Glycidyl ether alkoxylate block copolymers

Abstract

The present invention relates to a compound having the following structure I: ##STR00001##
where Ar.sup.1, Ar.sup.2; R.sup.1, m, and n are defined herein. The compound of the present invention is useful as an open time additive in waterborne coatings compositions, particularly waterborne paint compositions.

Claims

1. A compound having the following structure I: ##STR00005## where Ar.sup.1 is unsubstituted phenyl or naphthyl, or phenyl or naphthyl substituted with from 1 to 3 C.sub.1-C.sub.6 alkyl groups; and Ar.sup.2 is phenyl, phenyl-OCH.sub.2CH.sub.2, naphthyl, naphthyl-CH.sub.2, or naphthyl-OCH.sub.2CH.sub.2, wherein the phenyl or naphthyl portion of Ar.sup.2 are unsubstituted or substituted with from 1 to 3 C.sub.1-C.sub.6 alkyl groups; each R.sup.1 is independently H or C.sub.1-C.sub.6-alkyl; m is from 1 to 20; and n is from 2 to 100.

2. The compound of claim 1 wherein Ar.sup.1 is phenyl or o-methylphenyl; Ar.sup.2 is phenyl, phenyl-OCH.sub.2CH.sub.2, or o-methylphenyl; and each R.sup.1 is independently H or CH.sub.3.

3. The compound of claim 2 which has a number average molecular weight in the range of from 300 to 20,000 g/mol.

4. The compound of claim 3 which has a number average molecular weight in the range of from 500 to 10,000 g/mol is selected from the group consisting of: ##STR00006##

5. A coating composition comprising the compound of claim 1, a binder, a rheology modifier and at least one material selected from the group consisting of dispersants, pigments, defoamers, surfactants, solvents, extenders, coalescents, biocides, opaque polymers, and colorants.

6. A compound having the following structure: ##STR00007## where Ar.sup.1 is phenyl or phenyl substituted with from 1 to 3 C.sub.1-C.sub.6 alkyl groups; and with Ar.sup.2 is phenyl-OCH.sub.2CH.sub.2 and where the phenyl portion of Ar.sup.2 is unsubstituted or substituted with from 1 to 3 C.sub.1-C.sub.6 alkyl groups, where m is from 1 to 20; and n is from 1 to 100.

7. The compound of claim 6 which is represented by the following formula Ib: ##STR00008##

8. The compound of claim 6 which is represented by the following formula Ib: ##STR00009## wherein the compound has a number average molecular weight in the range of from 500 to 10,000 g/mol.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The present invention is a compound having the following structure I:

(2) ##STR00003##
where Ar.sup.1 is unsubstituted phenyl or naphthyl, or phenyl or naphthyl substituted with from 1 to 3 C.sub.1-C.sub.6 alkyl groups; and Ar.sup.2 is phenyl, phenyl-OCH.sub.2CH.sub.2, benzyl, naphthyl, naphthyl-CH.sub.2, or naphthyl-OCH.sub.2CH.sub.2, wherein the phenyl or naphthyl portion of Ar.sup.2 are unsubstituted or substituted with from 1 to 3 C.sub.1-C.sub.6 alkyl groups; each R.sup.1 is independently H or C.sub.1-C.sub.6-alkyl; m is from 1 to 20; and n is from 1 to 100.

(3) Examples of subclasses of compounds of the present invention are represented by the following structures:

(4) ##STR00004##

(5) Preferably, m is in the range of from 1, more preferably from 2, to 10, more preferably to 6; and n is in the range from 5 to 40. Because each R.sup.1 is independently H or C.sub.1-C.sub.6-alkyl, the alkylene oxide groups ((OCH.sub.2CHR.sup.1).sub.n) can be random or block copolymers. Preferably, each R.sup.1 is independently H, methyl, or ethyl; more preferably H or methyl; most preferably each R.sup.1 is H.

(6) The compound of the present invention can be conveniently prepared by first contacting an aryl alcohol, with an aryl glycidyl ether in the presence of a catalytic amount of a suitable base such as KOH, under conditions sufficient to prepare an aryl glycidyl ether oligomer intermediate, then contacting the intermediate with an alkylene oxide such as ethylene oxide under conditions sufficient to form the desired compound I. Preferably, the aryl alcohol is phenol, a cresol, or phenoxyethanol, and the aryl glycidyl ether is phenyl glycidyl ether or cresyl glycidyl ether.

(7) The number average molecular weight (M.sub.n) of the compound, as determined by matrix assisted laser desorption ion mass spectrometry (MALDI-MS), is preferably in the range of from 300, more preferably from 500 g/mol, to preferably 20,000, more preferably to 15,000, more preferably to 10,000, and most preferably to 5,000 g/mol.

(8) The compound of the present invention can be used as an open time additive for a coatings composition, which includes binder, rheology modifier, and any or all of the following materials: dispersants, pigments, defoamers, surfactants, solvents, extenders, coalescents, biocides, opaque polymers, and colorants.

EXAMPLES

Example 1Preparation of Phenyl Glycidyl Ether Ethoxylate Block Copolymer Ia

(9) A 2-L round-bottom flask equipped with a temperature controlled heating mantle, an addition funnel, a reflux/distillation head, and overhead stirrer was charged with phenol (102.44 g, 1.09 moles), toluene (337.83 g), and KOH flakes (8.12 g, 90% pure). The solution was heated under N.sub.2 to distil off a portion of the toluene (110 g). Phenyl glycidyl ether (490.78 g, 3.27 moles) was then added to the resulting concentrated solution at 110 C. to 120 C. over 4 h. The mixture was stirred for an additional 2 h and the flask was cooled. A portion of the resultant solution (302.3 g, 227.9 g of alkoxylate intermediate) was charged into a conical bottom 2-L Parr reactor. The reactor was sealed, pressure checked, purged with N.sub.2, then heated to 120 C. Ethylene oxide (363.2 g) was added at a rate of 1-2 g/min. The mixture was held at 120 C. for 1 h, then cooled to 60 C. before unloading the product (652.7 g). The product was treated with MagSil (34.8 g) and water (8.9 g), and filtered; solvent was removed in vacuo to produce Ia (n=3, m=20; 523.3 g).

Example 2Preparation of Phenyl Glycidyl Ether Ethoxylate Block Copolymer Ib

(10) A 250-mL round-bottom flask equipped with a temperature controlled heating mantle, an addition funnel, a reflux/distillation head, and overhead stirrer was charged with phenoxyethanol (62.26 g 0.45 mole) and KOH flakes (1.01 g, 90% pure). The solution was heated to 120 C. under N.sub.2 for 2 h. Phenyl glycidyl ether (203.8 g, 1.36 moles) was added to resulting solution at 120 C. to 125 C. over 2.5 h. The mixture was stirred overnight at 120 C., then cooled. A portion of this intermediate (240.32 g) was charged into a conical bottom 2-L Parr reactor. The reactor was sealed, pressure checked, purged with N.sub.2, then heated to 120 C. Ethylene oxide (357.6 g) was added at a rate of 1 to 2 g/min. The mixture was held at 120 C. overnight, then cooled to 80 C. before unloading the product (598.4 g). The reaction product was mixed with acetic acid (0.28 g) to produce Ib (m=3, n=20).

Example 3Preparation of Phenyl Glycidyl Ether Ethoxylate Block Copolymer Ic

(11) A 250-mL round-bottom flask equipped with a temperature controlled heating mantle, an addition funnel, a reflux/distillation head, and overhead stirrer was charged with m-cresol (48.5 g, 0.45 mole) and KOH flakes (1.34 g, 90% active). The solution was heated to 120 C. under N.sub.2 for 2.5 h. Phenyl glycidyl ether (203.17 g, 1.35 moles) was added to the solution at 120 C. to 130 C. over 3 h. The mixture was stirred overnight at 120 C., then cooled. A portion of this intermediate (236.77 g) was charged into a conical bottom 2-L Parr reactor. The reactor was sealed, pressure checked, purged with N.sub.2, then heated to 120 C. Ethylene oxide (368.9 g) was added at a rate of 1-2 g/min. The mixture was held at 120 C. overnight, then cooled to 80 C. before unloading the product (591.38 g). The reaction product was mixed with acetic acid (0.44 g) to produce Ic (m=3, n=20).

Example 4Preparation of Phenyl Glycidyl Ether Ethoxylate Block Copolymer Id

(12) A 250-mL round-bottom flask equipped with a temperature controlled heating mantle, an addition funnel, a reflux/distillation head, and overhead stirrer was charged with benzyl alcohol (44.60 g, 0.41 mole) and KOH flakes (2.35 g, 90% pure). The solution was heated to 120 C. under N.sub.2 for 1 h. Phenyl glycidyl ether (188.64 g, 1.26 moles) was added to the solution at 120 C. to 130 C. over 2 h. The mixture was stirred overnight at 120 C., then cooled. A portion of this intermediate (209.06 g) was charged into a conical bottom 2-L Parr reactor. The reactor was sealed, pressure checked, purged with N.sub.2, then heated to 120 C. Ethylene oxide (322.7 g) was added at a rate of 2 to 3 g/min. The mixture was held at 120 C. overnight, then cooled to 80 C. before unloading the product (519.56 g). The reaction product was mixed with acetic acid (0.73 g) to produce Id (m=3, n=20).

Example 5Preparation of Phenyl Glycidyl Ether Ethoxylate Block Copolymer Ia

(13) A 2-L round-bottom flask equipped with a temperature controlled heating mantle, an addition funnel, a reflux/distillation head, and overhead stirrer was charged with phenol (62.94 g, 0.67 mole), toluene (341.34 g), and KOH flakes (4.75 g, 90% pure). The solution was heated under N.sub.2 to distil off a portion of the toluene (82.81 g). Phenyl glycidyl ether (502.18 g, 3.34 moles) was then added to the resulting concentrated solution at 110 C. to 120 C. over 4 h, and the mixture was stirred for an addition 2 h. A portion of the resultant solution (374.9 g) was charged into a conical bottom 2-L Parr reactor. The reactor was sealed, pressure checked, purged with N.sub.2, then heated to 120 C. Ethylene oxide (289.3 g) was added at a rate of 1 to 2 g/min. The mixture was held at 120 C. for 1 h, then cooled to 60 C. before unloading the product (650.6 g). The reaction product was treated with acetic acid (1.07 g), and solvent was removed in vacuo to produce Ia (m=5, n=20; 541.6 g).

(14) The compounds prepared in the above examples were dissolved in water at 40 weight % solids prior to testing in paint. Paint formulations with and without the exemplified open time additives were prepared in accordance with the recipe shown in Table 1. The concentration of open time additives in the formulation was 1 weight percent, based on the weight of the formulation.

(15) TABLE-US-00001 TABLE 1 Paint Formulation with Open Time Additive Material Name Pounds Gallons RHOPLEX HG-706 Binder 584.1 66.0 BYK-024 Defoamer 1.0 0.1 Propylene Glycol 4.3 0.5 TRITON X-100 Surfactant 4.4 0.5 Water 16.7 2.0 KATHON LX 1.5% Biocide 1.5 0.2 TAMOL 2002 Dispersant 2.0 0.2 Ammonia (28%) 1.0 0.1 Ti-Pure R-746 TiO.sub.2 285.0 14.7 Water 20.0 2.4 Texanol Coalescent 7.9 1.0 ACRYSOL RM-2020E Rheology Modifier 20.0 2.3 ACRYSOL RM-725 Rheology Modifier 3.0 0.4 BYK-024 Defoamer 2.0 0.2 Open Time Additive (40% aq.) 25.8 2.84 Water 79 9.5 Totals 1030 100

(16) RHOPLEX, TRITON, KATHON, TAMOL, and ACRYSOL are all Trademarks of The Dow Chemical Company or its Affiliates.

(17) M.sub.n Measurement of Additive by MALDI-MS

(18) MALDI mass spectra were acquired on a Bruker Daltonics ultraflex MALDI-TOF mass spectrometer equipped with a nitrogen laser (=337 nm). In the MALDI experiment, 20 mg of 2,5-dihydroxybenzoic acid was dissolved in 1 mL of THF as the MALDI matrix. The sample solution in MeOH was premixed with the matrix solution at a ratio of 1:20. To facilitate ionization of the species in the sample mixture, NaI was added into the sample/matrix mixture. A 0.3 l sample of the mixture was then placed on the sample plate and was air dried for MALDI-MS analysis. Reflectron mode was selected in the analysis to enhance the resolution of the mass spectra.

(19) Table 2 shows the impact on open time when using the additives of the present invention.

(20) TABLE-US-00002 TABLE 2 Open Time Data M.sub.n MALDI- Open Time Ex. No. Additive MS (g/mole) (min) Example 1 Phenol (PGE).sub.3(EO).sub.20 1470 12.5 Example 2 Phenoxyethanol (PGE).sub.3(EO).sub.20 1514 12.5 Example 3 m-cresol (PGE).sub.3(EO).sub.20 1428 13.0 Example 4 Benzyl Alcohol (PGE).sub.3(EO).sub.20 1478 12.5 Example 5 Phenol (PGE).sub.5(EO).sub.20 1840 11.0 Comp. 1 none NA 6.0