METHODS OF MAKING VINYL ESTER RESINS AND S TARTING MATERIALS

FOR THE SAME

CROS S-REFERENCE TO RELATED APPLICATION

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

Application Serial No. 62/387,443 filed Dec. 23, 2015, the disclosure of which is

incorporated herein in its entirety by reference.

STATEMENT OF GOVERNMENT SUPPORT

[0002] This invention was made with Government support under SERDP WP-2317 awarded by Strategic Environmental Research and Development Program. The U.S.

Government has certain rights in this invention.

BACKGROUND

[0003] 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 processability . 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 sy stems, 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.

[0004] 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 diglycidyl ether (BADGE) is reacted with either methacry lie acid or methyl methacylate. These resins were first commercialized as Epocryl resins by Shell Chemical Company and later as Derakane resins by Dow Chemical Company . Currently these resins are produced predominantly by Ashland, DSM and Reichold.

[0005] BADGEis currently synthesized using BPA and epichlorohydrin as starting materials. Patents issued for the synthesis of BADGE using BPA and epichlorohydrin, include U.S. Pat. No. 3121727 A to Baliker et al. assigned to Shell Oil Co. and U.S. Pat. No. 4877857 A to Shirtum et al. assigned to TheDow Chemical Company .

[0006] BPA-based VER is synthesized from BADGE by the addition reaction of its epoxy groups with acrylic acid based monomers. Patents issued for the synthesis of VER using this synthetic protocol include U.S. Pat. No. 3256226 to Fekete et al, and No. 3317465 toDoyle et al., both assigned toH. H. Robertson Co.; No. 3345401 toMay; No. 3373221 to May; No. 3377406 toNewey; and No. 3432478 to May, all assigned to Shell Oil Co.; No. 3548030 to Jernigan; and No. 3564074 to Swisher et al., both assigned to Dow Chemical Co.; No. 3634542 toDowd et al.; and No. 3637618 to May, both assigned to Shell Oil Co.

[0007] The production of VER is still performed using the synthetic protocols reported more than 3 decades ago. Even though the synthetic protocol used is efficient, it requires the use of epichlorohydrin, which performs the dual role of a solvent and reactant. Epichlorohydrin however, has been identified by theU.S. Environmental Protection Agency (EPA) as a hazardous air pollutant and it also features on the list of controlled chemicals by the EPA. Hence, to ensure continued environmental sustainability and improved work place safety an alternative route for the synthesis of VER is required.

[0008] Most of the chemicals used for the synthesis of VER are derived from petroleum based feedstocks, which introduces price volatility . In 2014 all the major manufacturers of VER, namely Ashland, DSM and Reichold, announced an increase in the VER price due to theincreased cost of raw materials derived from petroleum feedstocks. Hence, an alternate route for improved sustainability and reduced cost volatility of this commercially important resin is required.

[0009] A typical VER composition includes sty rene as a reactive diluent. However, styreneis a highly carcinogenic chemical and has been identified as a hazardous air pollutant by the EPA. Hence, alternatives for sty rene as reactive diluent in VER compositions are required. SUMMARY OF THE INVENTION

[0010] In various embodiments, the present invention provides a method for producing a vinyl ester resin (VER). The method can include reacting a bis(hydroxy((Ci- Cio)hydrocarbyl)ether of the bisphenol with a vinyl carboxylic acid or a salt, ester, or acid halide thereof to form the VER.

[0011] In various embodiments, the present invention provides a method for producing a vinyl esterresin (VER). Themethod includes reacting bisphenol A with glycerin to form bisphenol A bis(2,3-dihydroxypropyl)ether (B ABDHPE). The method includes reacting the B ABDHPE with methyl methacrylate to form the VER. The VER has the structure:

[0012] In various embodiments, the present invention provides a method for producing a bis(hy droxy ((Ci-Cio)hy drocarbyl)ether of a bisphenol. The method includes reacting a bisphenol with a (Ci-Cio)hy drocarbylpoly ol to form thebis(hy droxy ((Ci- Cio)hydrocarbyl)ether of the bisphenol.

[0013] In various embodiments, the present invention provides a method for producing bisphenol A bis(2,3-dihy droxy prop yl)ether (B ABDHPE). The method includes reacting bisphenol A with a glycerin to form the B ABDHPE.

[0014] In various embodiments, the present invention provides a method for producing glycerol carbonate methacrylate. Themethod includes reacting glycerol carbonate with methyl methacrylate and zirconium acetylacetonate, to form the glycerol carbonate methacrylate. In some embodiments, the method further includes reacting glycerin and a dimethyl carbonate, to form the glycerol carbonate.

[0015] In various embodiments, the present invention provides a method for producing a vinyl esterresin (VER). The method includes reacting bisphenol A with glycerol carbonate methacrylate, to form the VER, wherein the VER has the structure:

In some embodiments, the method further includes reacting glycerin and a dimethyl carbonate, to form gly cerol carbonate; and reacting the glycerol carbonate with methyl methacrylate and zirconium acetylacetonate, to form the gly cerol carbonate methacrylate.

[0016] In various embodiments, the present invention has advantages over other methods of making VER, at least some of which are unexpected. For example, in various embodiments, the present invention provides an environmentally benign methodology for obtaining VER formulations with "green" reactive diluent. In various embodiments, the present invention provides an environmentally benign "green" methodology for the synthesis of BABDHPEand VER. In various embodiments, the present invention provides a novel two-step or single pot synthetic protocol. In various embodiments, the present invention provides a method that eliminates or decreases the amount of toxic chemicals in VER synthesis and VER formulations, such as epichlorohydrin and styrene. In various

embodiments, the use of a single pot synthetic method eliminates and/or significantly reduces the use of other chemical reagents required for purification of the VER. In various embodiments, the present invention provides a method that utilizes starting materials derived from bio-waste streams, which can improve the environmental and cost sustainability of the procedure.

[0017] In various embodiments, the method of synthesizinggly cerol carbonate methacrylate (GCM A) and gly cerol carbonate from glycerin has certain advantages over other methods. In some embodiments, glycerin generated at a biodiesel manufacturing plant can be used. In some embodiments, glycerol carbonate can be synthesized using waste glycerin. In some embodiments, the product can be made cataly st -free by simply passing over acidic resin. In some embodiments, the method forms GCM A at higher yields than other methods. In some embodiments, the method can form green vinyl ester resin from BPA or TBBPA and GCMA, such as using potassium carbonate as catalyst. In some

embodiments, the synthetic method can use fewer step s and can consume more renewable biowaste as starting materials than other methods.

[0018] In some embodiments, the materials using during the method can be free of epichlorohy drin and halide compounds that are both toxic and carcinogenic, in contrast with the conventional manufacturing process of vinyl ester resin based up on petroleum feed stock and using epichlorohy drin as one of the intermediates. In some embodiments, thepresent method avoids use of glycidol, a potential carcinogen having an energy -intensive production process including decarboxylation from glycerol carbonate to glycidol performed at 140 to 160 °C. In some embodiments, the present invention avoids the use of potassium cyanide, such as for a catalyst for transesterification between glycidol and methyl methacrylate, instead using materials such as using zirconium acetylacetonate as catalyst for

transesterification between glycerol carbonate and methyl methacrylate.

[0019] In some embodiments, the present invention eliminates steps of extraction, isolation, and synthesis of resins used to form petroleum-derived products. In some embodiments, the present invention offers potential for in situ synthesis and process development. In some embodiments, fabric reinforced (e.g., carbon fabric reinforced) GVER panels can be used in building ship parts such as bull and deck-house. BRIEF DES CRIPTION OF THE FIGURES

[0020] The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.

[0021] FIG. 1 illustrates a proton NMR of isolated BABDHPEin DM SO-d ⁶ .

[0022] FIG. 2 illustrates a proton NMR of a VER in DM SO-d ⁶ , in accordance with various embodiments.

[0023] FIG. 3 illustrates a proton NMRof the VER product in DM SO d ⁶ , according to various embodiments.

[0024] FIG. 4 illustrates a cured product of a VER and styrene, according to various embodiments.

[0025] FIG. 5 illustrates storage modulus, loss modulus, and tan delta versus temperature for a cured product of a VER and styrene, in accordance with various embodiments.

[0026] FIG. 6 illustrates a ^X H NMR of glycerol carbonate, in accordance with various embodiments.

[0027] FIG. 7 illustrates a ^X H NMRof glycerol carbonate methacrylate, in accordance with various embodiments.

[0028] FIG. 8 illustrates a ^X H NMR of a Vinyl Ester Resin synthesized by reaction of glycerol carbonate methacrylate and bisphenol A, in accordance with various embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0029] 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.

[0030] Throughout this document, values expressed 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.

[0031] 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 phraseology or terminology employ ed 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. All publications, patents, and patent documents referred to in this document are incorp orated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorp orated by reference, the usage in the incorp orated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.

[0032] In the methods described herein, the acts can be carried out in any order without dep arting from the principles 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. [0033] 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.

[0034] 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%.

[0035] The term "organic group" as used herein refers to any carbon-containing functional group . Examples can include an oxygen-containing group such as an alkoxy group, aryloxy group, aralkyloxy group, oxo(carbonyl) group; a carboxyl group including a carboxylic acid, carboxylate, and a carboxylate ester; a sulfur-containing group such as an alkyl and aryl sulfide group; and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(0)N(R) ₂ , CN, CF ₃ , OCF ₃ , R, C(O),

methylenedioxy, ethylenedioxy, N(R) ₂ , SR, SOR, S0 ₂ R, S0 ₂ N(R) ₂ , S0 ₃ R, C(0)R,

C(0)C(0)R, C(0)CH ₂ C(0)R, C(S)R, C(0)OR, OC(0)R, C(0)N(R) ₂ , OC(0)N(R) ₂ ,

C(S)N(R) ₂ , (CH ₂ )o- ₂ N(R)C(0)R, (CH ₂ ) _0-2 N(R)N(R) ₂ , N(R)N(R)C(0)R, N(R)N(R)C(0)OR, N(R)N(R)CON(R) ₂ , N(R)S0 ₂ R, N(R)S0 ₂ N(R) ₂ , N(R)C(0)OR, N(R)C(0)R, N(R)C(S)R, N(R)C(0)N(R) ₂ , N(R)C(S)N(R) ₂ , N(COR)COR, N(OR)R, C(=NH)N(R) ₂ , C(0)N(OR)R, C(=NOR)R, and substituted or unsubstituted (Ci-Cioo)hy drocarbyl, wherein R can be hydrogen (in examples that include other carbon atoms) or a carbon-based moiety, and wherein the carbon-based moiety can be substituted or unsubstituted.

[0036] 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. The term "functional group" or "substituent" as used herein refers to a group that can be or is substituted onto a molecule or onto an organic group . Examples of sub stituents or functional groups include, but are not limited to, a halogen (e.g., F, CI, Br, and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxy amines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of sub stituents that can be bonded to a substituted carbon (or other) atom include F, CI, Br, I, OR, OC(0)N(R) ₂ , CN, NO, N0 ₂ , ON0 ₂ , azido, CF ₃ , OCF ₃ , R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R) ₂ , SR, SOR, S0 ₂ R, S0 ₂ N(R) ₂ , S0 ₃ R, C(0)R, C(0)C(0)R, C(0)CH ₂ C(0)R, C(S)R, C(0)OR, OC(0)R, C(0)N(R) ₂ , OC(0)N(R) ₂ , C(S)N(R) ₂ , (CH ₂ ) _{0- 2} N(R)C(0)R, (CH ₂ )o _-2 N(R)N(R) ₂ , N(R)N(R)C(0)R, N(R)N(R)C(0)OR, N(R)N(R)CON(R) ₂ , N(R)S0 ₂ R, N(R)S0 ₂ N(R) ₂ , N(R)C(0)OR, N(R)C(0)R, N(R)C(S)R, N(R)C(0)N(R) ₂ , N(R)C(S)N(R) ₂ , N(COR)COR, N(OR)R, C(=NH)N(R) ₂ , C(0)N(OR)R, and C(=NOR)R, wherein R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (Ci- Cioo)hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or

heteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or to adjacent nitrogen atoms can together with the nitrogen atom or atoms form a heterocyclyl.

[0037] The term "alkyl" as used herein refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n- propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl group s. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used herein, the term "alkyl" encompasses n- alkyl, isoalkyl, and anteisoalkyl group s as well as other branched chain forms of alkyl.

Representative substituted alkyl group s can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen group s.

[0038] The term "alkenyl" as used herein refers to straight and branched chain and cyclic alkyl group s as defined herein, except that at least one double bond exists between two carbon atoms. Thus, alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbon atoms or, in some embodiments, from 2 to 8 carbon atoms.

Examples include, but are not limited to vinyl, -CH=CH(CH ₃ ), -CH=C(CH ₃ ) ₂ , -C(CH ₃ )=CH ₂ , -C(CH ₃ )=CH(CH ₃ ), -C(CH ₂ CH ₃ )=CH ₂ , cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl among others.

[0039] The term "aryl" as used herein refers to cyclic aromatic hydrocarbon groups that do not contain heteroatoms in the ring. Thus aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, p y reny 1, nap hthaceny 1, chry seny 1, bip heny leny 1, anthraceny 1, and nap hthy 1 group s . In some embodiments, aryl groups contain about 6 to about 14 carbons in thering portions of the group s. Aryl group s can be unsubstituted or substituted, as defined herein. Representative substituted aryl group s can be mono-substituted or substituted more than once, such as, but not limited to, a phenyl group substituted at any one or more of 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or a naphthyl group substituted at any one or more of 2- to 8-positions thereof.

[0040] The terms "halo," "halogen," or "halide" group, as used herein, by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.

[0041] The term "hydrocarbon" or "hy drocarby 1" as used herein refers to a molecule or functional group, respectively, that includes carbon and hydrogen atoms. Theterm 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.

[0042] As used herein, the term "hy drocarby 1" refers to a functional group derived from a straight chain, branched, or cyclic hydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof. Hy drocarby 1 groups can be shown as (C _a - Cb)hy drocarby 1, wherein a and b are integers and mean having any of a to b number of carbon atoms. For example, (Ci-C ₄ )hy drocarby 1 means the hy drocarby 1 group can be methyl (Ci), ethyl (C ₂ ), propyl (C ₃ ), or butyl (C ₄ ), and (Co-Cb)hy drocarby 1 means in certain embodiments there is no hy drocarby 1 group .

[0043] The term "solvent" as used herein refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.

[0044] The term "room temperature" as used herein refers to a temperature of about

15 °C to 28 °C.

[0045] The term "standard temperature and pressure" as used herein refers to 20 °C and 101 kPa.

[0046] As used herein, the term "polymer" refers to a molecule having at least one repeating unit and can include copolymers.

[0047] In various embodiments, salts having a positively charged counterion can include any suitable positively charged counterion. For example, the counterion can be ammonium(NH ₄ ⁺ ), or an alkali metal such as sodium (Na ⁺ ), potassium (K ⁺ ), or lithium (Li ⁺ ). In some embodiments, the counterion can have a positive charge greater than +1, which can in some embodiments complex to multiple ionized group s, such as Zn ²⁺ , Al ³⁺ , or alkaline earth metals such as Ca ²⁺ or Mg^.

[0048] In various embodiments, salts having a negatively charged counterion can include any suitable negatively charged counterion. For example, the counterion can be a halide, such as fluoride, chloride, iodide, or bromide. In other examples, the counterion can be nitrate, hydrogen sulfate, dihydrogen phosphate, bicarbonate, nitrite, perchl orate, iodate, chlorate, bromate, chlorite, hypochlorite, hyp obromite, cyanide, amide, cyanate, hydroxide, permanganate. The counterion can be a conjugate base of any carboxylic acid, such as acetate or formate. In some embodiments, a counterion can have a negative charge greater than -1, which can in some embodiments complex to multiple ionized groups, such as oxide, sulfide, nitride, arsenate, phosphate, arsenite, hydrogen phosphate, sulfate, thiosulfate, sulfite, carbonate, chromate, dichromate, peroxide, or oxalate.

[0049] The polymers described herein can terminate in any suitable way . In some embodiments, the poly mers can terminate with an end group that is independently chosen from a suitable polymerization initiator, -H, -OH, a substituted or unsubstituted (Ci- C2o)hydrocarbyl (e.g., (Ci-Cio)alkyl or (C6-C2o)aryl) interrupted with 0, 1, 2, or 3 groups independently selected from -0-, substituted or unsubstituted -NH-, and -S-, a

poly (substituted or unsubstituted (Ci-C2o)hydrocarbyloxy), and a poly (substituted or unsubstituted (Ci-C2o)hydrocarbylamino).

Method for producing a vinyl ester resin (VERY

[0050] In various embodiments, the present invention provides a method for producing a vinyl ester resin (VER). The method can include reacting a bisphenol or a bis(hy droxy ((Ci-Cio)hy drocarbyl)ether of the bisphenol with a vinyl carboxylic acid or a salt, ester, or acid halide thereof to form the VER. As used herein, an "acid halide" of a carboxylic acid -C(0)-OH is -C(0)-X, wherein -X is -CI, -Br, -F, or -I, such as -CI or -Br.

[0051] The method can further include polymerizing the obtained VER, such as polymerizing via the terminal vinyl groups. The polymerizing can include forming a homop oly mer or cop oly mer. The p oly merizing can include p oly merizing the VER with a vinyl- substituted organic compound. The vinyl- substituted organic compound can be styrene. The vinyl-substituted organic compound can be a vinyl ester formed from the (Ci- Cio)hydrocarbylpolyol and the vinyl carboxylic acid or the salt, ester, or acid halide thereof that is reacted with the bis(hy droxy ((Ci-Cio)hydrocarbyl)ether of the bisphenol to form the VER. In some embodiments, polymerizing with the vinyl ester formed from the (C i-

Cio)hydrocarbylpolyol and the vinyl carboxylic acid or the salt, ester, or acid halide thereof that is reacted with the bis(hydroxy((Ci-Cio)hydrocarbyl)ether of the bisphenol to form the VER can result in elimination or reduction in use of styrene as the reactive diluent. [0052] In some embodiments, the present invention provides a two-step method of forming VER from bisphenol. The reaction of the bisphenol with the (Ci- Cio)hy drocarby lpoly ol to form the bis(hy droxy ((Ci-Cio)hy drocarbyl)ether of the bisphenol can occur in single reaction vessel. The reaction of the bisphenol or the bis(hy droxy ((C i- C io)hy drocarby l)ether of the bisphenol with the vinyl carboxylic acid or the salt, ester, or acid halide thereof to form the VER can occur in a single reaction vessel.

[0053] The bisphenol can be any suitable bisphenol (e.g., a compound containing two hy droxyphenyl functionalities). The bisphenol can be chosen from bisphenol A (2,2-bis(4- hy droxy p heny l)p ropane), bisp henol AP (1, 1 -bis(4-hy droxy p heny 1)- 1 -phenyl-ethane), bisphenol AF (2,2-bis(4-hy droxy p heny l)hexafluorop ropane), bisphenol B (2,2-bis(4- hy droxy p heny l)butane), bisphenol BP (bis-(4-hy droxy p heny l)diphenylmethane), bisphenol C (2,2-bis(3 -methy 1-4-hy droxy p heny l)propane), bisp henol E ( 1 , 1 -bis(4-hy droxy p heny l)ethane), bisphenol F (bis(4-hy droxy dip heny l)methane), bisphenol G (2,2-bis(4-hy droxy -3-isopropyl- p heny l)p rop ane), bisp henol PH (5 , 5 ' -( 1 -methy lethy liden)-bis [ 1 , -(bisp heny l)-2-ol]propane), bisphenol TMC (1, l-bis(4-hy droyphenyl)-3, 3, 5-trimethyl-cyclohexane), bisphenol Z (1, 1- bis(4-hy droxy p heny l)-cyclohexane), and combinations thereof. The bisp henol can be bisphenol A (2,2-bis(4-hydroxyphenyl)propane).

[0054] The (Ci-Cio)hy drocarby lpoly ol can be any suitable (Ci-

Cio)hy drocarby lpoly ol. The (Ci-Cio)hydrocarbylpoly ol can be a (Ci-Cio)hy drocarby ltriol. The (Ci-Cio)hy drocarby lpoly ol can include at least two terminal hydroxy group s. The (Ci- Cio)hy drocarby lpoly ol can be a prop anetriol. The (Ci-Cio)hy drocarby lpoly ol can be gly cerol (1,2,3 -trihy droxy p rop ane).

[0055] The reaction of the bisphenol with the (Ci-Cio)hy drocarby lp oly ol can be performed in the presence of one or more etherification cataly sts. The reaction of the bisphenol with the (Ci-Cio)hydrocarbylpoly ol can be performed in the presence of a base. The base can be a carbonate salt. The carbonate salt can be potassium carbonate.

[0056] The reaction of the bisphenol with the (Ci-Cio)hy drocarby lp oly ol can be performed in the presence of an ester. The ester can be any suitable (Ci-Cio)alkyl ester of a (Ci-Cio)carboxylic acid. The ester can be diethyl carbonate.

[0057] The bis(hy droxy ((Ci-Cio)hy drocarby l)ether of the bisphenol can be bisphenol

A bis(2,3-dihy droxy p rop yl)ether (BABDHPE).

[0058] The vinyl carboxylic acid or the salt, ester, or acid halide thereof that is reacted with the bis(hy droxy ((Ci-Cio)hy drocarby l)ether ofthe bisp henol to form the VER can be any suitable vinyl carboxylic acid or salt, ester, or acid halide thereof. The vinyl carboxylic acid or salt, ester, or acid halide thereof can be a substituted or unsubstituted (Ci- Cio)hy drocarby 1 ester of (C3-Cio)vinylcarboxylic acid. The vinyl carboxylic acid or salt, ester, or acid halide thereof can be a substituted orunsubstituted (Ci-Cio)hydrocarbyl ester of methacrylic acid. The vinyl carboxylic acid or salt, ester, or acid halide thereof can be methyl methacry late. The vinyl carboxylic acid or the salt, ester, or acid halide thereof can be glycerol carbonate methacry late.

[0059] The reaction of the bis(hy droxy ((Ci-Cio)hy drocarby l)ether of the bisphenol with the vinyl carboxylic acid or salt, ester, or acid halide thereof to form the VER can be performed in the presence of one or more esterification or transesterification cataly sts. The reaction of the bis(hy droxy ((Ci-Cio)hy drocarby l)ether of the bisphenol with the vinyl carboxylic acid or salt, ester, or acid halide thereof to form the VER can be performed in the presence of a base. The base can be a carbonate salt. The carbonate salt can be potassium carbonate.

[0060] The VER can have the structure:

[0061] The VER can be purified using any suitable method, such as column chromatography or precipitation (e.g., from methanol/water).

[0062] The yield of the VER from the bisphenol can be any suitable yield, such as about 10% to about 100%, or such as about 10% or less, or less than, equal to, or greater than about 12%, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or about 99.99% or more. The conversion of the bisphenol (e.g., to the ester thereof or to the VER) can be any suitable conversion, such as 10%) to about 100%), or such as about 10%> or less, or less than, equal to, or greater than about 12%, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or about 99.99% or more. The yield of the VER from the bis(hy droxy ((Ci-Cio)hy drocarby l)ether of the bisphenol, or from the bisphenol, can be any suitable yield, such as about 10%> or less, or less than, equal to, or greater than about 12%>, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or about 99.99% or more. The conversion of the bis(hy droxy ((Ci- Cio)hy drocarby l)ether of the bisphenol can be any suitable conversion, such as about 10%> to about 100%, or such as about 10% or less, or less than, equal to, or greater than about 12%, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or about 99.99% or more.

[0063] In some embodiments, the present invention provides a one pot method of forming VER from bisphenol. Both the reaction of the bisphenol with the (Ci-

Cio)hy drocarby lpoly ol to form the bis(hy droxy ((Ci-Cio)hy drocarbyl)ether of the bisphenol, and the reaction of the bis(hy droxy ((Ci-Cio)hy drocarby l)ether ofthe bisphenol with the vinyl carboxylic acid or salt, ester, or acid halide thereof to form the VER, are p erformed in a single reaction vessel without any purification or workup between the reactions.

M ethod for p roducing a bisflry droxy ((C_-Cm)h drocarby Pettier of a bisp henol.

[0064] In various embodiments, the present invention provides a method for producing a bis(hy droxy ((Ci-Cio)hy drocarby l)ether of a bisphenol. The method can include any embodiment of reacting a bisphenol with a (Ci-Cio)hydrocarbylpolyol to formthe bis(hy droxy ((Ci-Cio)hy drocarby Oether ofthe bisphenol described herein. The reaction can occur in a single reaction vessel.

[0065] The method can be a method for producing bisphenol A bis(2,3- dihydroxypropyl)ether (BABDHPE) including reacting bisphenol A with a glycerin to form the B ABDHPE.

Method for producing gly cerol carbonate methacrylate.

[0066] In various embodiments, the present invention provides a method for producing glycerol carbonate methacrylate. The method can include reacting glycerol carbonate with methyl methacrylate and zirconium acetylacetonate, to form the glycerol carbonate methacrylate. The method can further include reacting glycerin and a dimethyl carbonate, to form the gly cerol carbonate.

Examples

[0067] 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.

Part i Example I-l . One pot synthesis ofbisphenol A bis(2.3-dihydroxypropynether (BABDHPE).

[0068] Materials: Bisphenol A, diethylene carbonate and potassium carbonate were procured from Sigma Aldrich and utilized without further purification. Crude glycerol as a bio-waste was procured from Maine Standard Biofuels. Glycerol in pure from was obtained using vacuum distillation.

[0069] In a single necked round bottom flask bisphenol A (10 g 43.80 mmol), glycerol (24.20 g 262.82 mmol), diethyl carbonate (15.52 g 131.4 mmol) and potassium carbonate (3 g 21.70 mmol) were introduced. The flask was connected to a Claisen distillation setup and the reaction mixture was vigorously stirred at 110 °C. After 18 h the reaction was stopped by first apply ing 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 crude reaction product was washed twice with 500 mL water to remove any unreacted glycerol. The 99% pure bisphenol A bis(2,3- dihy droxy prop yl)ether was isolated in quantitative yields. The reaction is illustrated in Scheme 1.

[0070] Scheme 1. Reaction scheme for synthesis ofbisphenol A bis(2,3- dihy droxy prop yl)ether (BABDHPE).

[0071] The purity of the reaction product was determined using protonNMR. FIG. 1 illustrates a protonNMR of isolated BABDHPE in DM SO-d ⁶ . This solvent free reaction occurs through in-situ formation of glycerol carbonate as described in literature. The reaction can also be performed using commercially available glycerol carbonate instead of glycerol and diethyl carbonate. Example 1-2. Synthesis of VER.

[0072] Materials: Methyl methacry late and Potassium Carbonate were procured from

Sigma Aldrich and utilized without further purification. The isolated BABDHPE was utilized for the reaction.

[0073] In a single necked round bottom flask bisphenol A bis(2,3- dihydroxypropyl)ether (l g, 2.65 mmol), as received methyl methacry late (1.32 g, 13.28 mmol) and potassium carbonate (300 mg, 2.17 mmol) were introduced. The flask was connected to a Claisen distillation setup and the reaction mixture was vigorously stirred at 90 °C. After 18 h the reaction was stopped by applying vacuum to remove any unreacted methyl methacry late and the methanol byproduct. The reaction is illustrated in Scheme 2.

[0074] Scheme 2. Reaction scheme for synthesis of VER by transesterification of

BABDHPE.

[0075] FIG. 2 illustrates a proton NMRof the synthesized VER in DM SO-d ⁶ .

Potassium carbonate was selected as an example here to demonstrate the feasibility of the reaction protocol. A 25% conversion was obtained in the current reaction protocol as evidenced by thepresence of vinyl protons around 6.04 and 5.61 ppm.

[0076] The experiment was re-performed using a reaction temperature of 110 °C and using low vacuum, obtaining a conversion of about 99%.

Example 1-3. Single pot synthesis of VER.

[0077] The cataly st (potassium carbonate) utilized for the reactions described in

Examples I-l and 1-2 is the same and it is used in same concentrations. Hence, the above two reactions can be combined to obtain VER.

[0078] Materials: Bisphenol A, diethylene carbonate, potassium carbonate, and methyl methacry late were procured from Sigma Aldrich and utilized without further purification. Crude glycerol as a bio-waste was procured from Maine Standard Biofuels. Glycerol in pure from was obtained using vacuum distillation.

[0079] Procedure: In a single necked round bottomflask Bisphenol A (1 g 4.38 mmol), Glycerol (2.42 g 26.28 mmol), Diethyl carbonate (1.552 g 1.314 mmol) and Potassium Carbonate (300 mg 2.17 mmol) were introduced. The flask was connected to a Claisen distillation setup and the reaction mixture was vigorously stirred at 110 °C. After 18 h the reaction was stopped by first applying vacuum to remove any unreacted diethyl carbonate, glycerol, and ethanol byproduct.

[0080] To the crude reaction mixture 5 mL of dimethyl sulfoxide was added to reduce the viscosity of the reaction mixture and 3 mL of methyl methacry late was added. The transesterification reaction was performed at 110 °C with the application of mild vacuum to remove the azeotrope formed by methanol and methyl methacry late. After 12 hours the vacuum was increased to remove any unreacted methyl methacry late and methanol byproduct. The crude reaction mixture in dimethyl sulfoxide was then introduced into 1 :8 mixture of methanol :deionized water to precipitate the product and centrifuged to obtain a viscous precipitate. The precipitate was washed 3 times with 1 :8 mixture of

methanol :deionized water to remove any trapped methyl methacry late and glycerol derivative. The resulting crude product was analyzed by proton NMR and a 99% conversion was observed. The purification of the product was done by column chromatography on silica gel with a mixture of 3 :7 hexanes:ethyl acetate as the eluent. The first fraction contained the VER product. A proton NMR of the VER product in DM SO d ⁶ is shown in FIG. 3.

Example 1-4. Polymerization of VER with sty rene.

[0081] The one pot-synthesized VER of Example 1-3 was mixed with 33 wt% sty rene, which is similar to the commercially available Derakane ^® 441-400. For curing 1.5 parts per hundred (phr) methyl ethyl ketone peroxide (MEKP) was used as the initiator and 0.2 phr cobalt napthenate (6%) was used as the accelerator. The formulation was then cured at 25 °C for 6 hours followed by post curing at 110 °C for 1 hour, providing a stiff non-tacky cured sample was obtained. A photograph of the cured sample is shown in FIG. 4.

[0082] The glass transition temp erature (T _g ) of the obtained sample was determined from the peak in Tan δ values using Dynamic Mechanical Analysis. The sample had a T _g of 118 °C (FIG. 5) compared to a reported 135 °C T _g for Derakane ^® 441-400. The flexural storage modulus of the sample was observed tobe around 3.1 GPA at room temperature which is similar to the 3.4 GPA flexural modulus for Derakane 441-400. Barcol Hardness measurements were performed according to ASTM D-2583 and a Barcol hardness of 40 was observed for the cured samples, which is comparable tothe barcol hardness of 35 reported for Derakane ^® 441-400.

Part II.

[0083] Materials. Glycerin (Maine Standard Biofuels), potassium carbonate (99 %

Sigma-Aldrich), dimethyl carbonate (99 % Alfa-Aesar), sodium sulfate (99.9 % Alfa-Aesar), methyl methacry late (99.9 % Alfa-Aesar).

[0084] Characterization. ¾ NMR spectra of the synthesized materials were recorded at 25 °C on a Bruker 500 MHz spectrometer using DM SO (Cambridge IsotopeLab., Inc.) as the solvent and tetramethy lsilane (TM S) as the internal reference (δ H 0.00).

Example II- 1. Refinement of glycerol carbonate methacry late (GCMA) from glycerin.

[0085] The GCMA was synthesized by atwo-step organic synthesis. Thefirst intermediate, glycerol carbonate, was synthesized from glycerin and dimethyl carbonate under basic condition. GCMA was synthesized by reaction of glycerol carbonate and methyl methacry late using zirconium acetylacetonate as illustrated in Scheme 3.

[0086] Scheme 3. Synthesis of vinyl ester oligomer from phenol and glycerin.

[0087] Glycerol carbonate. In a typical setup, a250 mL flask equipped with a magnetic stirrer, condenser and thermometer was charged with glycerin (40.05 g, 0.435 mol), dimethyl carbonate (117.45 g, 1.305 mol) and K2CO3 (1.8 g, 13.05 mmol). Thereaction mixture was refluxed (73-75 °C) for 3 h. After completion of the reaction, methanol and the excess of dimethyl carbonate were distilled off at 40 °C under reduced pressure. The remaining glycerol carbonate was analyzed by ¾ NMR and FT-IR spectroscopy .

[0088] Glycerol Carbonate Methacrylate. A round-bottomed flask was placed in an oil bath with magnetic stirring with a distillation apparatus over it. A flask was charged with 11.8 g (0.1 mole) of glycerol carbonate and 60.0 g (0.6 mole) of methyl methacrylate and 1.8 g of zirconium acetylacetonate and the mixture heated to 90 °C for 48 h. The reaction was terminated by removing the cataly st by addition of dilute phosphoric acid and removed by centrifugation. The organic layer was then washed with water to remove unreacted glycerol carbonate. Theremaining methyl methacrylate was removed using a rotary evaporator, and the product was confirmed by 1H NMR and ¹³ C NMR.

Example II-2. Synthesis of vinyl ester resins (VERY [0089] A 25 mL round-bottomed flask was charged with bisphenol A (1.14 g, 5 mmol), GCMA (1.86 g, 10 mmol), and potassium carbonate (0.030 g). The flask had a continuous flow of argon, and the temp erature was raised to 90 °C, which was maintained for 18 h. After the reaction, the highly viscous liquid was transferred to a glass vial, and the product was analyzed by TLC, 1H NMR, and FT-IR.

Example II-3. Analy sis of results.

[0090] GCMA was synthesized using glycerin as the main precursor. Gly cerin is a side-product of the transesterification of triglyceride in manufacturing of biodiesel or the hydroly sis of triglyceride during saponification. Vegetable glycerin was obtained from a local vendor Bulkapothecary (Streetsboro, OH), and crude glycerin from biodiesel manufacturing unit from Maine Standard Biofuel (Portland, ME).

[0091] Glycerol carbonate, a first intermediate in the synthetic route to GCMA from gly cerin, is an important material having a large number of applications in various fields. Various approaches had been adopted by different group s for the synthesis of glycerol carbonate; such as, using (a) Novozyme 435 cataly st and dimethyl carbonate as a precursor, and (b) metal oxide as a cataly st and urea as a precursor. In the present new approach, glycerol carbonate was synthesized by reaction between glycerin and dimethyl carbonate at 73 °C for 3 h in the presence of p otassium carbonate. Firstly, the reaction was performed at 73 °C and the glycerol carbonate was synthesized successfully . The product formation was confirmed by ¾ NMR as shown in FIG. 6. The peak integration value suggested -98.5 % conversion of glycerin to glycerol carbonate at 73 °C. In order to complete the reaction to 100.0 %, the reaction temp erature was increased to 100 °C; however, as the temperature increased to 100 °C, formation of some side product was observed and unreacted glycerin was also found in the final mixture.

[0092] Glycerol carbonate methacry late (GCMA) is one of the precursors for the synthesis of vinyl ester resin monomer along with bisphenol A and tetrabromobisphenol A. The GCMA is synthesized by transesterification between methyl methacry late and glycerol carbonate in the presence of zirconium acetylacetonate as a cataly st as mentioned previously . Firstly, the temperature was maintained in the reaction flask to 70 °C and then it was raised to 100 °C over a p eriod of 48 h. The cataly st was neutralized by hy droly sis with dilute phosphoric acid and removed by centrifugation. The remaining liquid was decanted in the flask and water was added to the reaction mixture. The organic layer was taken out and the excess of methyl methacry late was removed using a rotary evap orator. The structure of GCM A was confirmed by ¾ NMR as shown in FIG. 7. The GCM A was isolated with 81.0% yield.

[0093] VER are formulated from VER monomer using a solvent/reactive diluent, typically styrene, as well as additives to meet specific needs. In general, VER has several advantages over other polymers. For example, toughened and brominated VER produces resins with higher strengths than polyesters and lower viscosity than epoxies. This low viscosity is critical for fabricating large ship structures by vacuum infusion. Fiberglass- reinforced VER composites are preferred for many top side applications where low detectability and radar transmission are important. Recent advances in compatible sizing have enabled stiffer reinforcement of VERs using carbon fiber.

[0094] In the present Examples, the VER monomer was synthesized by aone pot reaction between BP A and GCMA in the presence of potassium carbonate as a cataly st. The reaction was performed at 90 °C using a magnetic stirrer. The ^X H NMR did not exhibit the - OH peak of the BP A, so it was presumed that the reaction was 100 % complete as shown in FIG. 8. The product was purified by initially dissolving in acetone and later precipitation in water. VER settled down in acetone-water mixture and was later isolated and dried under vacuum at room temperature.

[0095] 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.

Additional Embodiments.

[0096] The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance:

[0097] Embodiment 1 provides a method for producing a vinyl ester resin (VER), the method comprising:

reacting a bisphenol, a bis(hy droxy((Ci-Cio)hydrocarbyl)ether of the bisphenol, or a combination thereof with a vinyl carboxylic acid or a salt, ester, or acid halide thereof, to form the VER.

[0098] Embodiment 2 provides the method of Embodiment 1, further comprising reacting thebisphenol with a (Ci-Cio)hydrocarbylpolyol to form the bis(hydroxy((Ci- Cio)hydrocarbyl)ether of the bisphenol.

[0099] Embodiment 3 provides the method of any one of Embodiments 1-2, further comprising polymerizing the VER.

[00100] Embodiment 4 provides the method of any one of Embodiments 1-3, further comprising polymerizing the VER with a vinyl-substituted organic comp ound.

[00101] Embodiment 5 provides the method of Embodiment 4, wherein the vinyl- substituted organic compound is styrene.

[00102] Embodiment 6 provides the method of any one of Embodiments 4-5, wherein the vinyl- substituted organic compound is a vinyl ester formed from the (Ci- Cio)hydrocarbylpolyol and the vinyl carboxylic acid or the salt, ester, or acid halide thereof.

[00103] Embodiment 7 provides the method of any one of Embodiments 2-6, wherein the reaction of the bisphenol with the (Ci-Cio)hydrocarbylpoly ol to form the

bis(hydroxy((Ci-Cio)hydrocarbyl)ether ofthe bisphenol occurs in single reaction vessel.

[00104] Embodiment 8 provides the method of any one of Embodiments 1-7, wherein the bisphenol is chosen from bisphenol A (2,2-bis(4-hy droxyp heny l)p ropane), bisphenol AP (1, 1 -bis(4-hy droxy p heny 1)- 1 -p henyl-ethane), bisp henol AF (2,2-bis(4- hy droxy p heny l)hexafluorop rop ane), bisp henol B (2,2-bis(4-hy droxy p heny l)butane), bisphenol BP (bis-(4-hy droxyp heny l)dip heny lmethane), bisphenol C (2,2-bis(3 -methy 1-4- hy droxyp heny l)p ropane), bisp henol E (l, l-bis(4-hy droxyp heny l)ethane), bisp henol F (bis(4- hydroxy dip heny l)methane), bisphenol G (2,2-bis(4-hy droxy -3-isopropyl-phenyl)propane), bisp henol PH (5 , 5 ' -( 1 -methy lethy liden)-bis [ 1 , -(bisp heny l)-2-ol]p ropane), bisp henol TM C (1, 1 -bis(4-hy droy p henyl)-3 ,3,5 -trimethyl-cy clohexane), bisp henol Z ( 1 , 1 -bis(4- hy droxyp heny l)-cyclohexane), and combinations thereof. [00105] Embodiment 9 provides the method of any one of Embodiments 1-8, wherein the bisphenol is bisphenol A (2,2-bis(4-hydroxyphenyl)propane).

[00106] Embodiment 10 provides the method of any one of Embodiments 2-9, wherein the (Ci-Cio)hydrocarbylp olyol is a (Ci-Cio)hydrocarbyltriol.

[00107] Embodiment 1 1 provides the method of any one of Embodiments 2-10, wherein the (Ci-Cio)hy drocarbylpolyol comprises at least two terminal hydroxy group s.

[00108] Embodiment 12 provides the method of any one of Embodiments 2-1 1, wherein the (Ci-Cio)hy drocarbylpoly ol is a propanetriol.

[00109] Embodiment 13 provides the method of any one of Embodiments 2-12, wherein the (Ci-Cio)hy drocarbylpolyol is glycerol.

[00110] Embodiment 14 provides the method of any one of Embodiments 2-13, wherein the reaction of the bisphenol with the (Ci-Cio)hy drocarbylpoly ol is performed in the presence of one or more etherification cataly sts.

[00111] Embodiment 15 provides the method of any one of Embodiments 2-14, wherein the reaction of the bisphenol with the (Ci-Cio)hy drocarbylpoly ol is performed in the presence of a base.

[00112] Embodiment 16 provides the method of Embodiment 15, wherein the base is a carbonate salt.

[00113] Embodiment 17 provides the method of Embodiment 16, wherein the carbonate salt is p otassium carbonate.

[00114] Embodiment 18 provides the method of any one of Embodiments 2-17, wherein the reaction of the bisphenol with the (Ci-Cio)hy drocarbylpoly ol is performed in the presence of an ester.

[00115] Embodiment 19 provides the method of Embodiment 18, wherein the ester is diethyl carbonate.

[00116] Embodiment 20 provides the method of any one of Embodiments 1-19, wherein thebis(hydroxy ((Ci-Cio)hydrocarbyl)ether of the bisphenol is bisphenol A bis(2,3- dihy droxy propyl)ether (BABDHPE).

[00117] Embodiment 21 provides the method of any one of Embodiments 1-20, wherein the reaction of the bisphenol or the bis(hy droxy ((Ci-Cio)hy drocarbyl)ether of the bisphenol with the vinyl carboxylic acid or the salt, ester, or acid halide thereof to form the VER occurs in a single reaction vessel. [00118] Embodiment 22 provides the method of any one of Embodiments 1-21, wherein the vinyl carboxyhc acid or salt, ester, or acid halide thereof is a substituted or unsubstituted (Ci-Cio)hydrocarbyl ester of a (C3-Cio)vinylcarboxylic acid.

[00119] Embodiment 23 provides the method of Embodiment 22, wherein the vinyl carboxyhc acid or the salt, ester, or acid halide thereof is a substituted or unsubstituted (Ci- Cio)hydrocarbyl ester of methacrylic acid.

[00120] Embodiment 24 provides the method of any one of Embodiments 1-23, wherein the vinyl carboxyhc acid or the salt, ester, or acid halide thereof is methyl methacrylate.

[00121] Embodiment 25 provides the method of any one of Embodiments 1-24, wherein the vinyl carboxyhc acid or the salt, ester, or acid halide thereof is glycerol carbonate methacrylate.

[00122] Embodiment 26 provides the method of any one of Embodiments 1-25, wherein the reaction of the bisphenol or the bis(hy droxy((Ci-Cio)hy drocarbyl)ether of the bisphenol with the vinyl carboxyhc acid or the salt, ester, or acid halide thereof to form the VER is performed in the presence of one or more esterification or transesterification cataly sts.

[00123] Embodiment 27 provides the method of any one of Embodiments 1-26, wherein the reaction of the bisphenol or the bis(hydroxy((Ci-Cio)hy drocarbyl)ether of the bisphenol with the vinyl carboxyhc acid or the salt, ester, or acid halide thereof to form the VER is performed in the presence of a base.

[00124] Embodiment 28 provides the method of Embodiment 27, wherein thebase is a carbonate salt.

[00125] Embodiment 29 provides the method of Embodiment 28, wherein the carbonate salt is potassium carbonate.

[00126] Embodiment 30 provides the method of any one of Embodiments 1-29, wherein the VER has the structure:

[00127] Embodiment 31 provides the method of any one of Embodiments 2-30, wherein both the reaction of the bisphenol with the (Ci-Cio)hydrocarbylpoly ol to form the bis(hydroxy((Ci-Cio)hydrocarbyl)ether of the bisphenol, and the reaction of the bis(hydroxy((Ci-Cio)hydrocarbyl)ether ofthe bisphenol with the vinyl carboxylic acid or the salt, ester, or acid halide thereof to form the VER, are p erformed in a single reaction vessel without any purification or work up between the reactions.

[00128] Embodiment 32 provides a method for producing a vinyl ester resin (VER), the method comprising:

reacting bisphenol A with glycerin to form bisphenol A bis(2,3-dihydroxypropyl)ether (BABDHPE); and

reacting the BABDHPE with methyl methacry late to form the VER, wherein the VER has the structure:

[00129] Embodiment 33 provides a method for producing a bis(hy droxy((Ci-

Cio)hydrocarbyl)ether of a bisphenol, the method comprising:

reacting a bisphenol with a (Ci-Cio)hy drocarbylp oly ol to form thebis(hy droxy ((Ci- Cio)hydrocarbyl)ether of the bisphenol.

[00130] Embodiment 34 provides a method for producing bisphenol A bis(2,3- dihy droxy p rop yl)ether (BABDHPE), the method comp rising:

reacting bisphenol A with glycerin to form the BABDHPE.

[00131] Embodiment 35 provides a method for producing glycerol carbonate methacry late, the method comprising:

reacting gly cerol carbonate with methyl methacry late and zirconium acetylacetonate, to form the glycerol carbonate methacry late.

[00132] Embodiment 36 provides the method of Embodiment 35, further comprising reacting glycerin and a dimethyl carbonate, to form the glycerol carbonate.

[00133] Embodiment 37 provides a method for producing a vinyl ester resin (VER), the method comprising:

reacting bisphenol A with gly cerol carbonate methacry late, to form the VER, wherein the VER has the structure:

[00134] Embodiment 38 provides the method of Embodiment 37, further comprising: reacting glycerin and a dimethyl carbonate, to form glycerol carbonate; and reacting the glycerol carbonate with methyl methacrylate and zirconium

acetylacetonate, to form the glycerol carbonate methacrylate.

[00135] Embodiment 39 provides the method of any one or any combination of

Embodiments 1-38 optionally configured such that all elements or options recited are available to use or select from.