COMMERCIALLY USEFUL RESINOUS COMPOUNDS AND COMPOSITIONS WITH OPTIMIZED SUSTAINABLE CONTENTS

Abstract

A resinous polymer compound used as a durable surface coating that maximizes content of epoxidized soybean oil (“ESO”) in lieu of bisphenol-A epoxy and hydrogenated bisphenol-A epoxy at various proportions to produce a less brittle, more elastic (flexible) film that, at various weight-percentages of substitution, presents a rapid enough reaction rate for efficient commercial production and yields a colorless and transparent film while lessening the amount of synthetic, petroleum-derived ingredients.

Claims

1. An ESO-based resinous composition that may be used as a durable surface coating, including paint, polish, lacquer, enamel, said resinous composition comprising: a product of an arylsulfonamide and at least one epoxy compound comprising at least one diepoxy compound and optionally at least one monoepoxy compound; wherein between 1 to 100 weight-percent of bisphenol-A epoxy is substituted with epoxidized soybean oil.

2. The ESO-based resinous composition of claim 1 wherein a substitution of no more than 50 weight-percent is used in place of bisphenol-A epoxy resin to reduce the glass transition temperature by at least 10° C. thereby making the final coating less brittle and more elastic and therefore more flexible.

3. The ESO-based resinous composition of claim 1 wherein a substitution of epoxidized soybean oil in place of bisphenol-A epoxy optimizes the rate of reaction.

4. The ESO-based resinous composition of claim 1 wherein the weight-percent of epoxidized soybean oil substituted for bisphenol-A epoxy resin minimizes haze and/or discoloration of the final product.

5. An ESO-based resinous composition comprising 25 weight-percent epoxidized soybean oil, said coating further comprising: approximately 1 part bisphenol A/epichlorohydrin derived liquid epoxy resin; approximately 0.6 to 0.9 parts n-butyl acetate; approximately 1 to 1.1 parts tosylamide; approximately 0.0007 parts triethylamine; approximately 0.3 to 0.4 epoxidized soybean oil

Description

BRIEF DESCRIPTION OF THE DRAWINGS

FIGURES

[0017] FIG. 1 is a diagrammatic representation of an example embodiment of a diepoxide resin produced when ESO is reacted with para-TSA.

[0018] FIGS. 2A and 2B show Proton Nuclear Magnetic Resonance (“.sup.1HNMR”) spectroscopy data for samples of TSA-HBPA epoxy polymers and TSA-BPA epoxy polymers designated Polytex NX-55 and E-75, respectively.

[0019] FIGS. 2C and 2D show .sup.1HNMR spectroscopy data for derivative products where ESO was successfully incorporated into the material designated NX-55V1 and E-75V1.

[0020] FIGS. 3A and 3B are Fourier Transform Infrared (“FTIR”) spectroscopy data showing like characteristics for ESO-substituted resins, NX-55V1 and E-75V1.

[0021] FIG. 3C is FTIR spectroscopy data for ESO versus an epoxy resin.

[0022] FIG. 3D is FTIR spectroscopy data for TSA.

[0023] FIG. 4A shows Glass Transition Temperature (“Tg”) data for nitrocellulose films made with ESO-free polymers and also ESO-substituted material.

[0024] FIG. 4B shows Differential Scanning calorimetry (“DSC”) and Dynamic Mechanical Analysis (“DMA”) data for nitrocellulose films made with ESO-free polymers and also ESO-substituted material.

[0025] FIG. 5A shows Thermogravimetric Analysis (“TGA”) for NX-55V1 and E-75V1 relative to epoxy resins NX-55 and E-75.

[0026] FIG. 5B shows Size-Exclusion Chromatography (“SEC”) overlay between epoxy resin NX-55 and NX-55V1.

[0027] FIG. 5C shows SEC overlay between epoxy resin E-75 and E-75V1.

DETAILED DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 illustrates an example embodiment of a diepoxide resin formed from ESO reacted with para-TSA (similar results from reaction with ortho-TSA, or a mixture of para and ortho isomers, are suggested). The amide group of the TSA attaches to the oxirane groups of the ESO enabling the nitrogen to join to the aliphatic chain with the formation of hydroxyl group on the adjacent carbon. The result is an epoxidized resin with bio-based backbone. The diagrammatic form illustrated is for example purposes only. Groups identified by R could include hydrogen or other diepoxide resin.

[0029] Two control epoxy resins were analyzed relative to two derivative resins wherein BPA epoxy was substituted with varying proportions of ESO. These formulations are listed in Tables 1 through 3 below. Polytex NX-55 and Polytex E-75, products manufactured by Estron Chemical (Calvert City, Ky.) represent the control polymers. The two derivative products are styled NX-55V1 and E-75V1.

TABLE-US-00001 TABLE 1 Polytex NX-55 variant Polytex E-75 variant NX-55V1 (25 wt % E-75V1 (25 wt % ESO-substituted NX-55 variant) ESO-substituted E-75 variant)

TABLE-US-00002 TABLE 2 Polytex NX-55 NX-55V1 Polytex NX-55 Control (ESO-sub) % NV as-is 74.8% 75.0% % NV, lab-stripped solid 99.1% 98.2% Softening point, 69° C. 52° C. lab-stripped solid Mn, Mw, Mz, PDI, 740, 970, 1200, 820, 1000, 1200, online dn/dc.sup.1 1.3, 0.123 1.2, 0.114 TGA (nitrogen to 600° C. % wt remaining at % wt remaining at at 20° C./min).sup.2 300° C.: 91.6% 300° C.: 87.8% (evaporated for 2 days % wt remaining at % wt remaining at in 80° C. vacuum oven) 400° C.: 10.2% 400° C.: 16.2% Tg by DSC (evaporated 13° C. −6° C. for 2 days in 80° C. vacuum oven) Note.sup.1 Molecular weight data should be considered relative only. MWs reported to 2 significant figures. Peak at approx. 10 min (believed to be TSA) not included in calculations. Note.sup.2 Shape/morphology of low-Tg resins is difficult to control when preparing TGA samples and may affect results.

TABLE-US-00003 TABLE 3 Polytex E-75 E-75V1 Polytex E-75 Control ESO-sub) % NV as-is 73.8% 73.8% % NV, lab-stripped solid 97.7% 98.5% Softening point, 75 C. 62 C. lab-stripped solid Mn, Mw, Mz, PDI, 920, 1200, 1600, 800, 1100, 1400, online dn/dc.sup.1 1.3, 0.158 1.3, 0.146 TGA (nitrogen to 600° C. % wt remaining at % wt remaining at at 20° C./min).sup.2 300° C.: 90.9% 300° C.: 93.0% (evaporated for 2 days % wt remaining at % wt remaining at in 80° C. vacuum oven) 400° C.: 75.2% 400° C.: 69.7% Tg by DSC (evaporated 19° C. 9° C. for 2 days in 80° C. vacuum oven) Note.sup.1 Molecular weight data should be considered relative only. MWs reported to 2 significant figures. Peak at approx. 10 min (believed to be TSA) not included in calculations. Note.sup.2 Shape/morphology of low-Tg resins is difficult to control when preparing TGA samples and may affect results.

[0030] FIGS. 2A and 2B show Proton Nuclear Magnetic Resonance (“.sup.1HNMR”) spectroscopy data for two samples of a TSA reacted with BPA epoxy polymer, styled NX-55 and E-75 respectively. FIGS. 2C and 2D show .sup.1HNMR spectroscopy data for derivative ESO-substituted materials, NX-55V1 and E-75V1. The .sup.1HNMR data was collected on 21 May 2021 by K. Miller at Murray State University.

[0031] As shown in the corresponding Figures, the spectra indicate that ESO was successfully incorporated into the material. Three signals related to the ESO are discernible. A triplet (labeled “B”) was identified at 2.3 ppm, which is assigned to the —CH.sub.2— adjacent to the carbonyl. Two smaller multiplets (labeled as “A”) were observed for the —CH.sub.2— groups in the glycerol backbone of the ESO around 4.1 to 4.3 ppm. Finally, a signal at approximately 5.0 ppm is sometimes observable for the —CH— group of the glycerol backbone (labeled “C”). It is further suspected that some epoxides are present between 2.9 to 3.2 ppm. See Macromol. Rapid Comm. 2014, 35, 1068-1074 for sample .sup.1HNMR spectrum of ESO.

[0032] FIGS. 3A, 3B, 3C, show Fourier Transform Infrared (“FTIR”) data in relation to FTIR data of TSA, shown in FIG. 3D. Data was collected 7 Jun. 2021 at Estron Chemical by K. Whitson and A. Tumuluri. TSA shows model spectrum illustrated in FIG. 3D. Peaks corresponding to wavenumbers 3356, 3260 cm.sup.−1 to significant peaks at 1369, 1153 and 533 cm.sup.−1 demark the curve.

[0033] FIG. 3A shows the NX-55V1 ESO-substituted polymer spectrum relative to the NX-55 polymer (control). Differences relative the NX-55 spectrum include increased absorbance peaks for NX-55V1 at wavenumbers 3279 cm.sup.−1 and 2932 and 2860 cm.sup.−1 and decreased absorbance at 1092 cm.sup.−1. The increased absorbance at 3279 cm.sup.−1 may suggest a difference in the overall TSA content and the increased absorbance at 2932 cm.sup.−1 suggests stronger —CH— and —CH.sub.2— representations in the NX-55V1. The decreased absorbance at 1092 cm.sup.−1 may result from differences via ether linkage in the TSA versus ESO-substituted polymer.

[0034] FIG. 3B shows the E-75V1 ESO-substituted polymer spectrum relative to the E-75 polymer (control). Significant differences observed include decreased absorbance around wavenumber 3280 cm.sup.−1, suggesting a difference in the TSA content. Decreased absorbance at 1509 cm.sup.−1 may also suggest C—C stretching due to para-substitution in the aromatic ring.

[0035] FIG. 3C shows FTIR data for ESO versus an epoxy resin and illustrates ESO increased absorbance at the wavenumbers 2924 and 2854 cm.sup.−1. ESO shows dramatic absorbance at 1741 cm.sup.−1 relative to epoxy resin, and a shifted spectrum at lower wavenumbers, approximately 1240 to 1730 cm.sup.−1. FIG. 3D shows FTIR data for TSA.

[0036] FIG. 4A shows Glass Transition Temperature (“Tg”) for nitrocellulose polymer and film containing 10 wt % Polytex NX-55 as-made compared with 10 wt % NX-55V1, a composition of NX-55 with 25% ESO substitution, and 10 wt % Polytex E-75 as-made compared with E-75V1, a composition of E-75 having 25% ESO substitution. Reduced Glass Transition Temperatures are measurable in the case of ESO substituted materials.

[0037] FIG. 4B shows Differential Scanning calorimetry (“DSC”) data for nitrocellulose film to represent a nail lacquer application, nitrocellulose containing 10 wt % Polytex E-75 as-made, and 10 wt % of an E-75 polymer with 25 wt % substituted ESO for BPA epoxy. Nitrocellulose (RS ½ sec; 70% solids in IPA and n-butyl acetate) supplied by Cosmetics Coatings Corporation (Carlstadt, N.J.). The DSC data for the polymers was collected on 3 Jun. 2021 by K. Whitson at Estron Chemical. The DSC data for the polymer films was collected on 19 Jul. 2021 by K. Miller at Murray State University. A result appears to be that the softening points and glass transition temperature (“Tg”) values for the ESO-substituted materials are less than that of the nitrocellulose containing Polytex resins NX-55 and E-75 as-made.

[0038] FIG. 4B also shows Dynamic Mechanical Analysis (“DMA”) data for nitrocellulose films made with 10 wt % Polytex NX-55 and E-75 as-made relative to derivatives where HBPA epoxy and BPA epoxy were substituted with ESO respectively. In the NX-55 graph, ESO substitutes included an NX-55 polymer with 25 wt % ESO substituted and an NX-55 polymer with a 25 wt % ESO plus vacuum substituted. In the E-75 graph, the E-75 epoxy resin included a 25 wt % ESO substitute. In all data, the nitrocellulose films made with ESO-substituted material showed decreased stress relative the epoxy resin absent ESO, although strain (elasticity) was comparable.

[0039] FIG. 5A shows Thermogravimetric Analysis (“TGA”) data for epoxy resins NX-55 and E-75 relative to ESO-substituted epoxies, NX-55V1 and E-75V1. Data was collected on 7 Jun. 2021 at Estron Chemical by K. Whitson and A. Tumuluri. FIG. 5B shows Size Exclusion Chromatography (“SEC”) overlay of epoxy resin NX-55 relative to ESO-substituted NX-55V1. FIG. 5C shows SEC overlay of epoxy resin E-75 relative to ESO-substituted E-75V1.

[0040] From the above data, it appears the ESO-substituted resin material, specifically TSA-BPA epoxy and HBPA epoxy, enhances plastic behavior, offering a potential advantage for softer, more flexible, and less brittle polymer coatings, useful for example, when used in a fingernail polish or lacquer formulation.