HEAT-STABILISING AGENT

Abstract

Polyurethane heat-stabilizing agents may help resist temperature changes and preparations of an aqueous composition which may be resistant to temperature changes due to the use of such an agent (P). The viscosity may be thermally stabilized by such an aqueous composition in a wide temperature range and for many shear gradient values.

Claims

1. A heat stabilizing agent (P), comprising: a polyurethane (P1) comprising, in polymerized form: a diisocyanate compound (A1), a polyisocyanate compound (A2), or combination thereof in a range of from 0.1 to 28 wt. %; a polyhydroxylated compound (B) in a range of from 2 to 99.5 wt. %; and a monoisocyanate compound (C1) of formula I, a monohydroxylated compound (C2) of formula II, a compound (C3) of formula III, or a combination thereof, in a range of from 0.4 to 70 wt. %, T.sup.1-NCO (I), T.sup.2-OH (II), R.sup.1-(OE).sub.a(OP).sub.b-R.sup.2 (III) wherein T.sup.1 and T.sup.2 are independently a straight C.sub.28-C.sub.40-alkyl group or a branched C.sub.28-C.sub.40-alkyl group, a and b are independently 0 or an integer or decimal less than 150, a or b being different from 0, EO is independently a CH.sub.2CH.sub.2O group, PO is independently a combination of (i) at least one CH.sub.2CH.sub.2O group with (ii) at least one group chosen CH(CH.sub.3)CH.sub.2O and/or CH.sub.2CH(CH.sub.3)O, R.sup.1 is a group comprising at least one labile hydrogen atom, and R.sup.2 is independently a straight C.sub.28-C.sub.40-alkyl group or a branched C.sub.28-C.sub.40-alkyl group, or a polyurethane (P2) prepared in the absence of any diisocyanate compound, comprising, in reacted form: a polyisocyanate compound (A2) in a range of from 0.1 to 28 wt. %; a polyhydroxylated compound (B) in a range of from 2 to 99.5 wt. %; and a monoisocyanate compound (C1) of formula I, a monohydroxylated compound (C2) of formula II, a compound (C3) of formula III, or a combination thereof, in a range of from 0.4 to 70 wt. %.

2. The agent (P) of claim 1, wherein the polyisocyanate compound (A2) is present an comprises more than 2 isocyanate groups.

3. The agent (P) of claim 1, wherein the polyhydroxylated compound (B) is: a compound (B1) of formula IV:
(HO)-L.sub.n-(OH)   (IV) L being independently a poly(alkyleneglycol) residue, and n being independently a number in a range of from 30 to 1,000; a compound (B1) of formula (IV) combined with a non-alkoxylated compound (B2) comprising at least three hydroxyl groups; a polyalkoxylated compound (B3) comprising at least three hydroxyl groups; a compound (B4) of formula (V):
HO-(OA).sub.p-N(Q)-(OA).sub.q-OH   (V), Q independently being a straight C.sub.28-C.sub.40-alkyl group or a branched C.sub.28-C.sub.40-alkyl group, OA independently being an ethoxylated group or a combination of ethoxylated(—CH.sub.2CH.sub.2O—) groups and propoxylated (—CH.sub.2C(CH.sub.3)O—) groups, and p and q independently being a number in a range of from 50 to 200; or a combination thereof.

4. The agent (P) of claim 1, for which the compound (B) is: a compound (B1) of formula (IV):
(HO)-L.sub.n-(OH)   (IV), L independently being a poly(ethylene glycol) residue, and n independently being a number in a range of from 50 to 400; a compound (B2) comprising three hydroxyl groups; a polyethoxylated compound (B3) comprising three hydroxyl groups; a compound (B4) of formula (V) wherein Q is independently a branched C.sub.30-C.sub.36-alkyl group or a straight C.sub.30-C.sub.36-alkyl group.

5. Agent (P) of claim 1, wherein the compounds (B) has a molar mass (Mw) measured by SEC in a range of from 1,500 to 40,000 g/mol.

6. Agent (P) of claim 1, wherein the monoisocyanate compound (C1) is a compound of formula (I) wherein T.sup.1 is independently a straight C.sub.30-C.sub.36-alkyl group or a branched C.sub.30-C.sub.36-alkyl group, or wherein the monoisocyanate compound (C1) is prepared by a separate reaction of (i) at least one compound comprising at least one labile hydrogen atom and of (ii) at least one diisocyanate compound, or wherein the monoisocyanate compound (C2) is a compound of formula (II) wherein T.sup.2 is represents a straight C.sub.30-C.sub.36-alkyl group or a branched C.sub.30-C.sub.36-alkyl group, or wherein the compound (C3) is a compound of formula (III) wherein a is an integer or decimal ranging from 5 to 100, b represents is 0, R.sup.1 is a group comprising at least one labile hydrogen atom and R.sup.2 is a straight C.sub.30-C.sub.36-alkyl group or a branched C.sub.30-C.sub.36-alkyl group.

7. Agent (P) of claim 1, prepared by at least one polymerization reaction of: the monomer (A) in a range of from 0.2 to 26 wt. %, the monomer (B) in a range of from 6 to 99.3 wt. %, and the monomer (C) in a range of from 0.5 to 68 wt. %, relative to total monomer weight.

8. A method for preparing an aqueous composition that is heat-resistant to temperature changes, the method comprising: adding the heat-stabilizing agent (P) of claim 1, to the aqueous composition.

9. The method of claim 8 wherein the aqueous composition comprises the heat-stabilizing agent (P) in a range of from 0.05 to 5 wt. %, relative to total composition weight.

10. The method of claim 8, wherein the aqueous composition has, for a temperature variation in a range of from 5 to 50° C., a viscosity measured for a shear gradient in a range from: 0.1 to 1,000 s.sup.−1 in a range of from 30 to 98% of the an initial viscosity value of the aqueous composition, or 0.1 to 100 s.sup.−1, in a range of from 30 to 98% of the initial viscosity value of the aqueous composition, or 1 to 100 s.sup.−1, in a range of from 30 to 98% of the initial viscosity value of the aqueous composition, or 0.1 to 1 s.sup.−1, in a range of from 40 to 98% of the initial viscosity value of the aqueous composition.

11. An aqueous composition, made by the method of claim 8.

12. The composition of claim 11, which is a hydraulic binder composition, a bonding agent composition, a detergent composition, a cosmetic composition, an ink composition, an aqueous paper coating composition, or a coating composition.

13. A method for heat stabilizing a viscosity of an aqueous composition, the method comprising; adding the heat-stabilizing agent (P) of claim 1 to the aqueous composition, wherein, for a temperature ranging from 5° C. to 50° C., a decrease in viscosity measured for a shear gradient ranging from: 0.1 to 1,000 s.sup.−1 is less than 70% relative to an initial viscosity of the aqueous composition, or 0.1 to 100 s.sup.−1 is less than 70% relative to the initial viscosity of the aqueous composition, or 1 to 100 s.sup.−1 is less than 70% relative to the initial viscosity of the aqueous composition, or 0.1 to 1 s.sup.−1 is less than 60% relative to the initial viscosity of the aqueous composition.

14. The method of claim 13, wherein the heat-stabilizing agent (P) is added to the aqueous composition in an amount in a range of from 0.05 to 5 wt. %, relative to total composition weight.

15. A method for improving resistance to temperature changes of an aqueous composition, the method comprising: adding the heat-stabilizing agent (P) of claim 1 to the aqueous composition.

Description

EXAMPLE 1

Preparation of Urethane Compounds (P1a) and (P1b) According to the Invention and of a Comparative Urethane Compound (CP1)

[0216] In a 3 L glass reactor (container 1) equipped with a mechanical stirring rod, vacuum pump, and nitrogen inlet, and heated by means of a jacket for which oil circulates, 357 g of compound (B) (polyethylene glycol with a molecular mass (Mw) of 8,000 g/mol or PEG 8,000) is introduced and heated to 90° C. in an inert atmosphere. This is followed by the addition of 139.8 g of dotriacontane alcohol (monoalcohol comprising a branched C.sub.32-alkyl group) that is ethoxylated with 25 equivalents of ethylene oxide as a compound (C3) of formula III for which a represents 25, EO represents a CH.sub.2CH.sub.2O group, R.sup.1 represents OH and R.sup.2 represents a branched C.sub.32-alkyl group. This mixture is subjected to inert atmosphere/vacuum cycles until the water content reaches or is less than 1,500 ppm.

[0217] 29.7 g of isophorone diisocyanate (IPDI) as compound (A1) and containing 0.3 g of a bismuth carboxylate catalyst are then rapidly added. When the addition is complete, the reaction mixture is left to stir for 60 minutes at 90° C.±1° C. Then, the absence of isocyanate is checked by back titration. 1 g is collected from the reaction medium to which an excess of dibutylamine (1 mol, for example) is added, which reacts with any isocyanate groups that may be present in the medium. Any unreacted dibutylamine is then assayed with hydrochloric acid (1 N, for example). The number of isocyanate groups present in the reaction medium can then be deduced. If this number is not zero, the reaction is continued for 15-minute periods until the reaction is completed. The heat stabilizing agent (P1a) according to the invention is obtained.

[0218] Similarly, a heat-stabilizing agent (P1b) according to the invention is prepared using 382.1 g of PEG 8,000 as compound (B), 55.7 g of non-ethoxylated dotriacontane alcohol (monoalcohol comprising a branched C.sub.32-alkyl group) as compound (C2) of formula II wherein T.sup.2 represents a branched C.sub.32-alkyl group and 26.5 g of IPDI as compound (A1). The heat-stabilizing agent (P1b) according to the invention is obtained.

[0219] Similarly, a comparative urethane compound (CP1) is prepared using 437.8 g of PEG 8,000, 165 g of tristyrylphenol alcohol (monoalcohol comprising a tristyrylphenolyl group) which is ethoxylated with 25 equivalents of ethylene oxide and 36.8 g of IPDI as compound (A1). The comparative urethane compound (CP1a) is obtained.

EXAMPLE 2

Preparation and Evaluation of Aqueous Formulations Comprising a Heat-Stabilizing Agent According to the Invention or a Comparative Urethane Compound

[0220] In a 500 mL beaker, 400 mL of bi-permuted water is poured and heated to 60° C. Under mechanical stirring, 8.16 g of heat-stabilizing agent (P1a) is added. This addition is done slowly in order to allow a gradual homogenisation of the mixture. A gelled formulation F1 according to the invention is obtained.

[0221] Similarly, a gelled formulation F2 according to the invention is prepared by replacing the heat-stabilizing agent (P1) with 21.05 g of heat-stabilizing agent (P1b). Also similarly, a gelled formulation CF1 according to the invention is prepared by replacing the heat-stabilizing agent (P1a) with 44.04 g of comparative compound (CP1).

[0222] The amount of water in formulations F2 and CF1 is adjusted so that these formulations have starting viscosities comparable to that of formulation F1 for a shear gradient of 10 s.sup.−1. The thickening efficacy of the formulations is assessed after 24 hours by measuring flow curves for various shear gradients (Thermo Scientific Mars III rheometer using a plane-cone geometry of 60 mm in diameter with a 1° angle) and at different temperatures. The thermal stability of the formulation is then assessed by calculating the change in viscosity depending on the temperature change for the various shear gradients applied. The change in viscosity is calculated in a standardized manner relative to the viscosity measured at 4.9° C. For each viscosity value measured, the ratio R (viscosity measured at a certain temperature/viscosity measured at 4.9° C.) corresponding to the residual viscosity of each formulation assessed, is calculated.

[0223] The results of the viscosity values and R ratios for the formulation F1 comprising the agent (P1) according to the invention are shown in Table 1.

TABLE-US-00001 TABLE 1 Formulation F1 comprising the agent (P1a) Temperature Shear Gradient (s.sup.−1) (° C.) 0.1 1 10 100 Viscosity (mPa .Math. s) 4.9 192.00 29.33 7.35 0.77 10.0 188.50 29.43 7.18 0.67 14.9 182.40 28.23 6.96 0.63 20.0 171.70 27.83 6.58 0.58 24.9 163.30 26.83 6.32 0.54 29.9 154.10 25.64 6.05 0.51 35.0 139.80 23.61 5.61 0.47 39.9 130.50 21.98 5.28 0.44 45.1 117.60 19.24 4.73 0.39 50.0 106.90 17.23 4.30 0.35 R 4.9 1.00 1.00 1.00 1.00 10.0 0.98 1.00 0.98 0.86 14.9 0.95 0.96 0.95 0.81 20.0 0.89 0.95 0.90 0.74 24.9 0.85 0.91 0.86 0.70 29.9 0.80 0.87 0.82 0.66 35.0 0.73 0.80 0.76 0.60 39.9 0.68 0.75 0.72 0.57 45.1 0.61 0.66 0.64 0.50 50.0 0.56 0.59 0.59 0.46

[0224] The results for formulation F2 comprising the agent (P1b) according to the invention are shown in Table 2.

TABLE-US-00002 TABLE 2 Formulation F2 comprising the agent (P1b) Temperature Shear Gradient (s.sup.−1) (° C.) 0.1 1 10 100 Viscosity (mPa .Math. s) 4.9 292.30 37.93 9.41 1.03 10.0 289.60 36.30 8.71 0.98 14.9 285.70 34.70 7.87 0.89 20.0 281.20 33.27 7.10 0.79 24.9 277.70 31.82 6.42 0.73 29.9 274.40 30.53 5.96 0.67 35.0 266.10 28.69 5.34 0.60 39.9 254.30 27.57 4.95 0.55 45.1 223.00 25.84 4.36 0.49 50.0 197.30 24.62 3.94 0.45 R 4.9 1.00 1.00 1.00 1.00 10.0 0.99 0.96 0.93 0.95 14.9 0.98 0.91 0.84 0.87 20.0 0.96 0.88 0.75 0.76 24.9 0.95 0.84 0.68 0.70 29.9 0.94 0.80 0.63 0.65 35.0 0.91 0.76 0.57 0.58 39.9 0.87 0.73 0.53 0.53 45.1 0.76 0.68 0.46 0.48 50.0 0.67 0.65 0.42 0.44

[0225] The results for the comparative formulation CF1 comprising the comparative polymer (CP1) are shown in Table 3.

TABLE-US-00003 TABLE 3 Formulation CF1 comprising the polymer (CP1) Temperature Shear Gradient (s.sup.−1) (° C.) 0.1 1 10 100 Viscosity (mPa .Math. s) 4.9 9.20 8.61 8.85 8.41 10.0 8.56 8.16 8.02 7.46 14.9 7.67 7.41 7.36 6.69 20.0 6.30 6.16 6.22 5.49 24.9 5.39 5.36 5.50 4.76 29.9 4.64 4.64 4.84 4.11 35.0 3.67 3.68 3.88 3.25 39.9 3.15 3.14 3.34 2.77 45.1 2.50 2.46 2.63 2.18 50.0 2.15 2.10 2.26 1.86 R 4.9 1.00 1.00 1.00 1.00 10.0 0.93 0.95 0.91 0.89 14.9 0.83 0.86 0.79 0.79 20.0 0.68 0.72 0.70 0.65 24.9 0.59 0.62 0.62 0.57 29.9 0.50 0.54 0.55 0.49 35.0 0.40 0.43 0.44 0.39 39.9 0.34 0.36 0.38 0.33 45.1 0.27 0.29 0.30 0.26 50.0 0.23 0.24 0.25 0.22

[0226] For different shear gradients, the change in viscosity of the formulations comprising an agent according to the invention or a comparative polymer is compared for various temperature ranges by calculating the viscosity loss.

[0227] The viscosity loss results are shown in Table 4.

TABLE-US-00004 TABLE 4 Viscosity loss (%) per Temperature shear gradient (s.sup.−1) Formulation range (° C.) 0.1 1 10 100 with (P1a)  5->15  5%  4%  5% 19% 15->35 23% 16% 19% 25% 30->50 31% 33% 29% 31%  5->50 44% 41% 41% 54% with (P1b)  5->15  2%  9% 16% 13% 15->35  7% 17% 32% 34% 30->50 28% 19% 34% 32%  5->50 33% 35% 58% 56% with (CP1)  5->15 17% 14% 21% 21% 15->35 52% 50% 47% 51% 30->50 54% 55% 53% 55%  5->50 77% 76% 75% 78%

[0228] For many temperature ranges, it is possible to observe that the heat-stabilizing agents according to the invention make it possible to limit the viscosity loss much more significantly than the comparative polymer. This thermal stabilization of the viscosity is possible for shear gradients corresponding to many conditions of use or application of aqueous compositions.