POLYMER COMPOSITIONS AND USE OF THESE POLYMER COMPOSITIONS AS DISPERSANTS

Abstract

A polymer composition, obtainable by reacting a) a polymer P1 having at least one functional group of the formula (I) and a polymer backbone B, and b) a polymer P2 which is a polyolefine succinic anhydride:

##STR00001##

Claims

1. A polymer composition, which is obtainable by reacting a) a polymer P1 having at least one functional group of the formula (I), ##STR00010## and a polymer backbone where # indicates the point of attachment to the terminus and/or to the polymer backbone B of the polymer P1; k is 0, 1, 2, 3 or 4; m is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; A is a chemical bond or a divalent moiety selected from the group consisting of C.sub.1-C.sub.6 alkylene, —O—(C.sub.2-C.sub.6 alkylene), —C(═O)—O—(C.sub.2-C.sub.6 alkylene), —NR.sup.3—(C.sub.2-C.sub.6 alkylene) and C(═O)—NR.sup.3—(C.sub.2-C.sub.6 alkylene), where the C.sub.2-C.sub.6 alkylene part is attached to Q; Q is a divalent moiety selected from the group consisting of —O—, —NH— and —S—; R.sup.1 is independently selected from the group consisting of —OH, —COOH, —COOCH.sub.3, —NH.sub.2, —NH(C.sub.1-C.sub.6 alkyl), —N(C.sub.1-C.sub.6 alkyl).sub.2, —NO.sub.2, —S(═O).sub.2R.sup.4, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.4 alkoxy, halogen, aryloxy, aryl, heteroaryl, where aryl, hetaryl and aryloxy are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of —OH, —COOH, —COOCH.sub.3, —NH.sub.2, —NH(C.sub.1-C.sub.6 alkyl), —N(C.sub.1-C.sub.6 alkyl).sub.2, —NO.sub.2, —S(═O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; R.sup.2 is selected from the group consisting of hydrogen, —S(═O).sub.2R.sup.4, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.10 cycloalkyl, aryl, heteroaryl, aryl-C.sub.1-C.sub.4-alkyl and heteroaryl-C.sub.1-C.sub.4-alkyl, where aryl and hetaryl in the four last mentioned radical:, aryl, heteroaryl, aryl-C.sub.1-C.sub.4-alkyl and heteroaryl-C.sub.1-C.sub.4-alkyl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of —OH, —COOH, —COOCH.sub.3, —NH.sub.2, —NH(C.sub.1-C.sub.6 alkyl), —N(C.sub.1-C.sub.6 alkyl).sub.2, —NO.sub.2, —S(═O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; R.sup.3 is selected from the group consisting of hydrogen, —S(═O).sub.2R.sup.4, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.10 cycloalkyl, aryl and heteroaryl, where aryl and hetaryl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of —OH, —COON, —COOCH.sub.3, —NH.sub.2, —NH(C.sub.1-C.sub.6 alkyl), —N(C.sub.1-C.sub.6 alkyl).sub.2, —NO.sub.2, —S(═O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; and R.sup.4 is selected from the group consisting of OH, —NH.sub.2, —NH(C.sub.1-C.sub.6 alkyl), —N(C.sub.1-C.sub.6 alkyl).sub.2, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, aryl and heteroaryl, where aryl and hetaryl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; with b) a polymer P2 which is a polyolefine succinic anhydride.

2. The polymer composition as claimed in claim 1, where in the formula (I), the divalent moiety Q is —O—.

3. The polymer composition as claimed in claim 1, wherein the polymer P1 has 1 to 10 functional groups of the formula (I) per polymer molecule.

4. The polymer composition as claimed in claim 1, wherein in the formula (I) the radical R.sup.2 is hydrogen.

5. The polymer composition as claimed in claim 1, wherein in the formula (I), k is 0 or 1; m is 0 or 1, A is a chemical bond or a divalent moiety selected from the group consisting of —C(═O)—O—(C.sub.2-C.sub.4 alkylene) and C(═O)—NH—(C.sub.2-C.sub.4 alkylene), where the alkylene part is attached to Q; Q is a divalent moiety selected from the group consisting of —O— and —NH—; R.sup.1 is independently selected from the group consisting of —OH, —COOH, —COOCH.sub.3, —NH.sub.2, —NH(C.sub.1-C.sub.6 alkyl), —N(C.sub.1-C.sub.6 alkyl).sub.2, —NO.sub.2, —S(═O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, halogen, phenyl and pyridyl; and R.sup.4 is selected from the group consisting of —NH.sub.2, —NH(C.sub.1-C.sub.6 alkyl), —N(C.sub.1-C.sub.6 alkyl).sub.2 and C.sub.1-C.sub.4 alkyl.

6. The polymer composition as claimed in claim 1, wherein the polymer P1 has a linear or branched polymer backbone B, and the functional groups are located at the termini of the polymer backbone B.

7. The polymer composition as claimed in claim 1, wherein the polymer backbone B is selected from the group consisting of aliphatic polyesters, aliphatic polyethers, aliphatic polyetheresters, aliphatic polycarbonates and homo- and copolymers which predominately comprise repeating units Ml, and the repeating units M1 are selected from polymerized C.sub.1-C.sub.10-alkyl (meth)acrylates, polymerized C.sub.1-C.sub.10-alkyl-(poly-C.sub.2-C.sub.4-alkyleneglycol) (meth)acrylates and polymerized vinylaromatic hydrocarbon compounds.

8. The polymer composition as claimed in claim 7, wherein the polymer backbone B of the polymer P1 is a poly-(C.sub.2-C.sub.4-alkylene oxide).

9. The polymer composition as claimed in claim 8, wherein the polymer backbone B of the polymer P1 is a C.sub.1-C.sub.4-alkyl terminated poly(ethylene glycol).

10. The polymer composition as claimed in claim 7, wherein the polymer backbone B of the polymer P1 is an aliphatic polyester or an aliphatic polyetherester.

11. The polymer composition as claimed in claim 1, wherein the polymer P1 has a number-average molecular weight in the range of from 300 to 50000 daltons.

12. The polymer composition as claimed in claim 1, wherein the polymer P2 has a number-average molecular weight in the range of from 300 to 10000 daltons.

13. The polymer composition as claimed in claim 1, wherein the polymer P2 has a saponification number in the range of from 10 to 300 mg KOH/g.

14. The polymer composition as claimed in claim 1, wherein the polymer P2 comprises less than 20% by weight of polyolefine succinic anhydride with 2 succinic anhydride groups per polyolefine radical.

15. The polymer composition as claimed in claim 1, wherein the polyolefine succinic anhydride is a polyisobutene succinic anhydride.

16. The polymer composition as claimed in any of the claim 1, wherein the polymer P1 and the polymer P2 are reacted in a relative amount such that the molar ratio of functional groups of the formula (I) to the succinic anhydride groups in the polymer P2 is in the range of from 0.1:1 to 10:1.

17. The polymer composition as claimed in claim 1, which has an acid number in the range of from 3 to 500 mg KOH/g.

18. A process for manufacturing the polymer composition of claim 1, comprising: a) providing the polymer P1; and b) reacting the polymer P1 obtained in a) with the polymer P2.

19-22. (canceled)

23. A liquid composition, comprising: a fine particulate solid material, selected from the group consisting of pigments and fillers; the polymer composition of claim 1; and a liquid diluent, wherein the fine particulate solid material is dispersed in the liquid diluent, and the liquid composition is in the form of a dispersion.

24. The liquid composition of claim 23, wherein a weight ratio of the fine particulate solid material to polymer components in the polymer composition is in the range of from 100:1 to 1:50.

25. The liquid composition of claim 23, wherein i) an amount of the fine particulate solid material is 1 to 70% by weight, based on the total weight of the liquid composition. ii) an amount of the polymer composition is 0.1 to 50% by weight, based on the total weight of the liquid composition, and iii) an amount of the liquid diluent is 98.5% or less by weight, based on the total weight of the liquid composition.

26. The liquid composition of claim 23, which is in the form of a mill-base, in the form of an ink or in the form of a coating composition.

Description

PREPARATION EXAMPLES

[0249]

TABLE-US-00001 TABLE 1 Commercially available polymers used: Name of Polymer Composition Supplier Pluriol ® A350 E Methyl polyethylene glycol, BASF SE molecular mass M.sub.N approx. 350 g/mol Pluriol ® A500 E Methyl polyethylene glycol, BASF SE molecular mass M.sub.N approx. 500 g/mol Lutensol AT 11 C.sub.16-18-fatty alcohol ethoxylate with BASF SE 11 EO units Pluronic PE3500 poly(ethyleneoxide-co- BASF SE propyleneoxide) triblock copolymer with a central polypropyleneoxide block, molecular weight M.sub.N approx. 3800 Pluriol A15 TE ethoxylated trimethylolpropane BASF SE molecular weight M.sub.N approx. 840 Glissopal SA F Polyisobutene succinic anhydride, BASF SE molecular weight M.sub.N approx. 1000

Example 1

[0250] A mixture of 50.0 g (0.1 mol OH) of Pluriol® A500 E, 16.3 g (0.1 mol) of isatoic anhydride (IA) and 0.2 g (0.3 wt.-%) of 1,4-Diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. Then, the reaction mixture was cooled to 80° C. and 100.0 g (0.1 mol) Glissopal SA F was added and the reaction mixture was heated at 80° C. for additional 3 hours. The obtained product was a viscous liquid with an acid number of 35 mg KOH/g.

Example 2

[0251] A mixture of 74.0 g (0.1 mol OH) of Lutensol®AT11, 16.3 g (0.1 mol) of isatoic anhydride (IA) and 0.28 g (0.3 wt.-%) of 1,4-Diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. Then, the reaction mixture was cooled down to 80° C. and 100.0 g (0.1 mol) Glissopal SA F was added and the reaction mixture was heated at 80° C. for additional 3 hours. The obtained product was a wax with an acid number of 30 mg KOH/g.

Example 3

[0252] A mixture of 35 g (0.1 mol) of Pluriol® A350E, 45.6 g (0.4 mol) of epsilon-caprolactone and 10.0 g (0.1 mol) of delta-valerolactone was treated with 0.1 g of dibutyltin dilaurate under inert gas and heated to 160° C. until a solids content of 97% had been reached. The reaction mixture was cooled down to 60° C. and 16.3 g (0.1 mol) of isatoic anhydride and 0.31 g (0.3 wt.-%) of 1,4-Diazabicyclol[2.2.2]octan was added and cooked at 80 to 140° C. until no more carbon dioxide was evolved. Then, the reaction mixture was cooled down to 80° C. and 100.0 g (0.1 mol) Glissopal SA F was added and the reaction mixture was heated at 80° C. for additional 3 hours. The obtained product was a wax with an acid number of 27 mg KOH/g.

Example 4

[0253] A mixture of 80.0 g (0.2 mol OH) of Pluriol E800, 32.6 g (0.2 mol) of isatoic anhydride (IA) and 0.31 g (0.3 wt.-%) of 1,4-Diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. Then, the reaction mixture was cooled down to 80° C. and 200.0 g (0.2 mol) polyisobutenylsuccinanhydride (PIBSA, Glissopal SA F, BASF) were added and the reaction mixture was heated at 80° C. for additional 3 hours.

[0254] The obtained product was a wax with an acid number of 38 mg KOH/g.

Examples 5

[0255] A mixture of 190 g (0.1 mol OH) of Pluronic PE3500, 32.6 g (0.2 mol) of isatoic anhydride (IA) and 0.60 g (0.3 wt.-%) of 1,4-Diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. Then, the reaction mixture was cooled down to 80° C. and 200.0 g (0.2 mol) Glissopal SA F were added and the reaction mixture was heated at 80° C. for additional 3 hours. The obtained product was a wax with an acid number of 27 mg KOH/g.

Example 6

[0256] A mixture of 84 g (0.3 mol OH) of Pluriol A15 TE, 48.9 g (0.3 mol) of isatoic anhydride (IA) and 0.35 g (0.3 wt.-%) of 1,4-Diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. Then, the reaction mixture was cooled down to 80° C. and 300.0 g (0.3 mol) of Glissopal SA F were added and the reaction mixture was heated at 80° C. for additional 3 hours. The obtained product was a wax with an acid number of 39 mg KOH/g.

Example 7

[0257] A mixture of 50.0 g (0.1 mol OH) of Pluriol® A500 E, 16.3 g (0.1 mol) of isatoic anhydride (IA) and 0.2 g (0.3 wt.-%) of 1,4-Diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. Then, the reaction mixture was cooled down to 80° C. and 100.0 g (0.1 mol) of Glissopal SA F were added and the reaction mixture was heated at 150° C. for additional 3 hours. The obtained product was a viscous liquid with an acid number of 5 mg KOH/g.

Example 8

[0258] A mixture of 74.0 g (0.1 mol OH) of Lutensol®AT11, 16.3 g (0.1 mol) of isatoic anhydride (IA) and 0.28 g (0.3 wt.-%) of 1,4-Diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. Then, the reaction mixture was cooled down to 80° C. and 100.0 g (0.1 mol) of Glissopal SA F were added and the reaction mixture was heated at 160° C. for additional 3 hours. The obtained product was a wax with an acid number of 3 mg KOH/g.

Example 9

[0259] A mixture of 84 g (0.3 mol OH) of Pluriol A15 TE, 48.9 g (0.3 mol) of isatoic anhydride (IA) and 0.35 g (0.3 wt.-%) of 1,4-Diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. Then, the reaction mixture was cooled down to 80° C. and 300.0 g (0.3 mol) of Glissopal SA F were added and the reaction mixture was heated at 160° C. for additional 3 hours. The obtained product was a wax with an acid number of 4 mg KOH/g.

[0260] Performance Testing

[0261] a) Rheological Behavior of Mill-Base

[0262] In order to test the dispersion effect of the obtained samples, resin free pigment concentrates (mill-base) were prepared according to the following formulation recipes F and NF. The mill-base was dispersed in Scandex Shaker for 1 h with the help of glass beads. Afterwards the mill base was filtered and stored at room temperature overnight.

TABLE-US-00002 TABLE 2 Preparation of Mill-base Formulations F and NF: Ingredients/Mill-base No. F NF 1) EFKA-2550 1 1 2) Water 27.5 28 3) PEG 200 12 12 4) Inventive polymer composition 5 5 4) Quadrol L 0.5 — 5) PY42: Bayferrox 3910 LV [g] 54 54 6) 2.0 mm glass beads [g] 100.0 100.0 Total (g) 200.0 200.0 EFKA-2550: modified polydimethylsiloxane defoamer of BASF SE PY42: micronized iron oxide yellow pigment from Lanxess Quadrol L: a propoxylated ethylene diamine available from BASF

[0263] A comparative dispersant was synthesized according to example 4 of U.S. Pat. No. 8,247,353. The performance of these dispersants was tested according to Formulations F and NF.

[0264] The performance of the polymer compositions of examples 1 to 9 and the performance of the comparative dispersant A were tested by determining the rheological behavior of the Mill-base Formulations F1 and NF1.

[0265] The rheological behavior of the mill-bases was measured at 23° C. with a Thermo-Haake RheoStress 600 rheometer under CR-mode with rotation speed of 100 sec.sup.−1, respectively, using a cone-plate sensor. The mill-bases containing the examples flowed well and their viscosities were comparable or lower than the product of the comparative example. Results are summarized in table 3:

TABLE-US-00003 TABLE 3 The dispersion effect in clear coat paint system Viscosity of mill-bases F and NF (mPas) .sup.2) Example F NF1 A .sup.1) 1250 1500 1 120 250 2 950 1050 3 450 750 4 650 750 6 1200 1400 7 1500 1550 .sup.1) Comparative Example A: example 4 of U.S. Pat. No. 8,247,353. .sup.2) Measured at constant rotation speed of 100 sec.sup.−1

[0266] b) Performance of the polymer composition in solvent based clear coatings and water based clear coatings

[0267] The dispersant performance was also tested in clear coating systems with respect to gloss and anti-cratering effect. First, let-down formulations (formulations F2 and F3) based on a clear coating system were prepared.

TABLE-US-00004 TABLE 4 Formulation recipe F2 - Organic solvent based clear-coating system Ingredient % b.w. in Formulation Resin 1- 24.7% Resin 2 23.1% Resin 3 11.5% Plasticizer  2.9% Butyl Acetate 18.9% Xylene 18.9% Total  100% [0268] Resin 1: Saturated polyester resin in Solvent naphtha/Methoxy propanol/Xylene (Setal 173 VS-60) from Nuplex; [0269] Resin 2: Mixture of 64.8 g of a first cellulose acetate butyrate (CAB 381.2) and 25.2 g of a second cellulose acetate butyrate (CAB 381.20) in 255 g butyl acetate and 255 g of xylene, commercially available from Eastman Chemical; [0270] Resin 3: Maprenal MF 650: highly reactive isobutylated melamine-formaldehyde resin, commercially available from Ineos; [0271] Plasticizer: Resamine HF 480: Polyurea plasticizer, Carbamic resin based on butylurethane and formaldehyde, commercially available from Cytec.

TABLE-US-00005 TABLE 5 Formulation recipe F3 - Water based clear-coating system Ingredient % b.w. in Formulation Resin 4 99.9%  Levelling agent  0.1% Total 100% [0272] Resin 4: NeoCryl™ XK-90: 100% acrylic emulsion polymer from DSM; [0273] Levelling agent: EFKA-3570: Levelling and anti-cratering agent for aqueous coatings, neutralized fluorocarbon-modified polyacrylate, commercialy available from BASF.

[0274] Then, the following paint compositions were prepared by mixing 1.0 g of the respective mill-bases F1 or NF1 with 9.0 g of the clear coating systems F2 or F3, respectively, for 5 minutes at 2000 rpm:

TABLE-US-00006 TABLE 6 Paint compositions Paint compositions Mill-base formulations Clear coating systems (PC) F1 NF1 F2 F3 PC1 1.0 g — 9.0 g — PC11 — 1.0 g 9.0 g — PC2 1.0 g — — 9.0 g PC22 — 1.0 g — 9.0 g

[0275] The paint was applied on polyester film with a 150 μm film thickness.

[0276] The gloss of the obtained coatings at 20° angle was determined according to DIN 67530 using a commercial reflectometer (Micro-Tri-Gloss reflectometer from BYK Gardner). The performance was generally very good with satisfactory results, e.g. high gloss in let-down tests. The results are summarized in table 5.

TABLE-US-00007 TABLE 5 Gloss (20°) and crater ranking of paint compositions P1 and P2 Gloss (20°) Example PC1 .sup.2) PC11 .sup.2) PC2 .sup.2) PC22 .sup.2) A 46 50 35 41 1 53 57 42 48 2 48 50 38 45 3 51 57 43 50 4 46 50 36 41 6 47 50 36 41 7 52 58 43 42