Cationizing agents for saccharides and methods

Abstract

Compositions that may be used as cationizing agents for compounds that include hydroxyl groups, such as saccharides. Methods of forming compositions, such as cationizing agents, which may use starting materials from byproduct streams from processes for producing polymerizable monomers. Cationized saccharides and methods of forming cationized saccharides.

Description

CATIONIZING AGENTS FOR SACCHARIDES AND METHODSCross-reference to Related Applications

[0001] This application claims priority to Finnish Application No. 20245989, filed August 8, 2024, and U.S. Provisional Patent Application No. 63 / 661,196, filed June 18, 2024, which are incorporated by reference herein.Technical Field

[0002] The present disclosure generally relates to compositions, such as cationizing agents for hydroxyl-containing compounds, such as saccharides, methods of recovering compositions from byproduct streams, and methods of using compositions.Background

[0003] Byproduct streams from processes for producing (meth)acrylate monomers, such as processes for producing dimethylaminoethyl acrylate (ADAME), can include one or more useful materials.

[0004] Some ADAME process plants produce significant amounts of toxic organic byproducts (e.g., 3,000 tons / a or more), and, in some instances, the byproducts include about 1 % to about 15 %. by weight of methyl 3-(2-dimethylamino)ethoxy)propanoate. and about 10 % to about 30 %, by weight, of 2-(dimethylamino)ethyl 3-(2- dimethylamino)ethoxy)propanoate, which could be used as a starting material or precursor in a number of synthetic schemes.

[0005] There remains a need for potentially new precursors and reactants, such as cationizing agents, and methods of recovering precursor and reactors from discarded streams.Brief Summary

[0006] Provided herein are compositions, which may include a cationizing agent, and methods of using or forming compositions, including methods that rely on readily available and / or relatively inexpensive starting materials, such as starting materials that are present in a byproduct stream from other processes.

[0007] In one aspect, methods of forming compositions are provided. The methods, in some embodiments, include (i) providing a starting material that includes one or more byproducts of a process, such as a process that produces a polymerizable monomer or a precursor thereof; and (ii) contacting the starting material with a quatemizing agent to form aquatemized material. The starting material may include a tertiary amine. The process that produces the polymerizable monomer may be a process that produces dimethylaminoethyl acrylate (ADAME) or dimethylaminoethyl methacrylate. The methods also may include contacting the starting material and a reactant that includes one or more hydroxyl functional groups. The one or more hydroxyl functional groups of the reactant and an ester functional group of the starting material may react via a trans-esterification reaction. The contacting of the starting material and the reactant that includes one or more hydroxyl functional groups may occur before and / or after the contacting of the starting material and the quatemizing agent. The reactant that includes one or more hydroxyl groups may be a saccharide.

[0008] In another aspect, compositions are provided. In some embodiments, the compositions include a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), a compound of formula (V), a compound of formula (VI), a compound of formula (VII), a compound of formula (VIII), a compound of formula (IX), a compound of formula (X), a compound of formula (XI), a compound of formula (XII), or a combination thereof:

[0009] wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14are independently selected from a C1-C20 hydrocarbyl; and wherein Hal is a halide.

[0010] In some embodiments, the composition is of formula (A) or formula (B):

[0011] wherein Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, R1, R>, and Rkare independently selected from the group consisting of hydrogen, formula (1). and formula (2); wherein at least one ofRa, Rb, Rc, Rd, Re, and Rfis not hydrogen; wherein at least one of Rg, Rb, R1, Rf and Rkis not hydrogen;formula (1);formula (2);

[0012] wherein R is a C1-C20 hydrocarbyl;

[0013] wherein Hal is a halide; and

[0014] wherein n is 10 to 1,000,000.

[0015] Additional aspects will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the aspects described herein. The advantages described herein may be realized and attained by means of the elements and combinations particularly pointed out in the listing of embodiments and the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.Detailed Description

[0016] Provided herein are compositions, such as cationizing agents, which may be used to cationize a compound, such as a compound that includes a hydroxyl group. Also provided herein are methods of forming compositions, such as cationizing agents, and methods of using compositions for one or more purposes, such as cationizing a saccharide.

[0017] Compositions

[0018] In some embodiments, the compositions provided herein include a compound of formula (I), a compound of formula (II). a compound of formula (III), a compound of formula (IV), a compound of formula (V), a compound of formula (VI), a compound of formula (VII), a compound of formula (VIII), a compound of formula (IX), a compound of formula (X), a compound of formula (XI). a compound of formula (XII), or a combination thereof:

[0019] wherein R1. R2. R3. R4. R5. R6. R7, R8, R9, R10. R11, R12, R13. and R14are independently selected from a C1-C20 hydrocarbyl; and wherein Hal is a halide.

[0020] When the formulas or compounds depicted herein include a positively charged moiety or atom, such as a positively charged quaternary nitrogen atom, the formulas or compounds may include any counteranion. The counterion depicted in the formulas herein, for convenience, is a halide. The counteranions, however, may include other inorganic ions or organic ions, such as an alkyl sulfonate or an aryl sulfonate.

[0021] A compound of any one or more of formulas (I) — (XII) may be present in the compositions provided herein. In some embodiments, the compositions include a compoundof formula (III), a compound of formula (IV), a compound of formula (V), a compound of formula (VIII). a compound of formula (X). a compound of formula (XI), or a combination thereof.

[0022] The compounds of formulas (I) — (XII) may include any halide. In some embodiments, the halide is independently selected from the group consisting of fluoride, chloride, bromide, and iodide. In some embodiments, the halide is chloride.

[0023] Each R1, R2, R3, R4, R5, R6, R7, R8. R9. R10, R11, R12. R13, and R14of formulas (I) — (XII) may be independently selected from any of the substituents described herein, such as a C1-C20 hydrocarbyl. In some embodiments, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14are independently selected from a Ci-Cis hydrocarbyl, a C1-C16 hydrocarbyl, a C1-C14 hydrocarbyl, a C1-C12 hydrocarbyl. a C1-C10 hydrocarbyl, a Ci-Cs hydrocarbyl, a Ci-Ce hydrocarbyl, a C1-C4 hydrocarbyl, a Ci-Cs hydrocarbyl, a Ci-Cs hydrocarbyl, or a Ci hydrocarbyl. In some embodiments, R1, R2, R3, R4, R3, R6, R7, R8, R9, R10, R11, R12, R13, and R14are methy l.

[0024] In some embodiments, the compositions include a contact product of (i) one or more compounds of any one or more of formulas (I) — (XII), and (ii) a compound that includes at least one hydroxyl group, such as a saccharide. The compound that includes at least one hydroxyl group, such as a saccharide, may react with the one or more compounds of any one or more of formulas (I) — (XII) via a trans-esterifi cation reaction to form the contact product. When the compound that includes at least one hydroxyl group is a saccharide, the compositions described herein may include a compound of the following formula:A— O— R;

[0025] wherein A is a saccharide-derived moiety'; and

[0026] wherein R is selected from a substituent derived from one or more compounds of formulas (I) — (XII), or R is selected from formula (1) or formula (2);

[0027] wherein R is a C1-C20 hydrocarbyl; and wherein Hal is a halide.

[0028] In some embodiments, the compositions include one or more compounds of formula (A), formula (B), or a combination thereof:

[0029] wherein Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, R1. R'. and Rkare independently selected from the group consisting of hydrogen, formula (1). and formula (2);

[0030] wherein at least one of R“, Rb, Rc, Rd, Re, and R1is not hydrogen;

[0031] wherein at least one of Rg, Rh, R1, R>, and Rkis not hydrogen;

[0032]

[0033]

[0034] wherein R is a C1-C20 hydrocarbyl; wherein Hal is a halide, as described herein; and wherein n is 10 to 1,000,000.

[0035] The compositions provided herein may include compounds having any degree of substitution. For example, if a compound that includes at least one hydroxyl group has 4 hydroxyl groups per molecule or repeat unit, then the degree of substitution may be about 0.1 to 4, wherein a degree of substitution of 0.1 indicates that a hydroxyl group on one of every' 10 molecules or repeat units is substituted with a cationized moiety, and wherein a degree ofsubstitution of 4 indicates that all 4 hydroxyl groups of each molecule or repeat unit is substituted with a cationized moiety.

[0036] In some embodiments, a degree of substitution of formula (A) is about 0. 1 to about 3, about 0.5 to about 3, about 0. 1 to about 2, about 0.5 to about 2, about 0. 1 to about 2.5, about 0.5 to about 1.5, or about 1. In some embodiments, a degree of substitution of formula (B) is about 0. 1 to about 5, about 0.5 to about 5, about 0. 1 to about 4, about 0.5 to about 4, about 0. 1 to about 3, about 0.5 to about 3, about 0.1 to about 2, about 0.5 to about 2. about 0.1 to about 1.5, about 0.5 to about 1.5, or about 1.

[0037] In some embodiments, in formula (A) and formula (B), the C1-C20 hydrocarbyl is methyl, and the halide substituent is chloride.

[0038] Methods

[0039] Also provided herein are methods for forming compositions. In some embodiments, the methods of forming compositions include (i) providing a starting material, such as a starting material that includes one or more byproducts of a process that produces a polymerizable monomer or a precursor thereof; and (ii) contacting the starting material with a quatemizing agent to form a quatemized material. The starting material may include at least one amine functional group, such as at least one tertiary amine.

[0040] The methods also may include contacting the starting material and a reactant that includes one or more hydroxyl functional groups, such as a saccharide. The one or more hydroxyl functional groups of the reactant and an ester functional group of the starting material may react via a trans-esterification reaction or other reaction.

[0041] The contacting of the starting material and the reactant including one or more hydroxyl functional groups may occur before the contacting of the starting material and a quatemizing agent (see, e.g.. Scheme 2), or after the contacting of the starting material and the quatemizing agent (see, e.g.. Scheme 1).

[0042] After the contacting of the starting material and the reactant including one or more hydroxyl functional groups, the reactant that includes one or more hydroxyl functional groups may have any degree of substitution described herein.

[0043] Quatemizing Agents

[0044] The quatemizing agents used in the methods provided herein may include any compound that — upon contacting an amine (such as a tertiary' amine) — is effective to convert the amine to an ammonium salt (such as a quaternary ammonium salt). The quatemizing agent, as described herein, may form an ammonium salt that features any suitable counteranion, such as a halide or any other described herein.

[0045] In some embodiments, the quatemizing agent is of the following formula: R-Hal;

[0046] wherein R is a C1-C20 hydrocarbyl, and Hal is a halo-substituent. The halo- substituent may be independently selected from the group consisting of fluoro-, chloro-, bromo-, and iodo-. In some embodiments, the halo-substituent is chloro-. In some embodiments, R is selected from a Ci-Cis hydrocarbyl, a C1-C16 hydrocarbyl, a C1-C14 hydrocarbyl. a C1-C12 hydrocarbyl, a C1-C10 hydrocarbyl. a Ci-Cs hydrocarbyl. a Ci-Cs hydrocarbyl, a C1-C4 hydrocarbyl, a C1-C3 hydrocarbyl, a C1-C3 hydrocarbyl, or a Ci hydrocarbyl. In some embodiments, the quatemizing agent includes an alkyl halide. In some embodiments, Hal is chloro-, and R is methyl.

[0047] A starting material generally may be contacted with any amount of a quatemizing agent. In some embodiments, a starting material is contacted with an amount of moles of the quatemizing agent that equals or exceeds an amount of moles of nitrogen atoms, such as tertiary nitrogen atoms, in the starting material.

[0048] Starting Materials

[0049] Generally, any starting material may be used in the methods described herein. In some embodiments, the starting material includes one or more byproducts of a process that produces a polymerizable monomer or a precursor thereof. The polymerizable monomer may be an acrylate monomer, a methacrylate monomer, or a combination thereof.

[0050] In some embodiments, the polymerizable monomer includes dimethyl aminoethyl acrylate (ADAME). Therefore, the starting material may include methyl 3-(2-(dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl 3-methoxypropanoate, ethyl 3-(2-(dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl 3-ethoxypropanoate, 2-(dimethylamino)ethyl 3-(2-(dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl acrylate, 2-(dimethylamino)ethan- 1 -ol, or a combination thereof.

[0051] In some embodiments, the providing of the starting material includes (i) providing a byproduct stream comprising, consisting essentially of. or consisting of methyl 3- (2-(dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl 3-methoxypropanoate, ethyl 3-(2-(dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl 3 -ethoxy propanoate, 2- (dimethylamino)ethyl 3-(2-(dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl acrylate, 2-(dimethylamino)ethan-l-ol, methyl 3-methoxypropanoate, ethyl 3- ethoxypropanoate. or a combination thereof,2-(dimeOiyiam^ m^etlwH «dethyl 3*Mtaiwqp®rwte

[0052] and (ii) separating from the byproduct stream at least a portion of the methyl 3- (2-(dimethylamino)ethoxy)propanoate, at least a portion of the 2-(dimethylamino)ethyl 3- methoxy propanoate, at least a portion of the ethyl 3-(2-(dimethylamino)ethoxy)propanoate, at least a portion of the 2-(dimethylamino)ethyl 3 -ethoxy propanoate, at least a portion of the 2- (dimethylamino)ethyl 3-(2-(dimethylamino)ethoxy) propanoate, at least a portion of the 2-(dimethylamino)ethyl acrylate, at least a portion of the 2-(dimethylamino)ethan-l-ol. at least a portion of the methyl 3-methoxypropanoate. at least a portion of the ethyl 3- ethoxypropanoate, or a combination thereof.

[0053] In some embodiments, the polymerizable monomer includes dimethylaminoethyl methacrylate. Therefore, the starting material may include 2- (dimethylamino)ethyl 3-methoxy-2-methylpropanoate, methyl 3-[2-(dimethylamino)ethoxy]- 2-methylpropanoate. 2-(dimethylamino)ethyl 3-[2-(dimethylamino)ethoxy]-2- methylpropanoate, 2-(dimethylamino)ethyl methacrylate, 2-(dimethylamino)ethan-l-ol, or a combination thereof,2^tawth|riwih®^iiBri-1^i

[0054] In some embodiments, the producing of the starting material includes (i) providing a byproduct stream that includes 2-(dimethylamino)ethyl 3-methoxy-2- methylpropanoate, methyl 3-[2-(dimethylamino)ethoxy]-2-methylpropanoate, 2- (dimethylamino)ethyl 3-[2-(dimethylamino)ethoxy]-2-methylpropanoate, 2- (dimethylamino)ethyl methacry late, 2-(dimethylamino)ethan-l-ol, or a combination thereof,; and

[0055] (ii) separating from the byproduct stream at least a portion of the 2-(dimethylamino)ethyl 3-methoxy-2-methylpropanoate, at least a portion of the methyl 3-[2- (dimethylamino)ethoxy]-2-methylpropanoate, at least a portion of the 2-(dimethylamino)ethyl 3-[2-(dimethylamino)ethoxy]-2-methylpropanoate, at least a portion of the 2-(dimethylamino)ethyl methacrylate, at least a portion of the 2-(dimethylamino)ethan-l- ol, or a combination thereof.

[0056] Saccharides

[0057] Any saccharide may be used in the methods described herein. In some embodiments, the saccharide includes a monosaccharide, a disaccharide, an oligosaccharide, a polysaccharide, or a combination thereof. The monosaccharide may include glucose, fructose, galactose, mannose, or a combination thereof. The disaccharide may include sucrose, lactose, maltose, sucrose, or a combination thereof. The oligosaccharide may include glycan. raffinose, maltodextrin, cellodextrin, or a combination thereof. Thepolysaccharide may include starch, glycogen, galactogen, cellulose, chitosan, chitin, guar gum, pectin, dextran, alpha-glucan, cyclodextrin (such as beta-cyclodextrin), or a combination thereof.

[0058] When used herein with regard to the selection of a substituent (for example, any of the various “R” groups), the term “independently” indicates that (i) a substituent at a particular location may be the same or different for each molecule a formula (e.g., (i) an alkyd halide of formula R-Hal may include two molecules of the formula, with each molecule having the same or a different C1-C20 hydrocarbyl selected for R; or (ii) two differently labeled substituents selected from the same group of substituents may be the same or different (e.g., Raand Rbof formula (A) may both be selected from “a C1-C20 hydrocarbyl”, and the C1-C20 hydrocarbyls selected for Raand Rbmay be the same or different).

[0059] The phrases C1-C20 hydrocarbyl, C1-C12 hydrocarbyl , and the like, as used herein, generally refer to aliphatic, ary l, or arylalkyl groups containing 1 to 20 carbon atoms, or 1 to 12 carbon atoms, respectively, including substituted derivatives thereof. Examples of aliphatic groups, in each instance, include, but are not limited to, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclic group, and the like, and includes all substituted, unsubstituted, branched, and / or linear analogs or derivatives thereof, in each instance having, for example, 1 to 20 total carbon atoms or 1 to 12 total carbon atoms for a “C1-C20 hydrocarbyl ” and “C1-C12 hydrocarbyl”. respectively. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyd, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, and dodecyl. Cycloalkyl moieties may be monocyclic or multi cyclic, and examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl, including any heteroatom substituted derivative thereof.Additional examples of alkyl moieties have linear, branched and / or cyclic portions (e.g., 1- ethyl-4-methyl-cyclohexyl). Representative alkenyl moieties include vinyl, allyl, 1-butenyl, 2-butenyl, isobutylenyl, 1-pentenyl, 2-pentenyl, 3-methyl-l-butenyl, 2-methyl-2-butenyl, 2,3- dimethyl-2-butenyl, 1-hexenyl, 2-hexenyl. 3-hexenyl. 1-heptenyl. 2-heptenyl, 3-heptenyl, 1- octenyl, 2-octenyl, 3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1 -decenyl, 2-decenyl, and 3- decenyl. Representative alkynyl moieties include acety lenyl, propynyl, 1-butynyl, 2-butynyl, 1 -pentynyl, 2-pentynyl, 3 -methyl- 1-butynyl, 4-pentynyl, 1 -hexynyl, 2 -hexynyl, 5-hexynyl, 1- heptynyl. 2-heptynyl, 6-heptynyl, 1-octynyl, 2-octynyl, 7-octynyl, 1-nonynyl, 2-nonynyl, 8- nonynyl, 1 -decynyl, 2-decynyl and 9-decynyl. Examples of aryl or arylalkyl moietiesinclude, but are not limited to, anthracenyl, azulenyl, biphenyl, fluorenyl, indan, indenyl, naphthyl, phenanthrenyl. phenyl, 1,2,3,4-tetrahydro-naphthalene, anthracenyl, tolyl, xylyl, mesityl, benzyl, and the like, including any heteroatom substituted derivative thereof.

[0060] Unless otherwise indicated, the term “substituted”, when used to describe a chemical structure or moiety, refers to a derivative of that structure or moiety wherein (i) a multi-valent non-carbon atom (e.g., oxygen, nitrogen, sulfur, phosphorus, etc.) is bonded to one or more carbon atoms of the chemical structure or moiety (e.g.. a “substituted” C4 hydrocarbyl may include, but is not limited to, a pyrimidinyl moiety, a pyridinyl moiety, a dioxanyl moiety, a diethyl ether moiety, a methyl propionate moiety, an / V.,V- dimethylacetamide moiety, a butoxy moiety, etc., and a “substituted” aryl C12 hydrocarbyl may include, but is not limited to, an oxy dibenzene moiety, a benzophenone moiety, etc.) or (ii) one or more of its hydrogen atoms (e.g., chlorobenzene may be characterized generally as an aryl Ce hydrocarbyl “substituted” with a chlorine atom) is substituted with a chemical moiety or functional group such as acyl, alcohol, alkoxy, alkanoyloxy, alkoxy carbonyl, alkenyl, alkyl (e.g., methyl, ethyl, propyl, t-butyl), alkynyl, alkylcarbonyloxy (-OC(O)alkyl), amide (-C(O)NH-alkyl- or -alkylNHC(O)alkyl). primary, secondary, and tertiary amino (such as alkylamino, arylamino, arylalkylamino), aryl, arylalkyl, aryloxy, azo, azido, carbamoyl (- NHC(O)O-alkyl- or -OC(O)NH-alkyl), carbamyl (e.g., CONH2, as well as CONH-alkyl, CONH-aryl, and CONH-arylalkyl), carboxyl, carboxylic acid, cyano, cycloalkyl, cycloalkenyl, ester, ether (e.g.. methoxy, ethoxy), halo, haloalkyl (e.g., -CCI3, -CF3, - C(CF3)3), haloalkoxy, trihalomethanesulfonyl, trihalomethanesulfonamido, heteroalkyl, heterocycloalkyl, heteroaryl, heteroarylalkyl, isocyanate, isothiocyanate, nitrile, nitro, oxo, phosphodiester, silyl, sulfide, sulfonamide (e.g. SO2NH2), sulfone, sulfenyl, sulfinyl, sulfonyl (including alkylsulfonyl, arylsulfonyl and arylalkylsulfonyl), sulfoxide, thiocarbonyl, thiocarbamyl, thiocyanato, thiol (e.g, sulfhydryl, thioether) or urea (- NHCONH-alkyl-).

[0061] All referenced publications are incorporated herein by reference in their entirety. Furthermore, where a definition or use of a term in a reference, which is incorporated by reference herein, is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.

[0062] While certain aspects of conventional technologies have been discussed to facilitate disclosure of various embodiments, applicants in no way disclaim these technicalaspects, and it is contemplated that the present disclosure may encompass one or more of the conventional technical aspects discussed herein.

[0063] The present disclosure may address one or more of the problems and deficiencies of know n methods and processes. How ever, it is contemplated that various embodiments may prove useful in addressing other problems and deficiencies in a number of technical areas. Therefore, the present disclosure should not necessarily be construed as limited to addressing any of the particular problems or deficiencies discussed herein.

[0064] In this specification, where a document, act or item of know ledge is referred to or discussed, this reference or discussion is not an admission that the document, act or item of knowledge or any combination thereof was at the priority date, publicly available, known to the public, part of common general knowledge, or otherwise constitutes prior art under the applicable statutory provisions; or is known to be relevant to an attempt to solve any problem with which this specification is concerned.

[0065] In the descriptions provided herein, the terms “includes,” “is,” “containing,” “having,” and “comprises” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to.” When compositions or methods are claimed or described in terms of “comprising” various steps or components, the compositions or methods can also “consist essentially of’ or “consist of’ the various steps or components, unless stated otherwise.

[0066] The terms “a.” “an.” and “the” are intended to include plural alternatives, e.g., at least one. For instance, the disclosure of “a stream”, “a quatemizing agent”, and the like, is meant to encompass one, or mixtures or combinations of more than one stream, quatemizing agent, and the like, unless otherwise specified.

[0067] Various numerical ranges may be disclosed herein. When Applicant discloses or claims a range of any type, Applicant’s intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. Moreover, all numerical end points of ranges disclosed herein are approximate. As a representative example, Applicant discloses, in some embodiments, that one of several “R” groups may be a Ci-Cio hydrocarbyl. This range should be interpreted as encompassing a Ci hydrocarbyl and a Cio hydrocarbyl, and the further encompasses each of a C2, C3, C4, C5, Ce, C7, Cs, and C9, hy drocarbyl, including any ranges and sub-ranges between any of these values.

[0068] As used herein, the term “about’' means plus or minus 10 % of the numerical value of the number with which it is being used.

[0069] Examples

[0070] The present disclosure is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort may be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary' skill in the art without departing from the spirit of the present disclosure or the scope of the appended claims. Thus, other aspects of this disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the aspects disclosed herein.

[0071] Example 1 - Trans -esterification of a Saccharide

[0072] In this example, cationizing agents were prepared from the following starting materials, which were obtained from a byproduct stream of a process for making dimethylaminoethyl acrylate (ADAME).2-(dimethylamino)ethyl 3-[2- (dimethylamino)ethoxy]propanoatemethyl 3-[2-(dimetbylamino)ethoxy]propanoate

[0073] In this example, these starting materials were contacted with a quatemizing agent before or after the starting materials are contacted with a saccharide. Therefore, the starting materials were processed according to Scheme 1 and Scheme 2, and the reactants and products were analyzed via13C NMR.

[0074] Scheme 1. Trans-esteriflcation of saccharide with pre-quaternized agent

[0075] Scheme 2. Trans-esterification of saccharide with post-quaternized agent

[0076] In the foregoing reactions of this example, water was used as the solvent, and the carbon footprint of the process w as reduced because, as explained herein, the starting materials were obtained from byproduct streams from processes that produced a polymerizable monomer.

[0077] The product of the foregoing schemes of this example then may react w ith side products of the trans-esterification reactions, such as (i) methanol or (ii) choline chloride (Scheme 1) or 2-(dimethylamino)ethan-l-ol (Scheme 2).

[0078] Unlike the products of this example and other described herein, products formed by contacting a saccharide and other materials, such as 2,3-epoxypropyltrimethylammonium chloride (EPTAC), can result in products with no readily hydrolyzable function, making them less biodegradable. An example of such as compound is depicted below:2-hydroxy-A,A,A-trimethyl-3-(((2 A,3S,4S,5A)-3,4,5,6- tetrahy droxytetrahy dro-277-py ran-2-yl)methoxy )propan- 1 -aminium

[0079] Example 2 - Cationization of a Polysaccharide

[0080] In this example, a polysaccharide was contacted with 2-(dimethylamino)ethyl-3- [2-(dimethylamino)ethoxy]propanoate, which was obtained from a byproduct stream produced by a process for producing ADAME. This reaction is shown in the following scheme.

[0081] Scheme 4. Cationization of a polysaccharide

[0082] As show n in Scheme 4, the polysaccharide of this example was first contacted with 2-(dimethylamino)ethyl-3-[2-(dimethylamino)ethoxy]propanoate in the presence of a base, which resulted in a trans-esterification reaction. The product of the trans-esterificationreaction then was contacted with a quatemizing agent, which, in this example, was methyl chloride.

[0083] Embodiments

[0084] The following is a listing of non-limiting embodiments.

[0085] Compositions

[0086] Embodiment 1. A composition comprising, consisting essentially of, or consisting of a compound of formula (I), a compound of formula (II), a compound of formula(III), a compound of formula (IV), a compound of formula (V), a compound of formula (VI), a compound of formula (VII), a compound of formula (VIII), a compound of formula (IX), a compound of formula (X). a compound of formula (XI), a compound of formula (XII). or a combination thereof

[0087] wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14are independently selected from a C1-C20 hydrocarbyl;

[0088] and wherein Hal is a halide.

[0089] Embodiment 2. The composition of embodiment 1, wherein the composition comprises, consists essentially of, or consists of the compound of formula (III), the compound of formula (IV), the compound of formula (V), the compound of formula (VIII), the compound of formula (X), the compound of formula (XI), or a combination thereof.

[0090] Embodiment 3. The composition of any of the preceding embodiments, wherein the halide is independently selected from the group consisting of fluoride, chloride, bromide, and iodide.

[0091] Embodiment 4. The composition of any of the preceding embodiments, wherein R1, R2, R3, R4, R5. R6. R7. R8, R9, R10. R11, R12. R13, and R14are independently selected from a Ci-Cis hydrocarbyl, a C1-C16 hydrocarbyl, a C1-C14 hydrocarbyl, a C1-C12 hydrocarbyl, a C1-C10 hydrocarbyl, a Ci-Cs hydrocarbyl, a Ci-Ce hydrocarbyl, a C1-C4 hydrocarbyl, a C1-C3 hydrocarbyl, a C1-C3 hydrocarbyl, or a Ci hydrocarbyl.

[0092] Embodiment 5. A composition comprising, consisting essentially of, or consisting of a contact product of a saccharide and the composition of any of the preceding embodiments, wherein the saccharide and the composition of any of the preceding embodiments react via a trans-esterification reaction to form the contact product; wherein, optionally, the trans-esterification reaction occurs in the presence of a catalyst, such as a base (e g.. NaOH. KOH, K2CO3, etc ).

[0093] Embodiment 6. A composition comprising, consisting essentially of, or consisting of a compound of the following formula:

[0094] A— O— R;

[0095] wherein A is a saccharide-derived moiety;

[0096] wherein R is selected from a substituent derived from any of the compositions of the preceding embodiments, or R is selected from formula (1) or formula (2);

[0097] wherein R is a C1-C20 hydrocarbyl; and

[0098] wherein Hal is a halide.

[0099] Embodiment 7. A composition of formula (A) or formula (B):

[0100] wherein Ra. Rb. Rc. Rd. Re, Rf, Rg, Rh, R1. R'. and Rkare independently selected from the group consisting of hydrogen, formula (1 ), and formula (2);

[0101] wherein at least one of Ra, Rb, Rc, Rd, Re, and Rfis not hydrogen (for example, wherein 1 (e.g., Rd), 2 (e.g., Rdand Rf), 3 (e.g., Rd, Rf, and Re), 4, or 5 of Ra, Rb, Rc, Rd, Re, and Rfis not hydrogen);

[0102] wherein at least one of Rg, Rh, R1, R'. and Rkis not hydrogen (for example, wherein 1 (e.g., Rk) . 2 (e.g., Rkand Rg). 3, or 4 of Rg. Rh. R1, R'. and Rkis not hydrogen;

[0103] wherein R is a C1-C20 hydrocarbyl;

[0104] wherein Hal is a halide; and

[0105] wherein n is 10 to 1,000,000. 10 to 500,000. 10 to 100,000, 10 to 50,000, or 10 to 10,000.

[0106] Embodiment 8. The composition of embodiment 7, wherein a degree of substitution of formula (A) is about 0. 1 to about 3, about 0.5 to about 3, about 0. 1 to about 2, about 0.5 to about 2, about 0.1 to about 2.5, about 0.5 to about 1.5, or about 1; and wherein a degree of substitution of formula (B) is about 0. 1 to about 5, about 0.5 to about 5, about 0. 1 to about 4, about 0.5 to about 4, about 0. 1 to about 3, about 0.5 to about 3, about 0. 1 to about 2, about 0.5 to about 2, about 0.1 to about 1.5, about 0.5 to about 1.5, or about 1 (for example, if only one of RaRb, and Rcis not hydrogen, and only one of Rd, Re, and Rfis not hydrogen, then the polysaccharide of formula (A) would have a degree of substitution of 1, z.e., one substituent of formula (1) or formula (2) per repeated unit).

[0107] Embodiment 9. The composition of any of the preceding embodiments, wherein the halide is independently selected from the group consisting of fluoride, chloride, bromide, and iodide.

[0108] Embodiment 10. The composition of any of the preceding embodiments, wherein each R’ is independently selected from a Ci-Cis hydrocarbyl, a C1-C16 hydrocarbyl, a C1-C14 hydrocarbyl, a C1-C12 hydrocarbyl, a C1-C10 hydrocarbyl, a Ci-Cs hydrocarbyl, a Ci- Ce hydrocarbyl, a C1-C4 hydrocarbyl, a C1-C3 hydrocarbyl, a C1-C2 hydrocarbyl, or a Ci hydrocarbyl.

[0109] Embodiment 11. The composition of any of the preceding embodiments, wherein the C1-C20 hydrocarbyl is methyl, and the halide is chloride.

[0110] Methods[OlH] Embodiment 12. A method of forming a composition, the method comprising, consisting essentially of, or consisting of:

[0112] (i) providing a starting material comprising, consisting essentially of, or consisting of one or more byproducts of a process that produces a polymerizable monomer or a precursor thereof (for example, a starting material that includes an amine, such as a primary (RNH2), secondary' (RR’NH), or tertiary' amine (RR’R”N); and

[0113] (ii) contacting the starting material with a quatemizing agent to form a quatemized material.

[0114] Embodiment 13. The method of any of the preceding embodiments, further comprising, consisting essentially of, or consisting of:

[0115] contacting the starting material and a reactant comprising one or more hydroxyl functional groups,

[0116] wherein the one or more hydroxyl functional groups of the reactant and an ester functional group of the starting material react via a trans-esterification reaction.

[0117] Embodiment 14. The method of any of the preceding embodiments, wherein the contacting of the starting material and the reactant comprising one or more hydroxyl functional groups occurs before the contacting of the starting material and the quatemizing agent.

[0118] Embodiment 15. The method of any of the preceding embodiments, wherein the contacting of the starting material and the reactant comprising one or more hydroxyl functional groups occurs after the contacting of the starting material and the quatemizing agent.

[0119] Embodiment 16. The method of any7of the preceding embodiments, wherein the reactant comprising one or more hydroxyl groups comprises, consists essentially of, or consists of a saccharide.

[0120] Embodiment 17. The method of any of the preceding embodiments, wherein after the contacting of the starting material and the saccharide, the saccharide has the degree of substitution of about 0.1 to about 5, about 0.5 to about 5, about 0.1 to about 4, about 0.5 to about 4, about 0. 1 to about 3, about 0.5 to about 3, about 0. 1 to about 2, about 0.5 to about 2. about 0.1 to about 1.5, about 0.5 to about 1.5, or about 1.

[0121] Quatemizing Agent

[0122] Embodiment 18. The method of any of the preceding embodiments, wherein the quatemizing agent comprises, consists essentially of, or consists of a compound that — upon contacting an amine (such as a tertiary amine) — is effective to convert the amine to an ammonium salt (such as a quaternary ammonium salt).

[0123] Embodiment 19. The method of any of the preceding embodiments, wherein the quatemizing agent comprises, consists essentially of, or consists of an alkyl halide.

[0124] Embodiment 20. The method of any of the preceding embodiments, wherein the quatemizing agent is of the following formula:

[0125] R-Hal;

[0126] wherein R is a C1-C20 hydrocarbyl. and Hal is a halo-substituent.

[0127] Embodiment 21. The method of any of the preceding embodiments, wherein the halo- substituent is independently selected from the group consisting of fluoro-, chloro-, bromo-, and iodo-.

[0128] Embodiment 22. The method of any of the preceding embodiments, wherein R is selected from a Ci-Cis hydrocarbyl, a C1-C16 hydrocarbyl, a C1-C14 hydrocarbyl, a Ci- C12 hydrocarbyl, a C1-C10 hydrocarbyl, a Ci-Cs hydrocarbyl, a Ci-Ce hydrocarbyl, a C1-C4 hydrocarbyl, a C1-C3 hydrocarbyl, a C1-C3 hydrocarbyl, or a Ci hydrocarbyl.

[0129] Embodiment 23. The method of any of the preceding embodiments, wherein Hal is chloro-, and R is methyl.

[0130] Starting Material

[0131] Embodiment 24. The method of any of the preceding embodiments, wherein the polymerizable monomer comprises, consists essentially of, or consists of an acrylate monomer, a methacry late monomer, or a combination thereof.

[0132] Embodiment 25. The method of any of the preceding embodiments, wherein the polymerizable monomer comprises, consists essentially of, or consists of dimethylaminoethyl aery late (ADAME).

[0133] Embodiment 26. The method of embodiment 25, wherein the starting material comprises, consists essentially of, or consists of-

[0134] methyl 3-(2-(dimethylamino)ethoxy)propanoate.

[0135] 2-(dimethylamino)ethyl 3-methoxypropanoate,

[0136] ethyl 3-(2-(dimethylamino)ethoxy)propanoate,

[0137] 2-(dimethylamino)ethyl 3-ethoxypropanoate,

[0138] 2-(dimethylamino)ethyl 3-(2-(dimethylamino)ethoxy)propanoate.

[0139] 2-(dimethylamino)ethyl acrylate,

[0140] 2-(dimethylamino)ethan-l-ol, or

[0141] a combination thereof,

[0142] Embodiment 27. The method of any of the preceding embodiments, wherein the providing of the starting material comprises, consists essentially of, or consists of :

[0143] (i) providing a byproduct stream comprising, consisting essentially of, or consisting of-

[0144] methyl 3-(2-(dimethylamino)ethoxy)propanoate.

[0145] 2-(dimethylamino)ethyl 3-methoxypropanoate,

[0146] ethyl 3-(2-(dimethylamino)ethoxy)propanoate,

[0147] 2-(dimethylamino)ethyl 3-ethoxypropanoate,

[0148] 2-(dimethylamino)ethyl 3-(2-(dimethylamino)ethoxy)propanoate.

[0149] 2-(dimethylamino)ethyl acrylate,

[0150] 2-(dimethylamino)ethan-l-ol,

[0151] methyl 3-methoxypropanoate,

[0152] ethyl 3-ethoxypropanoate, or

[0153] a combination thereof,; and

[0154] (ii) separating from the byproduct stream -

[0155] at least a portion of the methyl 3-(2-(dimethylamino)ethoxy)propanoate,

[0156] at least a portion of the 2-(dimethylamino)ethyl 3 -methoxy propanoate,

[0157] at least a portion of the ethyl 3-(2-(dimethylamino)ethoxy)propanoate,

[0158] at least a portion of the 2-(dimethylamino)ethyl 3-ethoxypropanoate,

[0159] at least a portion of the 2-(dimethylamino)ethyl 3-(2-(dimethylamino)ethoxy) propanoate,

[0160] at least a portion of the 2-(dimethylamino)ethyl acrylate,

[0161] at least a portion of the 2-(dimethylamino)ethan-l -ol,

[0162] at least a portion of the methyl 3 -methoxy propanoate,

[0163] at least a portion of the ethyl 3-ethoxypropanoate, or

[0164] a combination thereof.

[0165] Embodiment 28. The method of any of the preceding embodiments, wherein the polymerizable monomer comprises, consists essentially of, or consists of dimethylaminoethyl methacrylate.

[0166] Embodiment 29. The method of embodiment 28, wherein the starting material comprises, consists essentially of, or consists of-

[0167] 2-(dimethylamino)ethyl 3-methoxy-2-methylpropanoate,

[0168] methyl 3 -[2-(dimethy lamino)ethoxy ] -2-methylpropanoate,

[0169] 2-(dimethylamino)ethyl 3-[2-(dimethylamino)ethoxy]-2-methylpropanoate,

[0170] 2-(dimethylamino)ethyl methacrylate,

[0171] 2-(dimethylamino)ethan-l-ol, or

[0172] a combination thereof,

[0173] Embodiment 30. The method of any of the preceding embodiments, wherein the producing of the starting material comprises, consists essentially of, or consists of -

[0174] (i) providing a byproduct stream comprising, consists essentially of, or consisting of -

[0175] 2-(dimethylamino)ethyl 3-methoxy-2-methylpropanoate,

[0176] methyl 3-[2-(dimethylamino)ethoxy]-2-methylpropanoate,

[0177] 2-(dimethylamino)ethyl 3-[2-(dimethylamino)ethoxy]-2-methylpropanoate,

[0178] 2-(dimethylamino)ethyl methacrylate,

[0179] 2-(dimethylamino)ethan-l-ol, or

[0180] a combination thereof,2<^toethyi»ir»>!h«-KI; and

[0181] (ii) separating from the byproduct stream -

[0182] at least a portion of the 2-(dimethylamino)ethyl 3-methoxy-2- methyl propanoat e.

[0183] at least a portion of the methyl 3-[2-(dimethylamino)ethoxy]-2- methylpropanoate,

[0184] at least a portion of the 2-(dimethylamino)ethyl 3-[2-(dimethylamino)ethoxy]- 2-methylpropanoate,

[0185] at least a portion of the 2-(dimethylamino)ethyl methacry late,

[0186] at least a portion of the 2-(dimethylamino)ethan-l-ol, or

[0187] a combination thereof,

[0188] Saccharides

[0189] Embodiment 31. The method or composition of any of the preceding embodiments, wherein the saccharide comprises, consists essentially of, or consists of a monosaccharide, a disaccharide, an oligosaccharide, a polysaccharide, or a combination thereof.

[0190] Embodiment 32. The method or composition of any of the preceding embodiments, wherein the monosaccharide comprises, consists essentially of, or consists of glucose, fructose, galactose, mannose, or a combination thereof.

[0191] Embodiment 33. The method or composition of any of the preceding embodiments, wherein the disaccharide comprises, consists essentially of, or consists of sucrose, lactose, maltose, sucrose, or a combination thereof.

[0192] Embodiment 34. The method or composition of any of the preceding embodiments, wherein the oligosaccharide comprises, consists essentially of. or consists of glycan, raffinose, maltodextrin, cellodextrin, or a combination thereof.

[0193] Embodiment 35. The method or composition of any of the preceding embodiments, wherein the polysaccharide comprises, consists essentially of, or consists of starch, glycogen, galactogen, cellulose, chitosan, chitin, guar gum, pectin, dextran, alphaglucan, cyclodextrin (such as beta-cyclodextrin), or a combination thereof.

Claims

We claim -1. A method of forming a composition, the method comprising:(i) providing a starting material comprising one or more byproducts of a process that produces a polymerizable monomer or a precursor thereof; and(ii) contacting the starting material with a quatemizing agent to form a quatemized material.

2. The method of claim 1, wherein the polymerizable monomer comprises dimethylaminoethyl acrylate (ADAME), and the starting material comprises methyl 3-(2-(dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl 3- methoxypropanoate, ethyl 3-(2-(dimethylamino)ethoxy)propanoate, 2- (dimethylamino)ethyl 3-ethoxypropanoate, 2-(dimethylamino)ethyl 3-(2- (dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl acrylate, 2- (dimethylamino)ethan-l-ol, or a combination thereof,3. The method of claim 1, wherein the polymerizable monomer comprises dimethylaminoethyl methacrylate, and the starting material comprises 2- (dimethylamino)ethyl 3-methoxy-2-methylpropanoate, methyl 3-[2- (dimethy lamino)ethoxy] -2-methylpropanoate, 2-(dimethy lamino)ethyl 3 - [2- (dimethylamino)ethoxy] -2-methylpropanoate, 2-(dimethy lamino)ethyl methacrylate, 2-(dimethylamino)ethan-l-ol, or a combination thereof,4. The method claim 1, wherein the providing of the starting material comprises:(i) providing a byproduct stream comprising methyl 3-(2- (dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl 3-methoxypropanoate, ethyl 3-(2-(dimethylamino)ethoxy)propanoate, 2-(dimethylamino)ethyl 3- ethoxypropanoate,2-(dimethy lamino)ethy 1 3 -(2-(dimethy lamin o)ethoxy )propanoate, 2- (dimethylamino)ethyl acrylate, 2-(dimethylamino)ethan-l-ol, methyl 3- methoxypropanoate, ethyl 3 -ethoxy propanoate, or a combination thereof,; and(ii) separating from the byproduct stream at least a portion of the methyl 3-(2- (dimethylamino)ethoxy)propanoate, at least a portion of the 2-(dimethylamino)ethyl 3-methoxypropanoate, at least a portion of the ethyl 3-(2- (dimethylamino)ethoxy)propanoate, at least a portion of the 2-(dimethylamino)ethyl 3-ethoxypropanoate, at least a portion of the 2-(dimethylamino)ethyl 3-(2- (dimethylamino)ethoxy)propanoate, at least a portion of the 2-(dimethylamino)ethyl acrylate, at least a portion of the 2-(dimethylamino)ethan-l-ol, at least a portion of the methyl 3-methoxypropanoate, at least a portion of the ethyl 3-ethoxypropanoate, or a combination thereof.

5. The method of claim 1, wherein the providing of the starting material comprises:(i) providing a byproduct stream comprising 2-(dimethylamino)ethyl 3- methoxy-2-methylpropanoate, methyl 3-[2-(dimethylamino)ethoxy]-2- methylpropanoate, 2-(dimethylamino)ethyl 3-[2-(dimethylamino)ethoxy]-2- methylpropanoate, 2-(dimethylamino)ethyl methacry late, 2-(dimethylamino)ethan-l- ol, or a combination thereof,and(ii) separating from the byproduct stream at least a portion of the 2- (dimethylamino)ethyl 3-methoxy-2-methylpropanoate, at least a portion of the methyl 3-[2-(dimethylamino)ethoxy]-2-methylpropanoate, at least a portion of the 2- (dimethylamino)ethyl 3-[2-(dimethylamino)ethoxy]-2-methylpropanoate, at least a portion of the 2-(dimethylamino)ethyl methacrylate, at least a portion of the 2- (dimethylamino)ethan-l-ol, or a combination thereof,6. The method of claim 1, wherein the quatemizing agent comprises an alkyl halide.

7. The method of claim 1, wherein the quatemizing agent is of the following formula:R-Hal; wherein R is a C1-C20 hydrocarbyl. and Hal is a halogen.

8. The method of claim 1, further comprising: contacting the starting material and a reactant comprising one or more hydroxyl functional groups, wherein the one or more hydroxyl functional groups of the reactant and an ester functional group of the starting material react via a transesterification reaction.

9. The method of claim 8, wherein the contacting of the starting material and the reactant comprising one or more hydroxyl functional groups occurs before the contacting of the starting material and the quatemizing agent.

10. The method of claim 8, wherein the contacting of the starting material and the reactant comprising one or more hydroxyl functional groups occurs after the contacting of the starting material and the quatemizing agent.

11. The method of claim 8, wherein the reactant comprising one or more hydroxyl groups comprises a saccharide.

12. The method of claim 1 1, wherein after the contacting of the starting material and the saccharide, the saccharide has a degree of substitution of about 0.5 to about 1.5.

13. A composition comprising a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), a compound of formula (V), a compound of formula (VI), a compound of formula (VII), a compound of formula (VIII), a compound of formula (IX), a compound of formula (X), a compound of formula (XI). a compound of formula (XII), or a combination thereof:wherein R1. R2. R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14are independently selected from a C1-C20 hydrocarbyl; and wherein Hal is a halide.

14. The composition of claim 13, wherein Hal is a chloride, and wherein R1, R2, R-, R4, R5, R6, R7, R8, R9, R10, R11. R12, R13, and R14are methyl.

15. A composition of formula (A) or formula (B):wherein Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, R1, RJ. and Rkare independently selected from the group consisting of hydrogen, formula (1), and formula (2); wherein at least one of Ra, Rb, Rc, Rd, Re, and Rfis not hydrogen; wherein at least one of Rg, Rh, R1, Rf and Rkis not hydrogen;wherein R is a C1-C20 hydrocarbyl; and wherein Hal is a halide.

Images