POLYMER COMPOSITIONS AND USE OF THESE POLYMER COMPOSITIONS AS VISCOSITY MODIFIERS

Abstract

The present invention relates to novel polymer compositions, to a process for their manufacturing, to the use of said polymer compositions for modifying the viscosity of aqueous compositions, and to water-borne coating compositions containing the novel polymer compositions as thickeners. The polymer compositions comprise a polymer material which is obtainable by reacting: a) a polymer P1 having at least one functional group of the formula (I), where k is an integer from 0 to 4; n is 0 or 1 p is an integer from 1 to 10, the number average of p being from 1.5 to 10; Q is a divalent moiety selected from the group consisting of —O— and —NH—; P is a p-valent hydrophilic neutral polymer radical; and R.sup.1 is as defined in the claims; with b) a succinic anhydride of the formula (II) where R is C.sub.4-C.sub.24-alkyl or C.sub.4-C.sub.24-alkenyl.

##STR00001##

Claims

1: A polymer composition comprising a polymer material which is obtained by reacting a) a polymer P1 of the formula (I) ##STR00008## where k is an integer from 0 to 4; n is 0 or 1 p is an integer from 1 to 10, the number average of p being from 1.5 to 10; Q is a divalent moiety selected from the group consisting of —O— and —NH—; P is a p-valent hydrophilic neutral polymer radical; R.sup.1 is independently selected from the group consisting of halogen, COOCH.sub.3, —N(C.sub.1-C.sub.6-alkyl).sub.2, —NO.sub.2, —S(═O).sub.2R.sup.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, 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, —COOCH.sub.3, —N(C.sub.1-C.sub.6-alkyl).sub.2, —NO.sub.2, —S(═O).sub.2R.sup.2, 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 —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 succinic anhydride of the formula (II) ##STR00009## where R is C.sub.4-C.sub.24-alkyl or C.sub.4-C.sub.24-alkenyl.

2: The polymer composition as claimed in claim 1, where P is p-valent polymer radical which is derived from a linear or branched poly-(C.sub.2-C.sub.4-alkylene oxide) polymer.

3: The polymer composition as claimed in claim 1, where P is a poly(ethylene oxide), a poly(propylene oxide) or a poly(ethylene oxide-co-propylene oxide).

4: The polymer composition as claimed in claim 1, where the number average of p in formula (I) is from 1.8 to 3.

5: The polymer composition as claimed in claim 1, where in formula (I) k is 0; n is 0; and Q is —O—.

6: The polymer composition as claimed in claim 1, where the polymer radical P has a number average molecular weight in the range from 500 to 50000 Dalton.

7: The polymer composition as claimed in claim 1, where R is linear C.sub.4-C.sub.24-alkyl or linear C.sub.4-C.sub.24-alkenyl.

8: The polymer composition as claimed in claim 1, where R is C.sub.6-C.sub.18-alkyl or C.sub.6-C.sub.18-alkenyl.

9: The polymer composition as claimed in claim 1, where the polymer P1 and the succinic anhydride of the formula (II) are reacted in a relative amount such that the molar ratio of —NH.sub.2 groups in the polymer P1 to the anhydride groups of the succinic anhydride of formula (II) is in the range from 1:1 to 1:5.

10: The polymer composition as claimed in claim 1, where the polymer P1 is obtained by reacting a polymer of the formula (III)
P-(Q-H).sub.p  (III) with a compound of the formulae (V), (VI) or (VII) ##STR00010## where p, k, P, Q and R.sup.1 are as defined in claim 1, and R.sup.L is hydrogen or a hydrocarbon radical having 1 to 8 carbon atoms.

11: The polymer composition as claimed in claim 1, which further comprises a non-ionic surfactant.

12: The polymer composition as claimed in claim 1, which is in the form of an aqueous solution of the polymer material.

13: The polymer composition as claimed in claim 1, which has a pH in the range from 5.0 to 10.0.

14: A process for the manufacturing of the polymer composition as claimed in claim 1, which comprises reacting the polymer P1 with a succinic anhydride of the formula (II).

15: A viscosity modifier comprising the polymer composition of claim 1.

16: The viscosity modifier of claim 15, wherein the polymer composition is a thickener in a water-borne coating composition.

17: A water-borne coating composition, comprising the polymer composition of claim 1 and a polymer P2 in the form of a polymer latex.

18: The coating composition of claim 17, comprising the polymer composition in such an amount that the polymer material of the polymer composition is from 0.1 to 5% by weight, based on the polymer P2.

19: The coating composition of claim 17, comprising i) 1 to 70% by weight, based on the total weight of the coating composition, of at least one fine particulate solid material, selected from the group consisting of pigments and fillers; ii) 5 to 40% by weight, based on the total weight of the coating composition, of a polymer P2 in the form of a polymer latex and calculated as solid polymer P2; iii) 0.01 to 3% by weight, based on the total weight of the coating composition, of the polymer composition, calculated as polymer material; and iv) 20 to 93% by weight, based on the total weight of the coating composition, of water.

Description

PREPARATION EXAMPLES

[0184]

TABLE-US-00001 TABLE 1 Commercially available products that were used as a polymer of the formula (III), a non-ionic surfactant and a polymer P2 in the form of a polymer latex: Name Composition Supplier Pluriol ® E8000 polyethylene glycol, average BASF SE molecular mass M.sub.N approx. 8000 g/mol; used as polymer of formula (III). Dehydol ® O4 C8-fatty alcohol ethoxylated with BASF SE 4 EO units; used as non-ionic surfactant. Acronal ® Plus 4670 Acrylic latex, solid content 49-51% BASF SE by weight, particle size approx. 140 nm; used as polymer P2 in the form of a polymer latex.

Preparation of Polymer P1-a:

[0185] A mixture of 80.0 g (0.02 mol of hydroxyl groups) Pluriol® E8000, 4.1 g (0.025 mol) isatoic anhydride (IA), and 0.25 g (0.3% by weight) 1,4-diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. The obtained product was a solid with an amine number of 15 mg KOH/g.

Preparation of Polymer Compositions Useful as Thickeners

Example 1 (According to the Invention)

[0186] A mixture of 41.0 g (0.005 mol) polymer P1-a and 4.0 g (0.015 mol) (2-Dodecen-1-yl)succinic anhydride was heated at 80° C. for 10 hours under nitrogen gas. Afterwards 22 g Dehydol® 04 and 158 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 2 (According to the Invention)

[0187] A mixture of 41.0 g (0.005 mol) polymer P1-a and 4.0 g (0.015 mol) (2-Dodecen-1-yl)-succinic anhydride was heated at 180° C. for 10 hours under nitrogen gas. Afterwards 22 g Dehydol® 04 and 158 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 3 (According to the Invention)

[0188] A mixture of 41.0 g (0.005 mol) polymer P1-a and 6.7 g (0.025 mol) (2-Dodecen-1-yl)-succinic anhydride was heated at 180° C. for 10 hours under nitrogen gas. Afterwards 23 g Dehydol® 04 and 165 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 4 (According to the Invention)

[0189] A mixture of 41.0 g (0.005 mol) polymer P1-a, 3.4 g (0.015 mol) of (2-Nonen-1-yl)-succinic anhydride was heated at 180° C. for 10 hours under nitrogen gas. Afterwards 22 g Dehydol® 04 and 154 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 5 (Comparative)

[0190] A mixture of 40.0 g (0.005 mol) Pluriol® E8000 and 4.0 g (0.015 mol) (2-Dodecen-1-yl)succinic anhydride was heated at 80° C. for 10 hours under nitrogen gas. Afterwards 22 g Dehydol® 04 and 154 g water were added. The resulting product was a viscous water solution including the obtained modified polyethylene glycol in a concentration of 20% by weight.

Example 6 (Comparative)

[0191] First, 44.0 g polymer P1-a was heated at 80° C. and then 22 g Dehydol® 04 and 154 g water were added. The resulting product was a viscous water solution with a concentration of 20% by weight.

Example 7 (According to the Invention)

[0192] A mixture of 41.0 g (0.005 mol) polymer P1-a, 5.3 g (0.015 mol) Octadecenylsuccinic anhydride was heated at 180° C. for 10 hours under nitrogen gas. Afterwards 23 g Dehydol® 04 and 161 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Example 8 (According to the Invention)

[0193] A mixture of 20.0 g (0.005 mol) Pluriol® E4000, 80 g Pluriol® E8000 (0.01 mol), 6.1 g (0.037 mol) isatoic anhydride (IA), and 0.3 g 1,4-diazabicyclol[2.2.2]octan was heated at 80 to 140° C. until no more carbon dioxide was evolved. Then, the material was cooled down to 80° C. and 20 g (2-Dodecen-1-yl)-succinic anhydride was added. The mixture was kept at 180° C. for 10 hours under nitrogen gas and afterwards 53 g Dehydol® 04 and 424 g water were added. The resulting product was a viscous water solution including the obtained polymer material in a concentration of 20% by weight.

Performance Testing

[0194] In order to test the thickening effect of the thickeners obtained in examples P1-a and 1 to 8, water-borne coating compositions were prepared by mixing 4.0 g of each of the above thickeners, 26 g water, and 70 g Acronal® Plus 4670. The mixtures were homogenized with the laboratory dissolver Dispermat® (VMA Getzmann GmbH) at 1500 rpm for 10 minutes and, after a standing time of at least 20 hours, slightly stirred with a wooden spatula. Afterwards the viscosities of the obtained homogenates were measured at shear rates in the range of 0.1 to 10000 sec.sup.−1 using the cone-plate viscometer Haake RC20 CPS P with cone C50-1. The results are summarized in Table 2.

TABLE-US-00002 TABLE 2 Rheological behavior of coating compositions Viscosity (mPas) at shear rates [sec.sup.−1] of Example 0.1 0.5 1 10 100 1000 10000 P1-a (comparative) 75 40 25 15 15 10 10 1 420 420 420 400 380 230 80 2 550 560 550 530 490 300 120 3 520 520 500 450 410 250 90 4 80 120 150 150 120 90 60 5 (comparative) 60 100 110 100 90 70 50 6 (comparative) 75 40 25 15 15 10 10 7 1500 1450 1200 1000 750 90 40 8 850 840 840 820 780 400 70

[0195] It can be seen from Table 2 that all six thickeners of examples 1 to 4, 7, and 8 that are in accordance to the present invention impart substantially higher viscosities to water-borne coating compositions than the comparative thickeners of examples P1-a, 5, and 6 which differs from the thickeners of the examples according to the invention in that it lacks anthranilate groups. As can also be seen from Table 2 this beneficial effect is present in all cases over the broad range of shear rates measured.