RHEOLOGY CONTROL ADDITIVE CONTAINING CYCLIC AMIDES

Abstract

The invention relates to a composition comprising one or more urea-based compounds (A) having a number average molecular weight (Mn) between 350 g/mol and 30000 g/mol and one or more N-substituted caprolactam derivatives (B) according to formula (I) wherein R1 is an organic group having 1 to 2 carbon atoms and wherein R1 contains no oxygen atoms linked by single bonds.

##STR00001##

Claims

1. A composition comprising one or more urea-based compounds (A) having a number average molecular weight (Mn) between 350 g/mol and 30000 g/mol, determined by gel permeation chromatography according to DIN 55672 part 2 (year 2016), wherein the urea-based compound is selected from the formulas ##STR00008## where AM is selected from a linear or branched, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or aliphatic-aromatic organic radical having 2 to 50 C atoms, in case of multiple occurrence of AM, AM is independently selected from a linear or branched, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or aliphatic-aromatic organic radical having 2 to 50 C atoms, AM1 and AM2 independently of one another represent a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic radical having 1 to 50 C atoms, in case of multiple occurrence of AM1 and AM2, AM1 and AM2 represent independently the radical described above for AM1 and AM2, IC1 and IC2 independently of one another represent a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having 2 to 40 C atoms, in case of multiple occurrence of IC1 and IC2, IC1 and IC2 represent independently the radical described above for IC1 and IC2, IC3 represents a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having 2 to 24 carbon atoms, in case of multiple occurrence of IC3, IC3 independently represents a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having 2 to 24 carbon atoms, RP1 and RP2 independently of one another represent a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic radical having 1 to 24 C atoms and/or a polyether radical having 1 to 120 ether oxygen atoms and/or a polyester radical having 1 to 100 ester groups and optionally containing ether groups, and/or a polyamide radical having 1 to 100 amide groups, and/or a polysiloxane radical having 3 to 100 silicon atoms, in case of multiple occurrence of RP1 and RP2, RP1 and RP2 represent independently the radicals described above for RP1 and RP2, RP3 represents a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic radical having 2 to 24 C atoms and/or a (poly)ether radical having 1 to 120 ether oxygen atoms and/or a polyamide radical having 1 to 100 amide groups and/or a polysiloxane radical having 3 to 100 silicon atoms and/or a polyester radical having 1 to 100 ester groups and optionally containing ether groups, in case of multiple occurrence of RP3, RP3 independently represents the radicals described above for RP3, and m is an integer from 1 to 5, p represents 0 and/or 1, q is an integer from 0 to 20, and when the composition comprises a urea-based compound of formula (U-2a), at least 50 wt. % of all urea-based compounds in the composition are according to formula (U-2a), one or more N-substituted caprolactam derivatives (B) according to formula (I) ##STR00009## wherein R.sup.1 is an organic group having 1 to 2 carbon atoms and wherein R.sup.1 contains no oxygen atoms linked by single bonds, and wherein the caprolactam derivative comprises at least one of N-methylcaprolactam, N-ethylcaprolactam, N-acetylcaprolactam, and mixtures thereof.

2. The composition according to claim 1, wherein the composition further comprises one or more salts (D).

3. The composition according to claim 2, wherein the one or more salts (D) include one or more of a lithium salt, an ammonium salt and a calcium salt.

4. The composition according to claim 1, comprising 3 to 75% by weight of the one or more urea-based compounds (A), 25 to 97% by weight of the one or more N-substituted caprolactam derivatives (B), wherein the % by weight are calculated on the sum of (A) and (B).

5-8. (canceled)

9. A liquid composition comprising the composition according to claim 1 and at least one of an organic diluent and water, the liquid composition being a liquid at 23° C.

10. The liquid composition according to claim 9 comprising 0.02 to 6.00% by weight of the one or more urea-based compounds (A) and 0.05 to 8.00% by weight of the one or more N-substituted caprolactam derivatives (B), wherein the % by weight are calculated on the weight of the liquid composition.

11. The liquid composition according to claim 9, wherein the liquid composition comprises one or more of a coating composition, a clear coat composition, a lacquer, a varnish, a plastic formulation, a pigment paste, an effect pigment paste, a polymer formulation, a sealant formulation, a cosmetic formulation, a homecare formulation, an industrial care formulation, a perfume formulation, a fragrance formulation, a ceramic formulation, an adhesive formulation, a liquid formulation for use in gas and oil production, a composition for the manufacture of electrical components and circuits, a liquid formulation for use in energy storage media, a cleaning agent, a potting compound, a building material formulation, a lubricant, a filling compound, a wax emulsion, a metalworking fluid, a metal-processing product, a liquid composition in the form of a spraying agent, a deposition aid, an ink, a printing ink, an ink jet ink, a composition that may be used as corrosion protection in the field of marine and protective coatings, and mixtures thereof.

12. A process for controlling the rheology of a liquid composition, the process comprising: providing a liquid composition; and mixing the composition according to claim 1 with the liquid composition.

13. A coated article, wherein at least a part of the surface of the article is coated with the liquid composition according to claim 9.

14. The composition of claim 3, the one or more salts (D) including one or more of a chloride salt, an acetate salt, and a nitrate salt.

15. The process according to claim 12, the liquid composition being a non-aqueous composition.

16. The process according to claim 12, the liquid composition being an aqueous composition.

17. The process according to claim 12, the liquid composition being a paint composition.

18. The process according to claim 12, the liquid composition being a coating composition.

Description

EXAMPLES

[0071] N-Acetylcaprolactam, N-methylcaprolactam, N-ethylcaprolactam, and N-vinylcaprolactam can be purchased from Sigma-Aldrich or synthesized according to state of the art literature, e.g., DE 2015172, Aust. J. Chem. 1976, 29, 2651, ARKIVOC 2002 (ii) 56-63 (F. Cuiban et al., “N-Substituted derivatives of ε-caprolactam and their thermal and chemical behavior”), and Chin. J. Chem., 2006, 24 (1), 17.

Inventive Examples

Preparation of Intermediates

Preparation of Intermediate I1

[0072] 0.25 mol (53 g) of butyl triglycol is added over 2 hours at 23° C. to 0.625 mol (108.75 g) toluene diisocyanate (TDI T65, a 65/35 mixture of 2,4-toluylene diisocyanate and 2,6-toluylene diisocyanate, Covestro AG). The temperature is held below 45° C. After the end of the addition, stirring is continued for 2.5 h. The excess isocyanate is removed by vacuum (0.1 mbar) distillation at from 150 to 170° C. The NCO content is 10.9 wt. %.

Preparation of Intermediate I2

[0073] The procedure described for Intermediate I1 was repeated using 0.4 mol (74.53 g) lauryl alcohol as the alcohol component and 0.8 mol (139.2 g) toluene diisocyanate (TDI T100, 2,4-toluylene diisocyanate, Covestro AG) as the isocyanate component. The temperature is held below 60° C. After the end of the addition, stirring is continued for 3 h. The excess isocyanate is removed by vacuum (0.1 mbar) distillation at from 150 to 170° C. The reaction product obtained is a waxy solid. The NCO content is 11.2 wt. %.

Preparation of Intermediate I3

[0074] The procedure described for Intermediate I1 was repeated using 0.4 mol (179.52 g) of a polyethylene glycol monomethyl ether with a hydroxyl number of 125 mg KOH/g as the alcohol component and 0.8 mol (139.2 g) toluene diisocyanate (TDI T80, a 80/20 mixture of 2,4-toluylene diisocyanate and 2,6-toluylene diisocyanate, Covestro AG) as the isocyanate component. The temperature is held between 50° C. and 55° C. After the end of the addition, stirring is continued for 3 h. The excess isocyanate is removed by vacuum (0.1 mbar) distillation at from 150 to 170° C. The NCO content is 7.0 wt. %.

[0075] The hydroxyl number was determined by acetylation of the free hydroxyl groups of the substance with acetic anhydride in pyridine solvent. After completion of the reaction, water was added, and the remaining unreacted acetic anhydride was converted to acetic acid and measured by titration with potassium hydroxide.

Preparation of Urea-Based Compound Solutions

Example E1

Preparation of Urea-Based Compound Solution E1

[0076] In a four-neck flask with stirrer 1.90 g lithium chloride was added to 53.10 g of N-methylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 6.68 g m-xylylenediamine were added and the mixture was homogenized. 38.32 g of the intermediate I1 were added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=2069 g/mol; D=1.15).

Example E2

Preparation of Urea-Based Compound Solution E2

[0077] In a four-neck flask with stirrer 1.65 g lithium chloride was added to 75.00 g of N-methylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 3.55 g m-xylylenediamine were added and the mixture was homogenized. 19.80 g of the intermediate I2 were added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=2386 g/mol; D=1.14).

Example E3

Preparation of Urea-Based Compound Solution E3

[0078] In a four-neck flask with stirrer 1.32 g lithium chloride was added to 48.00 g of N-methylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 5.66 g m-xylylenediamine were added and the mixture was homogenized. A homogenous mixture of 10.82 g of intermediate I1 and 34.2 g of intermediate I3 were added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=2401 g/mol; D=1.13).

Example E4

Preparation of Urea-Based Compound Solution E4

[0079] In a four-neck flask with stirrer 2.30 g lithium chloride was added to 57.70 g of N-methylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 5.94 g m-xylylenediamine were added and the mixture was homogenized. 34.06 g of the intermediate I1 were added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=2081 g/mol; D=1.16).

Example E5

Preparation of Urea-Based Compound Solution E5

[0080] In a four-neck flask with stirrer 1.90 g lithium chloride was added to 53.10 g of N-ethylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 6.68 g m-xylylenediamine were added and the mixture was homogenized. 38.32 g of intermediate I1 were added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=2108 g/mol; D=1.14).

Example E6

Preparation of Urea-Based Compound Solution E6

[0081] In a four-neck flask with stirrer 1.32 g lithium chloride was added to 48.00 g of N-ethylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 5.66 g m-xylylenediamine were added and the mixture was homogenized. A homogenously mixture of 10.82 g of intermediate I1 and 34.20 g of intermediate I3 were added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=2417 g/mol; D=1.13).

Example E7

Preparation of Urea-Based Compound Solution E7

[0082] In a four-neck flask with stirrer 1.90 g lithium chloride was added to 35.4 g N-methylcaprolactam and 17.7 g N-vinylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 6.68 g m-xylylenediamine were added and the mixture was homogenized. 38.32 g of the intermediate I1 was added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=2170 g/mol; D=1.12).

Example E8

Preparation of Urea-Based Compound Solution E8

[0083] In a four-neck flask with stirrer 1.65 g lithium chloride was added to 25 g N-vinylcaprolactam and 50 g N-methylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 3.55 g m-xylylenediamine were added and the mixture was homogenized. 19.8 g of the intermediate I2 was added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=1910 g/mol; D=1.26).

Example E9

Preparation of Urea-Based Compound Solution E9

[0084] In a four-neck flask with stirrer 1.32 g lithium chloride was added to 16 g N-vinylcaprolactam and 32 g N-methylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 5.66 g m-xylylenediamine were added and the mixture was homogenized. A homogenous mixture of 10.82 g of intermediate I1 and 34.20 g of intermediate I3 was added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=2419 g/mol; D=1.14).

Example E10

Preparation of Urea-Based Compound Solution E10

[0085] In a four-neck flask with stirrer 1.65 g lithium chloride was added to 19.2 g N-vinylcaprolactam and 38.5 g N-methylcaprolactam under stirring. The mixture was heated up to 80° C. under nitrogen atmosphere. The lithium chloride was dissolved within 30 min under stirring. 5.94 g m-xylylenediamine were added and the mixture was homogenized. 34.06 g of the intermediate I1 was added dropwise under stirring within 30 min in such a way that the temperature does not exceed 85° C. Afterwards the mixture was stirred for 3 hours at 80° C. The result is a transparent, yellowish product (GPC: M.sub.n=2118 g/mol; D=1.13).

Comparative Examples (not Inventive)

Comparative Example C1

[0086] The preparation was carried out according to example E1, but the same weight of N-methylbutyrolactam was used instead of N-methylcaprolactam.

Comparative Example C2

[0087] The preparation was carried out according to example E1, but the same weight of dimethyl sulfoxide was used instead of N-methylcaprolactam.

Comparative Example C3

[0088] The preparation was carried out according to example E3, but the same weight of N-methylbutyrolactam was used instead of N-methylcaprolactam.

Comparative Example C4

[0089] The preparation was carried out according to example E3, but the same weight of dimethyl sulfoxide was used instead of N-methylcaprolactam.

Comparative Example C5

[0090] The preparation was carried out according to example E3, but the same weight of N-butylbutyrolactam was used instead of N-methylcaprolactam.

Comparative Example C6

[0091] The preparation was carried out according to example E2, but the same weight of N-methylbutyrolactam was used instead of N-methylcaprolactam.

Comparative Example C7

[0092] The preparation was carried out according to example E2, but the same weight of methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate was used instead of N-methylcaprolactam

Application Test of the Rheology Additive Compositions

[0093]

TABLE-US-00001 TABLE 1 Raw materials Name Description Manufacturer Setal 1715 VX-74 Saturated polyester grade Allnex Xylene Isomeric mixture Overlack AG Aerosil R 972 Hydrophobic fumed silica Evonik Industries AG Disperbyk-2150 Solution of a block copolymer BYK-Chemie with basic, pigment-affinic GmbH groups Kronos 2160 Titandioxide Kronos Inc. Setamine US 138 Amino Resin (Melamine, Allnex BB-70 butylated) Butylglycolacetate 2-Butoxy-ethylacetate Oqema GmbH Nacure 5225 Amine neutralized King Industries dodecylbenzenesulfonic acid Inc. Shellsol A Aromatic hydrocarbons Shell Chemicals BYK-358 N Solution of a polyacrylate BYK Chemie GmbH Joncryl 8280 Acrylic dispersion BASF SE Propylenglycol 1,2-Propandiol Dow Chemical BYK-154 Solution of an ammonium salt BYK-Chemie of an acrylate copolymer GmbH Kronos 2190 Titan dioxide Kronos Inc. Butylglycol 2-Butoxy-ethanol BASF SE Texanol Isobutyric acid, ester with Krahn Chemie 2,2,4-trimethyl-1,3-pentanediol GmbH Ammonia 32% solution of ammonia in Merck KGaA water Worléekyd S 365 Long oil alkyd resin Worlée Testbenzin K30 Hydrocarbons, C9-C12, Julius Hoesch n-alkanes, isoalkanes, cyclics, GmbH & Co. KG aromatics (2-25%) Nuodex Combi APB Cobalt/Calcium/Zirconium drier Venator Materials combination BYK-066 N Solution of foam-destroying BYK-Chemie polysiloxanes GmbH Borchi Nox M2 Methyl ethyl ketoxime Borchers DI water Deionized water

Test System 1: Polyester-Melamine White Coating Composition

[0094] Production of a polyester-melamine white coating composition using the formulation in table 2. Ingredients 1 to 5 were grinded with a Dispermat CV with 1 mm glass beads (weight ratio glass beads to mill base 1:1) for 30 min at 18 m/s at 40° C. Afterwards ingredients 6 to 12 were added and homogenized by stirring manually at 23° C. Subsequently, 100 g of the formulation was filled in 150 ml glass bottles. After the formulation is cooled down to room temperature (23° C.) an amount of the urea-based compound solution corresponding to 0.3 g of the urea-based compound became incorporated into the formulation under stirring with a Dispermat CV (Fa. Getzmann) for 2 min. at 1000 rpm, using a 4 cm diameter toothed plate. Afterwards the samples were stored at 23° C. for 24 hours. After that the low shear viscosity of the samples were measured on a rheometer Physica MCR 301 from Anton Paar with a 2.5 cm diameter 1° cone at a shear rate of 0.1 1/s at 23° C.

TABLE-US-00002 TABLE 2 Polyester-Melamine white coating 1 Setal 1715 VX-74 10.0 g 2 Xylene 4.0 g 3 Aerosil R 972 0.3 g 4 Disperbyk 2150 0.7 g 5 Kronos 2160 21.5 g 6 Setal1715 VX-74 32.0 g 7 Setamine US 138 BB-70 17.4 g 8 Butylglycolacetate 3.6 g 9 Nacure 5225 0.4 g 10 Shellsol A 7.1 g 11 Xylene 2.8 g 12 BYK 358 N 0.2 g total 100.0 g Grinding: Dispermat CV, 30 min, 18 m/s, 40° C., 1 mm glass beads:mill base 1:1

TABLE-US-00003 TABLE 3 Results Product Viscosity [Pas] at 1/s Without rheol. additive 0.2 Comparative Example C1 32.1 Comparative Example C2 30.6 Example E1 47.1 Example E5 38.2

[0095] From the table 3 it is visible, that the comparison samples show a lower viscosity in the low shear rate range than the subject to concept samples.

[0096] The samples related to subject of concept are obviously better effective and are therefore better suitable to improve properties like anti-settling or anti-sagging where the low shear viscosity has a strong impact.

Test System 2: Acrylic Dispersion White Paint

[0097] Production of the acrylic dispersion white paint using the formulation in table 4. Ingredients 1 to 4 were grinded with a Dispermat CV with 1 mm glass beads (weight ratio glass beads to mill base 1:1) for 30 min at 18 m/s at 40° C. Afterwards ingredients 6 to 8 were added and homogenized by stirring manually at 23° C. Subsequently, 100 g of the formulation was filled in 150 ml glass bottles. After the formulation is cooled down to room temperature (23° C.) 0.8% of the active substance of the respective rheology additive became incorporated into the formulation under stirring with a Dispermat CV (Fa. Getzmann) for 5 min. at 1000 rpm, using a 4 cm diameter toothed plate. Afterwards the samples were stored at 23° C. for 24 hours. For the application, the samples were stirred with a spatula for homogenization and then applied with a stepped doctor blade Model 421/S (Erichsen GmbH & Co KG) with 30-300 μm wet film thickness. The application is done on contrast cards 2801 (BYK-Gardner GmbH) using the automatic applicator byko-drive XL (BYK-Gardner GmbH) with an application speed of 50 mm/s. Directly after application the draw down is hanged up vertical at 23° C. until it is dried. After drying, the visual evaluation of the sag resistance is done. Therefore, the wet film thickness is taken that shows after drying a clear separation of the draw down, no runner and also no bulge building between the applied film thickness.

TABLE-US-00004 TABLE 4 Acrylic dispersion white paint 1 Propylenglycol 5.6 g 2 BYK 154 0.6 g 3 DI water 2.0 g 4 Kronos 2190 22.1 g 5 Butylglycol/Texanol 70:30 (w/w) 3.1 g 6 Ammonia 25% in water 0.3 g 7 DI water 6.1 g 8 Joncryl 8280 60.2 g total 100.0 g Grinding: Dispermat CV, 20 min, 18 m/s, toothed plate at 23° C.

TABLE-US-00005 TABLE 5 Results Product Sag resistance [μm] Without rheological additive <30 Comparative Example C3 120 Comparative Example C4 60 Comparative Example C5 90 Example E3 150 Example E6 150

[0098] From the table 5 it is visible, that the comparison samples show a lower rheological effectiveness measured by sag resistance than the subject to concept samples. The samples related to subject of concept are obviously better suitable to improve the sag resistance than the comparison samples.

Test System 3: Long Oil Alkyd Clear Coat

[0099] Production of the long oil alkyd clear coat using the formulation in table 6. Subsequently, 100 g of the formulation was filled in 150 ml glass bottles and 0.8% of the active substance of the respective rheology additive became incorporated into the formulation under stirring with a Dispermat CV (Fa. Getzmann) for 5 min. at 1000 rpm, using a 4 cm diameter toothed plate. The samples were stored at 23° C. for 24 hours. After that the low shear viscosity of the samples were measured on a rheometer Physica MCR 301 from Anton Paar with a 2.5 cm diameter 1° cone at a shear rate of 0.1 1/s at 23° C.

TABLE-US-00006 TABLE 6 Long oil alkyd clear coat Worléekyd S 365, 60% in Testbenzin K30 80.9 g Testbenzin K30 13.7 g Nuodex Combi APB 4.9 g Borchi Nox M2 0.3 g BYK-066 0.2 g Total 100.0 g

[0100] Addition of the single components under stirring with a Dispermat CV with 2000 rpm for 10 min.

TABLE-US-00007 TABLE 7 Results Product Viscosity [Pas] at 1/s Without rheological additive 0.8 Comparative Example C6 3.4 Comparative Example C7 3.4 Example E2 6.6

[0101] From the table 7 it is visible, that the comparison samples show a lower viscosity in the low shear rate range than the subject to concept samples. The samples related to subject of concept are obviously better effective and are therefore better suitable to improve properties like anti-settling or anti-sagging where the low shear viscosity has a strong impact.