutralized poly(THF)urethane surfactants of examples 1 to 8 are water-dispersible, and those of examples 5 to 8 are additionally soluble in Agnique AMD 12.

(21) X % by weight (X=1, 2.5 or 5% by weight) of poly(THF)urethane surfactant and 2% by weight of active ingredient are dispersed in water. Thereafter, the mixture is stirred for 24 h (magnetic stirrer) and the undissolved active ingredient is filtered off (PVDF syringe filter with pore diameter 0.45 m).

(22) The solubilization capacities of the inventive poly(THF)urethane surfactants of examples 1, 3 and 4 in water were tested for fenofibrate and fluxapyroxad as sparingly water-soluble active ingredients (table 2). As a comparison, corresponding test results which were obtained with Pluronic 10400 are likewise given in table 2. Pluronic PE 10400 is a poly(a-oxyethylene-b-oxypropylene-a-oxyethylene) triblock copolymer (PEO-PPO-PEO monomer units: 25-56-25) having a molar mass of 5417 g/mol and 40% EO.

(23) TABLE-US-00002 TABLE 2 Surfactant Solubilization concentration Solubilization fluxapyroxad/ Surfactant % by weight fenofibrate/ppm ppm Pluronic 10400 1 139 77 (comparative) 2.5 552 289 5 1089 710 Example 1 1 747 595 2.5 1471 934 5 2896 1541 Example 3 1 646 570 2.5 1599 928 5 3242 1522 Example 4 1 748 586 2.5 1816 996 5 3584 1589

(24) In addition, the inventive poly(THF)urethane surfactants according to examples 7 and 8 were used in an oil formulation:

(25) Formulation: Poly(THF)urethane surfactants: 9% by weight Active ingredient (fluxapyroxad): 11% by weight Agnique AMD12: 54.5% by weight Solvesso: 12.5% by weight Plurafac LF1300: 11% by weight Plurafac LF 300: 2% by weight

(26) A corresponding formulation with Pluronic PE 10400 is turbid and unstable at room temperature.

(27) The active ingredient was dissolved to give a clear solution in the inventive oily formulation with the poly(THF)urethane surfactants of examples 7 and 8. The inventive formulations are stable even after 72 hours at 0 C.

(28) The results show that the inventive poly(THF)urethane surfactants, compared to the solubilizers known from the prior art, such as Pluronic PE 10400, have much better solubilizing action both in water and in oil.