WO2019226570A1

WO2019226570A1 - Processes for producing bio-based aromatic compounds and derivatives

Info

Publication number: WO2019226570A1
Application number: PCT/US2019/033172
Authority: WO
Inventors: Sadesh H. SOOKRAJ; Utpal Mahendra Vakil
Original assignee: Novomer, Inc.
Priority date: 2018-05-22
Filing date: 2019-05-20
Publication date: 2019-11-28
Also published as: TW202003440A; AR115153A1

Abstract

The processes include steps for catalytieally rearranging a bio-based beta-lactone to produce a bio-based unsaturated organic acid; contacting the bio-based unsaturated organic acid with a bio-based conjugated diene to produce a bio-based cyclohexene intermediate; and transforming the bio-based cyclohexene intermediate into a bio-based aromatic acid. Copolymers of the bio-based aromatic acid and a diol are also afforded.

Description

PROCESSES FOR PRODUCING BIO-BASED AROMATIC COMPOUNDS AND

DERIVATIVES

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 62/674,751, filed May 22, 2018, which is incorporated herein by reference in its entirety.

FIELD

[0002] The present invention is related to processes for producing bio-based aromatic carboxylic acids, bio-based diols, and copolymers thereof. Specifically, the processes of the present invention provide bio-based products such as terephthalic acid, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and/or other similar chemical compositions. Advantageously, the processes of the present invention use bio- based reagents to produce products with less deleterious effects on the environment.

BACKGROUND

[0003] There is global public concern regarding the release of carbon emissions into the environment and correlating trends in climate change. The negative environmental impact of many conventional industrial and commercial processes has caused the development of more sustainable processes which can recycle molecular components already present in the environment. Among the processes, gasification is appealing because it can be applied to practically any source of biological material and can recycle the molecular components to produce chemical reagents with bio-based content. Bio-based carbon monoxide is one such chemical reagent which can be produced by gasification. Introducing a bio-based carbon monoxide reagent into the chemical structure of a substrate molecule provides for a product which includes the bio-based characteristic of the carbon monoxide reagent. In this way, more complex molecules are produced as products with bio-based content. [0004] The term“carbonylation” generally refers to chemical reactions that introduce carbon monoxide molecules into other organic and/or inorganic substrate molecules.

Carbonylation results in a substrate molecule gaining a carbonyl (C=0) functional group. Specifically, catalytic carbonylation of cyclic compounds including epoxides, azindmes, thiiranes, oxetanes, lactones, lactams, and analogous compounds is useful for the synthesis of the ring-expanded products of such compounds. In one example, bio-based ethylene oxide, produced from ethylene or ethanol obtained from biological material, undergoes catalytic carbonylation with bio-based carbon monoxide to produce a bio-based ring-expanded product known as bio-based beta-propiolactone. In another example, bio-based beta- propiolactone undergoes carbonylation with bio-based carbon monoxide to produce bio based succinic anhydride. Bio-based ring-expanded products are valuable building blocks which are used to produce more complex bio-based products. For example, a ring opening polycondensation reaction of a bio-based beta-lactone produces a bio-based polylactone.

[0005] Bio-based polyiactones are biodegradable polymers that are useful materials in many manufacturing and industrial applications. The physical and chemical characteristics of polyiactones facilitate transportation and storage over extended periods of time with decreased quality concerns. Recent advances in the carbonylation of epoxides - such as in US Patent No. 6,852,865 - and the ring opening polycondensation of bio-based beta-lactone have provided more efficient synthetic routes to bio-based polyiactones. In one example, bio-based polypropiolactone is a commercially useful bio-based material because the polymer undergoes a chemical decomposition process known as thermolysis to produce a highly pure bio-based acrylic acid product.

[0006] Generally, thermolysis is a chemical decomposition reaction caused by heat.

Thermolysis of polyiactones proceeds by two known reaction mechanisms. A first reaction mechanism, known as unzipping, includes a polylactone polymer with a chain length equal to

(«) that decomposes into a poly lactone polymer with a chain length (w-l) and a molecule comprising an unsaturated organic acid. The second reaction mechanism, known as internal chain scission, includes a polylactone polymer with a chain length («) decomposing into a polylactone polymer with a chain length (n - x) and a polylactone polymer with a chain length (x), wherein (x) is greater than or equal to 2.

[0007] Terephthalic acid is an organic compound generally comprising an aromatic ring with two carboxylic acid functional groups. Terephthalic acid is useful as a monomer in many valuable polymers. Terephthalic acid is conventionally produced by oxidation of /^; xylene by oxygen in air. However, p-xylene is also conventionally produced by catalytic reforming of petroleum naphtha and generally is not considered sustainable or

environmentally friendly. Terephthalic acid is used in conjunction with certain diols to produce polyethylene terephthalate, which is used extensively in consumer goods packaging, most prominently in the now ubiquitous plastic water bottle.

[QQQ8] There is strong demand from consumers and consumer goods companies for sustainable alternatives to petroleum-based plastics for packaging applications. Indeed, Coca Cola© and others have recently introduced polyethylene terephthalate based bio-based monoethylene glycol. The resulting bottles are branded as“Plant Bottle™” and have been well received in the marketplace. Unfortunately, since about 70% of the mass in

polyethylene terephthalate derives from terephthalic and isophthahc acids, replacing petroleum -sourced monoethlyene glycol with bio-based material yields polyethylene terephthalate that is only about 30% bio-based. There is considerable interest in bio- based polymers similar to conventionally produced polyethylene terephthalate.

[0009] There is a need for more sustainable and environmentally friendly processes for producing terephthalic acid to responsibly satisfy high commercial demand for polymers comprised of terephthalic acid and its derivatives. The present invention satisfies this need by providing processes for producing bio-based terephthalic acid from sustainable biological material sources and bio-based polymers comprised of bio-based terephthalic acid and bio based diols. BRIEF SUMMARY

[0010] The present invention is directed to innovative processes for producing bio-based aromatic carboxylic acids such as terephthalic acid and bio-based polymers comprised of bio- based terephthalic acid. The bio-based properties result, m part, from the carbonylation of a bio-based epoxide with a bio-based carbon monoxide obtained from sources such as biological sources, recycled sources, renewable sources, and otherwise sustainable sources. More specifically, imparting bio-based content includes imparting bio-mass derived carbon, carbon from waste streams, and/or carbon from municipal solid waste.

[0011] In preferred embodiments, the compositions of the present invention have bio- based content which may be measured using the ASTM D6866 method, allowing for the determination of the bio-based content of materials using radiocarbon analysis such as by accelerator mass spectrometry, liquid scintillation counting, and isotope mass spectrometry. For example, when nitrogen in the atmosphere is struck by an ultraviolet light produced neutron, it loses a proton and forms carbon that has a molecular weight of 14, which is radioactive. This 14C is immediately oxidized into carbon dioxide, and represents a small, but measurable fraction of atmospheric carbon. Atmospheric carbon dioxide is cycled by green plants to make organic molecules during photosynthesis. The cycle is completed when the green plants or other forms of life metabolize the organic molecules producing carbon dioxide which is then able to return back to the atmosphere. Virtually all forms of life on Earth depend on this green plant production of organic molecules to produce the chemical energy that facilitates growth and reproduction. Therefore, the 14C that exists in the atmosphere becomes part of all life forms and their biological products. These renewably based organic molecules that biodegrade to carbon dioxide do not contribute to global warming because no net increase of carbon is emitted to the atmosphere. In contrast, fossil fuel-based carbon does not have the signature radiocarbon ratio of atmospheric carbon dioxide. See WO 2009/155086, incorporated herein by reference.

[0012] Petroleum-based carbon does not have the signature radiocarbon ratio of atmospheric carbon dioxide. Research has noted that fossil fuels and petrochemicals have less than about 1 pMC, and typically less than about 0. 1 pMC, for example, less than about 0.03 pMC. However, compounds derived entirely from renewable resources have at least about 95 percent modern carbon (pMC); they may have at least about 99 pMC, including about 100 pMC.

[0013] Combining fossil carbon with present day carbon into a material will result in a dilution of the present day pMC content. By presuming that 107 5 pMC represents present day bio-based materials and 0 pMC represents petroleum derivatives, the measured pMC value for that material will reflect the proportions of the two component types. A material derived 100% from present day biomass would give a radiocarbon signature near 107.5 pMC. If that material were diluted with 50% petroleum derivatives, it would give a radiocarbon signature near 54 pMC.

[0014] A bio-based content result is derived by assigning 100% equal to 107.5 pMC and 0% equal to 0 pMC. In this regard, a sample measuring 99 pMC will give an equivalent bio- based content result of 93%.

[0015] Assessment of the materials described herein according to the present

embodiments is performed in accordance with ASTM D6866 revision 12 (i.e. ASTM D6866- 12), the entirety of which is herein incorporated by reference. In some embodiments, the assessments are performed according to the procedures of Method B of ASTM-D6866-12. The mean values encompass an absolute range of 6% (plus and minus 3% on either side of the bio-based content value) to account for variations in end-component radiocarbon signatures. It is presumed that all materials are present day or fossil in origin and that the desired result is the amount of bio-based carbon“present” in the material, not the amount of bio-material“used” in the manufacturing process.

[QQ16] Other techniques for assessing the bio-based content of materials are described in US. Pat Nos. 3,885,155, 4,427,884, 4,973,841, 5,438,194, and 5,661,299, and WO

2009/155086, each of which is incorporated herein by⁷ reference. [QQ17] The inventive processes of the present invention are advantageous relative to other conventional processes for producing aromatic acids, such as terephthalic acid, and derivative polymers, in terms of cost and carbon efficiency. The inventive processes provide unprecedented flexibility in terms of the ability to select the bio-content and physical properties of the product. For example, the aromatic acid produced by the process of the present invention contains between 3 and 10 biomass-derived carbon atoms. In addition, the bio-based aromatic acids are copolymerized with bio-based diols, such as 1 ,4-butame diol, propane diol, and/or ethylene glycol, to produce bio-based polymers with varying physical properties such as flexibility and tensile strength. In certain embodiments, bio-based aromatic acids are copolymerized with conventional petroleum-based diols, for example, to decrease costs relating to specific raw material sources. This process flexibility allows industrial and commercial producers to leverage various combinations of bio-based and fossil-based feedstocks to provide the market with cost-effective low^r carbon footprint chemicals and polymers.

[0018] In certain preferred embodiments, the innovative processes of the present invention produce bio-based aromatic carboxylic acids. Preferred embodiments of the processes include the steps as follows: 1) thermolyzing a polylactone to produce a high purity unsaturated organic acid; 2) alternatively producing an unsaturated organic acid by directly transforming a beta-lactone; 3) reacting the unsaturated organic acid with a conjugated diene to produce a cyclohexene; and 4) aromatization of the cyclohexene to produce an aromatic carboxylic acid. In certain preferred embodiments, the aromatic carboxylic acid undergoes one or more subsequent steps to produce an aromatic carboxylic acid derivative. In certain preferred embodiments, the unsaturated organic acid comprises 3 carbons. In certain embodiments, the unsaturated organic acid is acrylic acid.

[0019] In other certain preferred embodiments of the present invention, the processes are directed to producing bio-based copolymers of bio-based aromatic acids and bio-based diols comprising the steps of: 1) mixing a bio-based aromatic acid and a bio-based diol to produce a generally homogenous reaction mixture; 2) esterifymg the generally homogenous reaction mixture to produce one or more ester intermediates; 3) oligomerizing the one or more ester intermediates to produce one or more oligomers; and 4) poly condensation polymerizing the one or more oligomers to produce the bio-based copolymer product of the desired molecular weight.

[0020] While this disclosure is susceptible to various modifications and alternative forms, specific exemplary embodiments are described in detail. There is no intent to limit the disclosure to the specific exemplary embodiments disclosed. The intention is to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure as defined by the appended claims.

DETAILED DESCRIPTION

[0021] The present invention is directed to processes for producing aromatic carboxylic acids and/or derivatives thereof with bio-based properties through a senes of innovative steps. The bio-based properties result, in part, from the carbonylation of reagents such as epoxides with carbon monoxide wherein the reagents are obtained from biological sources, recycled sources, renewable sources and otherwise sustainable sources.

Definitions

[0022] As referred to herein,“biological sources” means molecular components, such as carbon and/or hydrogen, derived from living or once living biological organisms. “Recycled sources” means molecular components, such as carbon and/or hydrogen, recovered from a previous use in a manufactured article. “Renewable sources” means molecular components, such as carbon and/or hydrogen, obtained from biological organisms that can replenish in less than one hundred years. “Sustainable sources” means molecular components, such as carbon and/or hydrogen, derived at least in part from sources with bio-content equal to a minimum of 10%, and more typically 20%, 50%, 75%, 90%, 95%, or 100% of the total amount of carbon and hydrogen in the material. In certain preferred embodiments, imparting bio-based content includes imparting bio-mass derived carbon, carbon from waste streams, and/or carbon from municipal solid waste. [0023] The term“polymer”, as used herein, refers to a molecule of high relative molecular mass, the structure of winch comprises the multiple repetitions of units derived, actually or conceptually, from molecules of lower relative molecular mass. In some aspects, a polymer is comprised of only one monomer species. In some aspects, a polymer is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer of one or more epoxides.

[0024] As referred to herein, the term“carhonylation” generally refers to chemical reactions that introduce carbon monoxide molecules into other organic and inorganic substrate molecules. Carhonylation results in a substrate molecule gaining a carbonyl (0=0) functional group.

[0025] The term“thermolysis” is means a process comprising chemical decomposition in which heat increases the likelihood of cleavage to one or more covalent bonds.

[0026] The terms bio-content and bio-based content mean biogenic carbon, also known as bio-mass derived carbon, carbon waste streams, and carbon from municipal solid waste.

In some variations, bio-content (also referred to as“bio-based content”) can be determined based on the following:

Bio-content or Bio-based content = [Bio (Organic) Carbon]/[Total (Organic) Carbon] x 100%, as determined by ASTM D6866 (Standard Test Methods for Determining the Bio based (biogenic) Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis).

[0027] As described herein, compounds may contain“optionally substituted” moieties.

In general, the term“substituted”, whether preceded by the term“optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an“optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned may include those that result m the formation of stable or chemically feasible compounds. The term“stable”, as used herein, refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in some aspects, their recovery, purification, and use for one or more of the purposes disclosed herein. As specific examples, an optionally substituted moiety may be halo, aliphatic (e.g. alkyl, alkenyl or alkyny!), alkoxy, cycloaliphatic, heteroaliphatic, aryl, heteroaryl, and the like.

[0028] The terms“halo” and“halogen” as used herein refer to an atom selected from fluorme (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (lodo, -I).

The term“halide” as used herein refers to a halogen bearing a negative charge selected from flouride -F , chloride -CT, bromide -Br , and iodide -G.

[0029] The terms“aliphatic” or“aliphatic group”, as used herein, denote a hydrocarbon moiety which may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and which may be completely saturated or which may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-30 carbon atoms. In some aspects, aliphatic groups contain 1—12 carbon atoms. In some aspects, aliphatic groups contain 1-8 carbon atoms. In some aspects, aliphatic groups contain 1-6 carbon atoms. In some aspects, aliphatic groups contain 1-5 carbon atoms, in some aspects, aliphatic groups contain 1—4 carbon atoms, in yet other aspects aliphatic groups contain 1-3 carbon atoms, and in yet other aspects, aliphatic groups contain 1-2 carbon atoms. Suitable aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as

(cycloalkyl)alkyl, (cycloalkenyl)alkyl or (eyeloaikyl)alkeiiyl.

[QQ3Q] “Alkyl” refers to a monoradical unbranched or branched saturated hydrocarbon chain. In some embodiments, alkyl has 1 to 6 carbon atoms (i.e., Cl -6 alkyl), 1 to 5 carbon atoms (i.e., Ci-5 alkyl), 1 to 4 carbon atoms (i.e., CI-4 alkyl), 1 to 3 carbon atoms (i.e., Cl-3 alkyl), or 1 to 2 carbon atoms (i.e., Cl -2, alkyl). In other embodiments, alkyl groups may include methyl, ethyl, propyl, isopropyl, «-butyl, see-butyl, -butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, and 3-methylpentyl. When an alkyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons may be encompassed; thus, for example,“butyl” can include «-butyl, sec-butyl, isobutyl and /-butyl;“propyl” can include «-propyl and isopropyl.

[0031] The term“alkenyl”, as used herein, denotes a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond. Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. In certain

embodiments, alkenyl groups contain 2-8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2-5 carbon atoms, in some embodiments, alkenyl groups contain 2-4 carbon atoms, in some

embodiments alkenyl groups contain 2-3 carbon atoms, and in some embodiments alkenyl groups contain 2 carbon atoms. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, l -methyl-2-buten-l-yl, and the like.

[0032] By“alkynyl” is meant a monovalent group derived from a straight- or branched- chain aliphatic moiety' having at least one carbon-carbon triple bond. Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms. In some embodiments, alkynyl groups contain 2-5 carbon atoms, in some embodiments, alkynyl groups contain 2-4 carbon atoms, m some embodiments alkynyl groups contain 2-3 carbon atoms, and in some embodiments alkynyl groups contain 2 carbon atoms.

Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl

(propargyl), 1 -propynyl, and the like.

[QQ33] By“alkoxy” is meant an oxy-containing radical having an alkyl portion.

Examples include, but are not limited to, methoxy, ethoxy, propoxy, butoxy and i-hutoxy.

The alkoxy group may also be optionally mono-, di-, or trisubstituted with, for example, halo, aryl, cycloalkyl or alkoxy and the like. [QQ34] The terms“cycloaliphatic”,“cycloalkyl”,“carbocycle”, or“carbocyclic”, used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cyclic aliphatic monocyclic, bicyclie, or polycyclic ring system, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined above and described herein. Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, eyc!oheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, and cyclooctadienyl. In some aspects, the cycloalkyl has 3-6 carbons. Representative carbocyles include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2,l]heptane, norbomene, cyclohexene and spiro[4.5]decane. The terms“cycloaliphatic”,“carbocycle” or“carbocyclic” also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring. In some aspects, a carbocyclic group is bicyciic. In some aspects, a carbocyclic group is tricyclic. In some aspects, a carbocyclic group is polycyclic.

[0035] The term“heteroaliphatic”, as used herein, refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, phosphorus, or boron. In some aspects, one or two carbon atoms are independently replaced by one or more of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include“heterocycle,”“heterocyclyl,”

“heterocycloaliphatic,” or“heterocyclic” groups.

[0036] The term“aryl” used alone or as part of a larger moiety as in“aralkyl”, “aralkoxy”, or“aryloxyaikyl”, refers to an aromatic carbocylic radical having a single ring (e.g. phenyl), multiple rings (e.g. biphenyl) or multiple fused rings in which at least one is aromatic (e.g. 1,2,3,4-tetrahydronaphthyl). The term“aryl” may be used interchangeably with the term“aryl ring”. In some aspects,“aryl” refers to an aromatic ring system which includes, but is not limited to, phenyl, naphthyl, anthracyl and the like, which may bear one or more substituents. Also, included within the scope of the term aryl”, as it is used herein, is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenanthridinyl, or tetrahydronaphthyl, and the like. The aryl group can also be optionally mono-, di-, or trisubstituted with, for example, halo, alkyl, alkenyl, cycloalkyl or alkoxy and the like.

[0037] The terms“heteroaryl” and“heteroar-”, used alone or as part of a larger moiety, e.g ,“heteroaralkyl”, or“heteroaralkoxy”, refer to groups having 5 to 14 ring atoms, preferably 5, 6, 9 or 10 ring atoms; having 6, 10, or 14 p electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms. The term

“heteroatom” refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quatermzed form of a basic nitrogen. Heteroaryl groups include, without limitation, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyndyl, pyridazmyl, pyrinudinyl, pyrazinyl, indolizinyl, purinyl, naphthyndinyi, benzofuranyl and pteridinyl.

The terms“heteroaryl” and“heteroar-”, as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, mdazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, qumazolinyl, quinoxalinyl, 4/f quinolizinyl, carbazolyl, acridinyi, phenazmyl, phenothiazmyl, phenoxazmyl, tetrahydroquinolinyl, tetrahydroisoquinoiinyl, and pyrido[2,3-b]-l,4-oxazin- 3(4H)-one. A heteroaryl group may be monocyclic or bicyclic. The term“heteroaryl” may be used interchangeably with the terms“heteroaryl ring”,“heteroaryl group”, or “heteroaromatic”, any of which terms include rings that are optionally substituted. The term “heteroaralkyl” refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.

[0038] As used herein, the terms“heterocycle”,“heterocyclyl”,“heterocyclic radical”, and“heterocyclic ring” are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7- to 14-membered bicyclic heterocyclic moiety that is either saturated or partially unsaturated, and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above. When used in reference to a ring atom of a heterocycle, the term“nitrogen” includes a substituted nitrogen. As an example, in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2/T-pyrrolyl), NH (as in pyrrolidinyl), or NR (as in TV- substituted pyrrolidinyl).

[0039] A heterocyclic ring can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted. Examples of such saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranyl, tetrahydrothieny!, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquino!inyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidmyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepmyl, tluazepmyl, morpholinyl, and quinuclidmyl. The terms“heterocycle”,“heterocyclyl”,“heteroeyclyi ring”,“heterocyclic group”,“heterocyclic moiety”, and“heterocyclic radical”, are used interchangeably herein, and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings, such as indolinyl, 3 f indolyl, chromany!, phenanthridinyl, or tetrahydroquinoJinyl, where the radical or point of attachment is on the heterocyclyl ring. A heterocyclyl group may be mono- or bicyclic. The term

“heterocyclylalkyl” refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions independently are optionally substituted.

[QQ4Q] The term“unsaturated”, as used herein, means that a moiety has one or more double or triple bonds.

[0041] As used herein, the term“partially unsaturated” refers to a moiety that includes at least one double or triple bond. The term“partially unsaturated” is intended to encompass rings having multiple sites of unsaturation but is not intended to include aryl or heteroaryl moieties, as herein defined.

Processes [0042] In certain preferred embodiments, the processes of the present in vention provide for carbonylation of epoxide using catalysts, systems, and methods described in U.S. Patent 9,327,280, herein incorporated by reference. Carboxylation of an epoxide with carbon monoxide to produce a beta-lactone proceeds according to the following general reaction:

wherein Ri, Rz, Rz and Rr are independently hydrogen or optionally substituted.

[0043] Table 1 illustrated below includes Column A directed to a non-exhaustive list of epoxides which may undergo carbonylation with carbon monoxide to produce a beta-lactone according to the processes of the present invention and Column B directed to a non- exhaustive list of the beta-lactones respective to the epoxides which may be produced according to the present invention.

[0044] In some embodiments, the processes comprise carbonylating a beta-lactone with carbon monoxide to form a compound termed a“four-carbon ring-expanded product” for the purposes of tins invention. In some embodiments, the four-carbon ring-expanded product may be produced by carbonylation of a beta-lactone chosen from the table above. The term “four-carbon ring-expanded product” is not limiting with regards to the molecules total carbon content and comprises compounds with more than four carbons, for example, products formed from the carbonylation of di-epoxides and/or di-beta-lactones. In certain embodiments, the four-carbon ring-expanded product is selected from the group consisting of succinic anhydride, succinic acid, a mono- or di ester of succinic acid, a mono- or bis salt of succinic acid, and a mixture of two or more of these. In certain embodiments, the four-carbon ring-expanded product comprises succinic anhydride. In certain embodiments, the four- carbon ring-expanded product comprises succinic acid.

[0045] Preferred embodiments of the present invention are directed to processes that incorporate bio-based beta-lactones into products comprising bio-based aromatic acids. In preferred embodiments, the processes include a step for catalytically rearranging a bio-based beta-lactone to produce a bio-based unsaturated organic acid which may undergo a Diels-

Alder reaction with certain bio-based conjugated dienes to produce a cyclohexene product. The cyclohexene product is then converted to an aromatic carboxylic acid and/or the derivative of an aromatic carboxylic acid.

[0046] In certain preferred embodiments, the processes of the present invention include contacting a bio-based beta-lactone, a heterogeneous catalyst, and optionally a solvent or diluent; maintaining the bio-based beta-lactone and optional solvent or diluent m vapor phase while contacting the catalyst; and producing a bio-based unsaturated organic acid, such as bio-based acrylic acid. In certain embodiments, the heterogeneous catalyst comprises a crystalline microporous solid. In certain embodiments, preferable heterogenous catalysts include alkaline-earth phosphates, supported phosphate salts, calcium hydroxyapatites, inorganic salts and zeolites. In preferred embodiments, the heterogeneous catalyst is an alumina silicate molecular sieve and more preferably a zeolite having Lewis and/or Bronsted acidity. The zeolites are, for example, in hydrogen form or in cation exchanged form.

Suitable cations are alkali metals such as Na⁺ or K7; alkali-earth cations such as Ca²⁺, Mg²⁺, Sr , or Ba^{2 r}; and Zn²⁺, Cu^r, and Cu ⁺. The direct conversion of the beta-lactone to an unsaturated organic acid generally proceeds according to the following reaction:

[0047] In certain preferred embodiments, the processes include: passing a vapor phase feed stream comprising a bio-based beta-lactone and a polymerization inhibitor to a heterogenous catalyst comprising a crystalline microporous solid at liquid or mixed phased conversion conditions to afford a vapor phase product stream comprising a bio-based unsaturated organic acid; recovering the vapor phase product stream; and separating the bio based unsaturated organic acid from the vapor phase product stream. In certain other embodiments, the processes include: passing the vapor phase feed stream to a fixed bed of a zeolite catalyst at conversion conditions; recovering the vapor phase product stream from the fixed bed; and separating the bio-based unsaturated organic acid from the vapor phase product stream. In other embodiments, the bio-based beta-lactone is diluted with an inert solvent or inert gas prior to being fed to a reactor. In still another embodiment, unreacted bio-based beta-lactone is recycled back to the reactor. In certain embodiments, separation of the bio-based unsaturated organic acid from the vapor phase product stream occurs in one or more distillation columns.

[0048] In certain other preferred embodiments, the bio-based unsaturated organic acid is produced by thermolysis of a bio-based polylactone. Embodiments of the present invention including steps for thermolysis of a bio-based polylactone first require polymerization of a bio-based beta-lactone to produce the bio-based polylactone. Advantageously, the relative stability of the bio-based polylactone allows for polymerization to proceed at a first location and for the resultant bio-based poly lactone to be transported to one or more remote locations (wherein rearrangement to the organic acid is performed) with decreased safety concerns. In certain embodiments, the processes include steps for producing high purity bio-based unsaturated organic acids, such as bio-based acrylic acid, by catalyzing a thermolysis reaction of the bio-based poly lactone with concentrations of an active salt, for example sodium acrylate. Advantageously, thermolysis of bio-based polylactones catalyzed with an active salt provides for decreased thermodynamic reaction conditions and results in lower costs for manufacturers.

[0049] In preferred embodiments including thermolysis, the processes comprise providing a feed stream comprising a bio- based polylactone. The feed stream is optionally introduced as a liquid and/or solid and the bio-based polylactone optionally has a varying chain length. In certain preferred embodiments, the bio-based polylactone preferably is present in the feed stream at a high concentration by weight. In some embodiments, the feed stream comprises a bio-based beta-propiolactone and/or bio-based sodium acrylate. In some embodiments, bio-based beta-propiolactone preferably is present in the feed stream at a lower concentration by weight. An active salt preferably is present in the feed stream at a lower concentration by weight. Phenothiazine is optionally present with the active salt for free radical polymerization inhibition. [QQ5Q] Certain preferred embodiments of the processes comprise steps for passing a feed stream comprising bio-based poly lactone to a thermal decomposition chamber for

thermolysis, the thermal decomposition chamber for thermolysis having an active salt present therein; maintaining the active salt in the thermal decomposition chamber at a predetermined concentration range; contacting the feed stream with the active salt in the thermal decomposition chamber at thermolysis conditions and converting at least a part of the feed stream to a bio-based unsaturated organic acid; withdrawing a product stream comprising the bio-based unsaturated organic acid; and recovering at least a portion of the bio-based unsaturated organic acid from the product stream.

[0051] Preferred embodiments of the present invention include a step for a Diels- Alder reaction wherein the bio-based unsaturated organic acid is reacted with a bio-based

conjugated diene in a Diels- Alder reaction to produce a bio-based cyclohexene intermediate. In certain preferred embodiments, the bio-based conjugated diene is bio-based isoprene or a derivative thereof. In certain preferred embodiments, bio-based isoprene or a derivative thereof is produced from a four-carbon ring-expanded product. In one example, bio-based isoprene is produced by: carbonylating a bio-based propylene oxide with bio-based carbon monoxide to produce a bio-based beta-methyl-beta-lactone for beta-hutyro!actone);

carbonylating the bio-based beta-methyl-beta-lactone with bio-based carbon monoxide to produce a bio-based methyl succinic anhydride; hydrogenating the bio-based methyl succinic anhydride to produce a bio-based 2-methyl butane- 1,4-diol; dehydrating the bio- based 2- methyl butane- 1,4-diol in the presence of acetic acid to produce a bio-based isoprene. In certain embodiments, the dehydration of the bio-based 2-methyl butane- 1 ,4-diol to produce bio-based isoprene includes the presence of glacial acetic acid.

[0052] In certain embodiments, carbonylating a bio-based propylene oxide includes a carbonylation catalyst. In some embodiments, the carbonylation catalyst comprises a metal carbonyl compound. In some embodiments, the carbonylation catalyst further comprises a

Lewis acidic co-catalyst. In some embodiments, carbonylating a bio-based propylene oxide occurs at a pressure between 300 psi and 500 psi. In some embodiments, carbonylating the bio-based propylene oxide occurs at a temperature between 50 ^C'C and 100 °C. In certain embodiments, carhonylating the bio-based beta-methyl -beta-lactone proceeds under similar reaction conditions for carbonylating the bio-based propylene oxide, wherein a stochiometnc excess of bio-based carbon monoxide is present, to produce bio-based methyl succinic anhydride.

[0053] In certain embodiments, hydrogenation of the bio-based methyl succinic anhydride to produce bio-based 2-methyl butane- 1,4-diol includes a hydrogenation catalyst. In certain embodiments, the hydrogenation catalyst is a single metal catalyst, such as for example, a ruthenium catalyst supported on a silica support. In certain embodiments, the hydrogenation catalyst is a bimetallic catalyst, such as a copper and zinc oxide catalyst. In certain embodiments, hydrogenation of the bio-based methyl succinic anhydride occurs at a temperature between 100 °C and 200 °C. In certain embodiments, hydrogenation of the bio- based methyl succinic anhydride occurs at a pressure between 300 psi and 1000 psi.

[0054] In certain embodiments, dehydration of the bio-based 2-methyl butane- 1 ,4-diol includes a dehydration catalyst. In certain embodiments, the dehydration catalyst is alumina based and/or lithium phosphate based. In certain preferred embodiments, the dehydration catalyst is a pyrophosphate and/or acid orthophosphate with a metal, the metal belonging to a group consisting of lithium, sodium, strontium, potassium and barium. In certain embodiments, dehydration of the bio-based 2-methyl butane- 1,4-diol occurs at a temperature between 300 °C and 800 °C and a pressure between 50 psi and 1000 psi.

[0055] Certain embodiments of the processes include the production of a bio-based p- toiuic acid intermediate from bio-based epoxide, bio-based carbon monoxide and bio-based isoprene reagents. The processes include a carbonylation step of the bio-based epoxide reagent with the bio-based carbon monoxide reagent to produce a bio-based beta-lactone intermediate. The processes include a step for catalyticaliy rearranging the bio-based beta- lactone intermediate to produce a bio-based organic acid intermediate, such as bio-based acrylic acid. The processes of the present invention optionally include a Diels- Alder reaction of the bio-based organic acid intermediate with the bio-based isoprene reagent to produce a bio-based cyclohexene carboxylic acid intermediate generally proceeding as follows (m this case specifically affording 4-methylcyclohex-3-ene-l-carboxylic acid):

[0056] In certain preferred embodiments of the present invention, the processes include a step for catalyzing a Diels- Alder reaction using a zeolite framework with Lewis acid centers. In certain other preferred embodiments, the processes of the present invention use Bronsted acid zeolites. The catalyst is prepared, for example, by the following: diluting 7.46g of an aqueous tetraethylammonium hydroxide 35% solution with 15g of water, adding 6.98 g of tetraethylorthosilicate 98% and stirring. To the mixture is added dropwise a solution of 0.123g of zirconium(IV) propoxide 70% in 2 g of ethanol. The resulting mixture is subsequently evaporated and 0.739 g of a 48% solution of hydrofluoric acid is added.

[0057] In other preferred embodiments of the present invention, the processes include a step for dehydrating the bio-based cyclohexene intermediate. In certain embodiments, the dehydration of the bio- based cyclohexene intermediate comprises heating the bio-based cyclohexene compound in the presence of a dehydrating agent. In certain embodiments, the step includes continuously removing water vapor from a reaction zone where the dehydration reaction is performed. In certain embodiments, the dehydration reaction is acid catalyzed. Preferably, the dehydration reaction catalyst is phosphoric acid, sulfuric acid or a solid supported acid catalyst. In certain embodiments, the dehydration is performed by heating the bio-based cyclohexene intermediate in the presence of sulfuric acid. In certain embodiments where the bio-based cyclohexene intermediate comprises a mono- or di-ester, the dehydration results in hydrolysis of ester groups. In certain embodiments where the bio-based cyclohexene intermediate comprises a mono- or di-ester, the dehydration conditions promote ester hydrolysis to produce a carboxylic acid and/or diacid. [QQ58] In certain preferred embodiments, the processes of the present in vention include steps for transforming the bio-based cyclohexene intermediate to a bio-based aromatic carboxylic acid using dehydro-aromatization. In certain preferred embodiments, the dehydro-aromatization transformation is acid catalyzed, wherein the acid catalyst is, for example, sulfuric acid, producing a bio-based aromatic carboxylic acid intermediate, such as ji-toluic acid. A suitable example for dehydro-aromatization methods is disclosed in Fei Wang et al, Dehydro-aromatization of cyclohexene-carboxylic acids by sulfuric acid:

critical route for bio-based terephthalic acid synthesis, Royal Society of Chemistry , 2014, incorporated herein by reference. In certain embodiments, the bio-based aromatic carboxylic acid intermediate undergoes aerobic oxidation to produce a bio-based aromatic dicarboxylic acid intermediate, such as through the processes described in U.S Patent No. 3,678,106, herein incorporated by reference. In certain embodiments, the bio-based dicarboxylic acid intermediate is bio-based terephthalic acid.

[0059] In certain embodiments of the present invention, bio-based 1 ,3-propanediol is produced from the steps as follows: carbonylatmg a bio-based epoxide with bio-based carbon monoxide to produce a bio-based beta-lactone; hydrolyzing the bio-based beta-lactone to produce a bio-based beta-hydroxy acid; dehydrating the bio-based beta-hydroxy acid to produce a bio-based aldehyde; hydrogenating the bio-based aldehyde to produce a bio-based dioi; and polymerizing the bio-based diol with bio-based terephthalic acid and/or an alkyl ester derivative thereof. In certain preferred embodiments, the bio-based diol is bio-based 1 ,3-propanediol. In yet other preferred embodiments, the bio-based aldehyde is bio-based propionaldehyde. In still other preferred embodiments, the bio-based beta-hydroxy acid is bio-based hydroxy propionic acid.

[0060] In certain embodiments, the processes of the present invention include steps for contacting bio-based beta-lactone with water to produce a bio-based beta- hydroxy acid.

Preferably, the bio-based beta-lactone is a composition and structure which is susceptible to nucleophilic attack. As used herein, the bio-based beta-hydroxy acid comprises a bio-based carboxylic acid substituted with a hydroxyl group. [0061] In certain embodiments, the processes of the present invention include steps for reducing a bio-based beta-hydroxy acid to produce a bio-based beta-hydroxy aldehyde. In certain embodiments, reducing a bio-based beta-hydroxy acid to produce a bio-based beta- hydroxy aldehyde is provided, wherein a reducing agent such as tetrahydroalumate contacts the bio-based beta-hydroxy acid to produce the bio-based beta-hydroxy aldehyde. In certain preferred embodiments, the hydroxya!dehyde is 3-hydroxypropanal.

[0062] In certain embodiments, 1, 3-propanediol is produced from a step wherein a beta- hydroxy acid is catalytically hydrogenated using known hydrogenation catalysts such as those, for example, comprising polyamine/polycarboxylic acid resins. The methods for catalytic hydrogenation are disclosed in U.S. Patent No. 5,334,778 and are herein incorporated by reference. Preferred hydrogenation catalysts used to produce 1 ,3- propanediol are Raney nickel, which is optionally doped with other catalytically active metals, platinum- coated supported catalysts based on metal oxides, or active carbon, such as for example, catalysts based on titanium dioxide containing 0.1 to 5 0% by weight nickel- coated oxide- or silicate-containing supported catalysts, such as Ni/AhQi/SiCb. In certain embodiments, the hydrogenation is carried out at temperatures in the range from 30 °C to 180 °C and pressures of from between 50 psi to 1000 psi.

[0063] In still other preferred embodiments, the processes of the present invention are directed to producing copolymer products comprising monomers of terephthalie acid and at least one diol. In certain preferred embodiments, the processes for producing copolymer products comprises monomers of terephthalie acid and at least one diol, the method comprising the steps of: mixing a monomer of terephthalie acid and at least one monomer of a diol; esterifying the monomer of terephthalie acid and the at least one monomer of the diol to produce an aromatic ester intermediate; pre-polymerizing the aromatic ester intermediate to produce an aromatic ester oligomer; and polycondensatmg the aromatic ester oligomer to produce a copolymer product. In certain preferred embodiments, the copolymer product comprises polytrimethylene ter ephtha late, polyethylene terephthalate, polybutylene terephthalate, or combinations thereof. Advantageously, the processes of the present invention is easily adapted to produce a variety' of bio-based copolymer products produced under similar reaction conditions, using similar reactor system configurations, and having similar properties. The advantages of the present invention provide for tailored formulations of copolymer products such as polytrimethylene terephthalate, polyethylene terephthalate and polybutylene terephthalate to be produced in one location. In preferred embodiments, the processes of the present invention produce copolymer products with a bio-based content of greater than 50%, preferably greater than 75%, and more preferably between 90% and 100%.

[0064] Preferred embodiments include a step for mixing the monomer of a bio- based terephthalie acid and at least one monomer of a bio-based diol to form a homogenous mass. In certain preferred embodiments, the step for mixing monomers of bio-based terephthalie acid and at least one bio-based diol includes mixing the monomers to create a homogenous mass with a soluble catalyst. In certain embodiments, the mixing is performed m a reaction vessel, such as for example, a continuous stirred tank reactor using well known means for mixing, such as for example, a vertical mixer or jet mixer. In certain embodiments, the catalyst and/or monomers of bio-based terephthalie acid and at least one bio-based diol are introduced to the reaction vessel through at least one inlet. In some embodiments, a pump is used to introduce the catalyst and/or the monomer of bio-based terephthalie acid and the monomer of at least one bio-based diol at a velocity sufficient for mixing.

[0065] In preferred embodiments, the processes include a step for esterifymg a bio-based monomer of terephthalie acid and at least one monomer of a bio-based diol to produce a bio based aromatic ester intermediate in the presence of a soluble catalyst. In certain preferred embodiments, the esterification reaction is performed when the soluble catalyst (as a homogenous mass) and monomers of bio-based terephthalie acid and at least one bio-based diol is heated at a temperature between 150 °C and 350 °C, preferably between 200 °C and

250 °C, and more preferably between 210 °C and 230 °C. In preferred embodiments, the average residence time for the esterification in the reaction vessels is between 0.1 and 24 hours, preferably between 4 and 12 hours, and more preferably between 2 and 6 hours. In preferred embodiments, the esterification reaction is performed in the pressure range between 50 psi and 1000 psi.

[0066] In certain preferred embodiments, the processes of the present invention produce bio-based polytrimethylene terephthalate having a high bio-based content preferably between 50% and 100%. Preferred embodiments of processes for producing bio-based

polytrimethylene terephthalate include the steps of: esterifiying bio-based 1,3-propanediol with bio-based terephthalic acid, optionally pre-polymerizing the resulting product to form a pre-polymerization bio-based oligomer intermediate, and polycondensating polymerizing the bio-based oligomer intermediate to produce bio-based polytrimethylene terephthalate. In preferred embodiments, the esterification reaction is performed at a temperature between 150 °C and 350 °C, preferably between 200 °C and 250 °C, and more preferably between 2lO°C and 230°C. In preferred embodiments, the average residence time for the esterification in the reaction vessels is between 0.1 and 24 hours, preferably between 4 and 12 hours, and more preferably between 2 and 6 hours. In preferred embodiments, the esterification reaction is performed in the pressure range of between 50 psi and 1000 psi. In preferred embodiments, the bio-based polytrimethylene terephthalate produced according to the present invention has a tensile strength between 56.5 MPa and 72.5 MPa; a flexural modulus between 2.34 GPa and 3.11 GPa; a Notched Izod impact between 37J/m and 53 J/m; a heat deflection temperature (HDT) at 1.8 MPa between 54 °C and 65 °C; a melt temperature between 225 °C and 265°C; and a specific gravity (g/cnfi) between 1.34 and 1 .40.

[0067] In preferred embodiments of the present invention, the processes for producing polyethylene terephthalate include the steps of: hydrolyzing bio-based ethylene oxide to produce bio-based ethylene glycol; and co-polymerizing bio-based terephthalic acid with the bio-based ethylene glycol in an esterification reaction. In certain embodiments, the processes for producing polyethylene terephthalate include a pre-polymerization step wherein an oligomer or low molecular mass prepolymer is formed by esterification of bio-based terephthalic acid and a molar excess of bio-based ethylene glycol to form a bio-based diethyleneglycol terephthalate intermediate, a specific example being bis(2-hydroxyethyl) terephthalate. The formation of the bio-based di ethyleneglycol terephthalate intermediate is generally self-catalyzed but is accelerated by adding metal-based catalyst such as Ti, Sn, Sb, Mn, Zn and/or Pb. The bio-based diethyleneglycol terephthalate intermediate undergoes polycondensation by transesterification to form higher molecular weight bio-based polyethylene terephthalate. The bio-based polyethylene terephthalate is optionally extruded into strands, quenched under water and cut to form pellets or chips.

[0068] In preferred embodiments, the esterification reaction is performed at a temperature between 150 °C and 350 °C, preferably between 200 °C and 250 °C, and more preferably between 210 °C and 230 °C. In preferred embodiments, the average residence time for the esterification in the reaction vessels is between 0.1 and 24 hours, preferably between 4 and 12 hours, and more preferably between 2 and 6 hours. In preferred embodiments, the esterification reaction is performed in the pressure range between 50 psi and 1000 psi. In preferred embodiments, the bio-based polyethylene terephthalate produced according to the present invention has a tensile strength between 56.5 MPa and 72.5 MPa; a flexural modulus between 2.34 GPa and 3.11 GPa; a Notched Izod impact between 37J/m and 53 J/m; an HDT at 1.8 MPa, between 54 °C and 65 °C; a melt temperature between 225 °C and 265 °C; and a specific gravity (g/cnT) between 1.34 and 1.40.

[0069] In preferred embodiments of the present invention, the processes for producing bio-based polybutylene terephthalate include the steps of: carbonylating bio-based beta- propio!actone to produce bio-based succinic anhydride; hydrolyzing the bio-based succinic anhydride to produce bio-based succinic acid; hydrogenating the bio-based succinic acid to produce bio-based 1,4-butanediol; optionally hydrogenating the bio-based succinic anhydride to produce bio-based 1,4-butanediol; and polymerizing bio-based terephthalic acid or an alkyl ester derivative of terephthalic acid with the bio-based 1,4-butanediol. In certain preferred embodiments, the processes for producing bio-based polybutylene terephthalate include a pre-polymerization step for subjecting bio-based terephthalic acid and bio-based 1,4-butanediol to an esterification reaction in the presence of a catalyst, such as for example, a titanium compound, followed by a step for subjecting the pre-polymerization intermediate to a poly condensation reaction in the presence of a catalyst.

[0070] In preferred embodiments, the esterification reaction is performed at a

temperature between 150 °C and 350 °C, preferably between 200 °C and 250°C, and more preferably between 210 °C and 230 °C, In preferred embodiments, the average residence time for the esterification in the reaction vessels is between 0.1 and 24 hours, preferably between 4 and 12 hours, and more preferably between 2 and 6 hours. In preferred embodiments, the esterification reaction is performed in the pressure range between 50 psi and 1000 psi. In preferred embodiments, the polybutylene terephthalate produced according to the present invention has a tensile strength between 56.5 MPa and 72 5 MPa; a flexural modulus between 2.34 GPa and 3.1 1 GPa; a Notched Izod impact between 37J/m and 53 J/m; an HDT at 1 8 MPa, between 54 °C and 65 °C; a melt temperature between 225 °C and 265 °C; and a specific gravity' (g/cm³) between 1.34 and 1.40.

[0071] In certain preferred embodiments, the processes for producing bio-based copolymers such as bio-based polybutylene terephthalate include a step for forming a pre- polymerisation bio-based oligomer intermediate from bio-based terephthahc acid or dimethyl terephthalate and bio-based 1,4-butanediol. In certain other preferred embodiments, the processes for producing bio-based copolymers such as bio-based polybutylene terephthalate include a step for direct continuous polycondensation polymerization of the bio-based oligomer intermediate. In certain embodiments, a titanium compound is used as a polymerization catalyst.

[0072] The embodiments described herein are not intended to be limited to the aspects shown but are to be accorded the widest scope consistent with the principles and features disclosed herein.

Claims

CLAIMS What is claimed is:

1. A process for producing a bio-based aromatic carboxylic acid product comprising: carhonylating a bio-based epoxide with a bio-based carbon monoxide to produce a bio-based beta-lactone;

cata!yticaliy rearranging the bio-based beta-lactone to produce a bio-based unsaturated organic acid;

contacting the bio-based unsaturated organic acid with a bio-based conjugated diene to produce a bio-based cyclohexene intermediate; and

transforming the bio-based cyclohexene intermediate into the bio-based aromatic carboxylic acid product using dehydroaromatization.

2. The process of claim 1, wherein the bio-based beta-lactone is polymerized to form a bio-based polylactone intermediate, and wherein the bio-based polylactone is rearranged to produce the bio-based unsaturated organic acid.

3. The process of claim 2, wherein the bio-based beta-lactone is polymerized in a first location and the bio-based polylactone is rearranged in a second location remote from the first location.

4. The process of any one of claims 1 to 3, wherein the bio-based beta-lactone is bio based beta-propiolactone.

5. The process of any one of claims 1 to 4, wherein the unsaturated bio-based organic acid is bio-based acrylic acid.

6. The process of any one of claims 1 to 5, wherein the bio-based conjugated diene is bio-based isoprene.

7. The process of any one of claims 1 to 6, wherein the bio-based cyclohexene intermediate is 4-methylcyclohex-3-ene-l -carboxylic acid.

8. The process of any one of claims 1 to 7, wherein the bio-based aromatic carboxylic acid product is bio-based p-toluic acid.

9. The process of claim 8, where the bio-based p-toluic acid is oxidized to produce bio based terephthalic acid.

10. The process of claim 9, wherein the bio-based terephthahc acid undergoes esterification with ethylene glycol to produce bis(2-hydroxyethyl) terephthalate aromatic ester intermediate.

11. The process of claim 10, wherein the bis(2-hydroxy ethyl) terephthalate is polymerized to produce polyethylene terephthalate.

12. A process for producing a bio-based copolymer of a bio-based aromatic acid and a bio-based diol comprising:

mixing a bio-based aromatic acid and a bio-based diol to produce a homogenous reaction mixture;

estenfying the homogenous reaction mixture to produce one or more ester intermediates;

oligomerizing the one or more ester intermediates to produce one or more oligomers; and

polycondensating polymerizing the one or more oligomers to produce the bio-based copolymer of a bio-based aromatic acid and a bio-based diol.

13. The process of claim 12, wherein the diol is bio-based 1,3-propane diol.

14. The process of claim 12 or 13, wherein the bio-based aromatic acid derivative is bio- based terephthahc acid.

15. The process of any one of claims 12 to 14, wherein the bio-based copolymer of a bio based aromatic acid and a bio-based diol is bio-based polytrimethylene terephthalate.

16. A process for producing a bio-based copolymer product comprising the steps:

producing a bio-based aromatic carboxylic acid from bio-based sources of ethylene oxide and carbon monoxide;

producing a bio-based diol from bio-based sources of ethylene oxide and carbon monoxide;

esterifiying the bio-based aromatic carboxylic acid and the bio-based diol to produce a bio-based aromatic ester intermediate;

pre-polymerizing the bio-based aromatic ester intermediate to produce a bio-based oligomer intermediate; polycondensating polymerizing the bio-based oligomer intermediate to produce the bio-based copolymer product

17. The process of claim 16, wherein the bio-based carboxylic acid is bio-based terephthalic acid

18. The process of claim 16 or 17, wherein the bio-based diol is bio-based 1,4-butanediol.

19. The process of any one of claims 16 to 18, wherein the bio-based copolymer product is bio-based polybutylene terephthalate.