RHEOLOGY ADDITIVES BASED ON HYDROXYLATED DI-OR TRI-AMIDES AND MIXTURES THEROF

Abstract

The invention relates to a fatty amide which is a di- or triamide based on a polyether diamine or triamine which can be used as organogelator and in particular as rheology additive, said amide comprising a specific mixture of hydroxylated fatty acids and short hydroxylated acids. The invention also relates to a formulation composition using said fatty amide as rheology additive and to its use with this aim in coating, adhesive or PVC plastisol compositions and in particular transparent or non-transparent mastic compositions. Said rheology additive has the advantage of not needing a specific activation process before use, in contrast to the other known fatty amide additives based on hydrogenated castor oil derivatives.

Claims

1. A polyfunctional fatty amide, which is a diamide, a triamide or a mixture thereof, wherein said polyfunctional fatty amide is represented by: A) according to formula (I):
R[(—X—R1-NHCO—R2).sub.n(1-y)][(—X—R1-NHCO—R2′).sub.ny]  (I) with n being 2 or 3, R(—X—R1-).sub.n being the residue of valency n of a primary polyamine R(—X—R1-NH2).sub.n which is a primary diamine or triamine, with each primary amine group —NH2 being a terminal group borne by a bivalent oligomer chain segment R1 chosen from alkoxylated polyester and polyether, R: C.sub.3-C.sub.10 alkylene residue of valency n resulting from a polyol R(OH).sub.n or from a polyamine R(NH.sub.2).sub.n or R(NH—R3).sub.n, X: O, NH or NR3, R2 being the C.sub.12-C.sub.52, fatty residue of hydroxylated fatty acid R2CO.sub.2H, R2′ being the C.sub.2 to C.sub.10 monocarboxylic acid R2′CO.sub.2H residue bearing at least one hydroxyl group, y representing the mean molar fraction of R2′CO.sub.2H relative to the sum of R2′CO.sub.2H+R2CO.sub.2H, in said diamide, with y varying from 0.05 to 0.50, with R2CO.sub.2H and/or R2′CO.sub.2H optionally being mixtures of respective acids, R3 being a C.sub.1-C.sub.2 alkyl substituent, or by B) according to formula (II) in the case in which said amide is a diamide:
(R2CONH).sub.(1-y)—R′—O—[CH.sub.2—CH(R4)-O].sub.x—CH.sub.2—CH(R4)-(NHCOR2′).sub.y  (II) with R′ being the residue of monopropylene glycol without OH: —CH(CH.sub.3)—CH.sub.2— and R2 and R2′ and y being defined as in formula (I) above, and x being the number of oxyalkylene units-CH2-CH(R4)-O— and x optionally varying from 5 to 45, R4 being H or methyl with the repeating oxyalkylene unit-CH2-CH(R4)-O— being ethoxy when R4 is H and propoxy when R4 is methyl or R4 corresponds to an ethoxy/propoxy mixture, and said amide having a melting point, meaning melting temperature, measured by DSC after two passes at 10° C./min, ranging from 10 to 110° C.

2. The fatty amide as claimed in claim 1, wherein a number-average molecular weight Mn of said fatty amide defined according to A) formula (I), measured by GPC in THF as polystyrene equivalents varies for: n=2 from 800 to 4000, n=3 from 1000 to 6000.

3. The fatty amide as claimed in claim 1 wherein said oligomer chain segment R1 for the fatty amide according to A) formula (I) is a polyether chain segment.

4. The fatty amide as claimed in claim 1 wherein said oligomer chain segment R1 is a polyoxypropylene chain segment.

5. The fatty amide as claimed in claim 1 wherein said oligomer chain segment R1 has a number-average molecular weight Mn ranging from 400 to 2000.

6. The fatty amide as claimed in claim 1 wherein said hydroxylated fatty acid R2CO.sub.2H is selected from 12-hydroxystearic acid (12-HSA); 9-hydroxystearic acid (9-HAS), 10-hydroxystearic acid (10-HSA), a mixture of 9- and 10-hydroxystearic acids; 14-hydroxyeicosanoic acid (14-HEA); and mixtures thereof.

7. The fatty amide as claimed in claim 1 wherein said hydroxylated fatty acid R2CO.sub.2H is 12-hydroxystearic acid.

8. The fatty amide as claimed in claim 1 wherein said monocarboxylic acid R2′CO.sub.2H is selected from: 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxymethyl)butyric acid, hydroxyacetic acid (or glycolic acid), 2-hydroxypropionic acid (lactic acid), 2-hydroxy-3-(3-pyridyl)propionic acid, 3-hydroxybutyric acid, 2-hydroxybutyric acid, 2-methyl-2-hydroxybutyric acid, 2-ethyl-2-hydroxybutyric acid, hydroxypentanoic acid, hydroxyhexanoic acid, hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid and mixtures thereof.

9. The fatty amide as claimed in claim 1 wherein said amide is a diamide according to A) or B) or a triamide according to A) with y/(1−y) varying from 1/20 to 1/2.

10. The fatty amide as claimed in claim 1 wherein said amide is a diamide according to A) or B), with y/(1−y) ranging from 1/10 to 1/2.

11. The fatty amide as claimed in claim 1 wherein said amide is a triamide according to A) with two R2 residues resulting from hydroxylated fatty acid R2CO.sub.2H and one resulting from acid R2′CO.sub.2H.

12. The fatty amide as claimed in claim 1 which is a diamide represented by option A) according to formula (I).

13. The fatty amide as claimed in claim 1 which is a diamide represented by option B) according to formula (II).

14. A formulation composition of an organic binder comprising: a) at least one organic binder, b) at least one fatty amide as defined in claim 1 as a rheological additive.

15. The composition as claimed in claim 14, wherein said binder a) is selected from: polysiloxane resins terminated by blocked silane groups, polyether resins terminated by blocked silane groups, polysulfide resins terminated by blocked silane groups, polyurethane prepolymer resins terminated by isocyanate groups, PVC resins for plastisols, and epoxy resins bearing epoxy groups.

16. The composition as claimed in claim 14 comprising in addition to a) and b) and depending on said binder, a plasticizer or a reactive diluent as defined below: c) a plasticizer for polysiloxane resins, polyurethane prepolymer resins and PVC resins for plastisols or d) a reactive diluent from epoxidized monomers for epoxy resins and optionally e) for two-component systems, a hardener for the epoxy or polyurethane resins.

17. The composition as claimed in claim 16, wherein said organic binder a) is a polysiloxane resin, a polyurethane prepolymer resin or a PVC resin for plastisols and in that said plasticizer is selected from: phthalates, adipates, trimellitates, sebacates, benzoates, citrates, phosphates, epoxides, polyesters, alkylsulfonate esters and non-phthalate substitutes for phthalates.

18. The composition as claimed in claim 17 which is a transparent or non-transparent mastic formulation composition.

19. (canceled)

20. (canceled)

21. (canceled)

22. (canceled)

23. (canceled)

24. (canceled)

Description

EXPERIMENTAL SECTION

1) Starting Materials Used and Codes

[0073] See Table 1 below

[0074] Table summarizing the starting materials used in synthesis and in formulations

TABLE-US-00001 TABLE 1 Product used Chemical name Function Supplier 12HSA 12-Hydroxystearic Hydroxylated fatty acid Jayant Agro acid Stearine Stearic acid Non-hydroxylated fatty acid, Sogis according to R2CO.sub.2H bMBA 2,2- Short hydroxylated acid Sigma Aldrich bis(hydroxymethyl) according to R2′CO.sub.2H butyric acid JEFFAMINE ® T- Jeffamine ® T-3000 Polyoxypropylene triamine Huntsman 3000 polyetheramine (primary) with overall ~50 Polyetheramine oxypropylene (OP) units JEFFAMINE ® D- Jeffamine ® D-2000 Polyoxypropylene diamine Huntsman 2000 polyetheramine (primary) with ~33 OP units Polyetheramine HCO (as flakes) Hydrogenated castor Reference rheology additive Gokul Agro oil Crayvallac ® Hydrogenated castor Reference rheology additive Arkema Antisettle CVP oil (micronized powder) Standard fatty 12HSA—HMDA— Reference diamide rheology / diamide 12HSA additive for comparison MS Polymer ® Silylated polyether Applicative formulation resin Kaneka S203H Jayflex ® DIUP Diisoundecyl Plasticizer for formulation BASF phthalate

[0075] For reasons of clarity, the following abbreviations will be used: [0076] 12HSA: 12-Hydroxystearic acid [0077] SA: Stearic acid [0078] HMDA: Hexamethylenediamine [0079] D2000: Jeffamine® D-2000 polyetheramine [0080] 13000: Jeffamine® T-3000 polyetheramine [0081] bMBA: 2,2-bis(hydroxymethyl)butyric acid

2) Examples

Example A According to the Invention—T3000-(12HSA-bMBA).SUB.3

[0082] 231.40 g of Jeffamine® T-3000 (0.078 mol, 1 eq), 63.11 g of 12-hydroxystearic acid (0.199 mol, 2.55 eq) and 5.2 g of 2,2-bis(hydroxymethyl)butyric acid (0.035 mol, 0.45 eq) are added to a 1 liter round-bottom flask equipped with a thermometer, a Dean-Stark apparatus, a condenser and a stirrer. The mixture is heated to 180° C. under an inert atmosphere. The water removed accumulates in the Dean-Stark apparatus from 150° C. The reaction is monitored by the acid number and the amine number. When the acid and amine numbers are respectively less than 6, the reaction is halted. The reaction mixture is cooled to 140° C. and is discharged into a silicone mold. Once cooled to ambient temperature, the product is converted into flakes.

Example B According to the Invention—D2000-(12HSA-bMBA).SUB.2

[0083] 232.3 g of Jeffamine® D-2000 (0.115 mol, 1 eq), 62.12 g of 12-hydroxystearic acid (0.196 mol, 1.7 eq) and 5.11 g of 2,2-bis(hydroxymethyl)butyric acid (0.034 mol, 0.3 eq) are added to a 1 liter round-bottom flask equipped with a thermometer, a Dean-Stark apparatus, a condenser and a stirrer. The mixture is heated to 180° C. under an inert atmosphere. The water removed accumulates in the Dean-Stark apparatus from 150° C. The reaction is monitored by the acid number and the amine number. When the acid and amine numbers are respectively less than 6, the reaction is halted. The reaction mixture is cooled to 140° C. and is discharged into a silicone mold. Once cooled to ambient temperature, the product is converted into flakes.

Comparative Example C—T3000-(SA).SUB.3

[0084] 313.6 g of Jeffamine® T-3000 (0.10 mol, 1 eq) and 86.4 g of stearic acid (0.3 mol, 3 eq) are added to a 1 liter round-bottom flask equipped with a thermometer, a Dean-Stark apparatus, a condenser and a stirrer. The mixture is heated to 180° C. under an inert atmosphere. The water removed accumulates in the Dean-Stark apparatus from 150° C. The reaction is monitored by the acid number and the amine number. When the acid and amine numbers are respectively less than 6, the reaction is halted. The reaction mixture is cooled to 140° C. and is discharged into a silicone mold.

Comparative Example D—D2000-(SA).SUB.2

[0085] 312.2 g of Jeffamine® D-2000 (0.15 mol, 1 eq) and 87.8 g of stearic acid (0.3 mol, 2 eq) are added to a 1 liter round-bottom flask equipped with a thermometer, a Dean-Stark apparatus, a condenser and a stirrer. The mixture is heated to 180° C. under an inert atmosphere. The water removed accumulates in the Dean-Stark apparatus from 150° C. The reaction is monitored by the acid number and the amine number. When the acid and amine numbers are respectively less than 6, the reaction is halted. The reaction mixture is cooled to 140° C. and is discharged into a silicone mold.

3) Study of the Gelling Power of the Organogelators

[0086] In this study, the ability of the tested rheology additives to form a gel in a simplified formulation containing solely a conventional plasticizer (Jayflex® DIUP) used in PVC plastisol formulations will be compared.

[0087] The formulations are prepared using a laboratory “planetary” mixer (Molteni® EMD 1 type) provided with a dispersing disk and a scraper which makes it possible to mix high-viscosity products but also powders in non-fluid systems. It is equipped with a vacuum pump which makes it possible to prevent the ingress of moisture during the dispersing. The temperature within the Molteni® EMD 1 is recorded by a probe attached to the scraper and can be regulated by virtue of a bath.

[0088] The simplified formulations tested/compared are presented in table 2 below with the common plasticizer being Jayflex® DIUP and the variable rheology additive tested and compared being the amides mentioned or other reference products mentioned.

Composition of the Simplified Formulations

[0089]

TABLE-US-00002 TABLE 2 Formulation Component Weight % F1 Jayflex ® DIUP plasticizer 95 Example A amide 5 F2 Jayflex ® DIUP plasticizer 95 Example B amide 5 F3 Jayflex ® DIUP plasticizer 95 Example C amide 5 F4 Jayflex ® DIUP plasticizer 95 Example D amide 5 F5 Jayflex ® DIUP plasticizer 95 12HSA-HMDA-12HSA 5 F6 Jayflex ® DIUP plasticizer 95 HCO 5 F7 Jayflex ® DIUP plasticizer 95 Crayvallac ® Antisettle CVP 5

[0090] The rheology additive is introduced into the plasticizer and the mixture is brought to the incorporation temperature (cf. table 3) and dispersed for 5 minutes. At the end of the dispersing, the mixture is cooled to ambient temperature and the behavior of the gel is studied visually (see table 3 below).

Behavior and Appearance of the Gel as a Function of the Incorporation Temperature

[0091]

TABLE-US-00003 TABLE 3 Formulation Temperature Behavior of the gel Appearance F1 60° C.** Strong gel Transparent 80° C.** Strong gel Transparent F2 60° C.** Strong gel Transparent 80° C.** Strong gel Transparent F3 60° C.** Liquid Transparent 80° C.** Liquid Transparent F4 60° C.** Liquid Transparent 80° C.** Liquid Transparent F5 60° C.*  Weak gel Opaque 80° C.*  Weak gel Opaque 100° C.**  Weak gel Opaque F6 60° C.*  Weak gel Opaque (presence of grains) 80° C.** Weak gel Opaque F7 60° C.*  Strong gel Opaque 80° C.** Weak gel Opaque (slight syneresis) *partial dissolution; **complete dissolution

[0092] The results of the gel tests show that the products according to the invention (amides according to examples A and B) form gels, while the comparative products are in the liquid form. Thus, the compound of example C described in particular in EP 1 514 912 A2 does not make it possible to obtain the gel (cf. formulation F3), which strongly indicates that the presence of the hydroxyl group, providing H bonds, is essential to the formation of the supramolecular assembly and of the three-dimensional (3D) network of fibers formed.

[0093] The behavior of the organogelator agents can also be influenced by the initial structure of the amine used. Thus, on comparing the organogelator described in WO 2014/053774A1 (12HSA-HMDA-12HSA) with the compound of example B according to the invention, a significant difference in gel strength may be observed. In particular, if the aliphatic amine is replaced with a polyether amine, the gelling power increases, making it possible, in addition, to obtain a transparent gel. It should be noted that, in order to be completely dissolved, the compound 12HSA-HMDA-12HSA (cf. formulation F5) requires greater temperatures than the products according to the invention.

[0094] Furthermore, the performance qualities of the gels can be linked to the physical nature of the rheology additive. Consequently, for formulations F6 and F7 to begin with at a constant temperature (60° C.) of incorporation of the rheology additive, a difference in gel strength is observed. Namely, if the additive is in the form of flakes (cf. formulation F5), the gel strength will decrease, which might well be explained by an incomplete incorporation of the product in the formulation due to the lack of solubility. Furthermore, grains could be observed, which might corroborate this hypothesis.

[0095] Also, it may be observed that, in the case where the additive is in the powder form and is incorporated at a higher temperature (80° C. in F7) than its optimum incorporation temperature (60° C. in F7), the gel strength will decrease, which shows in addition a sensitivity to the temperature due probably to the over-dissolution of the product. It is thus important, in the case of the standard products, to indeed observe an incorporation temperature window for which the organogelator is effective.

[0096] As regards formulations F1 and F2 containing the products according to the invention, the formation of a strong gel may be observed irrespective of the incorporation temperature. It should be mentioned that, at the temperatures studied, the rheology additive is completely dissolved. Furthermore, the formulations exhibit a completely transparent appearance.

[0097] 4) Evaluation of the Rheological Performance Qualities in a Simplified Hybrid Mastic Formulation

[0098] This study compares the rheological performance qualities of the additives of a simplified hybrid mastic formulation comprising, as plasticizer: Jayflex® DIUP and, as rheology additive, the mentioned product being compared.

Composition of the Simplified Hybrid Mastic Formulations

[0099]

TABLE-US-00004 TABLE 4 % by Formulation Component weight Function F8 Jayflex ® DIUP plasticizer 47.5 Plasticizer MS-Polymer ® S 203 H 47.5 Resin Amide according to example 5 Rheology additive A F9 Jayflex ® DIUP plasticizer 47.5 Plasticizer MS-Polymer ® S 203 H 47.5 Resin Crayvallac Antisettle CVP 5 Rheology additive F10 Jayflex ® DIUP plasticizer 47.5 Plasticizer MS-Polymer ® S 203 H 47.5 Resin Amide according to example 5 Rheology additive B F11 Jayflex ® DIUP plasticizer 47.5 Plasticizer MS-Polymer ® S 203 H 47.5 Resin 12HSA—HMDA— 5 Rheology additive 12HSA

[0100] The formulations are prepared using a Molteni® EMD 1 mixer. The resin and the plasticizer are added and homogenized in a first stage and in the proportions shown (table 4). The additive is weighed out and subsequently added during the second stage. Thus, the reaction mixture, which is kept under vacuum during the mixing phases, is brought to 80° C. for 5 minutes. At the end of this phase, the mixture is cooled to 25° C. and discharged. The performance qualities of these formulations are presented in table 5 below.

Rheological Performance Qualities

[0101]

TABLE-US-00005 TABLE 5 Viscosity at Viscosity at Yield Formu- 0.1 s.sup.−1 100 s.sup.−1 Thixotropic stress lation (Pa .Math. s) (Pa .Math. s) index (Pa) Appearance F8 717 3.50 205 73 Transparent F9 296 6.06 49 4.4 Opaque F10 313 2.78 113 30 Transparent F11 47 2.21 21 3.1 Opaque

[0102] The triamide rheology additive of example A according to the invention proves to be much more effective in terms of rheological performance qualities (cf. formulation F8), compared with the standard powder additive Crayvallac® Antisettle CVP (cf. formulation F9). With regard to the diamide product of example C, it also exhibits rheological performance qualities (cf. formulation F10) which are superior to that using the compound in the powder form 12HSA-HMDA-12HSA (cf. formulation F11).

[0103] Furthermore, the products according to the invention do not need a specific processing process to develop the rheology (gel), as is necessary in the case for conventional additives in the form of powders based on hydrogenated castor oil derivatives.

[0104] Furthermore, as the products according to the invention are in the form of flakes, problems encountered with the use of powders (micronization, handling, toxicity, and the like) are thus eliminated. It should also be noted that these products make it possible to obtain MS mastic formulations which are completely transparent.