Fatty diamide additive composition preconcentrated and pre-activated in a reactive diluent

Abstract

The invention relates to a fatty acid diamide-based rheology additive composition, which is pre-activated and pre-concentrated in fatty acid diamide, comprising: a) from 5% to 30% by weight of at least one fatty acid diamide based on 12 hydroxystearic acid and on a linear, in particular C5, C6 or C7, aliphatic diamine, b) from 70% to 95% by weight of at least one monofunctional (meth)acrylic reactive diluent comprising a cycloaliphatic group or several cycloaliphatic groups, the % being expressed relative to a)+b). It also relates to a process for preparing the composition and to the use thereof as a rheology additive in reactive binder compositions such as coating, moulding, composite material, anchor bolt or sealant compositions or photocrosslinkable compositions for stereolithography or for 3D printing of objects by inkjet.

Claims

1. A fatty acid diamide-based thixotropic rheology additive composition, already pre-activated and pre-concentrated in fatty acid diamide, comprising: a) from 5% to 3.0% by weight of at least one fatty acid diamide based on 12-hydroxystearic acid and on a linear C.sub.5, C.sub.6 or C.sub.7, aliphatic diamine, b) from 70% to 95% by weight of at least one monofunctional (meth)acrylic reactive diluent comprising a cycloaliphatic group or more than one cycloaliphatic groups, said cycloaliphatic groups optionally being substituted with at least one C.sub.1 to C.sub.4 alkyl, the % being expressed relative to a)+b), wherein the pre-activated, pre-concentrated fatty acid diamide-based thixotropic rheology additive composition is a gel or paste obtained by pre-activating and pre-concentrating the at least one fatty acid diamide in the presence of the at least one monofunctional (meth)arylic reactive diluent.

2. The composition according to claim 1, wherein said diamine is a C.sub.6 linear aliphatic diamine.

3. The composition according to claim 1 wherein said diamide is present in a content by weight ranging from 10% to 25% and said diluent b) is present in a content by weight ranging from 75% to 90% relative to a)+b).

4. The composition according to claim 1 wherein said monofunctional (meth)acrylic monomer reactive diluent b) is chosen from the group consisting of: dicyclopentadienyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate (IBO(M)A), tert-butyl cyclohexanol (meth)acrylate (TBCH(M)A), tricyclodecanediol mono(meth)acrylate and 3,3,5-trimethyl cyclohexanol (meth)acrylate (TMCH(M)A).

5. The composition according to claim 1 wherein said monofunctional (meth)acrylic monomer reactive diluent b) is a monoacrylate.

6. The composition according to claim 1 comprising, in addition to a) and b), a radical polymerization-inhibiting stabilizer at a content by weight relative to a)+b) ranging from 10 to 1000 ppm.

7. A process for preparing the diamide additive composition according to claim 1 comprising the following successive steps: i) gradual dispersion of said diamide a) in the form of a micronized powder, in said diluent b) until a homogeneous dispersion is obtained, at ambient temperature ranging from 5 to 25° C. controlled using temperature regulation, ii) maintaining of the homogeneous dispersion obtained during step i) in at least one set of stationary heating conditions ranging from 80 to 100° C., for a period of time of from 1 to 100 hours, and without any polymerization of said diluent b).

8. The process according to claim 7, wherein at the end of step ii), the maximum penetration value of the paste formed is less than 15 mm measured according to standard ASTM D 217.

9. A reactive-binder composition, comprising as rheology additive at least one composition as defined according to claim 1.

10. The reactive-binder composition according to claim 9, which is a polymerizable composition selected from the group consisting of coating compositions, adhesive and glue compositions, moulding compositions, composite material compositions, mastic compositions, chemical anchor bolt compositions, sealant compositions, and photocrosslinkable compositions for stereolithography and for 3D printing of objects.

11. The binder composition according to claim 9 which is crosslinkable by radical route, either under radiation, or by an initiating system based on peroxide or hydroperoxide.

12. The binder composition according to claim 10, which is polymerizable under radiation selected from UV, laser, LED and electron beam.

13. The binder composition according to claim 9 wherein said monofunctional (meth)acrylic reactive diluent b) is a monoacrylate.

14. The binder composition according to claim 13, which is polymerizable by means of a Michael addition reaction with an amine.

15. The binder composition according to claim 9 which is crosslinkable and comprises a two-component system based on epoxy resin and on an amine curing agent.

16. The binder composition according to claim 9 comprising as reactive diluent of said binder composition, at least one acrylic oligomer and/or at least one acrylic monomer.

17. The binder composition according to claim 9 wherein the content by weight of said composition ranges from 0.5% to 10% by weight relative to said reactive-binder composition.

Description

EXAMPLE 1 (INVENTION): PREPARATION OF THE PRE-ACTIVATED PASTE AT 15% IN 3,3,5-TRIMETHYL-CYCLOHEXANOL ACRYLATE (TMCHA)

(1) 150 g of the previously milled fatty acid diamide as prepared above and 850 g of acrylate monomer are charged to a 1 litre metal canister (height: 13 cm, diameter: 11 cm), at ambient temperature. Using a Dispermat® CV disperser fitted with a paddle 4 cm in diameter, the 2 products are mixed at 1500 rpm for 15 min, at a temperature not exceeding 20° C., by regulating the temperature by cold water circulation. The canister is then carefully closed again and placed in an oven preheated beforehand to 90° C., for 24 hours.

(2) The final product is a soft white paste characterized by a content of dry active material of 15% and a penetration resistance measured according to standard ASTM D 217 of 3.00 mm.

EXAMPLE 2 (INVENTION): PREPARATION OF THE PRE-ACTIVATED PASTE CONTAINING 20% OF DIAMIDE, IN 3,3,5-TRIMETHYL CYCLOHEXANOL ACRYLATE (TMCHA)

(3) 200 g of the previously milled fatty acid diamide as described above and 800 g of acrylate monomer are charged to a 1 litre metal canister (height: 13 cm, diameter: 11 cm), at ambient temperature. Using a Dispermat® CV disperser fitted with a paddle 4 cm in diameter, the 2 products are mixed at 1500 rpm for 15 min, at a temperature not exceeding 20° C., by regulation of the temperature by cold water circulation. The canister is then carefully closed again and placed in an oven preheated beforehand to 90° C., for 24 hours.

(4) The final product is a soft white paste characterized by a content of dry active material of 20% and a penetration resistance measured according to standard ASTM D 217 of 3.00 mm.

EXAMPLE 3 (COMPARATIVE): PREPARATION OF THE PRE-ACTIVATED PASTE IN CYCLIC TRIMETHYLOLPROPANE FORMAL ACRYLATE (CTFA)

(5) 150 g of the previously milled fatty acid diamide as described above and 850 g of acrylate monomer are charged to a 1 litre metal canister (height: 13 cm, diameter 11 cm), at ambient temperature. Using a Dispermat® CV disperser fitted with a paddle 4 cm in diameter, the 2 products are mixed at 1500 rpm for 15 min, at a temperature not exceeding 20° C., by regulation of the temperature by cold water circulation. The canister is then carefully closed again and placed in an oven preheated beforehand to 90° C., for 24 hours.

(6) The final product is a soft white paste characterized by a content of dry active material of 15%.

EXAMPLE 4 (COMPARATIVE): PREPARATION OF THE PRE-ACTIVATED PASTE IN TRIMETHYLOLPROPANE TRIACRYLATE (TMPTA)

(7) 150 g of the previously milled fatty acid diamide as described above and 850 g of acrylate monomer are charged to a 1 litre metal canister (height: 13 cm, diameter: 11 cm), at ambient temperature. Using a Dispermat® CV disperser fitted with a paddle 4 cm in diameter, the 2 products are mixed at 1500 rpm for 15 min, at a temperature not exceeding 20° C., by regulation of the temperature by cold water circulation. The canister is then carefully closed again and placed in an oven preheated beforehand to 90° C., for 24 hours.

(8) The final product is a soft white paste characterized by a content of dry active material of 15%.

EXAMPLE 5 (COMPARATIVE): PREPARATION OF THE PRE-ACTIVATED PASTE IN 2-PHENOXYETHYL ACRYLATE (2-PEA)

(9) 150 g of the previously milled fatty acid diamide as described above and 850 g of acrylate monomer are charged to a 1 litre metal canister (height: 13 cm, diameter: 11 cm), at ambient temperature. Using a Dispermat® CV disperser fitted with a paddle 4 cm in diameter, the 2 products are mixed at 1500 rpm for 15 min, at a temperature not exceeding 20° C., by regulation of the temperature by cold water circulation. The canister is then carefully closed again and placed in an oven preheated beforehand to 90° C., for 24 hours.

(10) The final product is a soft white paste characterized by a content of dry active material of 15%.

(11) 2) Characterization of the Rheology Additive According to the Invention and Comparative Additives

(12) The rheology additive in the form of a pre-activated paste is used in the preparation of photocrosslinkable coating formulations and of 2-component formulations without solvent.

(13) Use of the Theology Additives for Photocrosslinkable Formulations

(14) Production of the Coating Formulations

(15) The coating formulations are produced in the laboratory with a high-speed disperser of Dispermat® AE type, equipped with a deflocculator.

(16) The acrylate oligomer resin (CN203) and the reactive diluent (monomer of the formulation of reactive binder) propoxylated(3) glyceryl triacrylate, i.e. bearing 3 propoxy units per molecule (GPTA-SR 9020) are mixed at 1000 rpm, at a tangential speed of 2 m/s for 5 min.

(17) The rheology additive is then added and dispersed at 1500 rpm for 20 min.

(18) The crosslinking reaction between the oligomer and the reactive diluent takes place by action of UV radiation during the passage under a UV lamp, by means of initiators contained in said photocrosslinkable coating formulation.

(19) The characterization tests are carried out within 24 hours following the preparation of the formulations after conditioning at 23° C. and 50% RH.

(20) Six simplified formulae of crosslinkable coating compositions were prepared: Example 6: formula without additive. Example 7: formula with the additive Crayvallac® PA4X20 (20% of active material in xylene—non-reactive solvent). Example 8: formula with additive described in Example 1 (15% of active material in a monofunctional reactive diluent comprising a cycloaliphatic structure according to the invention). Example 9: formula with additive described in Example 2 (20% of active material in a monofunctional reactive diluent comprising a cycloaliphatic structure according to the invention). Example 10: formula with additive described in Example 3 (15% of active material in a heterocyclic monofunctional reactive diluent, comparative). Example 11: formula with additive described in Example 4 (15% of active material in a trifunctional reactive diluent, comparative). Example 12: formula with additive described in Example 5 (15% of active material in an aromatic monofunctional reactive diluent, comparative).

(21) The 6 examples were prepared according to the following formulae (see table 2):

(22) TABLE-US-00002 TABLE 2 Starting material reference Nature Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 CN 203 Acrylate 65 61.75 61.75 62.55 61.75 61.75 61.75 oligomer SR 9020 Reactive diluent 35 33.25 33.25 33.7 33.25 33.25 33.25 of the formulation (in reactive-binder composition) Crayvallac ® Pre-activated 5 PA4X20 diamide paste Additive of Pre-activated 5 3.75 Ex. 1 diamide paste (invention) Additive of Pre-activated Ex. 2 diamide paste (invention) Additive of Pre-activated 5 Ex. 3 diamide paste (comparative) Additive of Pre-activated 5 Ex. 4 diamide paste (comparative) Additive of Pre-activated 5 Ex. 5 diamide paste (comparative) Total 100 100 100 100 100 100 100

(23) TABLE-US-00003 TABLE 3 Sagging Viscosity (mPa .Math. s) resistance Example Rheology additive 1 rpm 5 rpm 10 rpm 50 rpm 100 rpm (μm) Ex. 6 Without additive 4000 3800 3780 3730 3200 50 Ex. 7 Crayvallac ® 128000 37000 22300 7820 5300 1000 PA4X20 Ex. 8 Additive of Ex. 1 70000 22000 14000 6200 4800 1075 Ex. 9 Additive of Ex. 2 88000 28000 18300 7700 5550 1500 Ex. 10 Additive of Ex. 3 22800 8960 6400 3500 2870 350 Ex. 11 Additive of Ex. 4 3600 3000 2780 2340 2200 70 Ex. 12 Additive of Ex. 5 7600 5200 4180 2700 2300 70/100

(24) Use of the Rheology Additives for the Epoxy Formulations without Solvent

(25) Production of the Coating Formulations

(26) The coating formulations are produced in the laboratory in 2 steps.

(27) The first consists in formulating a mixture called “part A”, which is a dispersion of the fillers in the epoxy resin. The rheology additive is also added to part A. The 2nd step is the addition, to this part A, of an amino curing agent, called “part B”, in ratios calculated to adjust the crosslinking reactivity.

(28) The reaction for crosslinking of the coating is provided by reaction of part A containing the epoxy resin with part B containing the amino curing agent.

(29) In the laboratory, part A is produced with a high-speed disperser of Dispermat AE type, equipped with a deflocculator.

(30) The epoxy resin—DER 324, the fillers (titanium dioxide, zinc phosphate, talc) and the defoaming agent are mixed at 3000 rpm, at a tangential speed of 6 m/s for 30 min.

(31) The rheology additive is then added to this part A and dispersed at 1500 rpm for 20 min.

(32) After standing for 24 h, part B is mixed with part A at 1500 rpm for 2 min.

(33) The characterization tests are then carried out in the 30 min that follow.

(34) Three epoxy coating formulae without solvent and comprising two components (epoxy/amine) were prepared: Example 13: formula without additive. Example 14: formula with additive described in Example 1. Example 15: formula with additive described in Example 2.

(35) TABLE-US-00004 TABLE 4 Starting material reference Nature Ex. 13 Ex. 14 Ex. 15 Part DER ® 324 Epoxy resin 55.6 55.6 55.6 A BYK ® A530 Defoaming  0.3 0.3 0.3 agent Tiona RCL Titanium 19.1 19.1 19.1 595 dioxide ZP 10 Zinc  7.3 7.3 7.3 phosphate Microtalc Talc 11.4 11.4 11.4 AT1 SR 420 Reactive    5.6 (*) diluent (as monomer diluent of the formulation) Additive of Pre-activated 6.3 example 1 diamide paste Additive of Pre-activated 6.3 example 2 diamide paste Total 99.3 100 100 Part Epikure ® Amine 32   32 32 B F205 Total 132   132 132 (*) The formulation of Comparative Example 13 comprises 5.6 parts of monomer reactive diluent so as to be under conditions strictly comparable to Examples 14 and 15.
Results

(36) TABLE-US-00005 TABLE 5 Sagging Viscosity (mPa .Math. s) resistance Example Rheology additive 1 rpm 5 rpm 10 rpm 50 rpm 100 rpm (μm) Ex. 13 Without additive 1600 1920 1760 1790 1744 100 Ex. 14 Additive of Ex. 1 67200 20800 13140 5536 4000 1100 Ex. 15 Additive of Ex. 2 91200 27840 17600 6720 4830 1500