Method for producing dispersant additives

Abstract

The present invention relates to a method for producing an additive composition which in particular contains specific urea urethanes. The additive composition is extremely suitable as a wetting agent and dispersant.

Claims

1. A method for producing an additive composition, comprising the steps i) to iii), wherein in step i) a hydroxy component of formula (I)
Y(OH).sub.q(I) or mixtures thereof, wherein Y is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having 1 to 1000 carbon atoms, q is the same or different and represented by an integer from 1 to 10 is reacted with a diisocyanate of formula (II) having NCO groups of different reactivity
R.sup.1(NCO).sub.2(II) or mixtures thereof, wherein R.sup.1 is the same or different and is represented by a hydrocarbon radical having 6 to 20 carbon atoms, comprising an arylene group, a branched or unbranched alkylarylene group, and/or an acyclic, cyclic, branched or unbranched alkylene group, wherein the diisocyanate of formula (II) is used with respect to the hydroxy component of formula (I) in a molar ratio of at least (1.1*arithmetic mean of q):1.0, so that an isocyanate adduct of formula (III)
Y(OCONHR.sup.1NCO).sub.q(III) or mixtures thereof, wherein Y, q and R.sup.1 are each as described above, and unreacted diisocyanate of formula (II) containing reaction mixture is formed, in step ii) at least 50 mol % of the unreacted portion of the diisocyanate of formula (II) is removed from the reaction mixture, in step iii) a compound of formula (IV) having at least one head group radical Z.sup.1
Y(OCONHR.sup.1NHCOXZ.sup.1).sub.q(IV) or mixtures thereof, wherein Y, q and R.sup.1 are each as described above, X is the same or different and is represented by O, NH and/or NZ.sup.2 wherein Z.sup.2 is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical, Z.sup.1 is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having at least two carbon atoms having at least one head group which is present in salifiable or salified form, and is selected from the group consisting of tertiary amino functions, quaternary ammonium functions, phosphoric acid ester functions, and carboxylic acid functions, wherein step iii) is carried out in a single stage iii-a) or a sequence of steps iii-b), in step iii-a) the isocyanate adduct of formula (III) present in the reaction mixture is reacted with an isocyanate-reactive compound of formula (V) having said head group radical Z.sup.1,
HXZ.sup.1(V) wherein X and Z.sup.1 are each as described above, and in the sequence of steps iii-b), first, the isocyanate adduct of the formula (III) which is present in the reaction mixture is reacted with a compound having a isocyanate-reactive group HX and at least one further functional group Q, wherein then Q is reacted with a reagent involved in the generation of the head group radical Z.sup.1 to form the head group radical Z.sup.1.

2. The method according to claim 1, characterized in that q is the same or different and is represented by an integer from 1 to 5.

3. A method for the preparation of an additive composition according to claim 1, characterized in that q=1, so that in the method including steps i) to iii) in step i) as a hydroxy component a monohydroxy compound of formula (Ia)
YOH(Ia) or mixtures thereof, wherein Y is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having 1 to 1000 carbon atoms is reacted with a diisocyanate of formula (II) having NCO groups of different reactivity
R.sup.1(NCO).sub.2(II) or mixtures thereof, wherein R.sup.1 is the same or different and is represented by a hydrocarbon radical having 6 to 20 carbon atoms, comprising an arylene group, a branched or unbranched alkylarylene group, and/or an acyclic, cyclic, branched or unbranched alkylene group, wherein the diisocyanate of formula (II) is used with respect to the monohydroxy component of formula (Ia) in a molar ratio of at least 1.1:1.0, so that a monoisocyanate adduct of formula (IIIa)
YOCONHR.sup.1NCO(IIIa) or mixtures thereof, wherein Y and R.sup.1 are each as described above, and unreacted diisocyanate of formula (II) containing reaction mixture is formed, in step ii) at least 50 mol % of the unreacted portion of the diisocyanate of formula (II) is removed from the reaction mixture, in step iii) a compound of formula (IVa) having at least one head group radical Z.sup.1
YOCONHR.sup.1NHCOXZ.sup.1(IVa) or mixtures thereof, wherein Y and R.sup.1 are each as described above, X is the same or different and is represented by O, NH and/or NZ.sup.2 wherein Z.sup.2 is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical, Z.sup.1 is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having at least two carbon atoms having at least one head group which is present in salifiable or salified form, and is selected from the group consisting of tertiary amino functions, quaternary ammonium functions, phosphoric acid ester functions, and carboxylic acid functions, wherein step iii) is carried out in a single stage iii-a) or a sequence of steps iii-b), in step iii-a) the monoisocyanate adduct of formula (IIIa) present in the reaction mixture is reacted with an isocyanate-reactive compound of formula (V) having said head group radical Z.sup.1,
HXZ.sup.1(V) wherein X and Z.sup.1 are each as described above, and in the sequence of steps iii-b), first, the monoisocyanate adduct of the formula (IIIa) which is present in the reaction mixture is reacted with a compound having a isocyanate-reactive group HX and at least one further functional group Q, wherein then Q is reacted with a reagent involved in the generation of the head group radical Z.sup.1 to form the head group radical Z.sup.1.

4. The method according to claim 1, characterized in that Y contains at least one polyether radical, polyester radical, hydrocarbon radical, and/or polysiloxane radical.

5. The method according to claim 1, characterized in that Y in total contains 1 to 450 ether oxygen atoms, which optionally are contained in radicals of polytetrahydrofuran, polyoxetanes and/or polyoxiranes.

6. The method according to claim 1, characterized in that Y in total contains 3 to 400 ether oxygen atoms, wherein at least 50 mol % of the ether oxygen atoms are present in ethylene oxide and/or propylene structural units.

7. The method according to claim 1, characterized in that R.sup.1 is the same or different and is a tolyl group and/or an isophoronyl group.

8. The method according to claim 1, characterized in that the diisocyanate of formula (II) is present as toluene-2,4-diisocyanate and/or isophorone diisocyanate.

9. The method according to claim 1, characterized in that the head group of the head group radical Z.sup.1 is present in the form of a phosphoric acid ester function, step iii) is carried out in the form of a sequence of steps iii-b), wherein the further functional group Q is present in the form of a hydroxyl group and the reagent involved in the generation of the head group moiety Z.sup.1 is present as a phosphorylization agent.

10. The method according to claim 1, characterized in that the head group radical Z.sup.1 has a phosphoric acid ester function as a head group, wherein Z.sup.1 is the same or different and is represented by formula (VII)
R.sup.2OPO(OR.sup.3).sub.n(OH).sub.2-n(VII) wherein R.sup.2 is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical having at least two carbon atoms, R.sup.3 is the same or different and is represented by a branched or unbranched, saturated or unsaturated organic radical; and n is the same or different and is represented by 0 and/or 1.

11. The method according to claim 10, characterized in that n is equal to 0 and R.sup.2 is the same or different and is represented by a saturated, linear C.sub.2-C.sub.40-alkylene radical.

12. The method according to claim 1, characterized in that the head group of the head group radical Z.sup.1 is the same or different and is present as tertiary amino function or quaternary ammonium function.

13. The method according to claim 1, characterized in that Z.sup.2 is the same or different and is represented by a C.sub.1-C.sub.50-organic radical having optionally ether oxygen atoms, and/or includes the equivalent of Z.sup.1, with the proviso that Z.sup.1 and Z.sup.2 each are represented independently from one another.

14. The method according to claim 1, characterized in that X is the same or different and is represented by NH and/or NZ.sup.2.

15. The method according to claim 1, characterized in that Z.sup.1 and Z.sup.2 each are represented independently from one another by radicals which in each case are either only relatively weakly reactive or inert towards isocyanates.

16. The method according to claim 1, characterized in that in step i) the diisocyanate of formula (II) is used with respect to the hydroxy component of formula (I) in a molar ratio of at least (1.5*arithmetic mean of q):1.0.

17. The method according to claim 1, characterized in that in step ii) at least 75 mol % of the unreacted portion of the diisocyanate of formula (II) is removed from the reaction mixture.

18. The method according to claim 3, characterized in that the molar ratio of the monohydroxy compounds of formula (Ia) reacted in total in step i) to the sum of the compounds of formula (V) reacted in step iii) and the compounds reacted in step iii) containing a isocyanate-reactive group HX and at least one further functional group Q, is 0.9 to 1.1.

19. The method according to claim 3, characterized in that in step iii) as much compounds of formula (V) and/or as much compounds having one isocyanate-reactive group HX and at least one further functional group Q, is used, that at least 90 mol % of the monoisocyanate adduct of formula (IIIa) formed in step i) is reacted.

20. The method according to claim 3, characterized in that in step i) the diisocyanate of formula (II) with respect to the monohydroxy compound of formula (Ia) is used in a molar ratio of at least 1.5:1.0.

21. An additive composition prepared by the method according to claim 1.

22. The additive composition of claim 21, containing i) 10 to 99.98% by weight of the compound according to formula (IVa) YOCONHR.sup.1NHCOXZ.sup.1, ii) 0.01 to 10% by weight diurethane according to formula YOCONHR.sup.1NHCOOY, wherein Y is the same or different, iii) 0.01 to 10% by weight diurea of formula Z.sup.1XCONHR.sup.1NHCOXZ.sup.1, wherein Z.sup.1 is the same or different; and iv) 0 to 8% by weight urethane of formula YOCONHR.sup.1NCO.

23. A process comprising utilizing an additive composition according to claim 21 as an additive, optionally as a wetting agent and dispersant in coatings, paints, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, casting compounds, fillers, printing colors and inks.

24. A solid mixture containing particles and/or fibers that have been treated with an additive composition according to claim 21.

25. Paint and/or plastic, containing an additive composition according to claim 21.

26. A process comprising utilizing an additive composition according to claim 22 as an additive, optionally as a wetting agent and dispersant in coatings, paints, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, casting compounds, fillers, printing colors and inks.

27. A solid mixture containing particles and/or fibers that have been treated with an additive composition according to claim 22.

28. Paint and/or plastic, containing an additive composition according to claim 22.

29. The method according to claim 20, characterized in that in step i) the diisocyanate of formula (II) with respect to the monohydroxy compound of formula (Ia) is used in a molar ratio of 2.5:1 to 20:1.

30. The method according to claim 1, wherein the removal from the reaction mixture in step ii) of the at least 50 mol % of the unreacted portion of the diisocyanate of formula (II), minimizes by-product formation in step iii).

Description

EXAMPLES

(1) In substances that are not uniform at the molecular level, the molecular weights indicated represent number average values. In the presence of titratable hydroxyl or amino groups, the molecular weights or number average molecular weights M.sub.n are determined by end-group determination via determining the OH value or amine value. In case of compounds that are not amenable to end-group determination, the number average molecular weight is determined by gel permeation chromatography against a polystyrene standard.

(2) Unless stated otherwise, data provided in parts means parts by weight and data provided as a percentage means percent by weight.

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

(4) Production of Polyether-Polyester Y1, Mn 780

(5) 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 solid of >95% is achieved.

(6) The OH value of the reaction product is 72 mg KOH/g

(7) Preparation of a Siloxane-Containing Epsilon-Caprolactone Polyester Y2, Mn 2800

(8) 35 g of an alpha, omega-hydroxyalkyl-functional dimethylpolysiloxane having a total molecular weight of about 900 g/mol are reacted with 75 g of epsilon-caprolactone. For this purpose, the mixture is allowed to react upon addition of 0.035 g of DBTL in an N2 atmosphere for about 8 hours at 160 C. The reaction is complete when the content of non-volatile components is larger than 98%. The alpha, omega-hydroxyalkyl-functional dimethylpolysiloxane used as the starting alcohol is obtained in the conventional manner known to the person skilled in the art, by the addition of suitable unsaturated alcohols (such as the allyl alcohol used in this example) to dimethyl polysiloxanes which carry terminal silane moieties.

(9) Other hydroxy-functional polyesters used as YOH are produced in an analogous manner.

(10) General Preparation of Monoadducts:

(11) A four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is charged with 430 g of Desmodur T 100 (about 100% 2,4-toluene diisocyanate, NCO content=48.8) and 7 g benzoyl chloride and mixed thoroughly. X g of the alcohol component, which is water-free and in case of polyethers alkali-free, are added slowly so that the temperature does not exceed 55 C. After dosing, the mixture is stirred for a further 3 hours at 55 C. Excess TDI is removed from the reaction mixture by thin-film evaporator at 150 C. The residual TDI content is <1%.

(12) TABLE-US-00001 Amount X Mono-adduct Alcohol component in [g] M1 Butanol-initiated PO-polyether Mn 800, OH value: 70 mg 800 KOH/g M2 MPEG 350, OH value: 162 mg KOH/g 350 M3 Butanol-initiated EO/PO-polyether (EO:PO 1:1) Mn 2240, OH 2240 value: 25 mg KOH/g M4 Polyester Y1, OH value: 72 mg KOH/g 780 M5 Hexadecanol-initiated monohydroxy-functional -caprolactone 600 polyester, Mn 600 M6 Hexadecanol-initiated monohydroxy-functional -caprolactone 1200 polyester, Mn 1200 M7 MPEG 500 = methoxypolyethylene glycol, Mn 500 500 M8 Butanol-initiated EO/PO-polyether (EO:PO 1:1) Mn 1100 1100 M9 B11/50 = butanol-initiated EO/PO-polyether (EO:PO 1:1) Mn 1700 1700 M10 Butanol-initiated EO/PO-polyether (EO:PO 1:1) Mn 2000 2000 M11 Butanol-initiated EO/PO-polyether (EO:PO 1:1) Mn 3100 3100 M12 Butanol-initiated EO/PO-polyether (EO:PO 1:1) Mn 4800 4800 M13 Hydroxyethyl acrylate-initiated -caprolactone polyester, Mn 1200 1200 M14 Monohydroxy-functional hydroxypropyl polydimethylsiloxane 1200 with butyl end group, Mn 1200 M15 Methanol-initiated EO/PO-polyether (EO:PO 3:1), Mn 1400 1400 M16 MPEG 500-initiated -caprolactone polyester Mn 900 900 M17 iso-Decanol-initiated -caprolactone polyester Mn 700 700 M18 iso-Decanol-initiated -caprolactone polyester Mn 1000 1000 M19 Monophenylglycol-initiated -caprolactone polyester Mn = 1200 1200 M20 n-Butanol-initiated -caprolactone polyester, Mn = 600 600 M21 n-Butanol-initiated -caprolactone polyester, Mn = 1200 1200 M22 Butanol-initiated PO-polyether, Mn 1100 1100 M23 iso-Decanol-initiated polyester made of -caprolactone and - 2000 valerolactone in the molar ratio 3:1, Mn = 2000 M24 B11/50-initiated -caprolactone polyester, mean molecular 2000 weight Mn = 2000 M25 MPEG 350-initiated -caprolactone polyester Mn 900 900 M26 MPEG 350-initiated polyester made of -caprolactone and - 950 valerolactone in the molar ratio 3:1, Mn = 950 M27 MPEG 500-initiated polyester made of -caprolactone and - 1100 valerolactone in the molar ratio 3:1, Mn = 1100 M28 MPEG 750-initiated polyester made of -caprolactone and - 1400 valerolactone in the molar ratio 3:1, Mn = 1400 M29 MPEG 750 750 M30 -Caprolactone polyester Mn 1600, started with a methanol- 1600 initiated EO/PO-polyether (EO:PO 3:1), Mn 1400 M31 Butanol-initiated EO/PO-polyether (EO:PO 1:1) Mn 3170 3170 M32 Butanol-initiated EO/PO-polyether (EO:PO 1:1) Mn 2540 2540 M33 Butanol-initiated PO-polyether, Mn 2240 2240 M34 Butanol-initiated butylenoxide-polyether, Mn 960 960 M35 Alpha, omega-dihydroxy-functional hydroxypropyl 1800 polydimethylsiloxane, Mn 1800 M36 Y2, dihydroxy-functional -caprolactone polyester Mn 2800, 2800 started with an alpha, omega-dihydroxy-functional hydroxypropyl polydimethylsiloxane, Mn 900 M37 Oleyl alcohol 268 M38 Monophenyl glycol 138 M39 Isotridecyl alcohol 200 M40 n-Decanol 158 M41 Isodecanol 158 M42 Benzylalkohol 108 M43 Cyclohexanol 100 M44 Isobutanol 74 M45 Polyethylene glycol (dihydroxy-functional), Mn 600 300 M46 Polyethylene glycol (dihydroxy-functionell), Mn 1000 500 M47 Dipropylene glycol monomethyl ether 148 M48 Butyl triglycol 206
General Procedure for the Reaction of the Mono-Adducts with Amines Under Formation of Mono-Adduct Ureas:

(13) A four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is charged with x g of mono-adduct and, with stirring y g of amine is then added dropwise over a period of 1 hour. In this case, the reaction temperature should not exceed 50 C. Optionally, during or after the reaction MPA may be added as a diluent.

(14) TABLE-US-00002 Ex- ample Mono-adduct Amine B1 90 g of M1 12.8 g of 3-aminopropyl imidazole B2 90 g of M1 10.3 g of DMAPA B3 100 g of M1 27.7 g of N,N-bis(3-dimethylaminopropyl)-N- isopropanolamine B4 100 g of M2 20.4 g of 3-aminopropyl imidazole B5 100 g of M2 49.3 g of DMAPA B6 100 g of M2 39.7 g of N,N-bis(3-dimethylaminopropyl)-N- isopropanolamine B7 17 g of M3 0.7 g of DMAPA 26 g of MPA B8 30 g of M4 4.4 g of 3-aminopropylimidazole 50 g of MPA B9 30 g of M4 3.5 g of DMAPA 50 g of MPA B10 30 g of M4 3.8 g of 4-aminomethylpyridine 50 g of MPA B11 770 g of M5 102 g of DMAPA B12 1370 g of M6 102 g of DMAPA B13 670 g of M7 102 g of DMAPA B14 1170 g of M8 102 g of DMAPA B15 1870 g of M9 102 g of DMAPA B16 2170 g of M10 102 g of DMAPA B17 3270 g of M11 102 g of DMAPA B18 5000 g of M12 102 g of DMAPA B19 1370 M13 102 g of DMAPA B20 1370 M14 102 g of DMAPA B21 1570 g of M15 102 g of DMAPA B22 1070 g of M16 102 g of DMAPA B23 870 g of M17 102 g of DMAPA B24 1170 g of M18 102 g of DMAPA B25 1370 g of M19 102 g of DMAPA B26 770 g of M20 102 g of DMAPA B27 1370 g of M21 102 g of DMAPA B28 1270 g of M22 102 g of DMAPA B29 2170 g of M23 102 g of DMAPA B30 2170 g of M24 102 g of DMAPA B31 1122 g of M26 145 g of 1,3-bis-(dimethylamino)-2-propanol B32 1122 g of M26 355 g of tetramethyliminobis-propylamine B33 4974 g of M12 144 g of TEA B34 974 g of M1 102 g of DMAPA B35 924 g of M29 102 g of DMAPA B36 1170 g of M8 117 g of DEEA B37 1170 g of M8 89 g of DMEA B38 1274 g of M27 102 g of DMAPA B39 1574 g of M28 102 g of DMAPA B40 924 g of M29 89 g of DMEA B41 1774 g of M30 102 g of DMAPA B42 3344 g of M31 102 g of DMAPA B43 2714 g of M32 102 g of DMAPA B44 2414 g of M33 102 g of DMAPA B45 1134 g of M34 102 g of DMAPA B46 2148 g of M35 102 g of DMAPA B47 3148 g of M36 102 g of DMAPA B48 442 g of M37 102 g of DMAPA B49 312 g of M38 102 g of DMAPA B50 374 g of M39 102 g of DMAPA B51 332 g of M40 102 g of DMAPA B52 332 g of M41 102 g of DMAPA B53 282 g of M42 102 g of DMAPA B54 274 g of M43 102 g of DMAPA B55 248 g of M44 102 g of DMAPA B56 474 g of M45 102 g of DMAPA B57 674 g of M46 102 g of DMAPA B58 332 g of M47 102 g of DMAPA B59 380 g of M48 102 g of DMAPA MPA = methoxypropyl acetate (solvent); DMAPA = N,N-dimethylaminopropylamine TEA = triethanolamine; DEEA = N,N-diethylethanolamine, DMEA = N,N-dimethylethanolamine
Preparation of a Non-Inventive Comparative Example BX1 without Excess of Diisocyanate

(15) A four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is charged with 174 g of Desmodur T 100 and 2.7 g of benzoyl chloride and mixed thoroughly. 780 g of polyester Y1 are slowly added so that the temperature does not exceed 55 C. After 1.5 h post-reaction the NCO value was 4.3. The reaction mixture is dissolved in 1540 g of MPA. Then, 102 g of DMAPA are added slowly over a period of 1 h such that the temperature does not exceed 50 C. After cooling, the product was cloudy and showed strong separation during storage. The comparable product according to the invention B9, however, is clear and has low viscosity after production and during storage.

(16) General Procedure for the Reaction of the Mono-Adducts with Amines and Polyphosphoric Acid Under Formation of Mono-Adduct Ureas:

(17) A four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is charged with x g of mono-adduct and, with stirring y g of aminoalcohol is then added dropwise over a period of 1 hour. In this case, the reaction temperature should not exceed 50 C. After 1 hour the temperature is increased to 80 C., and z g of polyphosphoric acid is added. The reaction is complete after 3 hours at 80 C. Optionally, during or after the reaction MPA may be added as a diluent.

(18) TABLE-US-00003 Polyphosphoric Example Mono-adduct Aminoalcohol acid in [g] P1 100 g of M1 6.9 g of EA 12.7 P2 100 g of M2 9.9 g of EA 16.4 P3 852 g of M25 61 g of EA 85 P4 852 g of M25 105 g of DEA 170 P5 1150 g of M26 61 g of EA 85 P6 1150 g of M26 105 g of DEA 170 P7 1150 g of M26 105 g of AEE 85 P8 1072 g of M16 61 g of EA 85 P9 1072 g of M16 105 g of DEA 170 P10 1072 g of M16 105 g of DEA 85 P11 1274 g of M27 105 g of DEA 170 P12 1574 g of M15 105 g of DEA 170 P13 1574 g of M28 105 g of DEA 170 P14 1274 g of M8 105 g of DEA 170 P15 974 g of M1 105 g of DEA 170 P16 924 g of M29 105 g of DEA 170 P17 1774 g of M30 105 g of DEA 170 P18 4974 g of M12 105 g of DEA 170 P19 4974 g of M12 105 g of DEA 85 P20 4974 g of M12 144 g of TEA 170 P21 3344 g of M31 105 g of DEA 170 P22 2714 g of M32 105 g of DEA 170 P23 2414 g of M33 105 g of DEA 170 P24 1134 g of M34 105 g of DEA 170 P25 2414 g of M3 105 g of DEA 170 P26 954 g of M4 105 g of DEA 170 P27 770 g of M5 105 g of DEA 170 P28 1370 g of M6 105 g of DEA 170 P29 670 g of M7 105 g of DEA 170 P30 1170 g of M8 61 g of EA 85 P31 1870 g of M9 105 g of DEA 170 P32 2170 g of M10 105 g of DEA 170 P33 3270 g of M11 105 g of DEA 170 P34 5000 g of M12 61 g of EA 85 P35 1370 M13 105 g of DEA 170 P36 1370 M14 105 g of DEA 170 P37 870 g of M17 105 g of DEA 170 P38 1170 g of M18 105 g of DEA 170 P39 1370 g of M19 105 g of DEA 170 P40 770 g of M20 105 g of DEA 170 P41 1370 g of M21 105 g of DEA 170 P42 1270 g of M22 105 g of DEA 170 P43 2170 g of M23 105 g of DEA 170 P44 2170 g of M24 105 g of DEA 170 P45 2148 g of M35 105 g of DEA 170 P46 3148 g of M36 105 g of DEA 170 P47 442 g of M37 61 g of EA 85 P48 312 g of M38 105 g of DEA 170 P49 374 g of M39 61 g of EA 85 P50 332 g of M40 61 g of EA 85 P51 332 g of M41 61 g of EA 85 P51 282 g of M42 61 g of EA 85 P53 274 g of M43 61 g of EA 85 P54 248 g of M44 105 g of DEA 170 P55 474 g of M45 105 g of DEA 170 P56 674 g of M46 105 g of DEA 170 P57 332 g of M47 105 g of DEA 170 P58 380 g of M48 105 g of DEA 170 EA = ethanolamine; DEA = diethanolamine; AEE = 2-(2-aminoethoxy) ethanol TEA = triethanolamine
Preparation of a Non-Inventive Comparative Example PX1

(19) 950 g of a MPEG 350-initiated polyester made of -caprolactone and 5-valerolactone in the molar ratio 3:1, Mn=950 and 85 g of polyphosphoric acid are stirred at 80 C. for 3 hours.

(20) Preparation of a Non-Inventive Comparative Example PX2

(21) 950 g of a butanol-initiated EO/PO polyether (EO:PO 1:1), Mn 4800 and 85 g of polyphosphoric acid are stirred at 80 C. for 3 hours.

(22) General Procedure for the Quaternization:

(23) In a four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube, mono-adduct urea 40 g of MPA (methoxypropyl acetate) and 40 g of butyl glycol, and x g of alkylating agent are reacted for 4 hours at 120 C. The solid is adjusted with a 1:1 mixture of MPA and butyl glycol to 40%.

(24) TABLE-US-00004 Example Mono-adduct urea Alkylating agent Q1 60 g of Example 2 6.9 g of benzyl chloride Q2 52 g of Example 2 14.7 g of Grilonite 1814 6.4 g of benzoic acid Q3 60 g of Example 5 9.5 g of benzyl chloride Q4 43 g of Example 5 16.8 g of Grilonite 1814 7.3 g of benzoic acid Grilonite RV 1814 = C.sub.13/C.sub.15-alkyl glycidyl ether, EMS-Chemie
General Procedure for Salification:

(25) In a four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube, mono-adduct urea in 40 g of MPA and 40 g of butyl glycol with x g of salification agent is stirred for 1 h at 60 C.

(26) TABLE-US-00005 Example Compound used Salification agent S1 1377 g of P9 234 g of DEEA S2 1377 g of P9 178 g of DMEA S3 1377 g of P9 346 g of N,N-dibutyl ethanolamin S4 1277 g of P10 117 g of DEEA S5 1480 g of P11 149 g of TEA S6 1570 g of P14 1400 g of Copolymer1 S7 1280 g of P15 1600 g of Copolymer2 S8 5280 g of P18 1400 g of Copolymer1 S9 5280 g of P18 1600 g of Copolymer2 S10 5180 g of P19 700 g of Copolymer1 S11 5180 g of P19 800 g of Copolymer2 S12 1076 g of B2 146 g of adipinic acid S13 52 g of B2 6.4 g of benzoic acid S14 43 g of B5 7.3 g of benzoic acid S15 1272 g of B14 73 g of adipinic acid S16 1272 g of B14 282 g of oleic acid S17 1272 g of B14 200 g of lauric acid S18 1272 g of B14 298 g of ricinoleic acid S19 1026 g of B35 60 g of acetic acid S20 685 g of P47 700 Copolymer1 S21 520 g of P49 700 g of Copolymer1 S22 2445 g of P43 1400 g of Copolymer1 S23 2445 g of P43 700 g of Copolymer1 S24 1145 g of P37 2545 g of B14 S25 1145 g of P37 1270 g of B14 S26 2690 g of P25 120 g of B4 S27 2690 g of P25 150 g of B5 S28 590 g of P48 85 g of B8 S29 655 g of P58 85 g of B9 DEEA = N,N-diethylethanolamine; DMEA = N,N-dimethylethanolamine
Copolymer 1 (Basic GTP Block Copolymer)

(27) Under a stream of nitrogen, a three-necked flask equipped with stirrer, reflux condenser and a gas inlet is charged with 69.70 g of MPA at 20 C. and mixed with 7.70 g of butyl methacrylate. Then, 3.75 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene and 0.375 g of tetrabutylammonium m-chlorobenzoate are added via syringe through a septum. Within 30 min, 60.00 g of butyl methacrylate are added. The reaction temperature rises to 40 C. and is kept at this level by cooling. After the addition of butyl methacrylate, 32.80 g of N,N-dimethylaminoethyl methacrylate are added within 20 min, ensuring by cooling again that the temperature does not rise above 40 C. After stirring for 30 min, 3 ml of ethanol are added. The monomers were reacted completely (residual monomer content determined by HPLC); product: M.sub.n=9100 g/mol, according to GPC.

(28) Copolymer 2 (Basic NMP Block Copolymer)

(29) Under a stream of nitrogen, a three-necked flask equipped with stirrer, reflux condenser and gas inlet is charged with 47.2 g of MPA, and 3.81 g of 2-[N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)]-nitroxy]-2-methyl-propanoic acid and 46.00 g of butyl acrylate in a three-necked round bottom flask, and heated to 120 C. Stirring is continued for 2.5 h at 120 C. Thereafter, 21.00 g of N,N-dimethylaminoethyl methacrylate is metered in at a rate of 2 ml/min. Thereafter, stirring is continued for a further 6 h at 120 C.; the conversion is then about 98% (residual monomer content determined by HPLC); product: M.sub.n=3000 g/mol, according to GPC.

(30) c) Application Testing

(31) Use of the polymers according to the invention as wetting agent and dispersant for producing pigment concentrates and their use in paint systems

(32) Starting Materials

(33) Uralac SN 831 polyester resin, manufacturer DSM Resins Cymel 303 melamine-formaldehyde resin, manufacturer: Cytec Industries Dynapol Catalyst 1203 catalyst, manufacturer Evonik Degussa Ti Pure R960 titanium dioxide pigment, manufacturer Du Pont Aerosil R972 hydrophobic fumed silica, manufacturer Degussa BYK 057 silicone-free polymeric defoamer from BYK-Chemie BYK 355 acrylic leveling additive, manufacturer BYK-Chemie Solvesso 150 ND, Solvesso 100 aromatic solvents from ExxonMobil MPA 1-methoxy-2-propyl acetate
Working Procedures
Producing Paints
Grinding Conditions:
Device: Lau Paint Shaker DAS H [/A]200-K
Grinding time: 60 min, normal speed, maximum cooling
Ratio of ground material to glass beads (1 mm diameter):1:1 (parts by weight)
Composition of the Pigment Concentrates:

(34) TABLE-US-00006 Ti pure R960 Special black 4 Uralac SN831 26.2 44.0 Additive 100% 1.7 3.6 a.S. MPA 5.0 5.0 Solvesso 11.2 17.5 150ND Aerosil R972 0.6 0.3 BYK-057 0.3 Ti pure R960 55.0 Special black 4 12.0 (carbon black, Firma Evonik) Special black 4: pigment carbon black from Evonik
Production of the Test Formulations
Composition of the Clear Varnish

(35) TABLE-US-00007 Clear varnish Uralac SN 831 64.0 Cymel 303 13.8 Dynapol Catalyst 1203 4.9 BYK-057 0.4 BYK-355 1.1 Solvesso 150ND 10.5 MPA 5.3 100.0
Composition of the Test Formulations

(36) TABLE-US-00008 White:black 97:3 Clear varnish 19.8 Ti pure R960 26.5 Special black 4 3.7 50.0

(37) Following the production, the viscosity of the test formulations was adjusted to 90-110 sec (DIN 4 flow cup, 23 C.) with Solvesso 150ND.

(38) A portion of the test formulation is stored at 50 C. for 1 week.

(39) Application of the Test Formulation

(40) The test formulations were applied to substrates on the day of the preparation under the following conditions. Substrates: Alcan aluminum sheets, pre-coated with an approximately 5 micron thick PU primer layer Blade application: 80 m (wet) Oven temperature: 320 C. Baking time: 30 s max. metal temperature: 235 C. Dry film thickness: 18-20 m

(41) The flooding, floating and flocculation properties were evaluated as follows.

(42) The respective test formulation was divided into 2 portions.

(43) Each first portion of the respective test formulation was stirred with a toothed disc at 6000 rpm for 1 minute and then immediately applied to the right half of the surface of the substrate. Simultaneously, the second portion of each of the respective test formulation was applied without prior stirring to the left half of the surface of the substrate.

(44) Rub-Out Test

(45) Immediately after application, the freshly applied paint layers on both halves of the surface of the substrate were subjected to a rub-out test. For this purpose, some areas of the fresh paint layers were mechanically rubbed following the application and then the color change caused by the rubbing (rub-out effect) was measured over the paint that has not been rubbed. Causes of the rub-out effect are, for example, flocculation and/or floating of pigments. If pigment flocculates are present, they will be destroyed by the shearing action when rubbed, and the originally targeted shade forms. The rub-out effect can be minimized by suitable dispersants and is thus a measure of the effectiveness of a dispersant.

(46) Colorimetric Measurements

(47) Device: color guide, BYK-Gardner Light type: standard light D65 (daylight) Measuring field: 10 Measuring geometry: d/8 spin (diffuse illumination, observation angle 8) Number of measurements: n=3

(48) The results of the colorimetry are shown in the following table. The E value determined for a formulation indicates the color difference between the rubbed and the non-rubbed areas of the coating (rub-out effect).

(49) E1=E not stirred

(50) E2=E stirred

(51) E3=E not stirred/stirred

(52) TABLE-US-00009 Viscosity of the black pigment E 1 E 2 E 3 Gloss 60 concentrate After grinding B5 0.63 0.53 0.05 88 low B8 0.40 0.51 0.04 89 low B9 0.61 0.46 0.04 93 low B10 0.65 0.55 0.06 86 low BX1 (non-inventive) 0.75 0.66 0.1 84 high S6 0.65 0.59 0.06 85 low S7 0.64 0.58 0.07 85 low S8 0.59 0.57 0.05 86 low S9 0.54 0.49 0.05 86 low P19 0.71 0.75 0.08 84 low P20 0.65 0.63 0.06 85 low PX2 (non-inventive) 0.98 1.02 0.18 79 high After 1 week of storage at 50 C. B5 0.60 0.51 0.05 88 low B8 0.40 0.51 0.05 92 low B9 0.39 0.39 0.07 96 low B10 0.65 0.55 0.06 86 low BX1 0.82 0.71 0.12 82 high S6 0.64 0.58 0.06 86 low S7 0.62 0.57 0.06 84 low S8 0.58 0.59 0.05 85 low S9 0.52 0.47 0.05 87 low P19 0.70 0.74 0.07 84 low P20 0.65 0.62 0.06 85 low PX2 1.23 1.22 0.26 76 high After rubbing S20 0.69 0.62 0.08 86 low S22 0.48 0.55 0.04 90 low S24 0.67 0.51 0.05 91 low S26 0.65 0.62 0.06 87 low
Formulation: Paraloid B 66 (Thermoplastic Acrylate from Dow Chemicals)
Ground Material:

(53) TABLE-US-00010 Paraloid B 66 (50% in xylene) 25.00 DIDP 2.00 Xylene 3.5 MPA 2.50 Additive 1.5 Aerosil R 972 0.50 Pigment 65.00 Total 100.00 Paraloid B 66 = thermoplastic acrylate resin from Dow Chemicals DIDP = diisodecyl phthalate
Let-Down:

(54) TABLE-US-00011 Ground stock paste 38.50 Paraloid B 66 50.00 MPA 3.40 Xylene 8.00 BYK-306 0.10 BYK-306: silicone additive from Byk-Chemie
Results Paraloid B 66

(55) TABLE-US-00012 Pigments Kronos 2310 Tioxide TR 92 Ti-Pure R 960 Additives Viscosity E Gloss Viscosity E Gloss Viscosity E Gloss PX1 3 4.5 85 4 2.5 83 4 3.9 73 PX2 4 5.1 81 5 3.1 79 5 5.7 63 P6 2 3.3 91 3 1.1 86 2 2.5 80 P18 2 2.5 95 3 0.5 88 1 2.1 83 Kronos 2310: titanium dioxide pigment with basic surface Tioxide TR 92: titanium dioxide pigment with basic surface Ti-Pure R 960: titanium dioxide pigment with acidic surface Viscosity: 1-5, 1 = low, 5 = high
Formulation: Macrynal SM 510 (2-K Acryl)
Ground Material:

(56) TABLE-US-00013 Macrynal SM 510 22.22 MPA 2.00 Solvesso 100 2.00 Xylene 3.00 Butyl acetate 3.5 BYK-066 N 0.30 Additive 1.5 Aerosil R 972 0.50 Pigment 65.00 Total 100.00 Macrynal SM 510 = polyacrylate resin from Cytec BYK-066 N: Silicone defoamer from Byk-Chemie
Let-Down:

(57) TABLE-US-00014 Ground material paste 38.50 Macrynal SM 510 45.00 MPA 1.00 Solvesso 100 7.00 Xylene 1.40 Butyl acetate 7.00 BYK-306 0.10 BYK-306: silicone-containing surface additive from Byk-Chemie Base to hardener: 2:1
Hardener Solution

(58) TABLE-US-00015 Desmodur N 75 25.0 Butyl acetate 8.70 Solvesso 100 8.80 MPA 2.50 Xylene 5.00 Total 50.00 Desmodur N 75: aliphatic polyisocyanate (HDI biuret) from Bayer, 75% in MPA
Results: Macrynal SM 510

(59) TABLE-US-00016 Pigments Kronos 2310 Tioxide TR 92 Ti-Pure R 960 Additives Viscosity E Gloss Viscosity E Gloss Viscosity E Gloss PX1 5 1.2 85 5 1.1 84 5 1.6 86 PX2 5 1.3 84 5 1.6 81 5 5.7 82 P6 2 0.6 95 1 0.3 90 2 0.7 91 P18 1 0.5 91 2 0.6 93 1 0.5 95 S6 1 0.5 94 1 0.5 92 2 0.7 90 S9 1 0.4 92 1 0.6 92 1 0.5 94

(60) Formulation: Setalux 1756 VV 65

(61) Ground Material:

(62) TABLE-US-00017 Setalux 1756 VV-65 22.22 Additive 1.5 Solvesso 100 5.5 Xylene 5.28 Aerosil R 972 0.50 Pigment 65.00 Total 100.00 Setalux 1756 VV-65: hydroxyacrylate copolymer from Nuplex, 50% in xylene/butanol
Let-Down:

(63) TABLE-US-00018 Ground material paste 38.50 Setalux 1756 VV-65 40.00 Setamine US 138-BB 70 16.00 Solvesso 100 3.00 Xylene 2.30 BYK-310 0.20 Total 100.00 Setamine US 138-BB 70: melamine resin from Nuplex BYK-310: polyester-modified polydimethylsiloxane from BYK-Chemie Pigment/binder: 0.8:1 in the paint Mixing: 29.5 g of clear varnish+0.5 g of black paste Baking conditions: drying for 10 minutes 20 minutes at 140 C.
Results: Setalux 1756 VV 65

(64) TABLE-US-00019 Pigments Kronos 2310 Tioxide TR 92 Ti-Pure R 960 Additives Viscosity E Gloss Viscosity E Gloss Viscosity E Gloss PX1 5 1.2 89 4 1.3 89 5 0.9 88 PX2 5 1.5 84 5 1.7 88 5 1.6 84 P6 1 0.6 95 1 0.3 92 2 0.5 93 P18 1 0.3 98 1 0.6 98 1 0.3 96 P22 1 0.7 95 1 0.3 92 2 0.3 94 S6 1 0.6 91 2 0.9 90 2 0.4 93 S9 1 0.8 94 1 0.8 91 1 0.3 94 BX1 4 1.0 89 3 1.3 88 4 0.9 90 B9 3 0.8 91 2 1.1 91 3 0.7 93 B34 3 0.9 90 2 1.0 90 3 0.8 95
Additional Results with Setalux 1756 VV 65

(65) TABLE-US-00020 Pigment Ti-Pure R 960 Additives Viscosity E Gloss P26 1 0.6 95 P28 1 0.5 94 P37 1 0.7 92 P38 1 0.4 96 P39 1 0.7 95 P41 1 0.6 92 P43 2 0.8 92 P47 3 0.9 90 S22 1 0.6 94 S24 2 0.8 91 S26 2 0.7 93 S28 3 0.9 90

CONCLUSION OF THE EXAMPLES

(66) The generally very good quality of the additive composition according to the invention is shown in gloss, viscosity and rub-out effect. Particularly noteworthy is the good universality with respect to acidic and basic pigment particles to be dispersed (see, inter alia, Results Paraloid B 66according to the above table). The additive composition according to the invention also differs positively by providing beneficial effects regarding solubility behavior, gloss and rub-out effect, which are alone caused by the particular technology of the method according to the invention (use of excess TDI, followed by removal of unreacted TDI).