VINYL HYDRO XYL ETHER RESINS

CROS S-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of priority to U.S. Provisional Patent

Application Serial No. 62/303,724, filed March 4, 2016, the disclosure of which is incorp orated herein in its entirety by reference.

BACKGROUND

[0002] Vinyl ester resins (VERs) are high performance unsaturated resins with exceptional mechanical strength and corrosion resistance. In addition to their superior performance, these resins display lower viscosities than conventional epoxy resins resulting in significantly improved process ability. Due to their superior properties and excellent processability , VERs find use, either in pure form or as a matrix in fiber reinforced composites, in diverse industries, such as, ship building, automotive part construction, infrastructure polymer concrete reinforcements, corrosion resistance coatings (on chemical storage tanks, pipes and ducting fume extraction systems, gas cleaning units), top -coat materials (with excellent adhesion to plastics, steel and concrete), optical fiber coating UV curing inks and printed circuit board manufacture {Jaswal S.; Gaur, B. 'New trends in vinyl ester resins ' Rev. Chem. Eng. 2014, DOI 10.1515/revce-2014-0012). The versatility of these resins for diverse applications has resulted in a huge global market and ever increasing potential.

[0003] VERs are currently synthesized by addition reaction of epoxide resins with unsaturated carboxy lie acids. A variety of chemical comp ounds containing the epoxy groups have been used for synthesis of VERs. Particularly bisphenol-A (BP A) based VER resins are widely utilized due to their exceptional mechanical strength and chemical resistance.

Currently for BPA based VER synthesis, the epoxy containing bisphenol-A dig ycidyl ether (BADGE) is reacted with either methacry lie acid or methyl methacylate. These resins were first commercialized as Epocrylresins by Shell Chemical Company and later as Derakane resins by Dow Chemical Company. Currently these resins are produced predominantly by Ashland, DSM and Reichold. 0004] VERs typically have the following structure:

[0005] Although VERs are widely utilized, the structure still contains ester linkages which are susceptibleto chemical and themial degradation. Thehydroxyi group present in the

VER, however, is vital for its interaction with a variety of substrates and fiber

reinforcements.

[0006] Hence, a structure containing thehydroxyi group and no ester linkages would result in significantly more stable class of resins. A compound displaying these structural motifs has not been reportedyet.

SUMMARY OF THE INVENTION

[0007] In various embodiments, the present invention provides a vinyl hydroxy! ether resin (VHER having the general structure:

in which m and n are integers. The end groups can be either be an allyl alcohol where m = 0 or comprised of multiple aliphatic repeating units where m > 1. In various embodiments, m ranges from 0 to 100, and n ranges from 1 to 100. At each occurrence, R' independently represents hydrogen, or mono-, di-, or tri-substitution of(Ci-Cio)hydrocarbyl. The variable R represents O, S0 ₂ , or C(R ¹ ) ₂ . Each occurrence of R ¹ is independently chosen from hydrogen, phenyl, and substituted or unsubstituted (Ci-Cio)hydrocarbyl. In one embodiment, R ⁵ is (Ci- Cio)hy drocarby 1 substituted with one or more halogens selected from F, CI, and Br. In some embodiments R is:

[0008] In one embodiment, R' is CH ₃ or CH(CH ₃ )2.

[0009] In various embodiments, the present invention p rovides a viny 1 hydroxy 1 ether resin (VHER) having the structure:

Some embodiments provide a polymerization product of a starting material composition that includes the VHER. Some embodiments provide a method of making the VHER including combining Bisphenol A:

with vinyl ethylene carbonate: or with 3-butene-(l,2-diol):

under conditions sufficient to give the VHER

[0010] Various embodiments rovide a vinyl hydroxy 1 ether resin (VHER) having the structure:

Some embodiments provide a polymerization product of a starting material composition, the starting material composition including the VHER. Some embodiments provide a method of making the VHER including combining Bisphenol A:

with 3-butene-(l,2-diol): under conditions sufficient to give the VHER. [0011] Various embodiments include a new class of resins, vinyl hydroxy 1 ether resin

(VHER). Various embodiments including an environmentally benign "green" methodology for the synthesis of the VHERs. Various embodiments provide a novel single-step synthetic protocol for the synthesis of the VHERs.

[0012] In some embodiments, the retention of hydroxy! moieties in the structure of the VHERs would introduce stronger interactions with a variety of substrates and fiber reinforcements, as compared to other resins. In various embodiments, the elimination of ester moieties in the structure of the VHERs can provide imp roved stability towards chemical and thermal degradation of the resin. In various embodiments, the VHER can be cured to produce a thermoset polymer with reduced polar ester groups, compared to polymer made from VERs. This can advantageously reduce or minimize blistering-type defects, often observed in long term use of VER poly mers in aquatic environments. In various

embodiments, the VHER has improved chemical stability compared to other resins, which can be used to produce thinner corrosion resistant coatings. Thinner coatings can help in lowering the environmental footprint of the materials.

[0013] In some embodiments a reactive diluent (e.g., styrene) can be used in formulations for reduction of VHER viscosity. The reduction in viscosity can aid in efficient processing of the resin. However, styrene is a carcinogenic compound, and hence a reduced amount in the formulations is desired for safer work environment. VHER displays lower viscosity than vinyl epoxy resin (VER), which would reduce the amount of required reactive diluent (e.g., styrene) in the formulations, resulting in "greener" formulations.

[0014] In various embodiments, the VHER can be a more stable alternative to widely utilized resins used in diverse industries, such as, ship building automotive part constraction, infrastructure polymer concrete reinforcements, corrosion resistance coatings (e.g., on chemical storage tanks, pipes and ducting, fume extraction systems, gas cleaning units), topcoat materials (e.g, with excellent adhesion to plastics, steel and concrete), optical fiber coating, UV curing inks, printed circuit board manufacture, and fiber-reinforced composites.

BRIEF DESCRIPTION OF THE FIGURES

[0015] The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments of the present invention.

[0016] FIG.1 is a reaction scheme for synthesis of model compound Bisphenol A bis(2-hy droxy p rop y l)ether (B ABHPE)

[0017] FIG. 2 is the p roton NMR spectrum of B ABHPE in DM SO-d ⁶ . [0018] FIG. 3 is a reaction scheme for synthesis ofVHER by em loying vinyl ethylene carbonate.

[0019] FIG. 4 is the proton NMRof a VHER in DM SO-d ⁶

[0020] FIG. 5 is a reaction scheme for the synthesis of VHER by employing 3- butene-( i ,2-diol).

[0021] FIG. 6 is a reaction scheme for synthesis of VHER by employing l,2-epoxy-5- hexene.

[0022] FIG. 7 shows photographs of Derakane and VHER formulations (top row).

Cured formulations and solid tack- free thermoset products (bottom row).

[0023] FIG. 8 is the protonNMRand FTIRspectra of a VHER. FIG. 8A is the proton NMR of VHER in DM SO d ⁶ . FIG. 8B is FT IR spectra for a VHER (upper line, red) and BPA (lower line, black).

[0024] FIG. 9 is a photograph of cured one pot synthesized VHER with 33% styrene.

[0025] FIG. 10 is a plot of Storage Modulus, Loss Modulus and Tan Delta traces obtained using the cured one pot synthesized VHER with 33% styrene.

[0026] FIG. 11 A is a plot of TGA traces for cured VHER. FIG. 1 IB is a plot of TGA traces for cured Derakane 411-400.

[0027] FIG. 12 is photographs of cured coatings of VHER (left) and Derakane 411-

400 (right) after immersion in cone. H2SO4 for 48 hours.

[0028] FIG. 13 is a plot ofwater uptake measurements for cured Derakane 41 1-400

(top, black) and VHER (bottom, red).

[0029] FIG. 14 is photographs of VHER (left) and Derakane (right) coatings after the

ASTM D3350 Adhesion Tape test.

[0030] FIG. 15 is photographs of the OT, IT, and 2T bend test results for VHER and Derakane 441-400 VER coatings after MEK double rub testing.

[0031] FIG. 16 is 0T bend test results for VHER (top) and Derakane (bottom) coatings after immersion in concentrated H2SO4 for 48 hours.

DETAILED DESCRIPTION OF THE INVENTION

[0032] Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings.

While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter. [0033] Throughout this document, values ex ressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of "about 0.1 % to about 5%" or "about 0.1% to 5%" should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement "about X to Y" has the same meaning as "about X to about Y," unless indicated otherwise. Likewise, the statement "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z," unless indicated otherwise.

[0034] In this document, the terms "a," "an," or "the" are used to include one or more than one unless the context clearly dictates otherwise. The term "or" is used to refer to a nonexclusive "or" unless otherwise indicated. The statement "at least one of A and B" has the same meaning as "A, B, or A and B." In addition, it is to be understood that the pliraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that p articular section

[0035] In the methods described herein, the acts can be carried out in any order without dep arting from the princip les of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0036] The term "about" as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.

[0037] The term "substantially" as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.

[0038] As used herein, the term "polymer" refers to a molecule having at least one repeating unit and can include copolymers. [0039] The polymers described herein can terminate in any suitable way. In some embodiments, thepolymers can terminate with an end group that is independently chosen from a suitable polymerization initiator, -H, -OH, a substituted or unsubstituted (Ci- C ₂ o)hydrocarbyl(e.g., (Ci-Cio)alkyl or (C6-C ₂ o)aryl) interrupted with 0, 1, 2, or 3 groups independently selected from -O-, substituted or unsubstituted -NH-, and -S-, a

poly (substituted or unsubstituted (Ci -C ₂ o)hy drocarby loxy ), and a p oly (substituted or unsubstituted (Ci-C2o)hydiOcarbylamino).Theterm "hydrocaibon" or "hy drocarby 1" as used herein refers to a molecule or functional group that includes carbon and hydrogen atoms. The term can also refer to a molecule or functional group that normally includes both carbon and hydrogen atoms but wherein all the hydrogen atoms are substituted with other functional groups.

[0040] As used herein, the term "substituted" as used herein in conjunction with a molecule or an organic group as defined herein refers to the state in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms.

[0041] In one embodiment the present invention provides a vinyl hydroxyl ether resin

(VHER) havin the structure:

in which m and n are integers. The end groups can be either be an ally 1 alcohol where m = 0 or comprised of multiple aliphatic repeating units where m > 1. In various embodiments, m ranges from 0 to 100, and n ranges from 1 to 100. At each occurrence, R' independently represents hydrogen, or mono-, di-, or tri-substitution of (Ci-Oo)hy drocarby 1. The variable R represents O, SO2, or C(R ¹ ) ₂ . Each occurrence of R ¹ is independently chosen from hydrogen, phenyl, and substituted or unsubstituted (Ci-Cio)hy drocarby 1. In one embodiment, R ¹ is (O- Cio)hy drocarby 1 substituted with one or more halogens selected from F, CI, and Br. In some embodiments R is

or the structure:

[0044] In one embodiment, a method of making the VHER with the structure

includes combining Bisphenol A:

with vinyl ethylene carbonate: under conditions sufficient to give the VHER. In some embodiments, the reaction is carried out under basic conditions. The base can be any suitable base that is ca able of

deprotonating the phenolic starting material. Suitable bases include, but are not limited to, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydride, sodium hydride, and potassium hydride. The reaction is typically conducted by heating the reagents neat (without solvent). A suitable reaction temperature can be between 50-200 °C, or between 100-150 °C.

[0045] Suitable phenols for the reaction are not limited to Bisphenol A. Other suitable phenols include, but are not limited to, bisphenol AP (l, l-bis(4-hydroxyphenyl)-l- phenyl-ethane), bisphenol AF (2,2-bis(4-hydroxyphenyl)hexafiuoropropane), bisphenolB (2,2-bis(4-hydroxyphenyl)butane), bisphenolBP (bis-(4-hydroxyphenyl)diphenylmethane), bisphenol C (2,2-bis(3-methyl-4-hydroxyphenyl)propane), bisphenol E (1,1 -bis(4- hydroxyphenyl)ethane), bisphenolF (bis(4-hydroxydiphenyl)methane), bisphenol G (2,2- bis(4 iydroxy-3-isopropyl-phenyl)propane), bisphenolPH (5,5'-(l-methylethyliden)- bis[l,l '-(bisphenyl)-2-ol]propane), bisphenol TMC (l,l-bis(4-hydroyphenyl)-3,3,5- trimethyl-cyclohexane), bisphenol Z (l ,l-bis(4-hydroxyphenyl)-cyclohexane), and combinations thereof.

[0046] In one embodiment, the VHER can be made by a method including, combining Bisphenol A:

with 3-butene-(I,2-diol):

under conditions sufficient to give the VHER, according to the conditions described above

[0047] In another embodiment, a method of making the VHER includes

combining Bisphenol A:

with l,2-epoxy-5-hexene: under conditions sufficient to give the VHER. Advantageously, when epoxide starting materials are used, an environmentally friendly solvent-free reaction single pot reaction can be conducted. Other suitable epoxides include, but are not limited to, 2-epoxy-6-heptene, l,2-epoxy-7-octene, l,2-epoxy-8-nonene, l,2-epoxy-9-decene, or combinations thereof. Suitable reaction conditions for reacting a phenol and an epoxide and a phenol are described in, for example, Lee et al. RSC Adv. 2015, 5, 38673-38679.

Examples [0048] Various embodiments of the present invention can be better understood by reference to the following Examples which are offered by way of illustration. The present invention is not limited to the Examples given herein. Example 1. One step protocol used for synthesis of a model compound bisphenol A bis(2- hv droxyp rop vDether (B ABHPE) .

[0049] Following is the detailed one step protocol used for synthesis of a model compound Bisphenol A bis(2-hydroxypropyl)ether(BABHPE).

[0050] Materials. Bisphenol A, propylene glycol, diethylene carbonate and potassium carbonate were procured from Sigma Aldrich and utilized without further purification.

[0051] In a single necked round bottom flask bisphenol A (1 g, 4.38 mmol), propylene glycol (1.99 g, 26.28 mmol), diethyl carbonate (1.55 g, 13.14 mmol), and potassium carbonate (0.302 g, 2.19 mmol) were introduced. The flask was connected to a

Claisen distillation setup and the reaction mixture was vigorously stirred at 1 15 °C. After 18 h the reaction was stopped by first applying vacuum to remove any unreacted diethylether and the ethanol byproduct. The hot reaction mixture was then added to a beaker containing 500 mL deionized water. A viscous reaction product was allowed to settle over time and the supernatant water removed. The 85% pure Bisphenol A bis(2-hydroxypropyl)ether

(BABHPE) was isolated in quantitativeyields. The purity of the reaction product was determined using proton NMR shown herein at Figure 2. This solvent free reaction occurs through in-situ formation of glycerol carbonate as described in literature (Truscello A. M . et al. Green Chemistry 2013, 15, 625).

Example 2. Synthesis of VF1ER.

[0052] The model reaction procedure given in Example 1 establishes the synthetic procedure for VHER. As in-situ formation of the cyclic carbonate occurs, two different synthesis strategies can be used as presented below (Figure 3 and 4). The reactions thus performed will be single step and single pot procedures. Investigations on these concepts are underway and the results will be included here. By changing the length of the alkyl segments (e.g., hexyl, octyletc.) used the viscosity and other properties ofthe final product can be tailored. The use of longer alkyl chains would also provide non-ally lie product. This can be performed by using longer chain 1,2-diols, for example by using 5-hexene-(l,2-dioi), as a reactant with Bisphenol A. [0053] Materials. Bisphenol A, vinyl ethylene carbonate, and potassium carbonate were procured from Sigma Aldrich and utilized without further purification.

[0054] In a single necked round bottom flask Bisphenol A (1 g), as received Vinyl ethylene carbonate (1.5 mL) and potassium carbonate (300 mg) were introduced. The flask was connected to a Claisen distillation setup and the reaction mixture was vigorously stirred at 115 °C. After 18 h the reaction was stopped by apply ingvacuum to remove any umeacted vinyl ethylene caibonate. The obtained product was dissolved in 3 mL of dimethyl sulfoxide and added dropwise to 40 mL deionized water. The isolated precipitate, in quantitative yield, was analyzed using proton NMR (Figure 4). As seen in the NMRa quantitative conversion of BP A to VHER was obtained.

[0055] A large scale synthesis of VHER can be also performed according to the following protocol as one embodiment of the invention.

[0056] Materials. Bisphenol A, vinyl ethylene carbonate, and potassium carbonate were procured from Sigma Aldrich and utilized without further purification.

[0057] The reaction scheme utilized for the synthesis of VHER is displayed in Figure

2. Bisphenol A (50 g), as received vinyl ethylene caibonate (75 mL) and potassium caibonate (5 g) were introduced in a single necked round bottom flask. The flask was connected to a Claisen distillation setup and the reaction mixture was vigorously stirred at 115 °C. After 18 h the reaction was stopped by applying vacuum to remove any unreacted vinylethylene carbonate. The obtained product was dissolved in 30 mL of dimethyl sulfoxide and added dropwise to 400 mL deionized water.

[0058] The isolated precipitate, in quantitative yield, was analyzed using proton NMR

(Figure 8A) and FTIR (Figure 8B). As seen in the NMR spectrum in Figure 8A, a

quantitative conversion of BP A to VHER was obtained. In the FTIR sp ectrum (Figure 8B), a strong peak around 930 cm ^"1 (boxed region in Figure 8 A) was observed for the VHER but was absent in the bisphenol A (BP A) spectrum. This peak is attributed to the bending of the vinyl groups. The absorption band associated with the ether moieties present in the VHER appeals in the same region as the C-0 stretch centered around 1200 cm ^"1 from the parent BPA.

[0059] Using the reaction procedure shown herein for BABHPE, VHER can also be synthesized using 3-butene-(l,2-diol) according to the reaction scheme presented in Figure 5.

[0060] In an alternate synthetic protocol VHER can be synthesized using cheap er commercially available starting materials (e.g. l,2-epoxy-5-hexene) through an environmentally benign solvent free single ot reaction methodology as conceptualized in Figure 6. The reaction between an epoxy group and the BP A hydroxy 1 moiety has been reported (Lee et al. RSC Adv. 2015, 5, 38673-38679). Example 3. Curing of VHER.

[0061] Preliminary curing experiments were performed with formulations containing the synthesized VHER, styrene(40 % w/w ^r ), methyl ethyl ketone peroxide (as free radical initiator) and cobalt naphthenate (promoter). These chemicals were chosen since they are used in all commercial VER formulations. As a control commercially available VER

(Derakane from Ashland) was cured using the same conditions as the VHER.

[0062] The curing reactions were performed at 25 °C for 24 hours. As seen from

Figure 7, curing of Derakane was successful with these reaction conditions. Importantly, curing of VHER was also successful with these curing conditions - typically used in the industry. The cured VHER formulation resulted in a solid and tack-free thermoset. These preliminary results indeed demonstrate the successful synthesis and curing of VHER.

Example 4. VHER Formulations and Characterization.

[0063] The synthesized VHER was mixed with 20, 33 and 40 wt % styrene to give formulations analogous to commercially available Derakane VERs. These mixtures were stored at room temperature in a dark location, and were stable under these conditions for over 6 months, with no gelation or precipitation.

[0064] In one embodiment, the synthesized VHER was mixed with 33 wt% styrene, which is similar to the commercially available Derakane 441-400. For curing, 1.5 phr methyl ethyl ketone peroxide ( EKP, Norox MEKP-925H) was used as the initiator and 0.2 phr cobalt naphthenate (6% in mineral spirits, Sigma Aldrich) was used as the accelerator. In a typical formulation step, theME P was first added to the VHER solution in Styrene and mixed at 1000 rpmfor 1 min using a FlackTek Speedmixer. The accelerator was then introduced to the formulation and mixed at 1000 rpm for 1 min using a FlackTek

Speedmixer. The formulation was then cured at 60°C for 16 hours followed by post curing at 110°C for 4 hours. In order to reduce the cure time of this formulation, 0.15 phr of dimethyl aniline (DMA) w ^r as added to the above VHER formulation as a secondary accelerator and mixed at 1000 rpmfor 1 min using a FlackTek Speedmixer. In order to reduce the curing time 0.15 phr dimethyl aniline was added to the above described VHER formulation as an accelerator. [0065] The resulting formulation was then aired at 60 °C for 10 hours followed by post curing at 1 10 °C for 1 hour. At the end of which a stiff non-tacky cured VER sample was obtained Figure 9. The Derakane 411-400 formulations w ^r ere obtained using same procedure used for VHER, and contained the same amounts of initiator and accelerator. The Derakane formulations were then cured at 60°C for 3 hours followed by post curing at 1 10°C for 1 hour.

[0066] The glass transition temperature (Tg) of the obtained samp le was determined from the peak in Tan δ values using Dynamic Mechanical Analysis. The sample displayed a Tg of 119 °C (Figure 10) compared to a reported 135 " T Tg for Derakane 441-400. The flexural storage modulus of the sample was observed to be around 2.4 GPA at room temperature.

[0067] The thermal stability of the cured VHER was determined using

thermogravimetric analysis (TGA). As seen in Figure 1 1 , the onset temperature for degradation cured VHER (T ₀ ) was observed at 417 °C, and the highest rate of degradation (Tmax) was observed at 453 °C. In comparison for Derakane 441-400 the T ₀ and T _max were observed at 412 °C and 446 °C respectively. Without being bound by theory, this higher stability of VHER to thermal degradation can be attributed to the presence of ether moieties as opposed to ester groups in the case of Derakane. A higher char yield of 10 wt% was also observed for VHER as opposed to 3 w ^r t% for Derakane.

[0068] Using the formulations coatings of VHER and Derakane were processed on

Aluminum Q panels. The coated panels were then immersed in cone. H2SO4 for 48 hours to determine their hydroly tic stability. As seen in Figure 12, the Derakane coatings displayed significant change in color as well as cracking and erosion of the coating. VHER coatings in contrast displayed slight change in color and the film integrity is retained. This indicates that VHER is more stable to hydrolysis as compared to Derakane. This can be attributed to the ether moieties present in VHER as compared to the hydroly sable ester moieties in Derakane.

[0069] Barcol hardness measurements were performed according to ASTM D-2583 and a Barcol hardness of 32 was observed for the cured samples, which is comparable to the Barcol hardness of 35 reported for Derakane 441-400.

Example 5: Marine Applications of VHER.

[0070] In marine applications continuous contact with an aqueous environment can cause osmotic blistering in boat hulls, which can have detrimental effects on the properties and reduce lifetime. In order to assess their affinity for water, cured Derakane and VHER samples with dimensions 40.2 mm x 12.4 mm x 3.1 mm, and 40.5 mm x 12.2 mm x 3.4 mm respectively were selected. The samples were immersed in deionized water at 60°C for 30 days according to the procedure reported in Sobrinho, L.L. et al, Materials Research, Vol. 12, No. 3, 353-361, 2009. Prior to immersion in water, the samples were placed under vacuum at 80°C for 48 hours and cooled under vacuum to remove and absorbed moisture under ambient conditions, then weighed carefully using an analytical balance. For each subsequent measurement, before weighing the samples were allowed to cool to room temperature and patted dry. The resultant data on weight increase as a function of time is displayed in Figure 13. As the data shows, there is a steady increase in the weight of both materials due to the diffusion of deionized water into the samples, followed by saturation after about 20 days. Due to the greater polarity of the ester moieties in the VER than the ether moieties in the VHER, the equilibrium water uptake of the former (0.6 wt%) substantially exceeded that of the latter (0.2 wt%). The lower water uptake observed in the VHER is an advantage of the VHER material for long-term durability of parts in marine applications.

[0071] Gardco wet film applicators (wire size 6, S6) were utilized for processing

VHER and Derakane 441-400 VER coatings on Q-panel uncoated 3" x 6" aluminum test panels. The aluminum substrates were cleaned first by immersion in a pH 2 aqueous sulfuric acid bath for 5 minutes at 25°C. The panels were then washed with deionized water and dried at 110°C in a convection oven for 5 min. Thepanels were cooled to room temperature, after which the VHER and Derakane 441-400 VER formulations with 1.5 phrMEKP (Norox MEKP-925H), 0.2 phr cobalt naphthenate (6% in mineral spirits, Sigma Aldrich), and in the case of VHER 0.15 phr of dimethyl aniline (DMA), were applied using the S6 wet film applicator. In a convection oven the Derakane 441-400 VER coating cured in 1 hour at

220°C. For coatings the VHER formulation containing 33% Styrene and DM A as the secondary accelerator, cure time was increased to 6 hours for complete curing at 220°C. Using this procedure, continuous, tack-free, clear, coatings of were obtained. In adhesion testing the results are obtained by visual examination of the marked area. In order to aid in this process, trace quantities of a luminescent dye, carboxv fluorescein, were introduced into the formulations.

[0072] To determine coating stability vs. solvent attack, the obtained coatings were characterized via theMEK double rub test (ASTM D5402) using cheese cloth and commercially available methyl ethyl ketone (Sigma Aldrich). In a typical test a doubled-over piece of cheese cloth was placed in a beaker containing MEK and saturated until dripping wet. The MEK-wetted cheese cloth was then placed on the test sample and pressed firmly with the index finger at a 45° angle, and 100 double rubs were performed on the central area of each coating, after which they were visually inspected. No visual changes were observed in any of the coatings after the MEK double rub test.

[0073] The coatings on which the M EK double rub test was p erformed were then utilized for ASTM D3359 adhesion testing. A Gardco Paint Adhesion Test Kit with an 1 1 tooth 1.0 mm cutter (PA-2053) was utilized for screening the obtained coatings via ASTM D3359 (Standard M ethod for M easuring Adhesion by Tap e Test, a.k.a. "Crosshatch Adhesion Test"), Test Method B, recommended for coatings with dry thicknesses below 50 μηχ The presence of the fluorescent dye in the coatings significantly improved the evaluation of coatings following adhesion testing. After cross-hatching, tape application and peeling the samples were observed under 365 nm UV illumination to evaluate the degree of coating removal from the substrate. Figure 13 disp lays photograp hs of the samp les after adhesion testing; neither coating experienced any loss of material from the substrate after the adhesion tape test, meaning both are classified as 5B coatings (the highest level of performance indicated by this testing standard). These results confirm that the equally high performance of both the VHER and Derakane 441-400 VER coatings.

[0074] A T-Bend tester was used to perform 0T, IT, and 2T coating flexibility bend tests (ASTM D4145) on all coated samples following MEK double rub testing (ASTM D5402). This test is important as it determines the flexibility and adhesion of the coatings on substrates that are deformed by bending. In this test, coated samples were bent using a T- Bend tester procured from Qualtech Products Industry .0T, IT, and 2T bends were produced, after which the coatings were inspected for damage. The pressure-sensitive tapeprovided in the ASTM D3359 Gardco Paint Adhesion Test Kit was used to determine the

adhesionpickoff of the coatings at the bent edge. The 0T bend test is the most challenging test to pass, as the radius of curvature at the T-bend is lowest in this case, nevertheless, neither the VHER nor theDerakane 441-400 VER coatings displayed anv damage or removal of coated material following this test (Figure 15). Hence, both can be classified as 0T coatings.

[0075] For use in applications such as chemical storage tanks, desulfurization flue stacks etc. enhanced chemical stability is desired. To determine the chemical stability of the processed VHER and Derakane 441-400 VER coatings, the coated panels were immersed in concentrated H2SO4 for 48 hours. As seen in Figure 12, the Derakane coatings displayed a significant change in color as well as cracking and erosion of the coating. VHER coatings in contrast displayed only a slight change in color and experienced no changes in film integrity. This indicates that VHER is more stable vs. hydrolysis as compared to a Derakane 441-400 VER. This can be attributed to the stable ether moieties present in the VHER coating as compared to thehydrolytically unstable ester moieties in the Derakane 441-400 coating.

[0076] Following immersion in concentrated H2SO4 for 48 hours, 0T bends were produced to determine the effect of hydrolysis on the flexibility and adhesion of the coatings. The pressure-sensitive tape provided in the ASTM D3359 Gardco Paint Adhesion Test Kit was used to assess the adhesion/pickoff of the coatings at the bent edge. Even after immersion in concentrated H2S04 for 48 hours, the VHER coatings displayed no damage or coating removal following the adhesion test (Figure 16). In contrast, Derakane 441-400 VER coatings failed the test due to the loss of a considerable portion of the coating at the 0T bend as seen in Figure 16.

[0077] The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present invention. Thus, it should be understood that although the present invention has been specifically disclosed by specific embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present invention.

Exemplary Embodiments.

[0078] The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance."

[0079] Embodiment 1 provides a vinyl hydroxy 1 ether resin (VHER) having the structure: wherein

m is an integer ranging from 0 to 100,

n is an integer ranging from 1 to 100,

at each occurrence R' is independently a substituted or unsubstituted (O-

Cio)hydrocarbyl,

R is O, S0 ₂ , or C(R ⁱ ) ₂ , and,

R ¹ is independently hydrogen, phenyl, or substituted or unsubstituted (O- Cio)hydrocarbyl.

[0080] Embodiment 2 provides the vinyl hydroxy 1 ether resin (VHER) of embodiment 1 having the structure:

[0081] Embodiment 3 provides the vinyl hydroxyl ether resin (VHER) of embodiment 1 having the structure:

[0082] Embodiment 4 provides the vinyl hydroxy 1 ether resin (VHER) of embodiment 1, wherein m is 1, 2, 3, 4, or 5.

[0083] Embodiment 5 provides a p olymerization product of a starting material composition, the starting material composition including the VHER according to any one or combination of embodiments 1-4.

[0084] Embodiment 6 provides a method of making the VHER of embodiment 2, including:

combining Bisphenol A:

with vinyl ethylene carbonate: under conditions sufficient to give theVHER of embodiment 2.

[0085] Embodiment 7 provides a method of making the VHER of embodiment 2, including:

combining Bisphenol A:

with 3-butene-(l,2-diol):

under conditions sufficient to give the VHER of embodiment 2.

[0086] Embodiment 8, provides a method of making the VHER of embodiment 3, including:

combining Bisphenol A:

with l,2-epoxy-5-hexene: under conditions sufficient to give theVHER of embodiment 3.

[0087] Embodiment 9 provides a method of making the VHER of embodiment 1, including:

combining Bisphenol A:

with 1,2 -epoxy-6-heptene, l,2-epoxy-7-octene, l,2-epoxy-8-nonene, l,2-epoxy-9- decene, or combinations thereof.

[0088] Embodiment 10 provides a polymerizationproduct of a starting material composition, the starting material composition including the VHER according to embodiment 3.