RHEOLOGY ADDITIVES BASED ON DI-OR TRI-AMIDES AND MIXTURES THEREOF

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. 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 or a triamide or a mixture thereof, wherein said fatty amide is represented by: A) according to following formula (I):
R[(XR1-NHCOR2)n-n.sub.1][(XR1-NHCOR2)n.sub.1](I) with n being 2 or 3, n.sub.1 being equal to 0 or 1, R(XR1-)n being the residue of valency n of a primary polyamine R(XR1-NH2)n which is a primary diamine or triamine, with each primary amine group NH2 being a terminal group carried 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)n or from a polyamine R(NH2)n or R(NHR3)n, X: O or N, R2 being the C.sub.12-C.sub.52 fatty residue of fatty acid R2CO2H, R2 being the C.sub.2 to C.sub.10 monocarboxylic acid residue with at least one R2 residue being residue(s) of hydroxylated fatty acid R2CO2H with a non-terminal hydroxyl group and wherein said R2 residues are identical or different, R3 being a C1-C2 alkyl substituent, or by B) according to following formula (II) in the case in which said amide is a diamide:
R2CONHRO[CH2-CH(R4)-O].sub.xCH2-CH(R4)-NHCOR2(II) with R being the monopropylene glycol residue without OH: CH(CH3)-CH2- R2 and R2 being defined as in formula (I) above, and R4 being H or methyl with the repeat 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 temperature, measured by DSC after two passes, 10 C./min, ranging from 10 to 110 C.

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

3. The polyfunctional fatty amide according to claim 1 wherein said oligomer chain segment R1 according to A) formula (I), is a polyether chain segment.

4. The polyfunctional fatty amide according to claim 1 wherein said oligomer chain segment R1 is a polyoxypropylene chain segment.

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

6. The polyfunctional fatty amide according to claim 1 wherein said hydroxylated fatty acid R2CO2H 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, and 14-hydroxyeicosanoic acid (14-HEA).

7. The polyfunctional fatty amide according to claim 1 wherein said hydroxylated fatty acid is 12-hydroxystearic acid.

8. The polyfunctional fatty amide according to claim 1 wherein said monocarboxylic acid R2CO2H is selected from the group consisting of: acetic acid, propionic acid, butyric acid, pentanoic (valeric) acid, hexanoic (caproic) acid, heptanoic acid, and octanoic acid.

9. The polyfunctional fatty amide according to claim 1 wherein said amide is a diamide according to A) or B) or a triamide according to A), with all R2 residues resulting from hydroxylated fatty acid R2CO2H.

10. The polyfunctional fatty amide according to claim 1 wherein said amide is a diamide according to A) or B), with one R2 residue resulting from hydroxylated fatty acid R2CO2H.

11. The polyfunctional fatty amide according to claim 1 wherein said amide is a triamide according to A), with two R2 residues resulting from hydroxylated fatty acid R2CO2H and one resulting from non-hydroxylated fatty acid.

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

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

14. A formulation composition of an organic binder comprising, a) at least one organic binder, and b) at least one polyfunctional fatty amide as defined according to according to claim 1.

15. The composition according to claim 14, wherein said binder a) is selected from the group consisting of: 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 carrying epoxy groups.

16. The composition according to 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 according to claim 1 wherein said fatty amide is a thixotropic agent.

18. The composition according to 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 the group consisting of: phthalates, adipates, trimellitates, sebacates, benzoates, citrates, phosphates, epoxides, polyesters, alkylsulfonate esters and non-phthalate substitutes for phthalates.

19. The composition according to claim 18, which is a transparent or non-transparent mastic formulation composition.

20. (canceled)

21. (canceled)

22. (canceled)

23. (canceled)

24. (canceled)

25. (canceled)

26. (canceled)

Description

EXPERIMENTAL PART

1) Starting Materials Used and Codes

[0071] See Table 1 below

TABLE-US-00001 TABLE 1 Table summarizing the starting materials used in synthesis and in formulations Product used Chemical name Function Supplier 12HSA 12-Hydroxystearic Hydroxylated Jayant Agro acid fatty acid Stearine Stearic acid Non-hydroxylated Sogis fatty acid Jeffamine Jeffamine Polyoxypropylene Huntsman T-3000 T-3000 triamine (primary) Polyetheramine polyetheramine with overall ~50 oxypropylene (OP) units Jeffamine Jeffamine Polyoxypropylene Huntsman D-2000 D-2000 diamine (primary) Polyetheramine polyetheramine with ~33 OP units HCO Hydrogenated Reference Gokul Agro (as flakes) castor oil rheology additive Crayvallac Hydrogenated Reference Arkema Antisettle CVP castor oil rheology additive (micronized powder) Standard 12HSA-HMDA- Reference diamide / fatty diamide 12HSA rheology additive for comparison MS Polymer Silylated Applicative Kaneka S203H polyether formulation resin Jayflex Diisoundecyl Plasticizer BASF DIUP phthalate

[0072] For reasons of clarity, the following abbreviations will be used: [0073] 12HSA: 12-Hydroxystearic acid [0074] SA: Stearic acid [0075] HMDA: Hexamethylenediamine [0076] D2000: Jeffamine D-2000 polyetheramine [0077] T3000: Jeffamine T-3000 polyetheramine

2) Examples

Example A According to the InventionT3000-12HSA.SUB.3

[0078] 305.9 g of Jeffamine T-3000 (0.099 mol, 1 eq) and 94.1 g of 12-hydroxystearic acid (0.297 mol, 3 eq) are added to a 1 litre round-bottomed flask equipped with a thermometer, a Dean and 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 and 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 mould. Once cooled to ambient temperature, the product is converted into flakes.

Example B According to the Invention12HSA-D2000-12HSA

[0079] 304.4 g of Jeffamine D-2000 (0.15 mol, 1 eq) and 95.6 g of 12-hydroxystearic acid (0.3 mol, 2 eq) are added to a 1 litre round-bottomed flask equipped with a thermometer, a Dean and 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 and 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 mould. Once cooled to ambient temperature, the product is converted into flakes.

Example C ComparativeT3000-SA.SUB.3

[0080] 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 litre round-bottomed flask equipped with a thermometer, a Dean and 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 and 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 mould.

Example D ComparativeSA-D2000-SA

[0081] 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 litre round-bottomed flask equipped with a thermometer, a Dean and 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 and 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 mould.

3) Study of the Gelling Power of the Organogelators

[0082] In this comparative example, the ability of the rheology additives to form a gel in a simplified formulation containing solely a conventional plasticizer (Jayflex DIUP) used in PVC plastisol formulations will be studied.

[0083] The formulations are prepared using a laboratory planetary mixer (Molteni EMD 1 type) provided with a dispersing disc 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.

TABLE-US-00002 TABLE 2 Composition of the simplified formulations Formulation Component % wt Function F1 Jayflex DIUP 95 Plasticizer T3000-12HSA.sub.3 5 Rheology additive F2 Jayflex DIUP 95 Plasticizer 12HSA-D2000-12HSA 5 Rheology additive F3 Jayflex DIUP 95 Plasticizer T3000-SA.sub.3 5 Rheology additive F4 Jayflex DIUP 95 Plasticizer SA-D2000-SA 5 Rheology additive F5 Jayflex DIUP 95 Plasticizer 12HSA-HMDA-12HSA 5 Rheology additive F6 Jayflex DIUP 95 Plasticizer HCO 5 Rheology additive F7 Jayflex DIUP 95 Plasticizer Crayvallac 5 Rheology additive Antisettle CVP

[0084] 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 behaviour of the gel is studied visually.

TABLE-US-00003 TABLE 3 Behaviour and appearance of the gel as a function of the incorporation temperature Behaviour of Formulation Temperature 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

[0085] The results of the gel tests show that the products according to the invention (T3000-12HSA.sub.3, 12HSA-D2000-12HSA) form gels, while the comparative products are in the liquid form. Thus, the compound T3000-SA.sub.3 described in particular in patent EP 1514 912 A2 does not make it possible to obtain the gel (cf Formulation F3), which strongly indicates that the presence of the hydroxyl group is essential to the formation of the supramolecular assemblage and of the 3D network of fibres.

[0086] The behaviour of the organogelator agents can also be influenced by the initial structure of the diamine used. Thus, on comparing the organogelator described in WO 2014/053774A1 (12HSA-HMDA-12HSA) with the compound 12HSA-D2000-12HSA 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.

[0087] 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 F6), 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.

[0088] Also, it may be observed that, if the additive in the powder form is incorporated at a higher temperature (80 C. in F7) than its optimum temperature (60 C. in F7), the gel strength will decrease, which shows in addition a sensitivity to the temperature due probably to the complete dissolution of the product. It is thus important, in the case of the standard products, to indeed observe a temperature window in which organogelator is effective.

[0089] As regards formulations F1 and F2 based on the products according to the invention, the formation of a strong gel, irrespective of the incorporation temperature, may be observed. It should be mentioned that, at the temperatures studied, the rheology additive is completely dissolved. Furthermore, the formulations exhibit a completely transparent appearance.

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

[0090] In this comparative example, the rheological performance qualities of the additives of a simplified hybrid mastic formulation will be illustrated.

TABLE-US-00004 TABLE 4 Composition of the simplified formulations Formulation Component % wt Function F8 Jayflex DIUP 47.5 Plasticizer MS-Polymer S 203 H 47.5 Resin T3000-12HSA.sub.3 5 Rheology additive F9 Jayflex DIUP 47.5 Plasticizer MS-Polymer S 203 H 47.5 Resin Crayvallac 5 Rheology additive Antisettle CVP F10 Jayflex DIUP 47.5 Plasticizer MS-Polymer S 203 H 47.5 Resin 12HSA-D2000-12HSA 5 Rheology additive F11 Jayflex DIUP 47.5 Plasticizer MS-Polymer S 203 H 47.5 Resin 12HSA-HMDA-12HSA 5 Rheology additive

[0091] In order to do this, the formulations are prepared using the same Molteni EMD1 mixer. The resin and the plasticizer are added and homogenized in a first stage and in the proportions shown. 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.

TABLE-US-00005 TABLE 5 Rheological performance qualities Viscosity Viscosity Yield at 0.1 s.sup.1 at 100 s.sup.1 Thixotropic point Formulation (Pa .Math. s) (Pa .Math. s) index (Pa) Appearance F8 995 4.57 218 86.0 Transparent F9 296 6.06 49 4.4 Opaque F10 374 3.40 110 32.0 Transparent F11 47 2.21 21 3.1 Opaque

[0092] The triamide rheology additive T3000-12HSA.sub.3 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 12HSA-D2000-12HSA, 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).

[0093] Furthermore, the products according to the invention do not need a specific processing process to develop the rheology, as is the case for conventional additives in the form of powders based on hydrogenated castor oil derivatives.

[0094] Furthermore, as the products according to the invention are in the form of flakes, problems encountered with the use of powders (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.