Markers for aqueous compositions

Abstract

The present invention provides aqueous polymer compositions containing one or more, or, preferably, two or more markers selected from a C.sub.1-C.sub.12 alkyl phenyl ether having a formula Ph(R.sup.2).sub.m(OR.sup.1).sub.n, wherein Ph is an aromatic ring containing group having from six to nine carbon atoms, R.sup.1 is a C.sub.1-C.sub.12 alkyl group, R.sup.2 is a C.sub.1-C.sub.12 alkyl group, m is an integer of from 0 to 5, n is an integer of from 1 to 3, and (m+n) is an integer of from 1 to 6. The markers are readily detectable, such as by mass spectroscopy, upon solvent extraction and separation from the aqueous polymer compositions, or from dried or cured coatings, film or layers thereof.

Claims

1. An aqueous composition comprising (i) one or more aqueous polymers, and (ii) from 100 ppb to 10 ppm of one or more compounds selected from a C1-C12 alkyl phenyl ether having a formula Ph(R.sup.2).sub.m(OR.sup.1).sub.n, wherein Ph is an aromatic ring containing group having from six to nine carbon atoms, R.sup.1 is a C.sub.1-C.sub.12 alkyl group, R.sup.2 is a C.sub.1-C.sub.12 alkyl group, m is an integer of from 0 to 5, n is an integer of from 1 to 3, and (m+n) is an integer of from 1 to 6.

2. The composition as claimed in claim 1, wherein the (i) one or more aqueous polymers is chosen from vinyl or acrylic emulsion polymers or polyurethane dispersions.

3. The composition as claimed in claim 1, wherein the amount of the (ii) one or more compounds selected from a C.sub.1-C.sub.12 alkyl phenyl ether having a formula Ph(R.sup.2).sub.m(OR.sup.1).sub.n ranges from 100 ppb to 2 ppm.

4. The composition as claimed in claim 1, wherein the composition comprises (ii) two compounds selected from a C.sub.1-C.sub.12 alkyl phenyl ether having a formula Ph(R.sup.2).sub.m(OR.sup.1).sub.n in a ratio in a range of 0.01:1 to 1:0.01.

5. The composition as claimed in claim 1, wherein at least one of the (ii) one or more compounds selected from a C.sub.1-C.sub.12 alkyl phenyl ether has a formula Ph(R.sup.2).sub.m(OR.sup.1).sub.n, wherein R.sup.1 is a C.sub.4 to C.sub.8 alkyl group.

6. The composition as claimed in claim 1, wherein at least one of the (ii) one or more compounds selected from a C.sub.1-C.sub.12 alkyl phenyl ether has a formula Ph(R.sup.2).sub.m(OR.sup.1).sub.n, wherein Ph is a phenyl group.

7. The composition as claimed in claim 1, wherein at least one of the (ii) one or more compounds selected from a C.sub.1-C.sub.12 alkyl phenyl ether has a formula Ph(R.sup.2).sub.m(OR.sup.1).sub.n, wherein (m+n) is an integer of from 1 to 3.

8. The composition as claimed in claim 1, having a pH of from 3 to 12.

9. The composition as claimed in claim 1, wherein the (i) one or more aqueous polymer is a vinyl or acrylic emulsion polymer which is an anionically stabilized emulsion polymer and, wherein the composition further comprises one or more polyamine and one or more volatile base.

10. The composition of claim 1 further comprising one or more of a pigment, an extender, and a filler.

11. The composition of claim 10 comprising a pigment which is a white or opacifier pigment.

12. The composition of claim 11 where the pigment is titanium dioxide.

13. The composition of claim 11 comprising a filler and/or extender selected from calcium carbonate, calcium oxide, silica, silicates and combinations thereof.

14. The composition of claim 10 which is a traffic paint.

15. A method of detecting a marker of (ii) one or more C.sub.1-C.sub.12 alkyl phenyl ethers in an aqueous composition of (i) one or more aqueous polymers, or a dried or cured film, coating or layer formed therefrom, the method comprising: extracting the one or more C.sub.1-C.sub.12 alkyl phenyl ethers from the aqueous composition or the dried or cured film, coating or layer formed therefrom using a solvent to form a marker extract; separating from the marker extract the (ii) one or more C.sub.1-C.sub.12 alkyl phenyl ethers by chromatographic separation; and, detecting the (ii) one or more C.sub.1-C.sub.12 alkyl phenyl ethers in the marker extract.

Description

EXAMPLES

(1) Preparation of an Aqueous Polymer Composition in a Butyl Phenyl ether (BPE) Marked Formulation:

(2) BPE was dissolved in Texanol isobutyrate ether high boiling point plasticizer (Eastman Chemical, Kingsport, Tenn.) at a 1000 ppm concentration. The marker solution was added to an acrylic emulsion polymer binder (anionically stabilized BA/MMA emulsion copolymer, 50.5 wt. % solids) to yield a marker concentration of 1 ppm, based on the total aqueous composition. The binder was split and half was placed in an oven for 10 days at 60 C. to heat age the binder (Example 2) and the other half was stored at room temperature (Example 1).

(3) Extraction Conditions:

(4) Both heat aged and control formulations were extracted using xylene. 1 mL of marked formulation was mixed with 10 mL of xylene in a 20-mL vial. The solution was shaken for 30 min. 1.5 mL of the solvent phase was then transferred to a centrifuge vial and centrifuged at 35000 rpm for 20 min. The supernatant was transferred to an autosampler vial for GC/MS analysis.

(5) GC/MS Conditions:

(6) A heart-cutting two-dimension GC system with mass selective detector was used in examples, as described in Table 1, below.

(7) TABLE-US-00001 TABLE 1 GC/MS Conditions Instrument: Agilent.sup.1 7890B GC with 5977A MSD with Extractor Electron Impact ionization source Column: First dimension: Agilent DB-17HT, 15 m 0.25 mm, 0.15 m film (P/N 122-1811) Second dimension: Agilent VF-WAXms, 30 m 0.25 mm, 1.0 m film (P/N CP9206) Restrictor: Agilent 0.64 m 0.1 mm fused silica (P/N 160-2635-5) or equivalent Injector: Injection volume: 1 L Solvent wash: 6 times pre-injection and 6 times post-injection with toluene Sample washes: 3 times Sample pump: 3 times Inlet: Liner: Agilent Ultra-inert Split liner (P/N 5190-2295) or equivalent Temperature: 250 C. Split ratio: 100:1 Carrier gas: helium Flow First dimension: 1.0 mL/min for 5.0 min, ramp to 1.0 mL/min at a rate of Programming: 99 mL/min, hold at 1.0 mL/min for 10.1 min (back flush step) Second dimension: 2.5 mL/min constant flow Oven 100 C. (0.5 min), 10 C./min to 180 C., then 30 C./min to 260 C. (4 min). Temperature Total run time: 15.167 min Programming: FID Temperature: 260 C. Parameters: Air flow: 400 mL/min H.sub.2 flow: 40 mL/min Makeup (N.sub.2) flow: 25 mL/min Heart-cutting Valve on at 4.43 min event: Valve off at 4.56 min MSD Transfer line temperature: 260 C. Parameters: El source temperature: 250 C. Quad temperature: 200 C. Gain factor: 1.0 SIM ion: m/z 94 (100 ms dwell time) and 150 (100 ms dwell time). Plot m/z 94 only. .sup.1Agilent Technologies, Santa Clara, CA.

(8) Three extraction solvents including methanol, xylene and hexane were explored at different solvent-to-sample ratios using as a substrate the composition of Example 1. With xylene extraction, nearly 100% of marked BPE was detected, as shown in Table 2, below. Other solvents also yielded acceptable results, which shows the flexibility of the marker molecule and detection method. As shown in Table 3, below, no difference was detected in the room temperature and heat aged samples, demonstrating good stability of the marker and good reproducibility of the method.

(9) TABLE-US-00002 TABLE 2 Measured BPE concentration from Aqueous Polymer Compositions of Example 1 marked with 1 ppm BPE using various extraction solvents Extraction Solvent to emulsion solvent ratio Extraction efficiency at 1 ppm MeOH 10 123% MeOH 5 113% Xylene 10 104% Xylene 5 99% Hexane 10 138%

(10) TABLE-US-00003 TABLE 3 Measured BPE concentration from room temperature and heat aged binder formulation marked with 1 ppm BPE using xylene extraction Markers in the aqueous polymer compositions of Example 1 and Example 2 (heat aged) were extracted and detected as shown in Table 3, below. Storage Added BPE Measured BPE condition Conc. (ppm) Conc. (ppm) Recovery Room temp 1 1.040 104.0% Heat aged 1 1.026 102.6%

(11) As shown in Table 3, above, the marker was readily detected in both the Example 1 aqueous polymer composition and in the heat aged aqueous polymer composition of Example 2. Accordingly, the marker C.sub.1-C.sub.12 alkyl phenyl ethers of the present invention provide desirable stability for use in aqueous polymer compositions so they can be tested after extended periods of time.