AN ACID FUNCTIONAL COMPOUND

Abstract

The invention relates to an acid functional compound comprising i. at least one segment consisting of at least one ether unit E and at least one ester unit, wherein the ether units and ester units are connected by an ether link or by an ester link, and wherein the sum of the number of ether units and ester units is at least three, and wherein the ether units and ester units are arranged in random order, and ii. at least one acidic group which is selected from the group consisting of a phosphoric acid group, an acidic phosphoric acid ester group, a sulfonic acid group, an acidic sulfonic acid ester group and a carboxylic acid group, wherein the at least one acidic group is covalently linked to the at least one segment.

Claims

1. An acid functional compound comprising i. at least one segment comprising at least one ether unit and at least one ester unit, wherein the at least one ether unit and the at least one ester unit are connected by an ether link or by an ester link, and wherein the sum of the number of the at least one ether unit and the at least one ester unit is at least three, and wherein the at least one ether unit and the at least one ester unit are arranged in random order, and ii. at least one acidic group selected from a phosphoric acid group, an acidic phosphoric acid ester group, a sulfonic acid group, an acidic sulfonic acid ester group and a carboxylic acid group, wherein the at least one acidic group is covalently linked to the at least one segment.

2. The acid functional compound according to claim 1, wherein the at least one segment is defined by the largest portion between two ester links, and wherein the at least one segment comprises an average number of ether links L between two adjacent ether units and an average number of ether units E, wherein a ratio R is defined according to formula (A):L/(E-1) and wherein, when E is larger than 1.0, R is smaller than 1.0.

3. The acid functional compound according to claim 2, wherein the ratio R is smaller than 0.9.

4. The acid functional compound according to claim 1, wherein the at least one segment is linked to a polymerization starter moiety comprising an amine group, selected from a tertiary amine group, a salt of a tertiary amine group and a quaternary ammonium group.

5. The acid functional compound according to claim 4, wherein the polymerization starter moiety is directly linked to said at least one segment via a group selected from an ether group, an ester group, a secondary amide group, a tertiary amide group, a secondary amine group and a tertiary amine group.

6. The acid functional compound according to claim 4, wherein the polymerization starter moiety is a polyethylenimine.

7. The acid functional compound according to claim 1, wherein the at least one ether unit includes a unit of formula (III) [CR.sup.30.sub.2].sub.nO, wherein n is an integer of 2 or 3, and R.sup.30 independent of each other represent organic groups having 1 to 25 carbon atoms or hydrogen.

8. The acid functional compound according to claim 7, wherein, in case n is equal to 2, at least one of the R.sup.30 represents an ether group having the formula R.sup.31OR.sup.32, wherein R.sup.31 and R.sup.32 independent of each other represent organic groups having 1 to 30 carbon atoms.

9. The acid functional compound according to claim 1, wherein the acid functional compound has the general formula:
Y(XWZ).sub.q (Ia), wherein Y is represented by an organic group containing 1-500 carbon atoms, X is represented by O, NH and/or NR.sup.1, R.sup.1 is independently selected and is represented by a chemical bond to a carbon atom of Y and/or an independently selected organic group containing 1-20 carbon atoms, W is one segment of the at least one segment i., q=1-100, and each Z is independently selected from hydrogen and moiety Z-a, each other each moiety Z-a is independently selected from an organic group containing 0-600 carbon atoms and at least one acidic group ii., wherein at least one Z is represented by moiety Z-a.

10. The acid functional compound according to claim 9, characterized in that each moiety Z-a is independently represented by general formula (II)
PO(V).sub.n(OH).sub.2-n(II) with each V independently represented by a chemical bond to an oxygen atom of the same molecule and/or a group OR.sup.33, each R.sup.33 independently represented by an organic group containing 1 to 500 carbon atoms, and n is 0 or 1.

11. The acid functional compound according to claim 10, characterized in that n=0.

12. The acid functional compound according to claim 1 that is present in salinized or partially salinized form.

13-14. (canceled)

15. A composition comprising particles and an acid functional compound according to claim 1.

16. A method for producing an acid functional compound, the method comprising: preparing a segment by reacting a cyclic ester and a cyclic ether together in a ring-opening polymerization reaction, wherein the ring-opening polymerization reaction is started by a polymerization starter compound comprising at least one functional group selected from a hydroxyl group, a secondary amine group and a primary amine group, and converting the segment of with an agent to covalently link the segment to at least one acidic group selected from a phosphoric acid group, an acidic phosphoric acid ester group, a sulfonic acid group, an acidic sulfonic acid ester group, and a carboxylic acid group, the method yielding an acid functional compound comprising i. at least one segment comprising at least one ether unit and at least one ester unit, wherein the at least one ether unit and the at least one ester unit are connected by an ether link or by an ester link, and wherein the sum of the number of the at least one ether unit and the at least one ester unit is at least three, and wherein the at least one ether unit and the at least one ester unit-are arranged in random order, and ii. at least one acidic group selected from a phosphoric acid group, an acidic phosphoric acid ester group, a sulfonic acid group, an acidic sulfonic acid ester group and a carboxylic acid group, wherein the at least one acidic group is covalently linked to the at least one segment.

17. The method according to claim 16, wherein the cyclic ester and the cyclic ether are added substantially simultaneously into a reaction mixture, which is maintained in reaction conditions.

18. The method according to claim 16, wherein the polymerization starter compound is added to a reaction mixture containing the cyclic ester and the cyclic ether, which reaction mixture is maintained in reaction conditions.

19. The acid functional compound according to claim 2, wherein the ratio R is smaller than 0.8.

20. The acid functional compound according to claim 2, wherein the ratio R is smaller than 0.7.

21. The acid functional compound according to claim 10, wherein each R.sup.33 independently represents an organic group containing 1 to 35 carbon atoms.

Description

EXAMPLES

[0195] General Remarks

[0196] In the case of substances without molecular uniformity the stated molecular weightsbelow as already in the foregoing descriptionrepresent average values of the numerical mean. The molecular weights or number-average molecular weights M.sub.n, are determined, when titratable hydroxyl or amino groups are present, by end-group determination via the determination of the OH number or amine number, respectively. In the case of compounds to which an end-group determination cannot be applied, the number-average molecular weight is determined by means of gel permeation chromatography against a polystyrene standard. Unless otherwise remarked percentages are percentages by weight.

[0197] Measurement of Non-volatile Components

[0198] The sample (2.00.1 g of the tested substance) was weighed in a previously dried aluminum crucible and dried in furnace for 20 minutes at 150 C., cooled in a desiccator and then reweighed. The residue corresponds to the solids content in the sample (ISO 3251).

[0199] Measurement of Acid Numbers

[0200] The acid number is the KOH quantity in mg that is required for neutralizing 1 g of substance under the defined conditions. The acid numbers were determined by a neutralization reaction with a 0.1 N KOH in Ethanol according to DIN EN ISO 2114.

##STR00004##

[0201] Measurement of Hydroxyl Numbers

[0202] The alcoholic hydroxyl groups were reacted by acetylation with an excess of acetic anhydride. The excess acetic anhydride was cracked into acetic acid by adding water and titrated back using ethanolic KOH. The hydroxyl number was understood to be the KOH quantity in mg, which is equivalent to the acetic acid quantity bound when acetylating 1 g of substance.

[0203] Measurement of Amine Numbers

[0204] Perchloric acid (HClO.sub.4) in acetic acid has proved to be a suitable titration agent for organic bases containing nitrogen as well as primary, secondary and tertiary amine groups. Acid solvents such as acetic acid have stood the test in determining weak organic bases (good dissolving properties, proton-donating acid solvent). Additions of inert solvents such as cyclohexane, dioxane, chlorobenzene, acetone and methyl ethyl ketone can improve the titration of very weak bases.

RNH.sub.2+HClO.sub.4.fwdarw.RNH.sub.3.sup.+ClO.sub.4.sup.

[0205] Measurement of Anhydride Acid Number

[0206] The anhydride groups were reacted with an excess of a primary amine to form a carboxylic acid and an amide. The excess primary amine was then titrated back with isopropanolic hydrochloric acid.

##STR00005##

[0207] DSC Measurements

[0208] This test method is applicable to copolymerization products which melting point and crystallization behavior is detectable under the specified conditions. The measurements were carried out on DSC Q2000 (TA Instruments) using aluminum crucible with cover, micro scale and platen press according to the manual and the manufacturer's instructions. The initial weight of the sample should be selected between 5 and 15 mg. For better handling, the sample was melted and accurately weighed into an aluminum crucible. The crucible was sealed with a perforated aluminum lid with the press and inserted into the sample plate. The measurement was carried out with the heating rate of 10 C./min.

[0209] The two measuring cycles (heating and cooling) were plotted and analyzed together in one diagram: On the abscissa was entered the temperature and on the ordinate the heat flow. If superimposed signals were recognized it was evaluated in such a way that several peak maxima can be read off.

[0210] NMR Measurements

[0211] The NMR measurements were carried out on a Bruker DPX 300 at 300 MHZ (.sup.1H) or 75 MHZ (.sup.13C). Solvents used were deuterated chloroform (CDCl.sub.3) and deuterated dimethyl sulfoxide (DMSO-d.sub.6).

[0212] Preparation of the Intermediate Products: First Step

[0213] Examples According to the Invention

[0214] Preparation method 1

[0215] A clean dry four-necked flask (500 ml) equipped with a condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with component Y(XH).sub.q (abbreviation in the table: component YX1) and the mixture of catalysts and heated up to 110 C. until the catalyst mixture was dissolved. A mixture of the lactone Sm (abbreviation in the table component S) and the epoxide Em (abbreviation in the table component E1-1) was added into the component YX1 so that the temperature did not exceed 120 C. After complete addition the reaction mixture was heated up to 140 C. and stirred at that temperature until the epoxide was completely reacted (controlled by the means of NMR) and the content of non-volatile components was >98% (measurement of non-volatile components according to ISO 3251).

TABLE-US-00001 TABLE 1 intermediate products prepared according to the method 1 component wt. % component wt. % component wt. % wt. % Intermedio Y-X1 Y-X1 S S E1-1 E1-1 catalyst catalyst Y-X1-W01 MPEG 350 35.34 CAPA 34.70 C12-C14- 29.34 AlCl.sub.3/DBN 0.52/0.10 AlkylGE Y-X1-W02 MPEG 350 31.58 CAPA 41.41 C12-C14- 26.29 AlCl.sub.3/DBN 0.61/0.11 AlkylGE Y-X1-W03 MPEG 350 28.59 CAPA 46.82 C12-C14- 23.77 AlCl.sub.3/DBN 0.69/0.13 AlkylGE Y-X1-W04 MPEG 500 34.10 CAPA 45.75 C12-C14- 19.35 AlCl.sub.3/DBN 0.67/0.13 AlkylGE Y-X1-W05 MPEG 750 46.16 CAPA 35.23 C12-C14- 17.99 AlCl.sub.3/DBN 0.52/0.10 AlkylGE Y-X1-W06 MPEG 750 43.12 CAPA 39.50 C12-C14- 16.70 AlCl.sub.3/DBN 0.58/0.10 AlkylGE Y-X1-W07 MPEG 350 34.76 CAPA 45.54 2-EHGE 18.75 AlCl.sub.3/DBN 0.80/0.15 Y-X1-W08 MPEG 350 28.32 CAPA 55.67 2-EHGE 15.06 AlCl.sub.3/DBN 0.80/0.15 Y-X1-W09 MPEG 350 20.17 CAPA 46.22 2-EHGE 32.65 AlCl.sub.3/DBN 0.81/0.15 Y-X1-W10 MPEG 500 48.53 CAPA 32.1 2-EHGE 17.90 AlCl.sub.3/DBN 0.81/0.15 Y-X1-W11 MPEG 500 17.17 CAPA 69.21 2-EHGE 12.67 AlCl.sub.3/DBN 0.80/0.15 Y-X1-W12 MPEG 500 14.30 CAPA 32.00 2-EHGE 52.75 AlCl.sub.3/DBN 0.80/0.15 Y-X1-W13 MPEG 500 10.80 CAPA 48.40 2-EHGE 39.85 AlCl.sub.3/DBN 0.80/0.15 Y-X1-W14 MPEG 750 57.95 CAPA 26.52 2-EHGE 14.58 AlCl.sub.3/DBN 0.80/0.15 Y-X1-W15 MPEG 750 53.15 CAPA 32.45 2-EHGE 13.36 AlCl.sub.3/DBN 0.89/0.15 MPEG (number) = methoxy polyethylene glycol (molecular weight in g/mol), CAPA = -Caprolactone, 2-EHGE = 2-ethylhexyl glycidyl ether, C12-C14-AlkylGE = C12-C14 alkyl glycidyl ether, DBN = 1,5-Diazabicyclo(4.3.0)non-5-ene, AlCl.sub.3 = aluminum trichloride

[0216] Preparation Method 2

[0217] A clean dry four-necked flask (500 mL) equipped with condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with a mixture of the lactone Sm (abbreviation in the table: component S) and the epoxide Em (abbreviation in the table component E1-1) and heated up to 80 C. Then a polyamine Y(XH).sub.q (abbreviation in the table component YX2) was slowly added into this mixture. After complete addition the mixture was heated up to 140 C. and stirred for 2 h. Then the reaction mixture was cooled down to 40 C., the catalysts were added and the temperature was increased up to 140 C. The incorporation of epoxide and the lactone monomers was determined by the means of NMR.

TABLE-US-00002 TABLE 2 Intermediate products prepared according to the method 2 component wt. % component wt. % component wt. % wt. % Intermedio Y-X2 Y-X2 S S E1-1 E1-1 catalyst catalyst Y-X2-W01 PEI300 3.72 CAPA 55.88 2-EHGE 39.45 AICl.sub.3/DBN 0.80/0.15 Y-X2-W02 PEI300 1.23 CAPA 53.60 2-EHGE 44.22 AICl.sub.3/DBN 0.80/0.15 Y-X2-W03 PEI300 8.12 VAL 61.88 2-EHGE 29.05 AICl.sub.3/DBN 0.80/0.15 Y-X2-W04 PEI300 3.91 VAL 67.13 2-EHGE 28.01 AICl.sub.3/DBN 0.80/0.15 Y-X2-W05 PEI300 4.41 CAPA 67.10 CGE 27.54 AICl.sub.3/DBN 0.80/0.15 Y-X2-W06 PEI300 6.51 CAPA 56.63 C12-C14- 35.91 AICl.sub.3/DBN 0.80/0.15 AlkylGE Y-X2-W07 PEI300 3.02 CAPA 46.01 C12-C14- 50.02 AICl.sub.3/DBN 0.80/0.15 AlkylGE Y-X2-W08 PEI 1300 7.46 CAPA 64.88 2-EHGE 26.71 AlCl.sub.3/DBN 0.80/0.15 Y-X2-W09 PEI 1300 4.33 CAPA 47.02 C12-C14- 47.70 AlCl.sub.3/DBN 0.80/0.15 AlkylGE Y-X2-W10 PEI 1300 6.61 CAPA 71.80 CGE 20.64 AlCl.sub.3/DBN 0.80/0.15 Y-X2-W11 PEI 2000 4.67 CAPA 60.93 2-EHGE 33.45 AlCl.sub.3/DBN 0.80/0.15 Y-X2-W12 PEI 2000 5.70 CAPA 61.94 C12-C14- 31.42 AlCl.sub.3/DBN 0.80/0.15 AlkylGE Y-X2-W13 PEI 2000 9.30 CAPA 60.68 CGE 29.07 AlCl.sub.3/DBN 0.80/0.15 Y-X2-W14 PEI 2000 3.67 CAPA 55.91 2-EHGE 39.47 AlCl.sub.3/DBN 0.80/0.15 PEI (number) = polyethylenimine (molecular weight), VAL = delta-Valerolactone, CAPA = -Caprolactone, 2-EHGE = 2-ethylhexyl glycidyl ether, CGE = o-cresyl glycidyl ether, C12-C14-AlkylGE = C12-C14 alkyl glycidyl ether, DBN = 1,5-Diazabicyclo(4.3.0)non-5-ene, AlCl.sub.3 = aluminum trichloride

[0218] Preparation Method 3

[0219] The alkoxylation was carried out in a pressure reactor equipped with a stirrer and a thermostat. Component Y(XH).sub.q (abbreviation in the table component YX1) and the catalyst was introduced into the reactor, and the reactor was closed, evacuated and rendered inert with nitrogen. The water (formed as a by-product in the reaction of potassium hydroxide with the alcohol used as a starter) in the reactor was evacuated under reduced pressure and the reactor rendered inert with nitrogen again. After heating to 135 C., a mixture of component Sm (abbreviation in the table component S) and component Em (abbreviation in the table component E1-2) were metered in at a rate such that a maximum pressure of 5 bar was not exceeded. After complete addition and subsequent reaction at 135 C. until the pressure remained constant, cooling took place to room temperature following with de-alkalization with an acidic cation exchanger resin (Amberlite IR-120(H) purchased from Sigma-Aldrich).

TABLE-US-00003 TABLE 3 Intermediate products prepared according to the method 3 component wt. % component wt. % component wt. % wt. % Intermedio Y-X1 Y-X1 S S E1-2 E1-2 catalyst catalyst Y-X1-W16 MPEG 350 46.40 CAPA 45.40 PO 7.70 KOH 0.50 Y-X1-W17 MPEG 500 44.56 CAPA 49.86 PO 5.08 KOH 0.50 Y-X1-W18 MPEG 350 47.29 CAPA 46.26 EO 5.95 KOH 0.50 Y-X1-W19 MPEG 500 48.12 VAL 47.23 EO 4.15 KOH 0.50 Y-X1-W20 MPEG 350 48.20 VAL 41.36 BuO 9.94 KOH 0.50 Y-X1-W21 MPEG 500 46.87 VAL 46.00 BuO 6.63 KOH 0.50 MPEG (number) = methoxy polyethylene glycol (molecular weight in g/mol), CAPA = -Caprolactone, VAL = delta-Valerolactone, PO = propylene oxide, EO = ethylene oxide, BuO = 1,2-Epoxybutane, KOH = potassium hydroxide

[0220] Preparation Method 4

[0221] A clean dry four-necked flask (500 ml) equipped with a condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with component Y(XH).sub.q (abbreviation in the table component YX1) and the catalyst and heated up to 80 C. A mixture of the lactone Sm (abbreviation in the table component S) with a oxetane Em (abbreviation in the table component E2) was slowly added into the component Y(XH).sub.q (abbreviation in the table component YX1) so that the temperature did not exceed 85 C. The incorporation of oxetane and the lactone monomers was evaluated by the means of NMR.

TABLE-US-00004 TABLE 4 Intermediate products prepared according to the method 4 component wt. % component wt. % component wt. % wt. % Intermedio Y-X1 Y-X1 S S E2 E2 catalyst catalyst Y-X1-W22 MPEG 500 52.60 CAPA 35.32 TMPOx 11.98 TfOH 0.10 Y-X1-W23 MPEG 500 54.99 VAL 32.38 TMPOx 12.53 TfOH 0.10 Y-X1-W24 MPEG 350 37.18 CAPA 36.38 3EO-TMPOx 26.34 TfOH 0.10 MPEG (number) = methoxy polyethylene glycol (molecular weight in g/mol, TMPOx = 3-ethyl-3-(hydroxymethyl) oxetane, 3EO-TMPOx = 3-Ethyl-3-(hydroxymethyl)oxetan, ethoxylated with average 3,3 mol ethylenoxide, TfOH = Trifluoromethanesulfonic acid, VAL = delta-Valerolactone, CAPA = -Caprolactone

[0222] Preparation of the Acid Functional Compounds Y(XW(Z).sub.c).sub.q: Second Step

[0223] Preparation Method 5

[0224] A clean dry four-necked flask (250 mL) with condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with component Y(XW(H).sub.c).sub.q (abbreviation in the table component YX1W) and heated up to 50 C. Then the polyphosphoric acid (abbreviation in the table component Z1) was slowly added to the mixture. After complete addition, the mixture was heated up to 80 C. and stirred 4 h at this temperature. The degree of completion was controlled by measurement of acid number.

TABLE-US-00005 TABLE 5 Products prepared according to the method 5 component wt. % component wt % Product Y-X1-W Y-X1-W Z1 Z1 Y-X1-W01-Z1 Y-X1-W01 89.80 PPS 10.20 Y-X1-W02-Z1 Y-X1-W02 90.84 PPS 9.16 Y-X1-W03-Z1 Y-X1-W03 91.57 PPS 8.43 Y-X1-W04-Z1 Y-X1-W04 92.97 PPS 7.03 Y-X1-W05-Z1 Y-X1-W05 93.51 PPS 6.49 Y-X1-W06-Z1 Y-X1-W06 93.95 PPS 6.05 Y-X1-W07-Z1 Y-X1-W07 89.93 PPS 10.07 Y-X1-W08-Z1 Y-X1-W08 91.66 PPS 8.34 Y-X1-W09-Z1 Y-X1-W09 93.89 PPS 6.11 Y-X1-W10-Z1 Y-X1-W10 90.39 PPS 9.61 Y-X1-W11-Z1 Y-X1-W11 96.38 PPS 3.62 Y-X1-W12-Z1 Y-X1-W12 96.93 PPS 3.07 Y-X1-W13-Z1 Y-X1-W13 97.66 PPS 2.34 Y-X1-W14-Z1 Y-X1-W14 92.02 PPS 7.98 Y-X1-W15-Z1 Y-X1-W15 92.63 PPS 7.37 Y-X1-W16-Z1 Y-X1-W16 87.00 PPS 13.00 Y-X1-W17-Z1 Y-X1-W17 90.88 PPS 9.12 Y-X1-W18-Z1 Y-X1-W18 86.79 PPS 13.21 Y-X1-W19-Z1 Y-X1-W19 90.22 PPS 9.78 Y-X1-W20-Z1 Y-X1-W20 86.57 PPS 13.43 Y-X1-W21-Z1 Y-X1-W21 90.45 PPS 9.55 Y-X1-W22-Z1 Y-X1-W22 74.70 PPS 25.30 Y-X1-W23-Z1 Y-X1-W23 80.14 PPS 19.86 Y-X1-W24-Z1 Y-X1-W24 80.69 PPS 19.31 PPS = polyphosphoric acid 85% available from Merck KGaA

[0225] Preparation Method 6

[0226] A clean dry four-necked flask (250 mL) with condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with component Y(XW(H).sub.c).sub.q (abbreviation in the table component YX2W) and an anhydride (abbreviation in the table component Z2). The mixture was heated up to 110 C. and stirred at this temperature until the anhydride acid number reached 0-3 mg KOH/g.

TABLE-US-00006 TABLE 6 Products prepared according to the method 6 component wt. % component wt. % Products Y-X2-W Y-X2-W Z2 Z2 Y-X2-W01-Z2 Y-X2-W01 95.21 BSA 4.79 Y-X2-W02-Z2 Y-X2-W02 96.56 BSA 3.44 Y-X2-W03-Z2 Y-X2-W03 90.18 MSA 9.82 Y-X2-W04-Z2 Y-X2-W04 95.02 BSA 4.98 Y-X2-W05-Z2 Y-X2-W05 94.42 PSA 5.58 Y-X2-W06-Z2 Y-X2-W06 91.97 BSA 8.03 Y-X2-W07-Z2 Y-X2-W07 96.11 BSA 3.89 Y-X2-W08-Z2 Y-X2-W08 90.91 MSA 9.09 Y-X2-W09-Z2 Y-X2-W09 94.51 BSA 5.49 Y-X2-W10-Z2 Y-X2-W10 91.86 PSA 8.14 Y-X2-W11-Z2 Y-X2-W11 94.11 MSA 5.89 Y-X2-W12-Z2 Y-X2-W12 92.90 BSA 7.10 Y-X2-W13-Z2 Y-X2-W13 88.91 PSA 11.09 Y-X2-W14-Z2 Y-X2-W14 95.31 MSA 4.69 BSA = succinic anhydride, MSA = maleic anhydride, PSA = phthalic anhydride

Comparative Examples (not According to the Invention)

[0227] Examples prepared not according to the invention are marked with (*).

[0228] Preparation Method 7

[0229] A clean dry four-necked flask (500 ml) equipped with a condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with component Y(XH).sub.q (abbreviation in the table component YX1) and a mixture of catalysts and heated up to 110 C. Then the epoxide Em (abbreviation in the table component E1-1) was slowly added so that the temperature did not exceed 120 C. After complete addition, the reaction mixture was heated up to 140 C. and stirred at that temperature until the epoxide was completely reacted (controlled by the means of NMR). Then the lactone Sm (abbreviation in the table component S) was slowly added and the mixture was stirred at 140 C. until the content of non-volatile components was >98% (measured according to ISO 3251).

TABLE-US-00007 TABLE 7 Intermediate products prepared according to the method 7 component wt % component wt % component wt % wt % Intermedio Y-X1 Y-X1 S S E1-1 E1-1 catalyst catalyst Y-X1-W25* MPEG 500 48.53 CAPA 32.58 2-EHGE 17.89 AlCl.sub.3/DBN 0.85/0.15 Y-X1-W26* MPEG 500 17.19 CAPA 69.19 2-EHGE 12.66 AlCl.sub.3/DBN 0.81/0.15 Y-X1-W27* MPEG 350 20.17 CAPA 46.24 2-EHGE 32.63 AlCl.sub.3/DBN 0.81/0.15 MPEG (number) = methoxy polyethylene glycol (molecular weight), CAPA = -Caprolactone, 2-EHGE = 2-ethylhexyl glycidyl ether, DBN = 1,5-Diazabicyclo(4.3.0)non-5-ene, AlCl.sub.3 = aluminum trichloride

[0230] Preparation Method 8

[0231] A clean dry four-necked flask (500 mL) equipped with condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with the epoxide Em (abbreviation in the table component E1-1) and heated up to 80 C. Then a polyamine Y(XH).sub.q (abbreviation in the table component YX2) was slowly added into this mixture. After complete addition the temperature was increased up to 140 C. and the mixture was stirred for 2 h. Then the reaction mixture was cooled down to 40 C., the catalysts were added and the temperature was increased up to 140 C. The reaction mixture was stirred at this temperature until the epoxide was completely reacted (controlled by the means of NMR). Then the lactone (abbreviation in the table component S) was slowly added at 140 C. The implementation of epoxide and the lactone monomers was determined by the means of NMR.

TABLE-US-00008 TABLE 8 Intermediate products prepared according to the method 8 component wt. % component wt. % component wt. % wt. % Intermedio Y-X2 Y-X2 S S T1-1 E1-1 catalyst catalyst Y-X2-W15* PEI300 3.72 CAPA 55.88 2-EHGE 39.45 AlCl.sub.3/DBN 0.80/0.15 Y-X2-W16* PEI300 1.23 CAPA 53.60 2-EHGE 44.22 AlCl.sub.3/DBN 0.80/0.15 PEI (number) = polyethylenimine (molecular weight), CAPA = -Caprolactone, 2-EHGE = 2-ethylhexyl glycidyl ether, DBN = 1,5-Diazabicyclo(4.3.0)non-5-ene, AlCl.sub.3 = aluminum trichloride

[0232] Preparation of the Acid Functional Compounds Y(XW(Z).sub.c).sub.q: Second Step

[0233] Preparation method 9

[0234] A clean dry four-necked flask (250 mL) with condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with component Y(XW(H).sub.c).sub.q (abbreviation in the table component YX1W) and heated up to 50 C. Then the polyphosphoric acid (abbreviation in the table component Z1) was slowly added to the mixture. After complete addition, the mixture was heated up to 80 C. and stirred 4 h at this temperature. The degree of completion was controlled by measurement of the acid number.

TABLE-US-00009 TABLE 9 Products prepared according to the method 9 component component product Y-X1-W wt. % Z1 wt. % Z1 Y-X1-W25-Z1* Y-X1-W25 90.34 PPS 9.66 Y-X1-W26-Z1* Y-X1-W26 96.37 PPS 3.63 Y-X1-W27-Z1* Y-X1-W27 93.90 PPS 6.10 PPS = polyphosphoric acid 85% available from Merck KGaA

[0235] Preparation Method 10

[0236] A clean dry four-necked flask (250 mL) with condenser, KPG-stirrer, temperature sensor and a nitrogen line was charged with component Y(XW(H).sub.c).sub.q (abbreviation in the table component YX2W) and an anhydride (abbreviation in the table component Z2). The mixture was heated up to 110 C. and stirred at this temperature until the anhydride acid number reached 0-3 mg KOH/g.

TABLE-US-00010 TABLE 10 Products prepared according to the method 10 component wt % component wt % product Y-X2-W Y-X2-W Z2 Z2 Y-X2-W15-Z2* Y-X2-W15 95.21 BSA 4.79 Y-X2-W16-Z2* Y-X2-W16 96.57 BSA 3.43 BSA = succinic anhydride

Application Examples

[0237]

TABLE-US-00011 TABLE 11 Overview of the products used for the application tests component component component component product Y-X1 S E1-1 Z1 Y-X1-W10- 1.00 3.00 1.00 0.33 Z1 Y-X1-W25- 1.00 3.00 1.00 0.33 Z1* component component component component product Y-X2 S E1-1 Z2 Y-X2-W01- 1.00 7.00 3.00 0.68 Z2 Y-X2-W02- 1.00 20.00 10.00 1.45 Z2 Y-X2-W15- 1.00 7.00 3.00 0.68 Z2* Y-X2-W16- 1.00 20.00 10.00 1.45 Z2*

[0238] The data (number values) in the table inform about the ratio of raw materials in the corresponding acid derivate. Samples marked with (*) are block polymers (comparative examples). Compared are: YX1W10Z1 with YX1W25Z1*, YX2W02Z2 with YX2W16Z2* and YX2W01Z2 with YX2W15Z2*. By the means of DSC measurement (explained above) it is possible to distinguish between the block polymers (*) and the corresponding random types: the DSC plot of the block structures (YX1W25613 Z1*, YX2W16Z2*, YX2W15Z2*) showed more narrow (not so broad) melting-/crystallization-peaks compared with the plot of the corresponding random structures (YX1W10Z1, YX2W02Z2, YX2W01Z2). Furthermore, the crystallization temperature of said block structures is higher than of corresponding random structures (s. table 12).

TABLE-US-00012 TABLE 12 Crystallization temperatures of tested samples Crystallization Sample Temperatures in C. Y-X1-W10-Z1 25 Y-X1-W25-Z1* 14 Y-X2-W01-Z2 2 Y-X2-W15-Z2* 5 Y-X2-W02-Z2 9 Y-X2-W16-Z2* 11

[0239] Application Example 1

[0240] Raw Materials used for the Application Tests:

[0241] Setal 189 XX65-Polyester resin purchased from Allnex/Nuplex

[0242] Sicotrans Red L2817-transparent iron oxide purchased from BASF

[0243] Working Method 1

[0244] Preparation of Millbase

[0245] Variation of parameters such as pigment/binder-ratio and additive dosage in the millbase formulation has a tremendous influence on the quality of the pigment dispersion and stabilization. The amount of resin could have an influence on flow behavior/viscosity, pigment wetting, storage stability of millbase and final paint for example. Only if there is an optimal amount of wetting & dispersing-additive available in the grinding phase the best pigment dispersion can be achieved. Consequently, for test purpose the system can be adjusted more or less sensitive by variation of parameters. In order to get a satisfactory differentiation of the tested additives, the pigment dispersions were prepared with different amounts of wetting & dispersing additives (s. table 13).

TABLE-US-00013 TABLE 13 Formulation of millbase Type of the additive dosage Pigment/binder-ratio formulation (solid on pigment) in % (solid on solids) Type 1 25 1:1.2 Type 2 15 1:1.2

[0246] The detailed composition of the formulation is described in the table 14.

TABLE-US-00014 TABLE 14 Composition of the formulation Type : 1 2 Position Millbase Control 25% Control 15% 1 Setal 189 25.0 19.7 25.0 21.8 XX-65 2 W&D- 6.5 3.9 additive 3 Butyl acetate 15.4 10.3 14.5 10.8 4 Sicotrans 13.5 13.5 13.5 13.5 Red L2817 Sum of 1-4 50.0 50.0 50.0 50.0 5 Glass beads 50.0 50.0 50.0 50.0 1 mm Pigment/binder- 1/1.2 1/1.2 ratio: Additive dosage: 0% 25% 0% 15% (solid on pigment)

[0247] For the preparation of the millbase a binder, a wetting and dispersing additive and a solvent (positions 1-3) were filled in a glass bottle (100 ml) and homogenized with a spatula. After this procedure the pigment and glass beads were added to the mixture and dispersed by high speed shaker (Disperser DAS A 200-K with cooling systemSYSTEM LAU) for 120 minutes at a maximum energy input (stage 3=100% power) using a teflon disk (4,5 cm O). After that, the glass beads were removed by filtration (using 240 m paper filter).

[0248] Judgement of Millbase Viscosity

[0249] The millbase viscosity can give a hint on the efficiency/quality of pigment dispersion. Therefor the viscosity of the millbases was measured after one day storage at room temperature (RT), three days storage at room temperature (RT). The following equipment and parameters were used to judge the viscosity of the samples: Rheologica Stresstech (rotational rheometer, cone/plate), Cone (25mm/1), shear rate 0-1000 (1/s), at 23 C. (according to DIN EN ISO 2884-1).

RESULTS

[0250] The results of the application tests are presented below (in the tables 15-16).

TABLE-US-00015 TABLE 15 Results of viscosity measurement in Type 1 formulation Type 1 1 d RT 1 d RT 3 d RT 3 d RT Y-X1- Y-X1- Y-X1- Y-X1- Shear W10-Z1 W25-Z1* W10-Z1 W25-Z1* rate Viscosity Viscosity Viscosity Viscosity 1/s mPa s mPa s mPa s mPa s 1 184 186 223 256 2 170 178 197 255 5 159 176 197 243 10 146 169 184 237 20 142 165 179 223 50 135 155 168 203 100 128 147 160 198 200 119 138 149 192 500 107 123 134 164 1000 100 114 126 153

TABLE-US-00016 TABLE 16 Results of viscosity measurement in Type 2 formulation Type 2 1 d RT 1 d RT 3 d RT 3 d RT Y-X1- Y-X1- Y-X1- Y-X1- Shear W10-Z1 W25-Z1* W10-Z1 W25-Z1* rate Viscosity Viscosity Viscosity Viscosity 1/s mPa s mPa s mPa s mPa s 1 3821 5742 298 339 2 2156 3569 265 311 5 1463 1799 240 278 10 814 1556 218 272 20 689 1360 208 260 50 258 1234 201 233 100 178 986 198 225 200 164 853 195 211 500 155 368 194 193 1000 143 179 193 183

[0251] In the tested millbase variations Type 1 and Type 2 the additive YX1W10Z1 which is a statistic polymer showed normally better viscosity reduction as compared to the corresponding block structure YX1W25Z1*. Furthermore, the inventive additive YX1W10Z1 demonstrates obvious advantage in viscosity reduction at lower additive dosages (Type 2) compared to corresponding block structure YX1W25Z1*.

Application Example 2

[0252] Raw Material Used for the Application Tests

[0253] Ebecryl 4381: UV/EB Curable Resinsunsaturated polyester resin diluted in 30% dipropylene glycol diacrylate (DPGDA), purchased from Allnex Laromer DPGDA: Dipropylene glycol diacrylate, purchased from BASF Irgacure 1173: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one used in reactive and radiation curing adhesives, purchased from IGM ACEMATT HK 440: Untreated silica-based matting agent, purchased from Evonik BYK-088: Defoamer for solvent-borne systems, purchased from BYK Chemie GmbH BYK-306: Silicone-containing surface additive for ambient-curing plastic systems and solvent-borne coating systems, purchased from BYK Chemie GmbH BYK-350: An acrylic leveling additive for solvent-borne and solvent-free systems, purchased from BYK Chemie GmbH

[0254] Working Method 2

[0255] Preparation of UV Matt Base

[0256] In order to achieve a high quality UV matt base, a sufficient wetting and dispersing of the matting agent is important. The following properties indicate the effect of the additives used: gloss reduction (preferable low gloss), surface appearance (preferable smooth and fine) and paint viscosity (preferable low/flowable).

[0257] The detailed composition of the formulation is presented in the table 17.

TABLE-US-00017 TABLE 17 Composition of the formulation Position Raw Materials Composition 1 Ebecryl 4381 18.1 2 Laromer DPGDA 27.9 3 Irgacure 1173 3.1 4 BYK-088 0.2 5 BYK-306 0.1 6 BYK-350 0.1 7 W&D-Additive 1.5 8 ACEMATT HK 440 9.0 9 PMA 40.0 total 100.0

[0258] For the preparation of the UV matt base raw materials listed in the position 1-3 were mixed shortly by dissolver (1865 rpm), then the additives listed in the positions 4-6 were added to this mixture and stirred for another 3 minutes at 1865 rpm. After that the W&D additive (position 7) and the solvent (PMA=1-methoxy-2-propylacetate) were added to the mixture under stirring. Finally, a matting agent (position 8) was added and the whole mixture stirred for 10 minutes at 1865 rpm.

[0259] The final paints were applied on black PMMA (poly methyl methacrylate) panels and cured using mercury UV lamp from IST Metz GmbH (speed 5 m/min, 100% intensity).

[0260] Matting Effect (Measurement of Gloss Reduction)

[0261] Gloss Measurement at 20/60/85 with Micro tri Gloss (BYK-Gardner).

[0262] The results of the application tests are presented below (in the tables 18-19).

TABLE-US-00018 TABLE 18 Results of the gloss measurement Gloss (angle) Gloss 20 Gloss 60 Gloss 85 Y-X2-W16-Z2* 0.2 2.5 39.5 Y-X2-W02-Z2 0.1 1.9 37.3 Y-X2-W15-Z2* 0.3 3.3 41.9 Y-X2-W01-Z2 0.2 2.1 36.8

TABLE-US-00019 TABLE 19 Results of the viscosity measurement sample Y-X2- Y-X2- Y-X2- Y-X2- Shear W16-Z2* W02-Z2 W15-Z2* W01-Z2 rate Viscosity Viscosity Viscosity Viscosity 1/s mPa s mPa s mPa s mPa s 1 63718 50500 92123 52560 10 9897 8862 9142 7265 100 1918 1892 1786 1586

[0263] In the tested paint system the additives YX2W02Z2 and YX2W01Z2 based on statistical polymers lead to better matting properties and better viscosity reduction in comparison to corresponding block copolymer YX2W16Z2* and YX2W15Z2*. This shows the high dispersing quality of the acid functional compounds according to the present invention.