REACTION PRODUCTS CONTAINING AMIDOAMINE GROUPS

Abstract

A reaction product containing amido amine groups, comprising one or more species of the general formula (I)

(R.sup.1X).sub.pZ.sup.1(XH).sub.y (I)

where p+y=w and w is an integer from 1 to 10, p is an integer from 1 to 10, y is an integer from 0 to 9, and X is independently O, NH and/or NZ.sup.2 and XH is independently a hydroxyl group OH, a primary amino group NH2 and/or a secondary amino group NHZ.sup.2 where Z.sup.2 is independently a branched or unbranched, saturated or unsaturated organic radical G(U)a where U is independently a hydroxyl group, a primary amino group or a secondary amino group and a is an integer from 0 to 9, where p+y+as 10, and G is a branched or unbranched, saturated or unsaturated organic radical, the p R.sup.1 radicals are independently a radical of the general formula (II)

YOCONHR.sup.2NHCO (II)

in which the p Y radicals are independently a branched or unbranched, saturated or unsaturated organic radical which has 1 to 1000 carbon atoms and does not contain any hydroxyl groups, any primary amino groups or any secondary amino groups, the p R.sup.2 radicals are independently a branched or unbranched, saturated or unsaturated organic radical having 6 to 20 carbon atoms, Z.sup.1 is a branched or unbranched, saturated or unsaturated organic radical containing at least two carbon atoms, having at least one amide group and at least one tertiary amino group.

Claims

1. A reaction product containing amido amine groups, comprising one or more species of the general formula (I)
(R.sup.1X).sub.pZ.sup.1(XH).sub.y (I) where p+y=w and w is an integer from 1 to 10, p is an integer from 1 to 10, y is an integer from 0 to 9, and X is independently O, NH and/or NZ.sup.2 and XH is independently a hydroxyl group OH, a primary amino group NH.sub.2 and/or a secondary amino group NHZ.sup.2 where Z.sup.2 is independently a branched or unbranched, saturated or unsaturated organic radical G(U).sub.a where U is independently a hydroxyl group, a primary amino group or a secondary amino group and a is an integer from 0 to 9, where p+y+a10, and G is a branched or unbranched, saturated or unsaturated radical, the p R.sup.1 radicals are independently a radical of the general formula (II)
YOCONHR.sup.2NHCO (II) in which the p Y radicals are independently a branched or unbranched, saturated or unsaturated organic radical which has 1 to 1000 carbon atoms and does not contain any hydroxyl groups, any primary amino groups or any secondary amino groups, the p R.sup.2 radicals are independently a branched or unbranched, saturated or unsaturated organic radical having 6 to 20 carbon atoms, Z.sup.1 is a branched or unbranched, saturated or unsaturated organic radical containing at least two carbon atoms, having at least one amide group and at least one tertiary amino group.

2. The reaction product containing amido amine groups as claimed in claim 1, containing at least 40% by weight of one or more species of the general formula (I).

3. The reaction product containing amido amine groups as claimed in claim 1, wherein the species of the general formula (IV) which is free of urethane groups, is reactive toward isocyanate groups and corresponds to the general formula (I)
(HX).sub.pZ.sup.1(HX).sub.y (IV) with p, y, X and Z.sup.1 as defined for the general formula (I), and which is reacted with p urethanes of the general formula (III) to give the reaction product containing amido amine groups comprising one or more species of the general formula (I), is obtained by reacting one or more components A with one or more components B and/or C, wherein component A is selected from the group of ethylenically unsaturated carboxylic acids, esters thereof and acid halides thereof, where at least one CC double bond and at least one CO double bond are in conjugated form and the CO double bond is selected from the group of the carboxylic acids, the carboxylic esters and the carbonyl halides; component B is of the general formula (V)
(R.sup.3).sub.xHN(R.sup.4).sub.z (V) where x+z=2 and x is an integer from 0 to 2, z is an integer from 0 to 2, and R.sup.3 is independently H or a branched or unbranched, saturated or unsaturated organic radical having 1 to 12 carbon atoms, and R.sup.4 is independently a branched or unbranched, saturated or unsaturated organic radical having 2 to 12 carbon atoms and 1 to 3 tertiary amino groups; and component C is of the general formula (VI)
(R.sup.5).sub.kHN(R.sup.6).sub.n (VI) where k+n=2 and k is an integer from 0 to 1, n is an integer from 1 to 2, and R.sup.5 is H or a branched or unbranched, saturated or unsaturated organic radical having 1 to 12 carbon atoms, and R.sup.6 is independently a branched or unbranched, saturated or unsaturated organic radical having 2 to 12 carbon atoms and 1 to 4 hydroxyl groups.

4. The reaction product containing amido amine groups as claimed in claim 3, wherein component A is an ethylenically unsaturated carboxylic ester.

5. The reaction product containing amido amine groups as claimed in claim 1, wherein the diisocyanate R.sup.2(NCO).sub.2 corresponding to the R.sup.2 radical has two isocyanate groups of different reactivity.

6. The reaction product containing amido amine groups as claimed in claim 1, wherein Y contains at least one polyether radical, polyester radical, hydrocarbyl radical and/or polysiloxane radical.

7. A process for preparing the reaction product containing amido amine groups as claimed in claim 3, wherein i) at least one diisocyanate R.sup.2(NCO).sub.2 is reacted with at least one monoalcohol YOH to form a urethane of the general formula (III)
YOCONHR.sup.2NCO (III) ii) p urethanes of the general formula (III) are reacted to give a reaction product containing amido amine groups, comprising one or more species of the general formula (I)
(R.sup.1X).sub.pZ.sup.1(XH).sub.y (I) and wherein step ii) is conducted in one stage ii-a) or in a stage sequence ii-b), in stage ii-a) p urethanes of the general formula (III) are reacted with a species of the general formula (IV) which is free of urethane groups and reactive toward isocyanate groups, and in stage ii-b) p urethanes of the general formula (III) are reacted with an intermediate I containing at least one HX group reactive toward isocyanate groups with X as defined for the general formula (I) to form an intermediate J, wherein I is a Michael addition product of at least one component A with a component B or C, and then the intermediate J formed is reacted in an amidation reaction with a component B or C.

8. The process as claimed in claim 7, wherein the diisocyanate R.sup.2(NCO).sub.2 is used in step i) relative to the monoalcohol YOH in a molar ratio of at least 1.1:1.0 and the diisocyanate R.sup.2(NCO).sub.2 that has not been converted to the urethane of the general formula (III) in step i) is removed from the reaction mixture, optionally by distillation, prior to the performance of step ii).

9. The process as claimed in claim 7, wherein the diisocyanate R.sup.2(NCO).sub.2 corresponding to the R.sup.2 radical has two isocyanate groups of different reactivity.

10. The process as claimed in claim 9, wherein the diisocyanate R.sup.2(NCO).sub.2 is selected from the group consisting of toluene 2,4-diisocyanate and isophorone diisocyanate.

11. A wetting agent and dispersant comprising the reaction product containing amido amine groups, as claimed in claim 1.

12. A composition comprising the reaction product containing amido amine groups, as claimed in claim 1.

13. A method of utilizing the reaction product containing amido amine groups as claimed in claim 1, comprising adding the reaction product as a wetting agent or dispersant or dispersion stabilizer or viscosity reducer or compatibilizer in coatings, varnishes, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, potting compounds, spackling compounds, printing inks or other inks.

14. A reaction product containing amido amine groups which is one species of the general formula (I) of the reaction product as claimed in claim 1.

15. A reaction product containing amido amine groups, comprising one or more salt(s) and/or one or more quaternization product(s) of the species of the general formula (I) of the reaction product as claimed in claim 1.

16. A reaction product containing amido amine groups, comprising one or more modification products of the species of the general formula (I) of the reaction product as claimed in claim 1, wherein the one or more tertiary amino groups of the general formula (I) have been converted to amine oxides with oxygen and/or peroxo compounds and/or XH groups still present in the general formula (I) have been reacted with carboxylic anhydrides.

17. The reaction product containing amido amine groups as claimed in claim 1, containing at least 90% by weight of one or more species of the general formula (I).

18. A wetting agent and dispersant comprising the reaction product containing amido amine groups, prepared by the process as claimed in claim 7.

19. A composition comprising the reaction product containing amido amine groups, prepared by the process as claimed in claim 7.

20. A method of utilizing the reaction product containing amido amine groups prepared by the process as claimed in claim 7, comprising adding the reaction product as a wetting agent or dispersant or dispersion stabilizer or viscosity reducer or compatibilizer in coatings, varnishes, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, potting compounds, spackling compounds, printing inks or other inks.

Description

EXAMPLES

[0226] In the case of molecularly inhomogeneous substances, the stated molecular weights hereinafter as already in the above descriptionare number-average values. The molecular weights or number-average molecular weights M.sub.n, in the event that titratable hydroxyl or amino groups are present, are determined by end group determination via the finding of the OH number, the amine number or the NCO number.

[0227] Unless stated otherwise, figures in parts are parts by weight and figures in percent s are percent by weight.

[0228] Solids Content

[0229] The sample (2.00.1 g of test substance) is weighed into an aluminum dish that has been dried beforehand and dried in a drying cabinet at 150 C. for 10 minutes, cooled down in a desiccator, and then re-weighed. The residue corresponds to the solids content.

[0230] NCO Number

[0231] The free NCO content of the polyisocyanates being used and the course of reaction of the NCO additions is determined according to EN ISO 9369 by reaction with butylamine and subsequent titration of the excess of amine. These methods are also described in Saul Patai The Chemistry of Cyanates and their Thioderivates, Part 1, Chapter 5, 1977.

[0232] OH Number

[0233] The OH number is determined according to DIN ISO 4629 by acetylation with an excess of acetic anhydride. Subsequently, the excess acetic anhydride is hydrolyzed to acetic acid by addition of water and back-titrated with ethanolic KOH solution. The OH number indicates the amount of KOH in mg equivalent to the amount of acetic acid bound in the acetylation of 1 g of substance.

[0234] Amine Number

[0235] The amine number (AN) is understood to mean the amount of KOH in mg corresponding to the amine content of 1 g of substance. The amine number is determined according to DIN 16945 by potentiometric titration with 0.1 N perchioric acid in acetic acid.

[0236] Starting Materials [0237] TDI toluene 2,4-diisocyanate (Desmodur T100), % NCO=48.8; manufacturer: Bayer Material Science [0238] PMA methoxypropyl acetate (solvent), manufacturer: Dow Chemical Comp. [0239] DBTL dibutyltin dilaurate, manufacturer: Merck [0240] DMAPA N,N-dimethylaminopropylamine, manufacturer: Huntsman Corp. [0241] TEA triethanolamine, manufacturer: BASF [0242] DEA N,N-diethanolamine, manufacturer: BASF [0243] EA ethanolamine, manufacturer: BASF [0244] IPA 3-imidazolyl-1-propylamine, manufacturer: BASF [0245] BDMAPA N,N-bis[3-(dimethylamino)propyl]amine=Jeffcat Z 130, manufacturer: Huntsman Corp. [0246] DMAE N,N-dimethylaminoethanol, manufacturer: BASF [0247] APDEA N-(3-aminopropyl)diethanolamine, TCI Deutschland GmbH [0248] AEE 2-(2-aminoethoxy)ethanol, manufacturer: BASF [0249] MA methyl acrylate, manufacturer: BASF [0250] BA butylamine, manufacturer: BASF [0251] BzA benzylamine, manufacturer: BASF [0252] Grilonit RV 1814 C.sub.13/C.sub.15-alkyl glycidyl ether, manufacturer: EMS-Chemie

[0253] Preparation of the Polyether-Polyester YOH 1, Mn 780

[0254] 350 g of MPEG 350 (methoxy polyethylene glycol, Mn 350), 434 g of -caprolactone and 1 g of DBTL (dibutyltin dilaurate) are reacted at 160 C. until a solids content of>97% has been attained.

[0255] The OH number of the reaction product is 72 mg KOH/g.

[0256] The further monohydroxy-functional polyesters used as YOH are prepared in an analogous manner.

[0257] General Preparation Method for the Monoadducts M of the General Formula (III) (table 1):

[0258] A four-neck flask provided with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is initially charged with 430 g of Desmodur T100 (TDI) (about 100% toluene 2,4-diisocyanate, NCO content=48.8) and 7 g of benzoyl chloride, and mixed thoroughly. X g of the alcohol component which is anhydrous, and alkali-free in the case of polyethers, are metered in gradually such that the temperature does not exceed 55 C. After the metered addition, the mixture is stirred at 55 C. for a further 3 hours. The excess TDI is removed from the reaction mixture by means of a thin-film evaporator at 150 C. The residual TDI content is <1%.

TABLE-US-00001 TABLE 1 Overview of the monoadducts M of the general formula (III) Mono- Amount X adduct Alcohol component YOH in [g] M1 n-Butanol-started PO polyether Mn 800, OH 800 number: 70 mg KOH/g M2 MPEG 350, OH number: 160 mg KOH/g 350 M3 n-Butanol-started EO/PO polyether (EO:PO 1:1) Mn 2240 2240, OH number: 25 mg KOH/g M4 Polyester YOH 1, OH number: 72 mg KOH/g 780 M5 Hexadecanol-started monohydroxy-functional - 600 caprolactone polyester, Mn 600 M6 Hexadecanol-started monohydroxy-functional - 1200 caprolactone polyester, Mn 1200 M7 MPEG 500 = methoxy polyethylene glycol, Mn 500 500 M8 n-Butanol-started EO/PO polyether (EO:PO 1:1) 1100 Mn 1100 M9 n-Butanol-started EO/PO polyether (EO:PO 1:1) 1500 Mn 1500 M10 n-Butanol-started EO/PO polyether (EO:PO 1:1) 1800 Mn 1800 M11 n-Butanol-started EO/PO polyether (EO:PO 1:1) 3100 Mn 3100 M12 n-Butanol-started EO/PO polyether (EO:PO 1:1) 4250 Mn 4250 M13 Monohydroxy-functional hydroxypropyl poly- 1200 dimethylsiloxane with butyl end group, Mn 1200 M14 Methanol-started EO/PO polyether (EO:PO 3:1), 1400 Mn 1400 M15 MPEG 500-started -caprolactone polyester Mn 900 900 M16 Isodecanol-started -caprolactone polyester Mn 700 700 M17 Isodecanol-started -caprolactone polyester Mn 1000 1000 M18 Monophenyl glycol-started -caprolactone polyester, 1200 Mn 1200 M19 n-Butanol-started -caprolactone polyester, Mn 600 600 M20 n-Butanol-started -caprolactone polyester, Mn 1200 1200 M21 n-Butanol-started PO polyether, Mn 1100 1100 M22 Isodecanol-started polyester formed from - 2000 caprolactone and -valerolactone in a molar ratio of 3:1, Mn = 2000 M23 -caprolactone polyester Mn 1950, started with an n- 1950 butanol-started EO/PO polyether (EO:PO 1:1), Mn 1500 M24 MPEG 350-started -caprolactone polyester Mn 900 900 M25 MPEG 350-started polyester formed from - 950 caprolactone and -valerolactone in a molar ratio of 3:1, Mn = 950 M26 MPEG 500-started polyester formed from - 1100 caprolactone and -valerolactone in a molar ratio of 3:1, Mn = 1100 M27 MPEG 750-started polyester formed from - 1400 caprolactone and -valerolactone in a molar ratio of 3:1, Mn = 1400 M28 MPEG 750 750 M29 -caprolactone polyester Mn 1630, started with a 1630 methanol-started EO/PO polyether (EO:PO 3:1), Mn 1400 M30 n-Butanol-started EO/PO polyether (EO:PO 1:1) 2540 Mn 2540 M31 n-Butanol-started PO polyether, Mn 2240 2240 M32 n-Butanol-started butylene oxide polyether, Mn 960 960 M33 Oleyl alcohol 268 M34 Monophenyl glycol 138 M35 n-Decanol 158

[0259] General Method for Preparation of the Amido Amines AA of the General Formula (IV)

[0260] First Step (Michael addition) to give Intermediate I (Table 2)

[0261] A four-neck flask provided with a stirrer, thermometer, water separator and nitrogen inlet tube is initially charged with y g of the amine B and/or z g of the amino alcohol C at room temperature. Subsequently, x g of component A are added gradually, such that the reaction temperature does not exceed 35-40 C. The progress of the reaction is monitored by means of 1H NMR. The reaction is considered to have ended when the CC double bond of the ethylenically unsaturated ester compound A has been fully converted.

[0262] Second Step (amidation) to give Amido Amine AA (Table 3)

[0263] On completion of conversion of the CC double bond of the ethylenically unsaturated ester compound A in the first step, the ester group of the intermediate I obtained is amidated with a primary or secondary amino group of an amine component B and/or

[0264] C, by heating the Michael adduct to 80 C. and adding the amine B and/or C to the reaction mixture at 80 C. and then increasing the temperature stepwise to 120 C. For better removal of the alcohol formed from the reaction mixture, a reduced pressure of 500 mbar is applied after one hour of reaction time at 120 C. The reaction mixture is stirred under these conditions until monitoring of the reaction by infrared spectroscopy shows complete conversion of the ester groups to amide groups. Dilution with PMA is optionally possible after the reaction.

[0265] Preparation of the Intermediates I

TABLE-US-00002 TABLE 2 Preparation of the intermediates I Amount x of Amount y of Amount z of component component component Example A B C I1 86 g MA 105 g DEA I2 172 g MA 73 g BA I3 172 g MA 107 g BzA I4 86 g MA 187 g BDMAPA I5 172 g MA 105 g AEE I6 172 g MA 61 g EA I7 172 g MA 162 g APDEA I8 172 g MA 102 g DMAPA DEA = N,N-diethanolamine, MA = methyl acrylate, BA = butylamine, BzA = benzylamine, BDMAPA = N,N-bis[3-(dimethylamino)propyl]amine, AEE = 2-(2-aminoethoxy)ethanol, EA = ethanolamine, APDEA = N-(3-aminopropyl)diethanolamine, DMAPA = N,N-dimethylaminopropylamine

[0266] Preparation of the Amido Amines AA

TABLE-US-00003 TABLE 3 Preparation of the amido amines AA Amount x of Amount y of Amount z of Example I B C AA1 197 g I1 102 g DMAPA AA2 197 g I1 125 g IPA AA3 223 g I6 204 g DMAPA AA4 236 g I2 122 g EA AA5 236 g I2 210 g DEA AA6 265 g I3 122 g EA AA7 265 g I4 105 g DEA AA8 320 g I7 204 g DMAPA AA9 263 g I5 204 g DMAPA AA10 197 g I1 187 g BDMAPA AA11 266 g I8 122 g EA AA12 266 g I8 324 g APDEA AA13 223 g I6 324 g APDEA AA14 320 g I7 324 g APDEA AA15 223 g I6 102 g DMAPA 61 g EA AA16 223 g I6 102 g DMAPA 162 g APDEA DMAPA = N,N-dimethylaminopropylamine, IPA = 3-imidazolyl-1-propylamine, EA = ethanolamine, DEA = N,N-diethanolamine, BDMAPA = N,N-bis[3-(dimethylamino)propyl]amine, APDEA = N-(3-aminopropyl)diethanolamine

[0267] General Method for Step ii) for Conversion of the Monoadducts M of the General Formula (III) to Reaction Products Containing Amido Amine Groups of the General Formula (I)

[0268] In One Single Stage ii-a) (Table 4)

[0269] A four-neck flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is initially charged with y g of the amido amine AA and heated to 70 C. while stirring under nitrogen. Subsequently, x g of monoadduct are added gradually, such that the reaction temperature does not exceed 80 C. Subsequently, the reaction mixture is stirred at 80 C. until the isocyanate has reacted to completion. The progress of the reaction is followed by means of titrimetric determination of the NCO number to EN ISO 9369. The reaction is considered to have ended when an NCO content of <0.1% is determined. Dilution with PMA is optionally possible during or after the reaction.

[0270] When any hydroxyl groups present in the amido amine AA are to be reacted with a monoadduct M of the general formula (III), the reaction is effected with addition of 200 ppm of dibutyltin dilaurate; otherwise, the preparation is conducted as described.

TABLE-US-00004 TABLE 4 Reaction of the monoadducts M with amido amines AA in step ii-a) Amount x of Amount y of monoadduct amido amine PMA Solids Example M AA in g in % P1 127.4 g M21 26.1 g AA1 97.8 P2 197.4 g M10 26.1 g AA1 98.2 P3 442.4 g M12 26.1 g AA1 468.5 g 49.5 P4 334.8 g M9 26.1 g AA1 98.6 P5 167.4 g M9 38.6 g AA3 98.4 P6 97.4 g M1 38.6 g AA3 97.9 P7 241.4 g M3 38.6 g AA3 99.2 P8 67.4 g M7 38.6 g AA3 97.3 P9 157.4 g M14 38.6 g AA3 98.5 P10 107.4 g M15 38.6 g AA3 98.7 P11 334.8 g M9 27.6 g AA2 97.6 P12 167.4 g M9 27.6 g AA2 97.9 P13 190.8 g M4 27.6 g AA2 99.1 P14 254.8 g M8 27.6 g AA2 98.9 P15 154.8 g M19 27.6 g AA2 97.7 P16 542.8 g M30 27.6 g AA2 98.5 P17 669.6 g M9 34.8 g AA5 98.1 P18 309.6 g M5 34.8 g AA5 99.0 P19 549.6 g M18 34.8 g AA5 98.8 P20 412.2 g M18 34.8 g AA5 98.3 P21 274.8 g M18 34.8 g AA5 97.6 P22 137.4 g M18 34.8 g AA5 97.1 P23 629.6 g M27 34.8 g AA5 664.4 g 48.7 P24 124.8 g M34 34.8 g AA5 97.8 P25 334.8 g M9 30.6 g AA6 98.4 P26 274.8 g M6 30.6 g AA6 98.8 P27 104.8 g M2 30.6 g AA6 98.0 P28 226.8 g M32 30.6 g AA6 98.1 P29 88.4 g M33 30.6 g AA6 97.9 P30 254.8 g M8 30.6 g AA6 97.4 P31 334.8 g M9 38.0 g AA10 96.8 P32 334.8 g M9 31.3 g AA4 97.5 P33 654.8 g M11 31.3 g AA4 97.7 P34 482.8 g M31 31.3 g AA4 97.8 P35 62.4 g M34 31.3 g AA4 98.1 P36 214.8 g M24 31.3 g AA4 98.9 P37 334.8 g M9 35.0 g AA7 98.2 P38 334.8 g M9 44.8 g AA8 96.4 P39 184.8 g M28 44.8 g AA8 97.1 P40 92.4 g M28 44.8 g AA8 96.8 P41 66.4 g M35 44.8 g AA8 98.8 P42 167.4 g M9 38.8 g AA9 99.2 P43 117.4 g M17 38.8 g AA9 97.4 P44 92.4 g M29 38.8 g AA9 98.2 P45 334.8 g M9 30.2 g AA11 98.8 P46 274.8 g M20 30.2 g AA11 96.7 P47 224.8 g M25 30.2 g AA11 255.0 g 49.8 P48 669.6 g M9 47.1 g AA12 97.6 P49 502.2 g M9 47.1 g AA12 98.6 P50 334.8 g M9 47.1 g AA12 98.2 P51 167.4 g M9 47.1 g AA12 98.7 P52 509.6 g M26 47.1 g AA12 97.8 P53 509.6 g M21 47.1 g AA12 99.0 P54 669.6 g M9 50.8 g AA13 99.4 P55 349.6 g M16 50.8 g AA13 98.8 P56 849.6 g M23 50.8 g AA13 98.2 P57 502.2 g M9 53.6 g AA14 99.1 P58* 167.4 g M9 10.2 g DMAPA 98.4 P59* 167.4 g M9 8.9 g DMAE 96.5 P60* 167.4 g M9 18.7 g BDMAPA 97.6 P61* 167.4 g M9 14.9 g TEA 98.0 P62 274.8 g M13 32.2 g AA15 97.8 P63 652.2 g M22 41.7 g AA 16 98.4 *noninventive examples/prior art PMA = methoxypropyl acetate (solvent), DMAPA = N,N-dimethylaminopropylamine, TEA = triethanolamine, DMAE = N,N-dimethylaminoethanol, BDMAPA = N,N-bis[3-(dimethylamino)propyl]amine

[0271] In a Stage Sequence ii-b) (Table 5)

[0272] First Step

[0273] A four-neck flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is initially charged with y g of the intermediate I and heated to 70 C. while stirring under nitrogen. Subsequently, x g of monoadduct M are added gradually, such that the reaction temperature does not exceed 80 C. Subsequently, the reaction mixture is stirred at 80 C. until the isocyanate has reacted to completion. The progress of the reaction is followed by means of titrimetric determination of the NCO number to EN ISO 9369. The reaction is considered to have ended when an NCO content of <0.1% is determined.

[0274] Second Step

[0275] On completion of reaction of the isocyanate group with an alcohol group, a primary amino group or a secondary amino group of an intermediate I in the first step, the intermediate J obtained is amidated with a primary or secondary amino group of an amine component B and/or C, by adding the amine B and/or C to the reaction mixture at 80 C. and increasing the temperature stepwise to 120 C. For better removal of the alcohol formed from the reaction mixture, a reduced pressure of 500 mbar is applied after one hour of reaction time at 120 C. The reaction mixture is stirred under these conditions until monitoring of the reaction by infrared spectroscopy shows complete conversion of the ester group to the amide group. In the case of products containing polyester in the Y radical, such that it becomes more difficult to monitor the reaction by infrared spectroscopy, the end of the reaction is s determined in that no further alcohol forms; thus, the amidation is considered to have ended. Dilution with PMA is optionally possible after the reaction.

TABLE-US-00005 TABLE 5 Reaction of the monoadducts M with an intermediate I and subsequent amidation in step ii-b) Amount x of Amount y of Amount z of monoadduct intermediate component Example M I B or C P64 127.4 g M21 19.7 g I1 10.2 g DMAPA P65 254.8 g M21 19.7 g I1 10.2 g DMAPA P66 97.4 g M1 22.3 g I6 20.4 g DMAPA P67 194.8 g M1 19.7 g I1 10.2 g DMAPA P68 127.4 g M21 19.7 g I1 6.1 g EA DMAPA = N,N-dimethylaminopropylamine, EA = ethanolamine

[0276] General Method for Quaternization (Table 6)

[0277] In a four-neck flask provided with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube, y g of the starting compound in 170 g of PMA (methoxypropyl acetate) and 170 g of butylglycol and x g of alkylating reagent are reacted at 120 C. for 4 h. The solids content is adjusted to 40% with a 1:1 mixture of PMA and butylglycol.

TABLE-US-00006 TABLE 6 Quaternization Amount y of Amount x of Example starting compound alkylating reagent Q1 224 g P2 6.9 g of benzyl chloride Q2 224 g P2 14.7 g of Grilonit 1814 6.4 g of benzoic acid Q3 224 g P2 9.5 g of benzyl chloride Q4 224 g P2 26.7 g of Grilonit 1814 11.6 g of benzoic acid Q5 224 g P2 12.0 g of benzyl chloride Grilonit RV 1814 = C.sub.13/C.sub.15-alkyl glycidyl ether, EMS-Chemie

[0278] General Method for Salt Formation (Table 7)

[0279] In a four-neck flask provided with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube, y g of the compound to be converted to a salt in s 170 g of PMA and 170 g of butylglycol is stirred with x g of salt conversion reagent at 60 C. for 1 h.

TABLE-US-00007 TABLE 7 Salt formation Amount y of Amount x of Example reaction product P salt conversion reagent S1 224 g P2 14.6 g of adipic acid S2 224 g P2 24.4 g of benzoic acid S3 224 g P2 12.2 g of benzoic acid S4 224 g P2 7.3 g of adipic acid S5 224 g P2 28.2 g of oleic acid S6 224 g P2 20.0 g of lauric acid S7 224 g P2 29.8 g of ricinoleic acid S8 224 g P2 9.0 g of lactic acid

[0280] c) Performance Testing

[0281] Use of the polymers of the invention as wetting agent and dispersing additive for production of pigment concentrates and use thereof in varnish systems

[0282] Starting Materials

TABLE-US-00008 Paraloid B-66 thermoplastic acrylate resin, manufacturer: DOW Chemicals Joncryl 500 hydroxy-functional acrylic resin, manufacturer: BASF Laropal A 81 aldehyde resin, manufacturer: BASF Cymel 303 amino crosslinker, manufacturer: Allnex MAK methyl amyl ketone, manufacturer: Eastman DIDP diisodecyl phthalate Nacure 2500 p-toluenesulfonic acid, manufacturer: King Industries Dowanol PMA propylene glycol methyl ether acetate, manufacturer: Dow Chemicals Raven 5000 carbon black pigment for high jetness, manufacturer Ultra III Paliogen Red perylene red pigment, manufacturer L3880 HD Hostaperm violet pigment, manufacturer RL NF Heliogen Blue phthalocyanine blue (P.B. 15:4), manufacturer: BASF L7101F Hostaperm quinacridone red (P.R. 122), manufacturer: Clariant Rosa E Colour Black carbon black pigment (P. Bk. 7), manufacturer: Orion FW 200 BYK 310 substrate wetting agent, manufacturer: BYK-Chemie BYK 306 substrate wetting agent, manufacturer: BYK-Chemie

[0283] Procedures

[0284] Production of Pigment Concentrates based on a Thermoplastic Acrylate

[0285] The Paraloid B-66 dispersion resin, solvent, dispersing additive and pigment were weighed into 100 mL glass bottles so as to obtain 50 g of millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in. Composition of the TPA pigment concentrates (figures in q)

TABLE-US-00009 TPA 1 TPA 2 TPA 3 (black) (red) (violet) Paraloid B-66 (50% in xylene) 24.0 24.0 24.0 Raven Ultra 5000 III 6.0 Paliogen Red L 3880 HD 8.0 Hostaperm RL-NF 5.0 Dispersing additive 4.2 2.0 2.0 n-Butanol 5.0 5.0 5.0 PMA 11.0 14.0 Butyl acetate 10.8 Total pigment content (%) 12 16 10 Dispersant (% s.o.p.) 70 25 40

[0286] Grinding Conditions

[0287] Equipment: Lau Disperser DAS 200

[0288] Dispersing time: 300 min, cooling power at level 3

[0289] Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

[0290] Assessment of Millbase Viscosity of the TPA Dispersions

[0291] The millbase viscosity of the TPA dispersions was determined with a Rheological Stresstech Rheometer (plate/cone, 25 mm,)1 at 23 C.

[0292] Millbase Viscosities

TABLE-US-00010 TPA 1 (black) TPA 2 (red) TPA 3 (violet) Raven 5000 Ultra III Paliogen Red L3880 HD Hostaperm RL-NF Viscosity in Pa * s 1/s 10/s 100/s 1/s 10/s 100/s 1/s 10/s 100/s P59* 45.890 7.727 1.828 15.370 2.876 0.814 42.110 4.786 1.085 P60* 48.380 7.022 1.663 15.440 2.879 0.864 38.460 4.680 1.005 P61* 51.610 7.534 1.774 22.470 3.808 1.011 57.960 7.762 1.432 P4 12.200 2.688 1.048 7.456 1.722 0.657 35.530 4.294 0.970 P11 24.470 4.746 1.419 9.462 1.881 0.677 37.990 4.614 0.968 P17 32.960 6.113 1.631 6.069 1.586 0.685 36.670 4.508 0.982 P25 18.390 3.661 1.132 8.977 1.888 0.688 39.180 4.647 1.027 The inventive dispersing additives P4, P11, P17 and P25 have a significant viscosity-reducing effect compared to the prior art P59*, P60* and P61* in TPA dispersions of 3 different pigments, which is manifested even at low shear rates.

[0293] Production of the TPA-Based Letdown System

[0294] Paraloid B-66, solvent and leveling additive were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

[0295] Composition of the TPA Letdown sSstem (figures in g)

TABLE-US-00011 TPA clearcoat Weight in g Paraloid B-66 (50% in xylene) 700 DIDP 20 Xylene 218 PMA 60 BYK-306 2

[0296] Production of the Pigmented TPA Letdown Systems

[0297] The TPA letdown system and the TPA-based pigment dispersion were weighed into a PE cup and mixed with a spatula. Subsequently, all the final TPA letdown systems were homogenized in an ANDALOK shaker for 10 min.

[0298] Composition of the Pigmented TPA Letdown Systems (figures in g)

TABLE-US-00012 TPA-B1 TPA-B2 TPA-B3 TPA letdown system 28.0 27.0 26.0 TPA 1 (black) 2.0 TPA 2 (red) 3.0 TPA 3 (violet) 4.0 Pigment content (%) 0.8 1.6 1.3

[0299] Application and Evaluation of the Pigmented TPA Letdown Systems

[0300] The pigmented TPA letdown systems were bar-coated onto PE film (50 m or 100 m) and dried at 22 C. for 24 h. Subsequently, the haze and gloss were measured with a BYK micro haze plus instrument at an angle of 20 . In each case, low values for haze and high values for gloss are considered to be positive results. In addition, the optical color intensity and transparency through the drawdowns onto PE film was assessed using grades 1 (excellent) to 5 (unacceptable).

TABLE-US-00013 TPA B1 (black) Raven 5000 Ultra III Masstone 100 m Dispersing PE film Trans- additive in Masstone 100 m Masstone 100 m parency/color the millbase PE film Haze PE film Gloss 20 intensity P59* 11 80 2-3 P60* 21 78 4 P61* 12 80 3 P4 11 80 2-3 P11 10 81 2 P17 10 82 1-2 P25 11 80 2

TABLE-US-00014 TPA B2 (red) Paliogen Red L3880 HD Masstone 50 m Dispersing PE film Trans- additive in Masstone 100 m Masstone 100 m parency/color the millbase PE film Haze PE film Gloss 20 intensity P59* 13 77 3-4 P61* 20 73 4 P4 11 80 3 P17 12 79 3

TABLE-US-00015 TPA B3 (violet) Hostaperm RL-NF Masstone 50 m Dispersing PE film Trans- additive in Masstone 50 m Masstone 50 m parency/color the millbase PE film Haze PE film Gloss 20 intensity P59* 43 71 3-4 P61* 45 71 3 P4 36 74 2-3 P25 36 75 2-3

[0301] The dispersing additives of the invention exhibit lower haze, better gloss values and higher transparency and color intensity compared to the prior art for TPA-based varnish systems.

[0302] Production of the Laropal A81 Pigment Dispersion

[0303] The Laropal A81 dispersion resin (60 parts) was weighed into a 2.5 L PE bucket together with PMA (40 parts) and homogenized by means of a Dispermat CV (65 mm toothed disk) at 2000 rpm for 30 min. Subsequently, the solution of the dispersion resin, solvent, dispersing additive and pigment was weighed into 100 mL glass bottles so as to obtain 50 g of millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.

[0304] Composition of the Laropal A81 Pigment Concentrates (figures in g)

TABLE-US-00016 LA 1 LA 2 LA 3 (black) (pink) (blue) Laropal A 81 (60% in PMA) 8.7 20.4 21.9 Colour Black FW 200 4.0 Hostaperm Pink E 7.0 Heliogen Blue 7101F 7.5 Dispersing additive 2.8 1.8 1.9 PMA 34.5 20.8 18.7 Total pigment content (%) 8 14 15 Dispersant (% s.o.p.) 70 25 25

[0305] Grinding Conditions

[0306] Equipment: Lau Disperser DAS 200

[0307] Grinding time: 300 min, cooling power at level 3

[0308] Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

[0309] Assessment of the Millbase Viscosity and the Laropal A81 Dispersions

[0310] The millbase viscosity of the Laropal A81 dispersions was determined with a Rheological Stresstech Rheometer (plate/cone, 25 mm,)1 at 23 C.

[0311] Millbase Viscosities

TABLE-US-00017 LA 1 (black) LA 2 (pink) LA 3 (blue) Viscosity in mPa * s Viscosity in mPa * s Viscosity in mPa * s 1/s 10/s 100/s 1/s 10/s 100/s 1/s 10/s 100/s P58* 44 13 10 34870 3934 794 9457 1017 214 P60* 185 86 34 28460 3656 939 10450 1474 228 P61* 232 25 9 33660 3399 995 10720 815 247 P4 26 12 9 25750 2907 519 6646 894 179 P11 36 12 9 24990 3252 519 6072 827 172 P17 19 11 9 18400 1857 381 7889 905 202 P25 31 13 9 25230 2841 555 6862 921 184

[0312] Production of a Baking Varnish JC1

[0313] Binder, solvent and substrate wetting agent were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

[0314] Composition of the Baking Varnish JC1 (figures in g)

TABLE-US-00018 Baking varnish JC1 Weight in g Joncryl 500 576.0 Cymel 303 198.0 Butanol 80.0 MAK 130.0 BYK-310 3.0 Nacure 2500 13.0

[0315] Production of Various Varnishes based on the Laropal A81 Pigment Dispersions

[0316] The Laropal A81-based pigment dispersions and the baking varnish JC1 were weighed into a PE cup and mixed by hand with a spatula. Subsequently, the pigmented varnishes were homogenized in an ANDALOK shaker for 10 min.

[0317] Composition of the Pigmented JC1 Letdown Systems (figures in g)

TABLE-US-00019 JC1-B1 JC1-B2 JC1-B3 (black) (pink) (blue) JC1 18.0 17.9 16.0 LA 1 (black) 2.0 LA 2 (pink) 2.1 LA 3 (blue) 4.0 Pigment content (%) 0.8 1.5 3.0

[0318] Application and evaluation of the pigmented baking varnishes JC.sub.1-B1 to JC.sub.1-B3

[0319] The pigmented baking varnishes JC1-B1-B3 were bar-coated onto PE film (50 m), flashed off at 22 C. for 15 min and baked at 150 C. for 20 min. Subsequently, haze and gloss were measured with a BYK micro haze plus instrument at an angle of 20 . In each case, low values for haze and high values for gloss are considered to be positive results. In addition, the optical transparency and color intensity through the drawdowns onto PE film was assessed using grades 1 (excellent) to 5 (unacceptable).

[0320] Comparison of the Black Baking Varnishes JC1-B1 (black)

TABLE-US-00020 Transparency/ Synthesis name Gloss 20 Haze color intensity P58* 106 11 4 P60* 103 24 3-4 P61* 105 14 1-2 P4 106 14 1 P11 105 10 1 P17 106 16 1 P25 107 10 2

[0321] Comparison of the Pink Baking Varnishes JC1-B2 (pink)

TABLE-US-00021 Transparency/ Synthesis name Gloss 20 Haze color intensity P59* 112 33 3 P60* 113 19 4 P61* 113 21 4 P4 116 14 3-4 P11 115 20 3 P17 116 18 3 P25 115 14 3-4

[0322] Comparison of the Blue Baking Varnishes JC1-B3 (blue)

TABLE-US-00022 Transparency/ Synthesis name Gloss 20 Haze color intensity P59* 115 21 4 P60* 112 38 3 P61* 114 27 3-4 P4 115 26 2 P11 116 27 1 P17 115 24 3 P25 117 20 2

[0323] The dispersing additives of the invention P4, P11, P17 and P25 exhibit lower haze, better gloss values and higher transparency and color intensity compared to the prior art P59*, P60* and P61* for pigment concentrates based on Laropal A81 used in an s acid-catalyzed baking varnish.