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    • 专利摘要:
    The present invention relates to high biobased biodegradable polyester polyol polymers and methods for producing high biobased biodegradable polyester polyol polymers. In preferred embodiments, β-lactone monomers may be produced from high biobased epoxide and carbon monoxide. In a preferred embodiment, ß-lactone is ß-propiolactone produced from ethylene oxide and carbon monoxide. In some embodiments, ß-lactones may be polymerized with diols, triols and polyols to form the high biobased biodegradable polyester polyol polymers. In some embodiments, the high biobased polyester polyol biodegradable polymers may be terpolymers formed from a first ß-lactone, a diol, triol or polyol, and a second ß-lactone. In other embodiments, the high biobased polyester polyol biodegradable polymers may be formed from a polylactone oligomer and a diol, triol or polyol.
    公开号:BR112019011539A2
    申请号:R112019011539
    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:

    BIODEGRADABLE POLYOLES WITH GREATER BIOLOGICAL CONTENT
    Field gives Invention [001] THE present invention refers to, in general, the polymers in polyester polyol environmentally responsible, derivatives and to the processes of production of polymers of
    polyester polyol and its derivatives. Specifically, preferred polymerization processes include monomers comprised of carbons obtained from sources of biological, recycled, renewable or otherwise sustainable raw materials. Advantageously, the unique characteristics of polyol polymers are ideal for use in environmentally responsible applications.
    Background of the Invention [002] For the purposes of the present invention, the terms biobased, biobased content and biocontents are used interchangeably to describe carbon atoms from biological sources, recycled sources, renewable sources and / or sustainable sources. Carbon atoms are fundamental to many materials manufactured due to their unique physical and chemical characteristics. An important use of carbon atoms is in the manufacture of polymers.
    [003] Generally, a polymer is a large molecule made up of several smaller repeated molecules known as monomers. During a process known as polymerization, the monomers can be covalently linked to each other, forming larger polymer chains. The composition and arrangement of the monomers can determine the characteristics of the polymer, for example, determine the biodegradability and bio-based content of the
    Petition 870190052464, of 6/4/2019, p. 8/39
    2/28 polymer.
    [004] The bio-based content of the polymer refers to the sources of raw material from which the monomers are derived. Specifically, the degree of bio-based content depends on the amount of carbon atoms in the monomers that is derived from biological sources, recycled sources, renewable sources or sustainable sources. Such materials may include sources such as crop residues, wood residues, grasses, municipal solid waste and algae. A polymer with a higher bio-based content may be preferable for use in sustainable and environmentally responsible applications.
    [005] Biodegradable polymers can also be advantageous in environmentally responsible applications. Biodegradable polymers generally include a main chain composed of joined organic molecules that can decompose by natural processes into small, environmentally compatible molecules. The specific chemical composition of the monomers in biodegradable polymers will determine which smaller molecules are produced by the decomposition, the mechanisms by which the decomposition occurs and the speed at which the decomposition occurs.
    [006] Many conventional polymers may not be composed of monomers that confer characteristics of
    biodegradability or some basic content degree biological. Beyond addition, the modification of processes conventional for to produce polymers environmentally responsible can be expensive, require long cycles of production and / or difficult 1. [007] Polymers polyol polyester (’ polyols) are
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    3/28 generally biodegradable polymers, with exceptional compositions and arrangements that make polyols an essential material in the production of many products. The production of polyols by the reaction of polycarboxylic acids, anhydrides or esters of polycarboxylic acids with polyhydric alcohols is well known. Generally, prior art processes involve a one-step reaction from a polycarbonate source with a stoichiometric excess of a polyhydric alcohol. These processes use large, expensive reactors with limited reagents, resulting in less modifiable products.
    [008] There is a need for highly customizable biodegradable polyols with a higher bio-based content, which can be produced through more versatile and economically efficient processes.
    [009] The present invention satisfies this need by providing biodegradable polyols with a higher bio-based content produced by biological processes that more efficiently use sources of raw materials with a high degree of bio-based content.
    Summary of the Invention [010] The present invention relates to biodegradable polyols with a higher bio-based content and production methods. The polyols of the present invention are produced through innovative processes for assigning unique characteristics.
    [011] In preferred modalities, polyol monomers can be produced from carbon sources of biological origin, biologically renewable, recycled and / or sustainable. In some preferred modalities,
    Petition 870190052464, of 6/4/2019, p. 10/39
    4/28 β-lactone monomers can be produced from carbonylation of an epoxide with carbon monoxide. Epoxide sources and carbon monoxide sources can have high bio-based carbon content. Β-lactone monomers can be reacted with monomers having hydroxyl functional groups, such as simple alcohols, diols, triols, polyols and sugar alcohols with a high bio-based carbon content. Advantageously, the polyols of the present invention can have increased biodegradability and can have increased biobased content. In some preferred embodiments, the polyols can be a terpolymer polymerized from two distinct β-lactone monomers and a monomer with hydroxyl functional groups. In some preferred embodiments, polyols can be formed by polymerizing polylactone oligomers with monomers having hydroxyl functional groups. In some preferred embodiments, the polyols can be further reacted with β-lactone monomers with a higher bio-based content to produce modified polyols with a higher bio-based content.
    [012] Some aspects of this invention provide a polyol produced from a feed stream of βlactone and a comonomer, in which β-lactone is obtained by carbonylating an epoxide and carbon monoxide, and in which at least part of the epoxide contains carbon from biomass sources, also known as biogenic carbon. In preferred aspects of this invention, all epoxide is derived from biogenic carbon. In highly preferred aspects of this invention, all epoxide and carbon monoxide are derived from biogenic carbon.
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    5/28 [013] Thus, in one aspect, the invention is a method for producing a β-propiolactone copolymer having carbon content from renewable sources. In this respect, a β-propiolactone monomer can be derived having biogenic carbon content. Preferably, at least a part of the β-propiolactone monomer is produced by carbonylating ethylene oxide having a biocontent of at least 10% with carbon monoxide which optionally has a biocontent of at least 10% and a comonomer derived from a lactone , except beta-propiolactone.
    [014] The ability to use β-lactones derived, at least in part, from epoxides and carbon monoxide containing renewable and recycled carbon extends the environmental benefits obtained from the polymers of the present invention and the production methods of this invention.
    [015] Preferred embodiments of the present invention include versatile processes for economically producing polyols by polymerizing β-lactone monomers and monomers including hydroxyl functional groups in a condensation polymerization reaction zone. Some types of processes include the recovery of β-lactone monomers with a high bio-based content from an β-lactone intermediate formed by combining at least one epoxide, carbon monoxide and carbonylation catalyst in a reaction zone of carbonylation. Advantageously, polyols produced from β-lactone with a high bio-based content may have a higher bio-based content and greater biodegradability.
    [016] In preferred applications of this invention, the
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    6/28 polyols described in this document may be suitable for use as thermoplastics with low melting temperatures. These uses include biodegradable foams, packaging, coatings, adhesives, surfactants and elastomers. Advantageously, applications that incorporate the embodiments of the present invention can be more biodegradable than applications that use some other alternative polymers. Another advantage for applications using the modalities of the present invention is a decrease in the carbon footprint, resulting from polyols composed of bio-based components.
    [017] Although this invention is susceptible to several modifications and alternative forms, specific and exemplary modalities have been shown through examples in the drawings and described in detail. There is no intention to limit the invention to the specific and exemplary modalities described in this document. The intention is to cover all modifications, alternatives and equivalents within the scope of the invention, as defined by the appended claims.
    Detailed Description of Modalities [018] The following description includes preferred embodiments of the present invention, which refer to biodegradable polyol polymers having a higher bio-based carbon content. It should be recognized, however, that this description is not intended to be a limitation on the scope of the present invention, but rather a description of exemplary aspects.
    [019] Definitions of functional groups and specific chemical terms are described in more detail below. The
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    7/28 chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th ed., Cover, and specific functional groups are generally defined as described therein. In addition, the general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March's Advanced Organic Chemistry, 5- 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 content incorporated herein by reference.
    [020] The terms halo and halogen, as used in this document, refer to an atom selected from fluorine (fluoro, -F), chlorine (chlorine, -Cl), bromine (bromine, -Br) and iodine (iodine, - I). The term halide, as used here, refers to a halogen with a negative charge, selected from fluoride -F - , chloride -Cl - , bromide -Br - and iodide -I - .
    [021] The term aliphatic or aliphatic group, as used here, means a hydrocarbon moiety that can be straight-chain (i.e., unbranched), branched or cyclic (including spiro-fused, bridged, fused polycyclic) and can be completely saturated or may contain one or more units of unsaturation, but that is not aromatic. Unless otherwise specified, aliphatic groups contain 1-30 carbon atoms. In some respects, aliphatic groups contain 1-12 atoms of
    Petition 870190052464, of 6/4/2019, p. 14/39
    8/28 carbon. In some ways, aliphatic groups contain 1-8 carbon atoms. In some respects, aliphatic groups contain 1-6 carbon atoms. In some respects, aliphatic groups contain 1-5 carbon atoms; in some aspects, aliphatic groups contain 14 carbon atoms, in still other aspects, aliphatic groups contain 1-3 carbon atoms, and in still other aspects, aliphatic groups contain 1-2 carbon atoms. Suitable aliphatic groups include, but are not limited to, linear, branched, branched alkyl, alkenyl and alkynyl groups and their hybrids, such as (cycloalkyl) alkyl, (cycloalkenyl) alkyl or (cycloalkyl) alkenyl.
    [022] The term heteroaliphatic, as used in this document, refers to aliphatic groups in which 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 respects, one or two carbon atoms 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.
    [023] The term acrylate or acrylates, as used in this document, refers to any acyl group having a vinyl group adjacent to the acyl carbonyl group. The terms include mono-, di- and tri-substituted vinyl groups. Examples of acrylates include, but are not limited to:
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    9/28 acrylate, methacrylate, ethacrylate, cinnamate (3-phenylacrylate), crotonate, tiglate and senecioate.
    [024] The term polymer, as used in this document, refers to a molecule of high relative molecular mass, whose structure comprises the various repetitions of units derived, real or conceptually, from molecules of low relative molecular mass. In some respects, a polymer is made up of just one species of monomer (for example, polyEO). In some respects, a polymer is a copolymer, terpolymer, heteropolymer, block copolymer, or conical heteropolymer of one or more epoxides.
    [025] The term unsaturated, as used in this
    document means that a portion has one or more double or triple connections. [026] 0 term cycloaliphatic, carbocycle or carbocyclic, used alone or how part of an
    Larger portion refers to a saturated or partially unsaturated monocyclic, bicyclic or polycyclic ring system, as described herein, having 3 to 12 members, where the aliphatic ring system is optionally substituted, as defined above and described in this document. Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexyl, 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 term cycloaliphatic,
    Petition 870190052464, of 6/4/2019, p. 16/39
    Carbocycle or carbocyclic also includes aliphatic rings that are fused to one or more aromatic or non-aromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or the point of attachment is in the aliphatic ring. In some ways, a group
    carbocyclic it is bicyclic. In some aspects, one group carbocyclic it is tricyclic. In some aspects, one group carbocyclic it is polycyclic. [027] 0 alkyl term, as used in this
    document 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 specified, 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 aspects, the alkyl groups contain 1-5 carbon atoms, in some aspects, the alkyl groups contain 1-4 carbon atoms, in still other aspects, the alkyl groups contain 1-3 carbon atoms, and in still others aspects, the alkyl groups contain 1-2 carbon atoms. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, npropyl, isopropyl, n-butyl, iso-butyl, sec-butyl, secpentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n- hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, nundecyl, dodecyl and the like.
    [028] The term aryl, used alone or as part of a larger portion such as aralkyl, aralkoxy or aryloxyalkyl, refers to monocyclic ring systems
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    11/28 and polycyclic having a total of 20 ring members, where at least one ring in the system is aromatic and where each ring in the system contains three to twelve ring members. 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. In addition, 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 tetrahydronaftila and the like.
    [029] The terms heteroaryl and heteroar-, used alone or as part of a larger portion, for example, heteroaralkyl or heteroaralkoxy, refer to groups with 5 to 14 ring atoms, preferably 5, 6, 9 or 10 atoms ring; with 6, 10 or 14 electrons p shared in a cyclic arrangement; 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 nitrogen. Heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridininyl, pyridininyl, pyrimidine, pyridine . The terms heteroaryl and heteroar-, as used in this document, also include groups in which a ring
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    12/28 heteroaromatic is fused to one or more aryl, cycloaliphatic or heterocyclyl rings, where the radical or the point of attachment is in the heteroaromatic ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinolinyl, phthalazinyl, quinazolinyl, phenyl, hydroxyl, quinoline, phenyl, quinoline, phenyl, zinc 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, wherein the alkyl and heteroaryl moieties are optionally independently substituted.
    [030] As used in this document, the terms heterocycle, heterocyclyl, heterocyclic radical and heterocyclic ring are used interchangeably and refer to a 5- to 7-membered monocyclic or 7 to 14-membered monocyclic heterocyclic, which is 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 substituted nitrogen. As an example, in a saturated or partially unsaturated ring,
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    13/28 having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, nitrogen can be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or + NR (as in N-substituted pyrrolidinyl).
    [031] 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, decahydroquinolinyl, dioxazinyl, thiazine, diazinyl, diazinyl, diazinyl, diazinyl, diazinyl, diazinyl, diazinyl, diazinyl, diazinyl, zinc. The terms heterocycle, heterocyclyl, heterocyclic ring, heterocyclic group, heterocyclic moiety and heterocyclic radical are used here interchangeably, and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl or cycloaliphatic rings, such as indolinyl, 3Hindolyl, chromanyl , phenantridinyl or tetrahydroquinolinola, where the radical or point of attachment is in the heterocyclic ring. A heterocyclyl group can be mono- or bicyclic. The term heterocyclylalkyl refers to an alkyl group substituted by a heterocyclyl, in which the alkyl and heterocyclyl moieties are optionally independently substituted.
    [032] As used herein, the term partially unsaturated refers to a ring portion that includes at least
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    14/28 minus a double or triple bond. The term partially unsaturated should encompass rings with several sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as defined herein.
    [033] As described herein, the compounds may contain optionally substituted moieties. In general, the term substituted, whether preceded by the expression optionally or not, means that one or more hydrogens in the designated moiety are replaced 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 given group, the substituent it can be the same or different in each position. Combinations of envisioned substituents can include those that result in the formation of chemically stable or viable compounds. The term stable, as used in this document, 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. .
    [034] In some chemical structures, substituents are shown attached to a bond that crosses a bond in a ring of the illustrated molecule. This means that one or more of the substituents can be attached to the ring in any available position (usually in place of a hydrogen atom in the original structure). In cases where a
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    15/28 atom of a ring so substituted has two substitutable positions, two groups can be present on the same ring atom. 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, it means that the ring is optionally replaced, as described in the previous paragraph.
    [035] As used in this document, the term catalyst refers to a substance whose presence increases the speed of a chemical reaction, while the substance itself is neither consumed nor subjected to permanent chemical change.
    [036] Renewable sources mean a source of carbon and / or hydrogen obtained from biological life forms that can be renewed in less than a hundred years.
    [037] Renewable carbon means carbon obtained from biological life forms that can be renewed in less than a hundred years.
    [038] Recycled sources mean carbon and / or hydrogen recovered from a previous use in a manufacturing article.
    [039] Recycled carbon means carbon recovered from a previous use in a manufacturing article.
    [040] Biodegradability and biodegradable refer to the ability of a material to be rapidly decomposed by the action of living organisms, such as bacteria, fungi, microorganisms or other biological means, in which quickly normally means less than 10 years, 5 years,
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    16/28 for example, 2 years.
    [041] Sustainable material and sustainable polymer mean, respectively, a biodegradable material and a biodegradable polymer, which is derived at least in part from sources with biocontent and has a biocontent 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.
    [042] As used in this document, the term about which precedes one or more numerical values means the numerical value ± 5%. It should be understood that the reference to about a value or parameter here includes (and describes) variations that refer to that value or parameter itself. For example, the description with reference to about x includes the description of x itself.
    [043] Furthermore, it should be understood that the reference to between two values or parameters in this document includes (and describes) aspects that include those two values or parameters themselves. For example, a description that refers to between x and y includes the description of x and y itself.
    [044] The mass fractions described here can be converted to% by weight by multiplying by 100.
    [045] Preferred embodiments of the present invention include a polyol produced by condensation polymerization of β-lactone monomers with monomers including hydroxyl functional groups such as diols, triols, polyols, and sugar alcohols in the presence of a condensation polymerization catalyst. In some embodiments, β-lactone can be beta-butyrolactone, betavalerolactone, beta-heptanolactone, beta-tridecanolactone,
    Petition 870190052464, of 6/4/2019, p. 23/39
    17/28 cis-3,4-dimethyloxetan-2-one, 4- (but-3-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. In some embodiments, β-lactones can be polymerized with diols, including ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, bis (hydroxymethyl) octadecanol and 1,6-hexanediol. In some embodiments, β-lactones can be polymerized with triols including glycerol, (D) -2-deoxyribose, butane1,2,3-triol, butane-1,2,3-triol, cycloane-1,2,3- triol, cyclohexane-1,2,4-triol and cyclohexane-1,3,5-triol. In some embodiments, β-lactones can be polymerized with sugar alcohols, including sorbitol, mannitol, xylitol, isomalt and hydrogenated starch hydrolysates. Polyol polymer compositions have a numerical average molecular weight (Μη) in the range of 500 g / mol to about 250,000 g / mol.
    [046] In some preferred embodiments, polyols have an Mn of less than about 100,000 g / mol. In some embodiments, polyols have an Mn of less than about 70,000 g / mol. In some embodiments, polyols have an Mn of less than about 50,000 g / mol. In some embodiments, polyols have an Mn between about 500 g / mol and about 40,000 g / mol. In some embodiments, polyols have an Mn of less than about 25,000 g / mol. In some embodiments, polyols have an Mn between about 500 g / mol and about 20,000 g / mol. In some embodiments, polyols have an Mn between about 500 g / mol and about 10,000 g / mol. In some embodiments, polyols have an Mn between about
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    18/28
    500 g / mol and about 5,000 g / mol. In some embodiments, polyols have a Μη between about 1,000 g / mol and about 5,000 g / mol. In some embodiments, polyols have an Mn between about 5,000 g / mol and about 10,000 g / mol. In some embodiments, polyols have an Mn between about 500 g / mol and about 1,000 g / mol. In some embodiments, polyols have an Mn between about 1,000 g / mol and about 3,000 g / mol. In some embodiments, polyols have an Mn of around 5,000 g / mol. In some embodiments, polyols have an Mn of around 4,000 g / mol. In some embodiments, polyols have an Mn of around 3,000 g / mol. In some embodiments, polyols have an Mn of around 2,500 g / mol. In some embodiments, polyols have an Mn of around 2,000 g / mol. In some embodiments, polyols have an Mn of around 1,500 g / mol. In some embodiments, polyols have an Mn of around 1,000 g / mol.
    [047] In some embodiments, at least 90% of the terminal groups of the polyol used are -OH groups. In some embodiments, at least 95%, at least 96%, at least 97% or at least 98% of the terminal groups of the polyol used are -OH groups. In some embodiments, more than 99%, more than 99.5%, more than 99.7% or more than 99.8% of the terminal groups of the polyol used are -OH groups. In some embodiments, more than 99.9% of the terminal groups of the polyol used are -OH groups.
    [048] In some embodiments, it is advantageous if the polyol compositions have a substantial proportion of the primary terminal hydroxyl groups. For polyols, it may be preferable that some or most of the ends of the chain are secondary hydroxyl groups. In some
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    19/28 modalities, polyols can be modified to increase the proportion of final primary --OH groups. This can be done by reacting the secondary hydroxyl groups with reagents such as ethylene oxide, reactive lactones and the like. In some embodiments, polyols can be modified with β-lactones, such as caprolactone and the like, to introduce primary primary hydroxyl groups.
    [049] The polymer of the present invention will use bPL which can be produced from EO and CO, according to the general reaction schemes shown below in Figures 1 and 2. In addition to the present invention, at least one among EO and / or CO used to produce the bPL monomer will have a biocontent 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 least 80%, at least 90%, at least 95%, at least 99% or 100%.
    [050] In preferred embodiments, comonomers, such as diols, thiols and polyols, can contain carbon with significant biocontent. In some variations, comonomers may have a biocontent of at least 10%, and preferably 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%.
    [051] In variations of the above, the resulting beta-propiolactone copolymer will have a biocontent greater than 0% and less than 100%. In some variations of the above, the copolymer has a biocontent 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 99%, at least
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    20/28
    99.5%, at least 99.9% or 100%.
    [052] In some preferred embodiments, polyols may include a terpolymer of a β-lactone monomer, a monomer containing the hydroxyl functional group, and one or more additional epoxides. The monomer of one or more epoxides can be selected from the group of propylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, esters of glycidyl, glycidyl ethers, styrene oxides and higher alphaolefin epoxides. In some embodiments, these terpolymers may contain a majority of repeating units derived from ethylene oxide, with fewer amounts of repeating units derived from one or more additional epoxides. In some embodiments, terpolymers may contain about 50% to about 99.5% of repeat units derived from ethylene oxide. In some embodiments, terpolymers may contain more than about 60% repeat units derived from ethylene oxide. In some embodiments, terpolymers may contain more than 75% repeat units derived from ethylene oxide. In some embodiments, terpolymers may contain more than 80% repeat units derived from ethylene oxide. In some embodiments, terpolymers may contain more than 85% repeat units derived from ethylene oxide. In some embodiments, terpolymers may contain more than 90% repeat units derived from ethylene oxide. In some embodiments, terpolymers may contain more than 95% repeat units derived from ethylene oxide.
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    21/28 [053] In some preferred embodiments, polyols can comprise a terpolymer of a βlactone monomer, a monomer containing hydroxyl functional groups, and an additional β-lactone monomer. The βlactone monomer can be chosen from the group of βbutyrolactone, β-valerolactone, β-heptanolactone, βtridecanolactone, cis-3,4-dimethyloxetan-2-one, 4- (but-3-en-
    1- yl) oxetan-2-one, 4- (butoxymethyl) -2-oxetanone, 4 - [[[(1,1, dimethylethyl) dimethylsilyl] oxy] methyl] - 2-oxetanone, 4 - [(2— propen -l-yloxy) methyl] - 2-oxetanone, 4- [(benzoyloxy) methyl] -
    2- oxetanone. In some embodiments, β-propiolactone can be polymerized with β-butyrolactone and monomers with hydroxyl functional groups. In one embodiment, β-propiolactone can be polymerized with β-butyrolactone and 1,4-butanediol to form a polyol of the present invention.
    [054] In some preferred embodiments, the β-lactone monomers of the present invention can be polymerized to form certain homopolymers of polylactone oligomers (polylactone oligomers) that can be further polymerized with one or more other monomers containing hydroxyl functional groups. The polylactone oligomers of the present invention can be characterized according to molecular weight distributions. In some embodiments, polylactone oligomers have an Mn of less than about 100,000 g / mol. In some embodiments, polylactone oligomers have an Mn of less than about 70,000 g / mol. In some embodiments, polylactone oligomers have an Mn of less than about 50,000 g / mol. In some embodiments, polylactone oligomers have an Mn between about 500 g / mol and about 40,000 g / mol. In
    Petition 870190052464, of 6/4/2019, p. 28/39
    22/28 some modalities, polylactone oligomers have an Mn of less than about 25,000 g / mol. In some embodiments, polylactone oligomers have an Mn between about 500 g / mol and about 20,000 g / mol. In some embodiments, polylactone oligomers have an Mn between about 500 g / mol and about 10,000 g / mol. In some embodiments, polylactone oligomers have an Mn between about 500 g / mol and about 5,000 g / mol. In some embodiments, polylactone oligomers have an Mn between about 1,000 g / mol and about 5,000 g / mol. In some embodiments, polylactone oligomers have an Mn between about 5,000 g / mol and about 10,000 g / mol. In some embodiments, polylactone oligomers have an Mn between about 500 g / mol and about 1,000 g / mol. In some embodiments, polylactone oligomers have an Mn between about 1,000 g / mol and about 3,000 g / mol. In some embodiments, polylactone oligomers have an Mn of about 5,000 g / mol. In some embodiments, polylactone oligomers have an Mn of about 4,000 g / mol. In some embodiments, polylactone oligomers have an Mn of about 3,000 g / mol. In some embodiments, polylactone oligomers have an Mn of about 2,500 g / mol. In some embodiments, polylactone oligomers have an Mn of about 2,000 g / mol. In some embodiments, polylactone oligomers have an Mn of about 1,500 g / mol. In some embodiments, polylactone oligomers have an Mn of about 1,000 g / mol. In some preferred embodiments, the polylactone oligomers can be polypropiolactone oligomers.
    [055] In some embodiments, PPL oligomers can be polymerized with monomers having groups
    Petition 870190052464, of 6/4/2019, p. 29/39
    23/28 hydroxyl functionalities, such as simple alcohols, diols, triols and sugar alcohols. In some embodiments, PPL oligomers can be polymerized with diols, including ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, bis (hydroxymethyl) octadecanol and 1,6hexanediol. In some embodiments, PPL oligomers can be polymerized with triols including glycerol, (D) 2-deoxyribose, butane-1,2,3-triol, butane-1,2,3-triol, cycloane-1,2,3 -triol, cyclohexane-1,2,4-triol and cyclohexane-1,3,5-triol. In some embodiments, PPL oligomers can be polymerized with sugar alcohols, including sorbitol, mannitol, xylitol, isomalt and hydrogenated starch hydrolysates.
    [056] In some variations of the above, the polyol copolymer has a biocontent greater than 0% and less than 100%. In some variations of the above, the polymer has
    a biocontent at least 10%, fur any less 20%, fur least 30%, at least least 40%, at least 50%, fur any less 60%, at least 70%, at least 80%, at least any less 90%, fur any less 95% at least 96%, at least 97%, fur any less 98%, fur least 99%, at least at least 99.5%, at least 9 9, 9%, fur any less 99.99% or 100%.[057] In some variations, the biocontent (also referred to as basic content biological) can to be determined with based on the following:
    % bio-content or bio-based content = [Biocarbon (Organic)] / [Total Carbon (Organic) * 100%, as determined by ASTM D6866 (Standard Test Methods for Determining the Bio-Based Content of Solid, Liquid and Gaseous Using
    Petition 870190052464, of 6/4/2019, p. 30/39
    24/28
    Radiocarbon Analysis).
    [058] The biocontent of the polymers may depend on the biocontent of the β-lactone used. For example, in some variations of the methods described in this document, the β-lactone used to produce the polymers described herein may have a biocontent greater than 0% and less than 100%. In some variations of the methods described in this document, the β-lactone used to produce the polymers described here
    can have a biocontent of fur any less 10%, fur any less 20%, fur minus 30%, fur any less 40%, fur any less 50%, fur any less 60%, at least 70%, fur any less ; 80%, fur any less 90%, fur any less 95% by any less 96%, fur any less 97%, fur any less 98%, fur minus 99%, fur minus 99, 5%, at least 9 9, 9%, fur any less 99, 99% or 100%.
    [059] In some preferred variations, β-lactone is βpropiolactone and is entirely derived from renewable sources. In other variations, at least a part of the β-propiolactone used is derived from renewable sources, and at least a part of the β-propiolactone is derived from non-renewable sources.
    [060] The bio-based content of β-propiolactone may depend, for example, on the biocontent of the ethylene oxide and carbon monoxide used. In some variations, both ethylene oxide and carbon monoxide are derived from renewable sources.
    [061] In some variations of the above, the polymer
    has biodegradability at least 10%, fur any less 20%, fur any less 30%, fur any less 40%, fur any less 50%, fur minus 60%, fur any less 70%, fur any less 80%, fur any less 90%, fur any less 95%, fur any less 96%, fur any less 97%, fur any less
    Petition 870190052464, of 6/4/2019, p. 31/39
    25/28
    98%, at least 99%, at least 99.5%, at least 99.9%, at least 99.99% or 100%.
    [062] In some variations of the above content, biodegradable has the meaning as 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).
    [063] Preferred embodiments of the present invention include a process for producing a biodegradable polyol having greater biocontent. The process includes the steps of combining at least one carbon-containing epoxide with biocontent, carbon-containing carbon monoxide with biocontent and carbonylation catalyst in a carbonylation reaction zone under carbonylation conditions and producing an β-lactone intermediate. Then, the process includes a step of recovering β-lactone monomers from the β-lactone intermediate. Next, the process includes a polymerization step of β-lactone monomers, monomers including hydroxyl functional groups, and a polymerization catalyst in a polymerization reaction zone to produce the biodegradable polyol.
    [064] In some embodiments, polymerization of the polylactone oligomers may include a catalyst such as an ionic initiator. In some embodiments, the ionic initiator has the general formula of MX, where M is cationic and X is anionic. In some modalities, 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
    Petition 870190052464, of 6/4/2019, p. 32/39
    26/28 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 tetraalkyl ammonium. In some embodiments, the temperature of the polymerization reaction can vary from 25 ° C to 180 ° C. In some embodiments, the temperature of the polymerization reaction can vary from 50 ° C to 150 ° C.
    [065] In some embodiments, β-lactone can be beta-butyrolactone, beta-valerolactone, beta-heptanolactone, beta-tridecanolactone, cis-3,4-dimethyloxetan-2-one, 4- (but-3-en-l-yl) oxetan-2-one, 4 (butoxymethyl) -2-oxetanone, 4 - [[[(l, l— dimethylethyl) dimethylsilyl] oxy] methyl] - 2-oxetanone, 4 - [(2— propen-l-yloxy) methyl] - 2-oxetanone, 4- [(benzoyloxy) methyl] 2-oxetanone.
    [066] In some embodiments, β-lactone monomers can be formed from carbonylation of an epoxide with carbon monoxide in the presence of a carbonylation catalyst. In some preferred embodiments, epoxide is ethylene oxide that can undergo a carbonylation reaction, with carbon monoxide, in the presence of a carbonylation catalyst to produce a β-lactone. In some embodiments, the epoxide is selected from the group consisting of propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, cyclohexene oxide; cyclopentane oxide, 1,2-epoxyiexane, 1,2-epoxidodecane, 2cyclohexyloxane, 3,3,3-trifluoro-1,2-epoxypropane, styrene oxide, n-butyl glycidyl ether, tert-butyldimethylsilyl glycidyl ether, benzyl glycidyl ether ether.
    Petition 870190052464, of 6/4/2019, p. 33/39
    27/28 [067] In some preferred embodiments, the combining step is carried out in the presence of a carbonylation catalyst comprising a metal-carbonyl compound. In some embodiments, the methyl carbonyl compound has the general formula [Qmy (CO) w ] x, where: Q is any ligand and does not need to be present; M is a metal atom; y is an integer from 1 to 6 inclusive; w is a number as to provide the stable metal-carbonyl compound; ex is an integer from -3 to +3 inclusive. In some modalities, M is selected from the group consisting of Co and Rh.
    [068] In some embodiments, the carbonylation catalyst further comprises a Lewis acid cocatalyst. In some embodiments, the metalcarbonyl compound is anionic, and the Lewis acid cocatalyst is cationic. In some embodiments, the metalcarbonyl complex comprises a carbonyl cobaltate and the Lewis acid cocatalyst comprises a metal-centered cationic Lewis acid.
    [069] In some embodiments, a metal-centered cationic Lewis acid is a metallic complex of the formula
    [M '(L) b] c +, where M 'is a metal, each L it is a binder, b is one whole of 1 to 6 inclusive, c is of 1 r 2 or 3; and in which, if more than one L is gift, each L can be the same or different.
    [070] In some embodiments, Lewis acid includes a four-stranded dianionic ligand. In some modalities, the four-stranded dianionic ligand is selected from the group consisting of: porphyrin derivatives; salen derivatives; dibenzotetramethyltetra-aza-anulene derivatives
    Petition 870190052464, of 6/4/2019, p. 34/39
    28/28 (TMTAA), phthalocyaninate derivatives and Trost ligand derivatives. In some embodiments, M 'is selected from the group consisting of Al, Cr and Co. In some embodiments, the metal-carbonyl complex comprises a cobaltate and the Lewis acid cocatalyst comprises a metal-centered cationic porphyrin.
    [071] In some embodiments, a carbonylation catalyst comprises a carbonyl cobaltate in combination with an aluminum porphyrin compound as a Lewis acid component. In some embodiments, a carbonylation catalyst comprises [(TPP) Al] [Co (CO) 4]. In some embodiments, a carbonylation catalyst comprises [(C1TPP) Al] [Co (CO) 4].
    [072] The modalities described here should not be limited to the aspects shown, but the widest scope should be granted in line with the principles and characteristics described here.
    权利要求:
    Claims (3)
    [1]
    1. Biodegradable polyol, characterized by the fact that it comprises:
    The. a β-lactone monomer derived from the carbonyl reaction of an epoxide with carbon monoxide, said epoxide having a biocontent greater than 10% and said carbon monoxide having a biocontent greater than 10%;
    B. wherein said β-lactone monomer is polymerized with at least one monomer including at least two hydroxyl functional groups to produce the biodegradable polyol.
    2. Polyol biodegradable, in wake up with The claim 1, characterized by fact that said β-lactone is formed by the reaction of an epoxide with monoxide of carbon. 3. Polyol biodegradable, in wake up with The claim 2, characterized by fact that the referred epoxide is oxide compound ethylene by carbons with biocontent. 4. Polyol biodegradable, in wake up with The claim 2, characterized by fact that the referred
    carbon monoxide is composed of carbons with biocontent.
    5. Polyol biodegradable, in wake up with the claim 1, characterized by fact that said β-lactone is β-propiolactone. 6. Polyol biodegradable, in wake up with the claim 1, characterized by fact that the referred at least one monomer including one group functional
    hydroxyl includes a diol.
    Petition 870190052464, of 6/4/2019, p. 36/39
    [2]
    2/3
    Biodegradable polyol according to claim 8, characterized in that said diol is 1,4-butanediol.
    Biodegradable polyol according to claim 1, characterized in that said at least one monomer including a hydroxyl functional group includes a triol.
    Biodegradable polyol according to claim 10, characterized in that said triol is glycerol.
    Biodegradable polyol according to claim 1, characterized in that said at least one monomer including a hydroxyl functional group includes erythritol.
    11. Biodegradable polyol according to claim 1, characterized in that said at least one monomer including a hydroxyl functional group includes a xylitol.
    12. Biodegradable polyol according to claim 1, characterized by the fact that the biodegradable polyol is reacted with a β-lactone to produce a modified biodegradable polyol.
    13. Modified biodegradable polyol according to claim 14, characterized by the fact that said β-lactone is β-propiolactone.
    14. Biodegradable polyol according to claim 1, characterized by the fact that the biodegradable polyol has a biocontent of at least 50%.
    15. Biodegradable polyol, according to claim 1, characterized by the fact that the polyol
    Petition 870190052464, of 6/4/2019, p. 37/39
    [3]
    3/3 biodegradable has a biocontent of at least 75%.
    16. Biodegradable polyol according to claim 1, characterized by the fact that the biodegradable polyol has a biocontent of at least 95%.
    17. Biodegradable polyol, characterized by the fact that it comprises:
    The. a monomer of a first β-lactone derived from the carbonyl reaction of an epoxide with carbon monoxide, said epoxide having a biocontent greater than 10% and said carbon monoxide having a biocontent greater than 10%;
    B. said monomer of said first βlactone polymerized with a monomer of a second βlactone and a monomer having at least two hydroxyl functional groups.
    18. Biodegradable polyol, characterized by the fact that it comprises:
    The. a monomer of a poly β-lactone oligomer having monomers derived from the carbonyl reaction of an epoxide with carbon monoxide, said epoxide having a biocontent greater than 10% and said carbon monoxide having a biocontent greater than 10%;
    B. said monomer of said poly β-lactone oligomer polymerized with a monomer having at least two hydroxyl functional groups.
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    同族专利:
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    US20180155490A1|2018-06-07|
    JP2021506988A|2021-02-22|
    AU2018204358A1|2019-06-20|
    EP3548537A1|2019-10-09|
    WO2018107185A1|2018-06-14|
    CO2019005778A2|2019-06-11|
    CN110352208A|2019-10-18|
    CA3046102A1|2018-06-14|
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    法律状态:
    2021-03-16| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 3A ANUIDADE. |
    2021-07-06| B08K| Patent lapsed as no evidence of payment of the annual fee has been furnished to inpi [chapter 8.11 patent gazette]|Free format text: EM VIRTUDE DO ARQUIVAMENTO PUBLICADO NA RPI 2619 DE 16-03-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDO O ARQUIVAMENTO DO PEDIDO DE PATENTE, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |
    2021-10-05| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    US15/369,821|US20180155490A1|2016-12-05|2016-12-05|Biodegradable polyols having higher biobased content|
    PCT/US2018/016859|WO2018107185A1|2016-12-05|2018-02-05|Biodegradable polyols having higher biobased content|
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