巴西专利BR112019011536A2 beta-propiolactone-based copolymers containing biogenic carbon, methods for their production and use

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专利摘要:
Methods and systems for producing biodegradable beta-propiolactone-based polyester polymers from renewable oil and co are provided herein on an industrial scale.
公开号:BR112019011536A2
申请号:R112019011536
申请日:2018-02-05
公开日:2019-10-08
发明作者:H Sookraj Sadesh
申请人:Novomer Inc；
IPC主号:

专利说明:

BETA-BASED COPOLYMERS — PROPIOLACTONE CONTAINING BIOGENIC CARBON, METHODS FOR THEIR PRODUCTION AND USES OF THE SAME FIELD [001] This description generally relates to polymeric materials and the production of polymers derived from beta-propiolactone that is produced from sources renewable food sources of ethylene oxide and carbon monoxide. More specifically, this invention relates to propiolactone copolymers suitable for use in thermoplastic applications, moisture barrier applications, packaging applications, etc. and as chemical precursors, together with methods of producing such polymers.
BACKGROUND [002] Poly (beta-propiolactone) is an aliphatic polyester and can be completely biodegradable to CO2 and water. Poly (beta-propiolactone) has potential applications in many different areas, including the medical, pharmaceutical and packaging industries, due to its biodegradability. The present invention relates to the production of copolymers from beta-propiolactone and a comonomer.
[003] Poly (propiolactone) (PPL) is a biodegradable polymer that can be used in many applications, such as fibers and films. It is also known that PPL can be thermally degraded into high-purity acrylic acid that has high demand for the production of superabsorbent polymers based on polyacrylic acid, detergent chore strengthers, dispersants, flocculants and thickeners.
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2/35 [004] Recent advances in epoxide carbonylation described in US Patent No. 6,852,865 and efficient beta-propiolactone ring polymerization have opened up the efficient synthetic pathways for poly (betapropiolactone) from ethylene oxide and CO. However, there are practical problems, preventing highly amorphous poly (betalactone) from being processed industrially. Highly amorphous poly (beta-propiolactone) has been almost impossible to produce at reasonable operating rates due to its low melting point.
[005] There is a need to provide highly biodegradable polymers for products that have a short shelf life and subsequently require rapid assimilation back into the environment. The production of such polymers from renewable sources and recycled sources will further reduce its ecological footprint. As such, there remains a need for methods to produce a beta-propiolactone copolymer, having improved processability and thermal stability.
BRIEF SUMMARY OF THE INVENTION [006] Polymerization of poly (propiolactone) (PPL) from beta-propiolactone (bPL) is generally known, however, the present invention is directed to systems and methods for including the bPL obtained from carbonyl oxide ethylene (EO), and preferably carbon monoxide (CO) from biomass sources in lactone-based copolymers. BPL from renewable sources can be polymerized to produce PPL homopolymers and PPL heteropolymers and PPL polymer derivatives. These exclusively sustainable polymers are highly biodegradable and still meet
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3/35 to the material performance requirements required in many applications. These PLB-derived polymers retain the biodegradability of the beta-propiolactone constituents and provide an environment-friendly benefit for many applications that now use polymers with poor biodegradable properties and a bio-based low carbon content. Combining the supply of precursors to the carbon-containing EO bPL copolymer from biomass sources, and preferably CO from biomass sources, provides significant and necessary environmental benefits.
[007] The ability to use the derivative of bPL, at least in part, from renewable and recycled carbon containing EO and CO increases the environmental benefit obtained from the polymers of this invention and the production methods of this invention.
[008] The present invention relates to the production of copolymers from beta-propiolactone and a comonomer, wherein at least beta-propiolactone has a bio-based content.
[009] Some aspects of this invention provide a linear bPL copolymer produced from a bPL feed stream and a comonomer where bPL is obtained by carbonylation of EO and CO, and in which at least a portion of the EO contains carbon sources of biomass, also known as biogenic carbon. In preferred aspects of this invention, all EO is derived from biogenic carbon. In highly preferred aspects of this invention, all EO and CO are derived from biogenic carbon.
[0010] Certain aspects of this invention provide a method of producing a bPL copolymer, comprising the combination of bPL and an initiator in the presence of a cation
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4/35 metal and a comonomer to produce the copolymer based on bPL (hereinafter also called copolymer), in which bPL is produced by carbonylation of EO and CO originating, at least in part, from one or more fillers renewable power supplies. In preferred aspects of this invention, all EO is derived from renewable sources. In other preferred aspects of this invention, at least a portion of the CO is derived from renewable sources. In highly preferred aspects of this invention, all EO and CO are derived from renewable sources.
[0011] In a broad modality, the bPL copolymer is produced by polymerization by opening a biogenic betapropiolactone ring and a comonomer. In a preferred embodiment, the comonomer is selected from the group comprising lactones and anhydrides.
[0012] In some respects, the comonomer is a lactone that has a greater number of carbon atoms than bPL and is referred to here as a superior lactone.
[0013] In some respects, the comonomer is a betalactone having a greater number of bPL carbon atoms and here referred to as a superior beta-lactone.
[0014] In additional aspects, superior beta-lactones suitable for copolymerization include betabutyrolactone, beta-valerolactone, beta-heptanolactone, beta-tridecanolactone, cis-3,4-dimethyloxetan-2-one, 4 (butoxymethyl) -2-oxetanone , 4 - [[[[(1, l— dimethylethyl) dimethylsilyl] oxy] methyl] -2-oxetanone, 4 - [(2propen-1-yloxy) methyl] -2-oxetanone, 4- [(benzoyloxy) methyl] -2oxetanone.
[0015] In some aspects of this invention, the comonomer is
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5/35 a cyclic anhydride. In preferred aspects, cyclic anhydrides include succinic anhydride, and maleic anhydride.
[0016] In some embodiments, the copolymerization of beta-lactones and cyclic anhydride is carried out in the presence of a polymerization catalyst. The polymerization catalyst initiates polymerization by opening a ring of beta-lactones or cyclic anhydrides to produce
copolymers. An broad banner of catalysts in polymerization can to be used to the initiation gives polymerization by opening of ring • [0017] On other aspect, the gift invention is one
linear polyester comprising a bPL-based copolymer having linear chains of repetitive units (O (CH2) 2CO) X containing carbon atoms and oxygen provided by a bPL charge produced from carbonyl carbonyl containing EO and oxygen atoms which originate from a renewable source. Where X is a comonomer unit of paragraphs 0014 and / or 0015. In another variation of the invention, the carbon source is CO which contains carbon and oxygen atoms that originate from a renewable source. In another variation of the invention, all atoms in EO are derived from a renewable source. In another variation of the invention, all atoms in EO and CO are derived from a renewable source. In certain variations, the polymer chains have opposite terminal groups of primer and a cation. In other variations, the primer comprises an anionic nucleophile.
[0018] In preferred applications of this invention, the copolymers described herein, may be suitable for use as thermoplastics. PPL polymers are known for
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6/35 have relatively low melting points. The melting point of the thermoplastics obtained by this invention can be adjusted by selecting the comonomer. Thus, the thermoplastics of this invention can use as fiber, films and structural components.
[0019] The structural components that can be formed using the copolymers of this invention include any article that requires rigidity or load bearing capacity. Examples of structural components include household items, furniture, building components, sculptures and machine sets. For application as structural components, the copolymer of this invention, the comonomers will be selected to provide the copolymer with a relatively high melting temperature.
[0020] The application of fibers and films to the copolymers of this invention can also include a wide range of products. Such products may include biodegradable packaging and biodegradable moisture barriers for multilayers that comprise a diaper component, adult incontinence products or feminine hygiene products. In these applications, comonomers will typically be selected to result in the copolymer at a relatively low melting temperature.
[0021] In preferred applications of this invention, the copolymers described herein, may be suitable for use as thermoplastics having low melting temperatures. Such thermoplastics can be used as molding materials.
[0022] In another embodiment, this invention is a method
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7/35 to produce a bPL copolymer. Thus, in several respects, production systems / production processes are provided to produce the bPL copolymer.
[0023] Therefore, in one aspect, the invention is a method for producing a bPL copolymer having renewable carbon content. In this respect, a food component is a monomer derived from bPL having a biogenic carbon content. Another food component is a comonomer. The method combines the monomer and comonomer with the polymerization catalyst in a polymerization reaction zone under polymerization conditions to produce a bPL-based copolymer that is recovered as at least part of a product stream. Preferably, at least a portion of the bPL monomer feed component comprises bPL produced by carbonylating ethylene oxide having a bio-based content of at least 10% with carbon monoxide which optionally has a bio-based content of at least 10% and a comonomer derived from a lactone other than betapropiolactone.
[0024] In another aspect, the method of this invention combines the bPL monomer, comonomer and optional polymerization catalyst or initiator to produce the bPL-based copolymer. This can be done in one or more reactors in series.
[0025] In another aspect of the method of this invention, a product stream containing the bPL-based copolymer includes at least one of the bPL monomers, the comonomer and the polymerization catalyst is recovered from the polymerization reaction zone. In this respect, at least a portion of the bPL-based copolymer is separated from any
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8/35 bPL monomer, comonomer and / or polymerization catalyst and a purified bPL-based copolymer having a higher bPL content than the bPL product stream, is recovered. In a preferred form of this aspect, at least a portion of any bPL monomer, the comonomer and / or polymerization catalyst separated from the product stream is recycled to the polymerization reaction zone.
[0026] In an additional aspect, the polymerization zone includes multiple polymerization reactors and one or more intermediate product stream (s) comprising the bPL-based polymer, the bPL monomer, the comonomer and the polymerization catalyst a polymerization reactor to another polymerization reactor. Polymerization reactors in this regard have one or more inlets and one or more outlets and one or more transfer ducts to transfer the intermediate product stream between the polymerization reactors.
[0027] In another aspect, the invention is a process for the production of a sustainable bPL-based copolymer comprising beta-propiolactone monomers and higher lactone monomers, which begins with the production of the bPL monomers having a bio-based content appropriate. The process begins by combining EO having a bio-based content, CO, preferably having a bio-based content, carbonylation catalyst, and solvent in a carbonylation zone under carbonylation conditions; producing bPL; and recovering at least a portion of the bPL as a bPL output stream. At least a portion of the bPL output current passes into a zone
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9/35 purification of bPL which produces a recycle stream comprising at least one of EO, CO, carbonylation catalyst, and solvent and the output stream of bPL; and, at least a portion for the bPL recycle stream is returned to the carbonylation reaction zone. This aspect combines feed components comprising a bPL polymerization initiator and a cation donor, and at least a portion of the bPL output stream, and contacts the feed components in a polymerization reactor under polymerization conditions to produce a copolymer based on bPL. At least a portion of the bPL-based copolymer is recovered when this aspect combines feed components comprising a bPL polymerization initiator and a cation donor, and at least a portion of the bPL output stream, and contacts the feed components in a polymerization reactor under polymerization conditions to produce a bPL-based copolymer. At least a portion of the bPL-based copolymer is recovered as a bPL copolymer outlet stream.
[0028] The present application can be better understood by reference to the following description.
DETAILED DESCRIPTION [0029] The following description sets out exemplary methods, parameters and the like. It should be recognized, however, that such a description is not intended to be a limitation on the scope of this description, but rather as a description of exemplary aspects.
Definitions [0030] The terms biobased content and content
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10/35 based on bio means biogenic carbon also known as carbon derived from biomass.
[0031] In some variations, bio-based content (also referred to as bio-based content) can be determined based on the following:
% of bio-based content or bio-based content = [Bio (Organic) Carbon] / [Total (Organic) Carbon] 100% as determined by ASTM D6866 (Standard Test Methods for Determining Bio-Based Content) of Solid, Liquid and Gaseous Samples Using Radiocarbon Analysis).
[0032] The bio-based content of the polymers may depend on the basis of the bio-based content of the betapropiolactone used. For example, in some variations of the methods described herein, the beta-propiolactone used to produce the polymers described herein may have a biobased content greater than 0% and less than 100%. In certain variations of the methods described herein, the beta-propiolactone used to produce the polymers described herein may have a bio-based content of at least 10%, at least 20%, at least 30%, at least 40%, at least 50 %, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99 , 5%, at least 99.9%, at least 99.99% or 100%. In certain variations, beta-propiolactone derived from renewable sources is used. In other variations, at least a portion of the beta-propiolactone used is derived from renewable sources, and at least a portion of the beta-propiolactone is derived from non-renewable sources.
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11/35 renewable.
[0033] The bio-based content of betapropiolactone may depend, for example, on the bio-based content of ethylene oxide and the carbon monoxide used. In some variations, both ethylene oxide and carbon monoxide are derived from sources of
biogenic carbon or based biomass. Biodegradability [0034] In some variations of the above, the polymer has a biodegradability of at least least 10%, at least 20%, at least 30%, at least minus 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least least 95%, at least 96% by at least 97%, at least 98%, at least 99%, at least minus 99, 5%, at least 99, 9%, at least minus 99.99% or 100%. [0035] Biodegradable and biodegradability is like
defined and determined based on ASTM D5338-15 (Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials Under Controlled Composting Conditions, Incorporating Thermophilic Temperatures).
[0036] In other respects, the product stream comprises at least one bPL polymerization initiator and cation donor and at least a portion of the product stream passes into a purification zone. The purification zone recovers at least one of beta-propiolactone, bPL polymerization initiator and cation donor from the product stream in one or more recycle stream (s), and produces a stream of purified product and at least a portion of a recycle stream is returned to the polymerization reaction zone to provide a stream of
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12/35 purified product comprising a bPL-based copolymer in a higher concentration than the product stream recovered from the process. In other respects, the polymerization reaction zone comprises multiple reactors, one reactor upstream produces the product stream; at least a portion of the purified product stream enters a downstream reactor and a high purity product stream is recovered from the downstream reactor. A portion of the recycle stream can pass to the upstream reactor.
[0037] Definitions of specific functional groups and chemical terms are described in more detail below. Chemical elements are identified according to the Periodic Table of Elements, CAS version, Handbook of Chemistry and Physics, 75 ^to Ed., Back cover, and specific functional groups are generally defined as described herein. In addition, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, Science Books University, Sausalito, 1999; Smith and March March's Advanced Organic Chemistry, 5th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3rd Edition, Cambridge University Press, Cambridge, 1987; all the content of each of them is incorporated by reference.
[0038] The terms halo and halogen, as used herein, refer to an atom selected from fluorine (fluorine, -F), chlorine (chlorine, -Cl), bromine (bromine, -Br) and iodine (iodine, - I).
[0039] The terms halide, as used herein, refer to
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13/35 if to a halogen that contains a selected negative charge of fluoride -F ^- , chloride -Cl ^- , bromide -Br ^- and iodide -I ^- .
[0040] The term aliphatic group or aliphatic group, as used here, denotes a portion of hydrocarbon that may be straight (i.e., unbranched), branched or cyclic (including fused, bridged, fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but that is not aromatic. Unless otherwise specified, aliphatic groups contain 1 to 30 carbon atoms. In some ways, aliphatic groups contain 1-12 carbon atoms. In some ways, aliphatic groups contain 1-8 carbon atoms. In some respects, aliphatic groups contain 1 to 6 carbon atoms. In some respects, aliphatic groups contain 1-5 carbon atoms, in some respects aliphatic groups contain 1-4 carbon atoms, yet in other respects, aliphatic groups contain 1-3 carbon atoms, and in still other aspects, the aliphatic groups contain 1-3 carbon atoms, and in yet other aspects, the 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 their hybrids, such as (cycloalkyl) alkyl, (cycloalkenyl) alkyl or (cycloalkyl) alkenyl.
[0041] The term heteroaliphatic, as used here, refers to aliphatic groups, in which one or more carbon atoms is (are) independently replaced (s) by one or more atom (s) selected from the group that consists (m) of
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14/35 oxygen, sulfur, nitrogen, phosphorus or boron. In some respects, one or more carbon atoms is (are) independently replaced by one or more of oxygen, sulfur, nitrogen or phosphorus. Heteroaliphatic groups can be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include heterocycle, heterocyclyl, heterocycloaliphatic or heterocyclic groups.
[0042] The term acrylate or acrylates, as used herein, refers to any acyl group having a vinyl group adjacent to the acylcarbonyl. The terms include mono-, di- and tri-substituted vinyl groups. Examples of acrylates include, but are not limited to: acrylate, methacrylate, ethacrylate, cinnamate (3-phenylacrylate), crotonate, tiglate and senecioate.
[0043] The term polymer, as used here, refers to a molecule of high relative molecular mass, whose structure comprises the multiple repetitions of units derived, really or conceptually, from molecules of low relative molecular mass. In some respects, a polymer is comprised of only one monomeric species (for example, polyEO). In some respects, a polymer is a copolymer, terpolymer, heteropolymer, block copolymer or tapered heteropolymer of one or more epoxides.
[0044] The term unsaturated, as used here, means that a portion has one or more double or triple bonds.
[0045] The terms cycloaliphatic, carbocycle or carbocyclic, used alone or as part of a larger portion, refer to saturated or cyclic aliphatic monocyclic, bicyclic or polycyclic ring systems
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15/35 partially unsaturated, as described herein, having 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, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl and cyclooctadienyl. In some ways, cycloalkyl has 3-6 carbons. Representative carbocycles include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo [2,2,1] heptane, norbornene, phenyl, cyclohexene, naphthalene and spiro [4,5] decane. The terms cycloaliphatic, carbocycle or carbocyclic also include aliphatic rings that are fused to one or more aromatic or non-aromatic rings, such as, decahydronaphil or tetrahydronaphthyl, where the radical or point of attachment is in the aliphatic ring. In some respects, a carbocyclic group is bicyclic. In some respects, a carbocyclic group is tricyclic. In some respects, a carbocyclic group is polycyclic.
[0046] The term alkyl, as used herein, refers to saturated, straight or branched chain hydrocarbon radicals derived from an aliphatic portion containing between one and six carbon atoms by removing a single hydrogen atom. Unless otherwise indicated, alkyl groups contain 1-12 carbon atoms. In some ways, alkyl groups contain 1-8 carbon atoms. In some ways, alkyl groups contain 1-6 carbon atoms. In some ways, alkyl groups contain 1-5 carbon atoms; in some ways, alkyl groups contain
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1-4 carbon atoms; in still other aspects, the alkyl groups contain 1-3 carbon atoms; and in still other aspects, the alkyl groups contain 1-2 carbon atoms. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tercbutyl, n-pentyl, neopentyl, n -hexyl, sec-hexyl, nheptila, n-octyl, n-decyl, n-undecyl, dodecyl and the like.
[0047] The term aryl used alone or as part of a larger portion such as aralkyl, aralkoxy or aryloxyalkyl, refers to monocyclic and polycyclic ring systems having a total of five to 20 ring members, at least one ring in the system it is aromatic, and each ring in the system contains three to twelve members in the ring. The term aryl can be used interchangeably with the term aryl ring. In some respects, aryl refers to an aromatic ring system that includes, but is not limited to, phenyl, naphthyl, anthracyl and the like, which may contain one or more substituents. Also included within the scope of the term aryl, as used herein, is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthymidyl, phenanthridinyl, or tetrahydronaftyl, and the like.
[0048] The terms heteroaryl and heteroar-, used alone or as part of a larger portion, for example, heteroaralkyl or heteroaralkoxy, refer to groups having 5 to 14 ring atoms, preferably 5, 6, 9 or 10 atoms in the ring; having 6, 10 or 14 π electrons
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17/35 shared in a cyclic matrix; and having, in addition to carbon atoms, from one to five hetero atoms. The term heteroatom refers to nitrogen, oxygen or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen. Heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridininyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridazinyl, pyridinyl, 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 the point of attachment is on the heteroaromatic ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, cinolinyl, phthalazinyl, quinazolinyl, phenyl, quinoline, phenyl, quinoline, phenyl, zinc pyrido [2,3-b] -1,4-oxazin-3 (4H) -one. A heteroaryl group can be monocyclic or bicyclic. The term heteroaryl may be used interchangeably with the terms heteroaryl ring, heteroaryl or heteroaromatic group, any of which includes rings that are optionally substituted. The term heteroaralkyl refers to an alkyl group substituted by a heteroaryl, where the alkyl and heteroaryl moieties are,
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18/35 independently, optionally replaced.
[0049] As used here, the terms heterocycle, heterocyclyl, heterocyclic radical and heterocyclic ring are used interchangeably and refer to a 5- to 7-membered stable monocyclic portion or a 7 to 14-membered heterocyclic portion that is saturated or partially unsaturated and having, in addition to the carbon atoms, one or more, preferably one to four, hetero atoms, as defined above. When used in reference to a ring atom on a heterocycle, the term nitrogen includes substituted nitrogen. As an example, in a saturated or partially unsaturated ring having 0 to 3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen can be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or ⁺ NR (as in N-substituted pyrrolidinyl).
[0050] A heterocyclic ring can be attached to its pendant group on 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, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, dioxazininyl, dioxan, piperazinol, dioxan, piperazine oxazepinyl, thiazepinyl, morpholinyl and quinuclidinyl. The terms heterocycle, heterocyclyl, heterocyclic ring, heterocyclic group, heterocyclic radical and heterocyclic radical, are used herein
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19/35 indistinctly, and also include groups in which a heterocyclyl ring is fused to one or more of aryl, heteroaryl or cycloaliphatic rings, such as indolinyl, 3Hindolyl, chromanyl, phenanthridinyl or tetrahydroquinolinyl, where the radical or point of attachment is in the heterocyclyl ring. A heterocyclyl group can be mono- or bicyclic. The term heterocyclylalkyl refers to an alkyl group substituted by a heterocyclyl, where the
alkyl portions and heterocyclyl are independently replaced. [0051] Like here used, the term partially unsaturated refers to to a portion of ring which 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 defined herein.
[0052] As described here, the compounds can 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 is (are) replaced (s) with a suitable substituent. Unless otherwise indicated, an optionally substituted group may have a suitable substituent at each replaceable position in 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 the same or different in all positions. Combinations of predicted substituents can include those that result in the formation of stable or chemically viable compounds.
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20/35
The term stable, as used here, refers to compounds that are not substantially altered when subjected to conditions to permit their production, detection and, in some respects, their recovery, purification and use for one or more of the purposes described herein.
[0053] In some chemical structures here, the substituents are shown attached to a bond that goes through a bond in a ring of the represented molecule. This means that one or more of the substituents may be attached to the ring in any available position (usually in place of a hydrogen atom in the precursor structure). In cases where an atom of a ring so substituted has two substitutable positions, two groups can be present on the same atom of the ring. When more than one substituent is present, each is defined independently of the others, and each can have a different structure. In cases where the substituent shown crossing a ring bond is -R, this has the same meaning as if the ring was optionally substituted as described in the preceding paragraph.
[0054] As used here, the term catalyst refers to a substance whose presence increases the rate of a chemical reaction, while it is not being consumed or undergoing its own permanent chemical change.
[0055] Renewable sources means a source of carbon and / or hydrogen obtained from biological forms of life that can be replenished in less than a hundred years.
[0056] Renewable carbon means carbon obtained from biological forms of life that can be replenished in less than a hundred years.
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21/35 [0057] Recycled sources mean carbon and / or hydrogen recovered from a previous use in a manufactured article.
[0058] Recycled carbon means carbon recovered from a previous use in a manufactured article.
[0059] Green constituents mean carbon atoms and hydrogen atoms from renewable sources and from recycled sources in a material.
[0060] Green carbon means the total renewable carbon and carbon recycled in a material.
[0061] Biodegradability and biodegradability refer to the ability of a material to be broken (decomposed) quickly by the action of living organisms, such as bacteria, fungi, microorganisms or other biological means, in which quickly typically less than 10 years, 5 years , to 2 years.
[0062] Sustainable material and sustainable polymer means a biodegradable material and polymer, respectively, which is derived at least in part for green sources and has a percentage of green substituents 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.
[0063] As used herein, the term about preceding one or more numerical values means the numerical value of ± 5%. It should be understood that the reference to a value or parameter here includes (and describes) aspects that are directed to that value or parameter per se. For example, the description about x includes the description of x itself.
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22/35 [0064] Furthermore, it should be understood that the reference to between two values or parameters here includes (and describes) aspects that include these two values or parameters per se. For example, the description between x and y includes the description of x and y alone.
[0065] The mass fractions described here can be converted to% by weight by multiplying by 100.
Biogenic Content and Supply of bPL Monomer [0066] The polymer of this invention will use the bPL that can be produced from EO and CO according to the general reaction schemes shown in Figures 1 and 2. In addition, in this invention, by at least one of EO and / or CO used to produce the bPL monomer will have a bio-based content of at least 10%, and preferably at least 20%, at least 30%, at least 40%, at least 50% at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99% or 100%.
[0067] Comonomers used in addition to bPL monomers may contain carbon with a significant bio-based content. In some variations, comonomers may have a bio-based content of at least 10%, and preferably at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99% or 100%.
[0068] In variations of the above, the resulting GLP copolymer will have a bio-based content greater than 0% and less than 100%. In certain variations of the foregoing, the polymer has a bio-based content of at least 10%, at least 20%, at least 30%, at least 40%, at least
Petition 870190052454, of June 4, 2019, p. 29/48
23/35 minus 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, at least 99.5%, at least 99.9% or 100%.
[0069] In this aspect of the invention, ο EO undergoes a carbonylation reaction, for example, with CO, in the presence of a carbonylation catalyst to produce the bPL monomer for the production of the bPL-based copolymer.
[0070] In the carbonylation reaction system, EO can be converted to bPL by a carbonylation reaction, as represented in the reaction scheme below.
[0071] The chemistry involved in a carbonylation reaction system may include, but is not limited to, the following three reactions: (1) CO + EO to bPL; (2) EO to acetaldehyde; (3) bPL for succinic anhydride. Conversions for the three reactions can vary depending on many factors, including quantity of reagents, quantity of catalyst, temperature, pressure, flow, etc.
[0072] Carbonylation methods can use a Lewis acid-carbonyl metal catalyst such as those described in US Patent No. 6,852,865. In other aspects, the carbonylation step is carried out with one or more of the carbonylation catalysts described in US Patent Applications Serial ^Nos 10 / 820,958; and 10 / 586,826. In other aspects, the carbonylation step is carried out with one or more of the catalysts described in US Patents ^Nos 5,310,948; 7,420,064; and 5,359,081. Additional catalysts for carbonylation of epoxides are discussed in a
Petition 870190052454, of June 4, 2019, p. 30/48
24/35 review in Chem. Commun., 2007, 657-674. The entirety of each of the previous references is incorporated herein by reference.
[0073] The carbonylation catalyst feed can be pumped under CO pressure to help ensure the stability of the catalyst and can be cooled, optionally together with the feed, below room temperature to ensure stability. The carbonylation catalyst can reach the source of the carbonylation catalyst as solids, which can be covered under CO or a suitable inert gas) or in a solvent solution, such as hexane or THF. The carbonylation catalyst feed can be pumped under CO pressure to help ensure the stability of the catalyst and can be cooled, optionally along with the feed, below room temperature to ensure stability.
[0074] In still other variations, the systems / processes provided for the practice of the method here are also configured to manage and integrate the heat produced. The carbonylation reaction to produce the bPL and the polymerization reaction to produce the bPL-based copolymer are exothermic. Thus, the heat generated from the operations of the exothermic unit, such as the carbonylation reactor and the polymerization reactor, can be captured and used for cooling in endothermic unit operations, such as the distillation apparatus and the thermolysis reactor. For example, in some variations of the systems and methods provided here, steam may be generated in heat transfer equipment (for example,
Petition 870190052454, of June 4, 2019, p. 31/48
25/35 hull and tube and reactor cooling jacket) through a temperature gradient between process fluid and water / steam. This steam can be used for thermal integration between exothermic and endothermic unit operations. In other variations of the systems and methods provided herein, other suitable heat transfer fluids can be used.
[0075] In other variations, thermal integration can be achieved through the combination of certain unitary operations. For example, thermal integration can be achieved by combining polymerization of bPL and vaporization of the solvent (eg, THF) from the distillation column within a single unit operation. In such a configuration, the heat released from the bPL polymerization reaction is used directly to vaporize the solvent in the distillation apparatus, and the outlet of the unit produces PPL. In other variations, the heat released from the polymerization reaction can be exported to other systems at the same production site. The distillation apparatus can recover at least a portion of the carbonylation catalyst present in the bPL product stream using a multi-solvent system.
[0076] The EO and CO have, in preferably a concentration less water and oxygen what fence in 500 ppm, lower what about 250 ppm, less what fence in 100 ppm, lower what
about 50 ppm, less than about 10 ppm, less than about 2 ppm or less than 1 ppm.
[0077] The carbonylation reactor can be a continuous reactor, such as a continuous agitated tank reactor (CSTR). Other reactors described here, such as reactors
Petition 870190052454, of June 4, 2019, p. 32/48
Batch 26/35, piston flow reactors (PFR), and semi-stack reactors can also be employed.
[0078] In certain variations, the reactor is equipped with an external cooler (heat exchanger). In some variations, the carbonylation reaction achieves a bPL selectivity above 99%.
The post-isolation GLP product stream can have any concentration of GLP, solvent, EO, CO, by-products (such as acetaldehyde and succinic anhydride), carbonylation catalyst, or carbonylation catalyst components described herein. In some respects, the mass fraction of bPL in the post-isolation bPL product stream may be about 0.1 to 0.4, or the molar fraction of bPL in the post-isolation bPL product stream may be about 0 , 1 to about 0.4. The post-isolation GLP product stream can also include other components including unreacted EO (in a mass fraction of about 0.005 to 0.1), unreacted CO (in a mass fraction of about 0.0005 to 0.001, or in maximum about 0.002), acetaldehyde (in a mass fraction of about 0.0005 to 0.001, or at most about 0.002), succinic anhydride (in a mass fraction of about 0.0005 to 0.01, or at most about 0.02), carbonylation catalyst, carbonylation catalyst and the remaining solvent. In some respects, the post-insulation GLP product stream of the carbonylation catalyst recycling system can have a temperature of about 20 ° C to about 60 ° C. In some respects, the post-isolation GLP product stream can have a pressure of about 1 (100 KPa) to about 5 bar (500 KPa).
Petition 870190052454, of June 4, 2019, p. 33/48
27/35 [0080] The production process / production system of GLP can receive additional components comprising diluents that do not participate directly in the chemical reactions of EO. Diluents can include one or more inert gases (for example, nitrogen, argon, helium and the like) or volatile organic molecules such as hydrocarbons, ethers and the like. The reaction stream may comprise hydrogen, carbon dioxide CO, methane and other compounds commonly found in industrial CO streams. Such additional components can have a direct or indirect chemical function in one or more of the processes involved in the conversion of EO to bPL and in several final products. CO can be supplied in a mixture with hydrogen from renewable sources, such as syngas.
[0081] More details of methods and processes for the production of EO by carbonylation with CO are described in US NS 15 / 197.838, deposited on June 30, 2016, the content of which is incorporated by reference in its entirety.
Composition of bPL-based copolymer [0082] In one embodiment, the copolymer is produced by polymerization by opening a beta-propiolactone ring and a comonomer. A wide variety of comonomers can be used with the bPL monomer and it will generally be those comonomers that will add biodegradability to the resulting copolymer.
[0083] In addition to biodegradability and bio-based content, comonomers and additives that can transmit other desired characteristics to the resulting GLP-based copolymer. Of particular interest are the
Petition 870190052454, of June 4, 2019, p. 34/48
28/35 phase behavior and mechanical properties. A wide variety of additives can be used. Such additives include flame retardants, plasticizers, pigments, heat and light stabilizers, fillers and fiber reinforcement.
[0084] Suitable comonomers include lactone comonomers having a higher number of carbon atoms than beta-propiolactone, in particular betalactones, anhydrides and alcohols. Specific examples of compounds suitable for providing comonomers include diols, caprolactone and lactic acid.
[0085] In some respects, the comonomer is a superior betalactone having a greater number of carbon atoms than bPL and here referred to as a superior beta-lactone. Superior beta-lactones suitable for copolymerization include beta-butyrolactone, beta-valerolactone, betaheptanolactone, beta-tridecanolactone, cis-3,4-dimethyloxetan-2-one, 4- (but-3-en-l-yl) oxetan-2- one, 4 (butoxymethyl) -2-oxetanone, 4 - [[[(1,1 l-dimethylethyl) dimethylsilyl] oxy] methyl] -2-oxetanone, 4 - [(2propen-l-yloxy) methyl] -2-oxetanone , 4- [(benzoyloxy) methyl] -2oxetanone.
[0086] In some aspects of this invention, the comonomer is a cyclic anhydride. In preferred aspects, cyclic anhydrides include succinic anhydride and maleic anhydride. In some aspects of this invention, the comonomer is a cyclic anhydride. In preferred aspects, cyclic anhydrides include succinic anhydride and maleic anhydride.
[0087] The bPL-based copolymers produced by this invention will have the structure shown below:
Petition 870190052454, of June 4, 2019, p. 35/48
29/35
Or
Cw ° V ' ⁰ [0088] In some embodiments, the copolymerization of beta-lactones and cyclic anhydride is carried out in the presence of a polymerization initiator. The polymerization initiator initiates polymerization by opening a ring of betalactones and cyclic anhydrides to produce copolymers. A wide range of polymerization catalysts can be used to initiate ring-opening polymerization.
[0089] In some aspects of this invention, the polymerization initiator is an ionic initiator. In variations of this aspect, the ionic initiator has the general formula of MX where M is cationic and X is anionic.
[0090] M is selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺² , Ca ⁺² and Al ⁺³ . In some modalities, M is Na ⁺ . In some embodiments, M is an organic cation. In some modalities, the organic cation is selected from the group consisting of quaternary ammonium, imidazolium and bis (triphenylphosphine) imine. In some embodiments, the quaternary ammonium cation is tetraalkylammonium.
[0091] X is a nucleophilic anion. Suitable nucleophilic anions include, but are not limited to, compounds comprising at least one carbonyl group, at least one alkoxide group, at least one phenoxide group, and combinations thereof. In some embodiments, the nucleophilic anion is selected from the group consisting of halides, hydroxide, alkoxide, carboxylate and combinations
Petition 870190052454, of June 4, 2019, p. 36/48
30/35 of them. In some embodiments, the ionic initiator is sodium acrylate. In some embodiments, the ionic initiator is tetrabutylammonium acrylate.
[0092] In some embodiments, polymerization is carried out in the presence of a solvent. The solvent can be selected from any solvent, and mixtures of solvents.
[0093] Suitable solvents for polymerization with cyclic anhydride monomers include methylene chloride chloroform tetrahydrofuran sulfolane
N-methyl pyrrolidone diglima triglima tetraglima and dibasic esters.
[0094] In one embodiment, said copolymer is produced by reaction of beta-propiolactone and an alcohol comprising at least two hydroxyl groups. Although the applicants are not bound by any theory about how the beta-lactone copolymer alcohol comprising at least two hydroxyl beta-propiolactone groups can react with the alcohol to form a carboxylic acid comprising at least two carboxylic acid groups as shown in the scheme below . The carboxylic acid having at least two carboxylic acid groups can further react with the alcohol having at least two hydroxyl groups by condensation polymerization to produce the copolymer.
9 ~ T
HO OH
HO
OH θ '/ -o
HO · > ·
The V-OH
THE
Scheme 1.
Petition 870190052454, of June 4, 2019, p. 37/48
31/35 ₀ HO Ο -λ OH
Q-f HO OH ’- (.
j__j + λλλ / O poIhnerízBçSo per condensation f
J ^ O y-o / 0 ^. OH HO -j- * 'ArnvV' / o% b
Scheme 2.
[0095] In variations of these modalities, alcohol is a diol. In some embodiments, suitable diols include ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, bis (hydroxymethyl) octadecanol and 1,6-hexanediol.
[0096] In another variation of this modality, the reaction can be conducted in the presence of a solvent. In some embodiments, suitable solvents include toluene, xylene and mesitylene. In some embodiments, the reaction configuration allows for the continuous removal of water formed during the esterification reaction. In certain variations, polymer chains have opposite end groups of an initiator and a cation. In other variations, the primer comprises an anionic nucleophile.
[0097] Suitable anionic nucleophiles include R ^X O ^- , R ^X C (= O) O ^- , R ^X S ^- , R ^X O (C = O) O ^- , halide (for example, Br, I ^- , Cl ^- ), R ^x (SO2) O ^- and PR ^X ₃ O ^- , where each R ^x is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted aryl, optionally substituted aryl and optionally substituted heteroaryl.
[0098] In certain aspects where the nucleophile is anionic R ^X C (= O) O ^- , R ^x is selected from optionally substituted aliphatic, fluorinated aliphatic compound, optionally substituted heteroaliphatic, optionally substituted aryl,
Petition 870190052454, of June 4, 2019, p. 38/48
32/35 fluorinated aryl, and optionally substituted heteroaryl. For example, in some respects, the initiator may be CH ₂ = CHCO ₂ -, CH ₃ CO ₂ ~, or cf ₃ co ₂ ~.
[0099] In certain respects, where the primer is R ^X O ~, R ^x is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl. For example, in some ways, the initiator is hydroxide, methoxide or ethoxide.
[00100] In some respects, the cation is selected from the group of inorganic and organic cations given above.
[00101] A wide variety of other polymerization initiators and catalyst can be used. Any suitable polymerization initiators and / or catalysts can be used to convert the bPL monomer and comonomers in the copolymer product stream entering the copolymer production system / production process into a copolymer product stream.
[00102] In addition to the following description, suitable catalysts, initiators, additives and solvent for the polymerization of bPL monomer and comonomers can be found in US NS 15 / 197.838, deposited on June 30, 2016, the content of which is incorporated herein by reference in its entirety.
[00103] Other catalysts suitable for the ring-opening polymerization step of the methods described herein are described, for example, in: Journal of the American Chemical Society (2002), 124 (51), 15239-15248 Macromolecules, vol. 24, No. 20, p. 5732-5733, Journal of Polymer Science, Part A-1, vol. 9, No. 10, p. 2775-2787;
Petition 870190052454, of June 4, 2019, p. 39/48
33/35
Inoue, S., Y. Tomoi, T. Tsuruta & J. Furukawa; Macromolecules vol. 26, No. 20, p. 5533-5534; Macromolecules vol. 23, No. 13, p. 3206-3212; Polymer Preprints (1999), 40 (1), 508-509; Macromolecules vol. 21, No. 9, pgs. 2657-2668; and Journal of Organometallic Chemistry, vol. 341, No. 1-3, p. 83-9; and in US Patents ^Nos 3,678,069, 3,169,945, 6,133,402; 5,648,452; 6,316,590; 6,538,101; and 6,608,170. The totality of each of which is incorporated herein by reference.
[00104] The polymerization process can also comprise a polymerization initiator including, but not limited to, amines, polyamines, phosphines, among others. In addition, a variety of polymerization initiators can be used in the polymerization process, including by not being limited to alkali and alkaline earth metal carbonates. In certain aspects, suitable polymerization initiators include carboxylate salts of metal ions or organic cations. In some respects, a polymerization initiator is combined with the production stream containing bPL. In some respects, the molar ratio of the polymerization initiator to bPL in the production stream is about 1: 15,000. In certain respects, the polymerization initiator: bPL molar ratio is about 1: 100, 1: 10000, 1: 1000, 1: 20000 or a range including any two of these ratios.
[00105] The polymerization initiator may comprise a carboxylate salt, the carboxylate having a structure such that when initiating the polymerization of bPL, the polymer chains produced have an acrylate chain termination. In some ways, the carboxylate ion in a
Petition 870190052454, of June 4, 2019, p. 40/48
34/35 polymerization initiator is the anionic form of an agent
transfer of chain used in the process in polymerization •[00106] In some aspects, the initiator in polymerization homogeneous is a salt from ammon io quaternary (per
example, tetrabutylammonium acrylate (TBA), TBA acetate, trimethylphenylammonium acrylate, or trimethylphenylammonium acetate) or a phosphine (eg, tetrafenyl phosphonium acrylate).
[00107] In some respects, the catalyst is tetrabutylammonium acrylate, sodium acrylate, potassium acrylate, iron chloride, tetrabutylammonium acetate, trimethylphenylammonium acrylate, trimethylphenylammonium acetate or tetrafenyl phosphonium acrylate.
[00108] In some respects, the homogeneous polymerization initiator is added to a polymerization reactor as a liquid. In other respects, it is added as a solid, which then becomes homogeneous in the polymerization reaction. In some aspects, when the polymerization initiator is added as a liquid, the polymerization initiator can be added to the polymerization reactor as a melt or any suitable solvent. For example, in some variations, molten GLP is used as a solvent.
[00109] In some respects, the solvent for the polymerization initiator is selected so that the initiator is soluble, the solvent does not contaminate the product polymer, and the solvent is dried. In certain variations, solid PPL is added to a polymerization reactor, heated above room temperature to liquid, and used as
Petition 870190052454, of June 4, 2019, p. 41/48
35/35 polymerization initiator solvent.
[00110] In some variations, the process uses polymerization catalyst as described below and as described in US NS. 15 / 197.38, the content of which has been incorporated by reference.
[00111] In some aspects of the invention, the catalyst comprises a carboxylate salt as a homogeneous polymerization catalyst.
[00112] In some respects, the catalyst is a heterogeneous polymerization catalyst in the form of a solid supported quaternary ammonium salt (eg, tetrabutylammonium acrylate (TBA), TBA acetate, trimethylphenylammonium acrylate, or trimethylphenylammonium acetate) or a phosphine (for example, tetrafenyl phosphonium acrylate), iron chloride.
[00113] In addition to those already mentioned, the polymerization process can include one or more solvents, including hydrocarbons, ethers, esters, ketones, nitriles, amides, sulfones, halogenated hydrocarbons and the like. In certain aspects, the solvent is selected so that the copolymeric product stream is soluble in the reaction medium. The solvents may also comprise Lewis bases with low to moderate polarity.

权利要求:
Claims (22)
[1]
1. Copolymer, characterized by the fact that it comprises beta-propiolactone monomers and at least one comonomer of the group consisting of other beta-lactones, anhydrides, or alcohol having at least two hydroxyl groups, and in which the monomeric units of poly (propiolactone ) are produced by deciclizing beta-propiolactone derived from carbonylation of ethylene oxide with carbon monoxide using ethylene oxide having a bio-based content greater than 10% and using carbon monoxide which optionally has a bio-based content greater than 10 %.
[2]
2. Copolymer, according to claim 1, characterized by the fact that ethylene oxide has a bio-based content of at least 75%, and preferably at least 95%, and optionally carbon monoxide has a content of biological base of at least 75%, and preferably at least 95%.
[3]
3. Copolymer, according to claim 1, characterized by the fact that the comonomer has a bio-based content.
[4]
4. Copolymer according to any one of claims 1 to 3, characterized by the fact that the comonomer has a bio-based content of at least 50%.
[5]
5. Copolymer according to any one of claims 1 to 3, characterized in that the copolymer has a bio-based content of at least 50% and, optionally, at least 75%.
[6]
6. Copolymer, according to any one of claims 1 to 3, characterized by the fact that the
Petition 870190052454, of June 4, 2019, p. 43/48
2/5 copolymer is a linear polymer including an anionic nucleophile and cationic chain endings.
[7]
7. Copolymer according to claim 6, characterized by the fact that the anionic nucleophile is at least one compound with the formula R ^x 0 ^- , R ^X C (= O) O ^- , R ^X S ^- , R ^X O (C = O) O ^- , R ^x (SC> 2) Cr and PR ^X 3Ü ^- , where each R ^x is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.
[8]
8. Copolymer, according to claim 6, characterized in that it comprises R ^x 0 ^- , R ^x is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.
9. Copolymer, in wake up with The claim 8, characterized by fact that the anionic nucleophile is one hydroxide, methoxide and / or ethoxide. 10. Copolymer , in wake up with The claim 6, characterized by fact that the anionic nucleophile is one halide.11. Copolymer , in wake up with The claim 6,
characterized by the fact that the anionic nucleophile is at least one compound with the formula CH2 = CHCO2 ~, CH3CO2-, or CF3CO2-.
[9]
12. Copolymer, according to claim 6, characterized by the fact that the cation is selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺² , Ca ⁺² , Al ⁺³ and Na ⁺ .
[10]
13. Copolymer according to claim 6,
Petition 870190052454, of June 4, 2019, p. 44/48
3/5
characterized by fact that the cation is a cation organic. 14. Copolymer, in a deal with claim 13, characterized by fact that the organic cation is selected from the group what consisting of quaternary ammonium,
imidazolium, bis (triphenylphosphine) imine and tetraalkyl ammonium.
[11]
15. Copolymer according to any one of claims 1 to 3, characterized in that the comonomer is derived from a beta-lactone.
[12]
16. Copolymer according to any one of claims 1 to 3, characterized in that the copolymer is formed from at least part of a hygienic product.
[13]
17. Copolymer according to any one of claims 1 to 3, characterized in that the copolymer is formed from at least part of a structural product.
[14]
18. Copolymer according to any one of claims 1 to 3, characterized in that the copolymer is a linear polymer.
[15]
19. Copolymer according to claim 15, characterized by the fact that the upper beta-lactones are selected from the group consisting of betabutyrolactone, beta-valerolactone, beta-heptanolactone, beta-tridecanolactone, cis-3,4-dimethyloxetan- 2-one, 4- (but3-en-1-yl) oxetan-2-one, 4- (butoxymethyl) -2-oxetanone, 4 [[[(1,1-dimethylethyl) dimethylsilyl] oxy] methyl] -2 -oxetanone, 4 [(2-propen-1-yloxy) methyl] -2-oxetanone, 4 [(benzoyloxy) methyl] -2-oxetanone.
Petition 870190052454, of June 4, 2019, p. 45/48
4/5
[16]
20. Copolymer according to any one of claims 1 to 3, characterized in that the comonomer is a cyclic anhydride.
[17]
21. Copolymer according to claim 20, characterized in that the cyclic anhydride comprises at least one succinic anhydride and maleic anhydride.
[18]
22. Copolymer according to any one of claims 1 to 3, characterized in that the comonomer comprises a diol.
[19]
23. Copolymer according to claim 22, characterized in that the diol is selected from the group comprising ethylene glycol, propylene glycol, 1,4butanediol, diethylene glycol, bis (hydroxymethyl) octadecanol, 1,6-hexanediol and combinations of themselves.
[20]
24. Linear copolymer, characterized by the fact that it comprises chains of monomeric units of propiolactone and at least one comonomer derived from at least a portion of the upper beta-lactone, wherein the portion of the upper beta-lactone is derived from a beta-lactone other than propiolactone, and in which the monomeric units of poly (propiolactone) are produced by deciclizing the beta-propiolactone derived from the carbonylation of ethylene oxide with carbon monoxide using ethylene oxide which
have a content in biological basis in at least 10% and using monoxide in carbon that has optionally one content base biological greater than 10%. 25. Copolymer, according The claim 24,
characterized by the fact that ethylene oxide has a bio-based content of at least 75%, and
Petition 870190052454, of June 4, 2019, p. 46/48
5/5 preferably at least 95%, and optionally carbon monoxide has a bio-based content of at least 75%, and preferably at least 95%.
[21]
26. Copolymer according to claim 24 or 25, characterized in that the copolymer is formed in at least part of a hygienic product.
[22]
27. Copolymer according to claim 24 or 25, characterized by the fact that the copolymer is formed in a structural product.

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