巴西专利BR112019019313A2 polyamides and methods of producing them

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专利摘要:
methods of producing polyamides from beta-lactones are provided. polyamides include polyamides of biological origin that can be obtained, either in part or completely, from renewable sources.
公开号:BR112019019313A2
申请号:R112019019313
申请日:2018-03-13
公开日:2020-04-14
发明作者:Tseitlin Alexander；Lee Han；H Sookraj Sadesh
申请人:Novomer Inc；
IPC主号:

专利说明:

POLYAMIDES AND SAME PRODUCTION METHODS
CROSS REFERENCE TO RELATED APPLICATION [001] This application claims priority for US Provisional Patent Application No. 62 / 473,008, filed on March 17, 2017, which is incorporated herein by reference in its entirety.
FIELD [002] The present description relates, in general, to polyamides and methods of producing them and, more specifically, to polyamides that can be produced from beta-lactones.
FOUNDATIONS [003] Polyamides are used in many applications, including textiles, fabrics, automotive applications, carpets and coverings. Nylon is an example of a polyamide, often used in fibers (for example, for clothing, floor covering and rubber reinforcement), in moldings (for example, for molded parts for cars and electrical equipment), and in films (for example, example, for food packaging). Various methods are known in the art for industrially synthesizing polyamides. For example, polyamides can be synthesized from dinitriles using acid catalysis via a Ritter reaction. See, for example, Lakouraj, M.M. & Mokhtary, M., J. Polym. Res. (2009) 16: 681.
[004] Alternative methods of producing polyamides are desired in the art, including methods of producing polyamides of biological origin that can be obtained, in part or completely, from renewable sources.
BRIEF SUMMARY
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2/28 [005] Here are methods of producing polyamides that can be obtained, in part or completely, from renewable sources. For example, in some respects, polyamides can be produced from betapropiolactone, which can be obtained from bio-based ethylene oxide and / or bio-based carbon monoxide.
[006] In some respects, a method of producing a polymer is provided, comprising:
combining a compound of formula (3-a) with a weak base to produce the polymer, where:
OR ^1a R ^1b ^R x N OH
H / the compound of formula (3-a) is R ^c R (3-a) where each R ^la , R ^lb , R ^lc , R ^ld and R ² is independently H or alkyl, and the polymer comprises units of repetition of formula OR ^1b R ^1a ^RR R ² or a salt thereof where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-a).
[007] In other respects, a method of producing a polymer is provided, comprising:
a) combining a compound of formula (3-b) with an alcohol of formula (4) and a halogenating agent to produce a compound of formula (5), wherein:
R ^1a , R ^1b O
R ² , / C //
N OH
H / the compound of formula (3-b) is R ^c R ^a (3-b) where each R ^la , R ^lb , R ^lc , R ^ld and R ² is independently H or alkyl, □ 3ηι_ι the alcohol of formula (4) is where R ³ is alkyl, and
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3/28
R ^1a . _R 1b O p2 / JI ^ ^N ^ / O ^R3
I 'n 1C, 1 of the compound of formula (5) is RR where R ^la ,
R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3b), and R ³ is as defined above for formula (4); and
b) condensing the compound of formula (5) to produce the polymer, the polymer comprising repeating units of
OR ^1b R ^1a '' 1d * formula ^R R ² where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-b).
[008] In some variations of the above, the compound of formula (3-a) or (3-b) is produced by combining a compound of formula (1) with a nitrogen-containing compound of formula (2), where:
the compound of formula (D
Z ° ⁰ _R 1a --- _R 1c
R ^1b R ^1d where each R ^la ,
R ^lb , R ^lc and R ^ld is independently H or alkyl, and p2 κιi_1 the nitrogen-containing compound of formula (2) and ^π · ^ππ 2 where R ² is H or alkyl.
[009] In certain variations, when the compound of formula (1) is combined with a nitrogen-containing compound of formula (2) under aqueous conditions, the compound of formula (3-a) is selectively produced. For example, in certain variations, when the compound of formula (1) is combined with an aqueous nitrogen-containing compound of formula (2), the compound of formula (3-a) is selectively produced.
[0010] In other variations, when the compound of formula (1) is combined with a compound containing nitrogen
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4/28 of formula (2) under non-aqueous conditions, the compound of formula (3-b) is selectively produced. For example, in certain variations, when the compound of formula (1) is combined with a nitrogen-containing compound of formula (2) in the presence of an organic solvent, the compound of formula (3-b) is selectively produced.
DESCRIPTION OF THE FIGURES [0011] The present application can be better understood by reference to the following description considered in conjunction with the attached figures, in which similar parts can be indicated by similar numbers.
[0012] Figures 1 and 2 show exemplary reaction schemes for producing polyamides from betalactones.
DETAILED DESCRIPTION [0013] The following description specifies exemplary methods, parameters and the like. It should be recognized, however, that this description is not intended to be a limitation on the scope of the present description, but rather is provided as a description of exemplary modalities.
[0014] Methods are provided here for producing polyamides from beta-lactones. In some aspects, a method of producing a polyamide is provided which includes combining a compound of formula (3-a) with a weak base to produce the polyamide. The compound of formula (3-a) is OR ^1a . R ^1b r <
N OH
H /
R ^1c R ^1d (3-a) where each R ^la , R ^lb , R ^lc , R ^ld and R ² is independently H or alkyl. Polyamide is a polymer
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5/28 comprising formula repeat units
or a salt of the same as R ^la ,
R ^lb and R ² are as defined above for formula (3-a). Without wishing to be bound by any theory, in some variations combining the compound of formula (3-a) to the weak base to produce an intermediate having structure undergoes an addition of
Michael for
The can
R ^1a
Rx
N
H
R ^1c
R ^1b _R 1d produce that, then the polyamide described above.
[0015] In other respects, a method of producing a polyamide is provided which includes combining a compound of formula (3-b) with an alcohol of formula (4) and a halogenating agent to produce a compound of formula (5). O _R ¹ to _R 1b O
Rx n yc oh H / compound of formula (3-b) is R ^c R (3-b) where each
Ria, Rib, R ^lc , R ^ld and R ² are independently H or alkyl. The alcohol of formula (4) and where R ^{3 is} alkyl. O
R ¹ to _R 1b The p2 / LI H / compound of formula (5) is R ^1c R ^ia where R ^la , R ^lb ,
R ^lc , R ^ld and R ² are as defined above for formula (3-b), and
R ³ is as defined above for formula (4). The resulting compound of formula (5) then undergoes condensation polymerization to produce the polyamide. Polyamide is a polymer comprising repeat units of formula
OR ^1b R ^1a
1σ '1d *
RRR ² where R ^la , R ^lb and R ² are as defined above
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6/28 for formula (3-b).
[0016] In some variations of the above methods, ο compound of formula (3-a) or (3-b), or a combination thereof, can be produced from beta-lactone. For example, in a variation, a compound of formula (1) is combined with a nitrogen-containing compound of formula (2) to produce the compound of formula (3-a) or (3-b), or a combination thereof. O
Z ° ⁰
Ria --- R ^1c
R ^1b R ^1d _in _which each R ^la , R ^lb , compound of formula (1) is
R ^lc and R ^ld is independently
H or alkyl. The nitrogen-containing compound of formula (2) p2 κιi_1 is ² _{in which} _{U and} r2 is H or alkyl. As discussed in further detail here, the production of the compound of formula (3-a) can be favored over the production of the compound of formula (3-b), and vice versa, based on conditions under which the compound of formula (1 ) is combined with the nitrogen-containing compound of formula (2).
[0017] In still other aspects, a polyamide produced according to any of the methods described here is provided.
[0018] The methods, compounds and other agents used to produce the polyamides, and the resulting polyamides, are described in further detail below.
Polymerization of a compound of formula (3-a) to produce a polyamide [0019] With reference to Figure 1, an exemplary method for producing the polyamide is provided. In some embodiments, a compound of formula (3-a) is polymerized in the presence of a weak base to produce the polyamide.
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Compound of formula (3-a) [0020] In some embodiments, the compound of formula OR ^1a . R ^1b r <N OH (3-a) is R ^1c R ^1d (3-a) where each R ^la , R ^lb , R ^lc , R ^ld and R ² is independently H or alkyl. In one variation, R ^la is H. In other variations, R ^la is alkyl. In certain variations, ^la R is Ci-6 alkyl. In another variation, R ^la is methyl, ethyl or propyl. In one variation, R ^lb is H. In other variations, R ^lb is alkyl. In certain variations, R ^lb is C1-6 alkyl. In another variation, R ^lb is methyl, ethyl or propyl. In one variation, R ^lc is H. In other variations, R ^lc is alkyl. In certain variations, R ^lc is C1-6 alkyl. In another variation, R ^lc is methyl, ethyl or propyl. In one variation, R ^ld is H. In other variations, R ^ld is alkyl. In certain variations, R ^ld is C1-6 alkyl. In another variation, R ^ld is methyl, ethyl or propyl. In one variation, R ² is H. In other variations, R ² is alkyl. In certain variations, R ² is C1-6 alkyl. In another variation, R ² is methyl, ethyl or propyl.
[0021] Alkyl refers to a saturated hydrocarbon chain, mono-radical, unbranched or branched. In some embodiments, alkyl has 1 to 6 carbon atoms (ie, C1-6 alkyl), 1 to 5 carbon atoms (ie, C1-5 alkyl), 1 to 4 carbon atoms (ie, C1- 4 alkyl), 1 to 3 carbon atoms (i.e., C1-3 alkyl), or 1 to 2 carbon atoms (i.e., C1-2 alkyl). In certain variations, alkyl groups may include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2hexyl, 3-hexyl, and 3-methylpentyl . When an alkyl residue having a specific number of carbons is called,
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8/28 all geometric isomers having this number of carbons can be included; thus, for example, butyl can include n-butyl, sec-butyl, isobutyl and t-butyl; propyl can include n-propyl and isopropyl.
[0022] Additionally, it should be understood that when the range of values is listed, it is intended to encompass each value and sub-range within the range. For example, Ci-6 alkyl (which may also be referred to as 1-6C alkyl, C1-C6 alkyl, or Cl-6 alkyl) is intended to encompass, Ci, C _2, C _3, C _4, C _5, C ₆ , Ci- ₆ , C1-5, C1-4, C1-3, C1-2, C2-6, C2-5, C2-4, C2-3, C3-6, C3-5, C3-4, C4-6, C4-5, and C5-6 alkyl.
[0023] It should be generally understood that any description of R ^la , R ^lb , R ^lc , R ^ld and R ² described here can be combined in the same way as if each and every combination were individually listed. For example, in an O | _ | In one embodiment, the compound of formula (3-a) and ² (also referred to as 3-hydroxypropanamide), where R ^la , R ^lb , R ^lc , R ^ld and R ² are all H. In another embodiment, the compound of formula (3-a) is OH, _{in which} _{U a} Ria and R ^lb is H, the remaining R ^la and R ^lb are methyl, and R ^lc , R ^ld and R ² are all H. In yet another embodiment, the compound The formula (3-a) is H, where R ^la , R ^lb , R ^lc and R ^ld are all H, and R ² is ethyl.
Base [0024] In some variations, the compound of formula (3a) is polymerized in the presence of a weak base to produce the polyamide. In some variations, the weak base
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9/28 has a pKb value between 7.2 and 10.4. Thus, in certain aspects, a method is provided comprising polymerizing the compound of formula (3-a) in the presence of a base having a pKb value between 7.2 and 10.4 to produce the polyamide. In certain variations of the above, the pKb value is between 7.4 and 10, 3.
[0025] It should also be understood that reference to between two values or parameters here includes (and describes) modalities that include these two values or parameters per se. For example, description with reference to between x and y includes description of x and y per se.
[0026] In certain variations, the base is a carbonate salt or a bicarbonate salt, or a combination thereof. In a variation, the base is sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, or magnesium bicarbonate or any combination thereof.
Reaction temperature [0027] In some embodiments, polyamide is produced from the compound of formula (3-a) at a temperature of at least 70 ° C, at least 80 ° C, at least 90 ° C, at least at least 100 ° C, at least 110 ° C, at least 120 ° C, at least 130 ° C, at least 140 ° C, or at least 150 ° C; or between 80 ° C to 160 ° C.
Condensation polymerization to produce a polyamide [0028] Referring to Figure 2, another exemplary method for producing a polyamide is provided. In some embodiments, a compound of formula (3-b) is combined with
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10/28 an alcohol to produce the compound of formula (5), which can then undergo condensation polymerization to produce the polyamide. In some variations, the compound of formula (3b) is combined with an alcohol and any appropriate agent that can convert a carboxylic acid to an acyl halide. In certain variations, such an agent can be a halogenating agent.
[0029] In some embodiments of the exemplary method shown in Figure 2, the compound of formula (5) can be isolated, and optionally purified, before undergoing condensation polymerization to produce the polyamide. In other embodiments, the compound of formula (5) is neither isolated nor purified before further use.
Compound of formula (3-b) [0030] In some embodiments, the compound of formula
R ^1a . _R 1b The R <N OH (3-b) is R ^1c R ^1d (3-b) where each R ^la , R ^lb , R ^lc , R ^ld and R ² is independently H or alkyl. In one variation, R ^la is H. In other variations, R ^la is alkyl. In certain variations, ^la R is Ci-6 alkyl. In another variation, R ^la is methyl, ethyl or propyl. In one variation, R ^lb is H. In other variations, R ^lb is alkyl. In certain variations, R ^lb is C1-6 alkyl. In another variation, R ^lb is methyl, ethyl or propyl. In one variation, R ^lc is H. In other variations, R ^lc is alkyl. In certain variations, R ^lc is C1-6 alkyl. In another variation, R ^lc is methyl, ethyl or propyl. In one variation, R ^ld is H. In other variations, R ^ld is alkyl. In certain variations, R ^ld is C1-6 alkyl. In another variation, R ^ld is methyl, ethyl or propyl. In one variation, R ² is H. In other variations, R ² is alkyl. In certain variations, R ² is C1-6 alkyl. In another
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11/28 variation, R ² is methyl, ethyl or propyl.
[0031] It should be generally understood that any description of R ^la , R ^lb , R ^lc , R ^ld and R ² described here can be combined in the same way as if each and every combination were individually listed. For example, in a | _i Kl ΌΙ-Ί modality, the compound of formula (3-b) and ² (also referred to as 3-aminopropanoic acid), in which
Ria, Rib, R ^lc , R ^ld and R ² are all H. In another modality, | _ | Kl composed of formula (3-b) and ² θΗ, _in q _{Ue a} d _e Ria and R ^lb is H, the remaining R ^la and R ^lb are methyl, and R ^lc , R ^ld and R ² are all H. In yet another embodiment, the compound of formula (3-b) is wherein R ^la, R ^lb and R ^lc ^ld R are all H, and R ² is ethyl.
Alcohol [0032] In some modalities, alcohol is a compound
R ^ ni4 of formula (4) and where R ^{3 is} alkyl.
In some variations, R ³ is C1-6 alkyl. In a variation, R ³ is methyl or ethyl.
Compound of formula (5) [0033] In some embodiments, the compound of formula
R ^1a _K R ^1b O (5) is yÇ OR ³
R ^1c R ^1d where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-b), and R ³ is as defined above for formula (4).
[0034] It should be generally understood that any of the compounds of formula (3-b), described herein, can be combined with any of the alcohols of formula (4)
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12/28 described here in the same way as if each and every combination were individually listed. For example, in one embodiment, when the compound of formula (3-b) is and the alcohol is methanol, the compound of formula O
Halogenating agent [0035] In some variations, the halogenating agent is a chlorinating agent. In other variations, the halogenating agent is a brooding agent. In a variation, the halogenating agent is SOCI2, POCI3, PCI3, SOBr2, POBrs, or PBrs, or any combination thereof.
Anhydrous conditions [0036] In some embodiments, the exemplary method shown in Figure 2 is performed under anhydrous conditions. In some variations, the compound of formula (3-b) is combined with the alcohol of formula (4) and the halogenating agent under anhydrous conditions to produce the compound of formula (5). In other variations, the compound of formula (3-b), the alcohol of formula (4), and the halogenating agent are dry reagents In one variation, the compound of formula (3-b), the alcohol of formula (4) , and the halogenating agent is each independently less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.5%, less than 0.1%, or less than 0.01% by weight of water.
Condensation polymerization [0037] Any conditions suitable for converting the compound of formula (5) via condensation polymerization to polyamide can be employed.
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Production of a compound of formula (3-a) or (3-b) from Beta-Lactone [0038] The compounds of formulas (3-a) and (3-b) used in the methods described here can be obtained from from any commercially available sources or produced according to any methods known in the art. For example, the compounds of formulas (3-a) and (3-b) can be produced by reacting a beta-lactone with a primary amine. With reference to Figures 1 and 2, in the exemplary methods provided, the compound of formula (1) is an exemplary beta-lactone which is reacted with primary amine, p2 κιi_1 ² _in q _Ue r2 θ H or alkyl.
[0039] In some embodiments of the exemplary methods shown in Figures 1 and 2, the compound of formulas (3-a) or (3-b) can be isolated, and optionally purified, before use in subsequent steps. In other embodiments, the compound of formula (3-a) or (3-b) is neither isolated nor purified before further use.
Selectively producing the compound of formula (3-a) versus (3-b) [0040] The compound of formula (1) can be combined with the primary amine under conditions that selectively favor the production of the compound of formula (3-a) on the compound of formula (3-b), and vice versa.
[0041] In certain variations, the compound of formula (1) is combined with a nitrogen-containing compound of formula (2) under aqueous conditions to favor the production of the compound of formula (3-a) over the compound of formula (3b) . In certain variations, an aqueous nitrogen-containing compound of formula (2) is used. For example, in a
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14/28 variation when the nitrogen-containing compound of formula (2) is ammonia, aqueous ammonia can be used. Under such conditions, the compound of formula (3-a) is produced in excess, as compared to the compound of formula (3-b).
[0042] In other variations, the compound of formula (1) is combined with a compound containing nitrogen of formula (2) and an organic solvent to favor the production of the compound of formula (3-b) over the compound of formula (3a ). In certain variations, the organic solvent comprises alcohols. In other variations, the organic solvent comprises acetonitrile. In other variations, the compound of formula (1) is combined with a nitrogen-containing compound of formula (2) under non-aqueous conditions to favor production of the compound of formula (3-b) over the compound of formula (3-a). Under such conditions, the compound of formula (3-b) is produced in excess as compared to the compound of formula (3-a).
Compound of formula (1) [0043] In some embodiments, the compound of formula
R ^1a (1) is R ^1b R ^1d where each R ^la , R ^lb , R ^lc and R ^ld is independently H or alkyl. In one variation, R ^la is H. In other variations, R ^la is alkyl. In certain variations, ^la R is Ci-6 alkyl. In another variation, R ^la is methyl, ethyl or propyl. In one variation, R ^lb is H. In other variations, R ^lb is alkyl. In certain variations, R ^lb is C1-6 alkyl. In another variation, R ^lb is methyl, ethyl or propyl. In one variation, R ^lc is H. In other variations, R ^lc is alkyl. In certain variations, R ^lc is C1-6 alkyl. In another variation, R ^lc is
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15/28 methyl, ethyl or propyl. In one variation, R ^ld is H. In other variations, R ^ld is alkyl. In certain variations, R ^ld is C1-6 alkyl. In another variation, R ^ld is methyl, ethyl or propyl.
[0044] It should be generally understood that any description of R ^la , R ^lb , R ^lc and R ^ld described here can be combined in the same way as if each and every combination were individually listed. For example, in one embodiment, the compound of formula (1) (also referred to as beta-propiolactone), where R ^la , R ^lb , R ^lc and R ^ld are all H.
[0045] Beta-lactone, like the compound of formula (1), can be obtained from any commercially available sources or produced according to any methods known in the art. For example, betapropiolactone can be obtained by reacting ethylene oxide and carbon monoxide under appropriate conditions.
[0046] Beta-lactone, like the compound of formula (1), can be obtained from renewable feed charge. For example, when beta-propiolactone is produced from ethylene oxide and carbon monoxide, one or both of ethylene oxide and carbon monoxide can be obtained from renewable feed charge using methods known in the art. When beta-lactone, like the compound of formula (1), is obtained in part or completely from the renewable feed charge, the polyamide produced according to the methods described here from such beta-lactone has a biocontent greater than 0%.
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16/28 [0047] Various techniques are known in the art to determine the bio-content (ie, bio-based content) of a material. For example, in some variations, the bio-content of a material can be measured using the ASTM D6866 method, which allows the determination of the bio-content of materials using radiocarbon analysis by accelerator mass spectrometry, liquid scintillation counting and gas spectrometry. mass of isotopes. A biocontent result can be obtained by assigning 100% equal to 107.5 pMC (percentage of modern carbon) and 0% equal to 0 pMC. For example, a sample measuring 99 pMC will give an equivalent bio-content result of 93%. In one variation, bio-content can be determined according to revision 12 of ASTM D6866 (ie, ASTM D6866-12). In another variation, the bio-content can be determined according to the procedures of Method B of ASTM-D6866-12. Other techniques for assessing the bio-content of materials are described in US Patent Nos. 3,885,155, 4,427,884,
4,973,841, 5,438,194, and 5,661,299, as well as in
W02009 / 155086.
Compound of formula (2) [0048] In some embodiments, the compound of formula p2 _N i_i (2) is ² _in q _{U and} r 2 £ h or alkyl. In some variations, R ² is H, and the compound of formula (2) is NH3 or ammonia. In other variations, R ² is alkyl. In certain variations, R ² is C1-6 alkyl. In a variation, R ² is methyl, ethyl, propyl or butyl.
[0049] The primary amine, like the compound of formula (2), can be obtained from any commercially available sources or produced according to
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17/28 any methods known in the art.
[0050] The primary amine, like the compound of formula (2), can be obtained from the renewable feed charge. When the primary amine, such as the compound of formula (2), is obtained from a renewable feed charge, the polyamide produced according to the methods described here from such beta-lactone has a biocontent greater than 0% .
[0051] It should be generally understood that any of the compounds of formula (1) described here can be combined with any of the amines of formula (2) described here in the same way as if one and each combination were individually listed. In addition, a person skilled in the art must recognize how to select appropriate compounds of formulas (1) and (2) in order to produce the compound of formula (3-a) or (3-b). Specifically, R ^la , R ^lb , R ^lc and R ^ld for formula (3-a) or (3-b) are as defined here for formula (1), and R ² is as defined here for formula (2). For example, in one embodiment, when the compound of formula (1) is compound of formula (2) is NH3, then the resulting compound of formula (3-a) is H2N and the resulting compound of formula (3-b) is H2N
OH _r depending on the reaction conditions.
Polyamide [0052] In some respects, the polyamide produced using the methods described here is a polymer
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OR ^1b R ^1a , o1c old —2 comprising repeating units of formula K or a salt thereof where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-a) or ( 3-b), as the case may be. For example, in one embodiment, when the compound of formula (3-a) is reacted with a weak base, the resulting polymer comprises repeat units of formula
N or a salt thereof.
In another embodiment, when the compound of formula (3-b) is and is reacted with an alcohol and a halogenating agent, followed by condensation polymerization, the resulting polymer comprises repeat units of formula [0053] In some embodiments, it is provided a polyamide having a bio-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% or about 100%.
[0054] It should be understood that reference to about a value or parameter here includes (and describes) modalities that are directed to the value or parameter per se. For example, description with reference to about x includes description of x per se. In other instances, the term about when used in association with other measurements, or used to modify a value, a unit, an
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19/28 constant, or a range of values, refers to variations of +/- 10%.
Compositions [0055] In some respects, a composition is provided comprising:
a compound of formula (3-a) having the structure:
OR ^1a . R ^1b
R ^1c R ^1d
Rlb _R 1C
R ^ld and R ² is independently H or alkyl; and a weak base.
[0056] In some embodiments of the above, the composition additionally comprises:
a polymer comprising repeat units of formula
R ^ld and R ² are as defined above for formula (3-a).
[0057] In other respects, a composition is provided comprising:
a compound of formula (3-b) having the structure:
R ¹ R ^1b Q
R ^1a , R ^1b O, 2 VU ^H R ^1c R ^1d
R ^1c R ^1d (3-b) where each R ^la , R ^lb , R ^lc , R ^ld and R ² is independently H or alkyl;
an alcohol of formula (4) having the structure
R ³ is alkyl; and a halogenating agent.
[0058] In some embodiments of the above, the composition additionally comprises:
a compound of formula (5) having the structure:
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20/28
R ^1a . _R 1b O p2 / JI
H /
R ^1c R ^1d where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-b), and R ³ is as defined above for formula (4).
[0059] In other respects, a composition is provided comprising:
a compound of formula (5) having the structure: R ¹ to _R 1b O p2 / II ^ N ^} ÇOR ³
H /
R ^1c R ^1d where each R ^la , R ^lb , R ^lc , R ^ld and R ² is independently H or alkyl, and R ³ is alkyl; and a polymer comprises repeating units of formula OR ^1b R ^1a
RRR ² where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (5).
[0060] It should be understood that any of the variations described here with respect to the methods for the compound of formula (3-a), the compound of formula (3-b), the alcohol of formula (4), the compound of formula (5), the weak base, the halogenating agent, and the polymer apply to the compositions described here.
Enumerated modalities [0061] The following enumerated modalities are representative of some aspects of the invention.
[0062] 1. A method of producing a polymer, comprising:
combining a compound of formula (3-a) with a weak base to produce the polymer, where:
Petition 870190129849, of 12/09/2019, p. 27/36
21/28 the compound of formula (3-a)
that each R ^la ,
R ^lb , R ^lc , R ^ld and R ² are independently H or alkyl, and the polymer comprises repeating units of the formula OR ^1t > R ^1a ^RR R ² , or a salt thereof where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-a).
[0063] 2. A method of producing a polymer comprising:
a) combining a compound of formula (1) with a nitrogen-containing compound of formula (2) under aqueous conditions to produce a compound of formula (3-a), in which:
the compound of formula (D
Rla --- R ^1c
R ^1b R ^1d where each
R ^la ,
R ^lb , R ^lc and R ^ld is independently H or alkyl, p2 NJI — I the nitrogen-containing compound of formula (2) and ^π · ^ππ 2 where R ² is H or alkyl, and
OR ^1a R ^1b
N OH
H / the compound of formula (3-a) is R ^c R (3-a) where R ^la , R ^lb , R ^lc and R ^ld are as defined above for formula and R ² is as defined above for formula ( 2); and
b) combining the compound of formula (3-a) with a weak base to produce the polymer, wherein the polymer comprises repeating units of OR ^1b R ^1a / i _z p1c p1d _d 2 formula R, or a salt thereof where R ^la , R ^lb , R ^lc ,
Petition 870190129849, of 12/09/2019, p. 28/36
22/28
R ^ld and R ² are as defined above for formula (3-a).
[0064] 3. Method 2 method, further comprising isolating the compound of formula (3-a) before combining with the weak base to produce the polymer.
[0065] 4. The method of any one of modalities 1 a in which the nitrogen-containing compound of formula (2) is an aqueous nitrogen-containing compound of formula (2).
[0066] 5. The method of any of the modalities 1 a in which the weak base has a pKb value between 7.2 and 10.4.
[0067] 6. The method of any of the modalities 1 to 4 in which the weak base is a carbonate salt or a bicarbonate salt, or a combination thereof.
[0068] 7. The method of any of modalities 1 to 4 in which the weak base is sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, or magnesium bicarbonate or any combination thereof.
[0069] 8. The method of any of the modalities 1 to 7 in which the polymer is produced from the compound of formula (3-a) at a temperature of at least 70 ° C.
[0070] 9. The method of any of the modalities 1 to 7 in which the polymer is produced from the compound of formula (3-a) at a temperature between 80 ° C to 160 ° C.
[0071] 10. A method of producing a polymer, comprising:
a) combining a compound of formula (3-b) with an alcohol of formula (4) and a halogenating agent to produce a compound of formula (5), wherein:
Petition 870190129849, of 12/09/2019, p. 29/36
23/28 the compound of formula that each R ^la , R ^lb , R ^lc , R ^ld alkyl, the alcohol of formula (4) the compound of formula R ^lb , R ^lc , R ^ld and R ² are as <b), and R ³ is as defined at ac.
R ^1a > R ^1b OR ² , N OH (3-b) is ^H R ^1c R ^1d (3-b) in and R ² is independently H or □ 3ηι_ι is where R ³ is alkyl, and
R ¹ 1 R ^1b O p2
K ^ / OR ³ (5) is R ^1c R ^1d where R ^la , defined above for formula (3.ma for formula (4); and
b) condensing the compound of formula (5) to produce the polymer, wherein the polymer comprises repeat units of OR ^1b R ^1a '' 1d * formula RR ² in which R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-b).
[0072] 11. A method of producing a polymer comprising:
a) combining a compound of formula (1) with a compound containing nitrogen of formula (2) and an organic solvent, or combining a compound of formula with a compound containing nitrogen of formula under non-aqueous conditions, to produce a compound of formula ( 3-b) in which the compound of formula (1) is
R ^1a
R ^1c
R ^1b R ^1d where each
R ^la
Rlb _R lc _{and R} ld independently H or alkyl the nitrogen-containing compound of formula _is r ² -nh ₂ where R ² is H or alkyl; and
Petition 870190129849, of 12/09/2019, p. 30/36
24/28
R ¹ R ^1b 0
NA the compound of formula (3-b) is R ^c R ^a
ΌΗ (3-b) where R ^la , R ^lb , R ^lc and R ^ld are as defined above for formula (1), and R ² is as defined above for formula (2);
b) combining the compound of formula (3-b) with an alcohol of formula (4) and a halogenating agent to produce a compound of formula (5), wherein:
the alcohol of formula (4) and wherein R ^{3 is} alkyl; and
R ¹ to _R 1b O
R ² ^ ^N a ^H _R ic ^Z id where R ^la
R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3b), and R ³ is as defined above for formula (4); and
c) condensing the compound of formula (5) to produce the polymer, wherein the polymer comprises repetition units of formula ^RR R ² in which R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-b).
[0073] 12. The method of modality 10 or 11 where R ³ is C1-6 alkyl.
[0074] 13. The method of modality 10 or 11 in which R ³ is methyl or ethyl.
[0075] 14. The method of any of embodiments 10 to 13, further comprising isolating the compound of formula (5) before condensing to produce the polymer.
[0076] 15. The method of any of embodiments 11 to 14, further comprising isolating the compound of formula (3-b) before combining with the alcohol of formula (4) and the halogenating agent to produce the compound of formula
Petition 870190129849, of 12/09/2019, p. 31/36
25/28 (5).
[0077] 16. The method of any of the modalities 10 to 15, wherein the halogenating agent is a chlorinating agent.
[0078] 17. The method of any of the modalities 10 to 15, in which the halogenating agent is SOCI2, POCI3, PCI3, SOBr2, POBrs, or PBrs, or any combinations thereof.
[0079] 18. The method of any of the modalities 10 to 17, in which the method is performed under anhydrous conditions.
[0080] 19. The method of any of the modalities 10 to 17, wherein the compound of formula (3-b) is combined with the alcohol of formula (4) and the halogenating agent under anhydrous conditions to produce the compound of formula (5).
[0081] 20. The method of any of the modalities 10 to 17, wherein the compound of formula (3-b), the alcohol of formula (4), and the halogenating agent each independently has less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% by weight of water.
[0082] 21. The method of any of modalities 1 to 20, where R ^la is H.
[0083] 22. The method of any one of embodiments 1 to 20, where R is alkyl ^it.
[0084] 23. The method of method 22 wherein R is C1-6 alkyl ^it.
[0085] 24. The method of modality 22 in which R ^la is methyl, ethyl or propyl.
[0086] 25. The method of any of the modalities 1 to 24, where R ^lb is H.
[0087] 26. The method of any of the modalities 1 to 24, where R ^lb is alkyl.
[0088] 27. Modality method 2 6, where R ^lb is C1-6
Petition 870190129849, of 12/09/2019, p. 32/36
26/28 alkyl.
[0089] 28. The method of modality 26, in which R ^lb is methyl, ethyl or propyl.
[0090] 29. 0 method of any of modalities 1 to 28, on what R1C is H. [0091] 30. 0 method of any of modalities 1 to 28, on what R1C is alkyl. [0092] 31. 0 method of mode 30, where R ^lc is Cl-6
alkyl.
[0093] 32. The method of modality 30, in which R ^lc is methyl, ethyl or propyl.
[0094] 33. The method of any of modalities 1 to 32, where R ^ld is H.
[0095] 34. The method of any of modalities 1 to 32, where R ^ld is alkyl.
[0096] 35. The method of modality 34, wherein R ^ld is C1-6 alkyl.
[0097] 36. The method of modality 34, in which R ^ld is methyl, ethyl or propyl.
[0098] 37. Anyone's method of modalities 1 The 36, where R ² is H.[0099] 38. Anyone's method of modalities 1 The 36, where R ² is alkyl.[00100] 39 . 0 method of modality 38, where R ² is Ci -6
alkyl.
[00101] 40. Method 38, where R ² is methyl, ethyl, propyl or butyl.
[00102] 41. The method of any of modalities 1 to 40, in which the polymer has a bio-content of at least 10%, at least 20%, at least 30%, at least 40%, at least
Petition 870190129849, of 12/09/2019, p. 33/36
27/28 minus 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95% or about 100%.
[00103] 42. The method of any of the modalities 1 to 9 and 21 to 41, in which the compound of formula (3-a) is obtained from renewable feed charge.
[00104] 43. The method of any of the modalities 10 to 41, in which the compound of formula (3-a) is obtained from renewable feed charge.
[00105] 44. The method of any of the modalities 2, 4, and 11 to 43, in which the compound of formula (1) is obtained from renewable feed charge.
[00106] 45. The method of any of the modalities 2, 4, and 11 to 44, in which the compound of formula (2) is obtained from renewable feed charge.
[00107] 46. A polymer produced according to the method of any one of modalities 1 to 45.
EXAMPLES [00108] The following Examples are illustrative only and are not intended to limit any aspect of the present description in any way.
Example 1
Synthesis of poly (β-alanine)
[00109] This Example demonstrates the synthesis of ροϋ (βalanine) from beta-propiolactone.
Synthesis of 3-hydroxypropioamide [00110] In a 300 mL Parr reactor, 60 mL of 28-30% ammonia in water solution were added. To this solution, 5.0 mL of beta-propiolactone was added to
Petition 870190129849, of 12/09/2019, p. 34/36
28/28 about 26 ° C. The reaction mixture was stirred for 4 h. The reaction mixture was then extracted from volatiles by rotovap and high vacuum. The product of this first step was analyzed by 1 H-NMR.
[00111] ^X H NMR (DMSO-d6) δ (ppm), 7.28 (s, 1H, NH),
6.78 (s, 1H, NH), 5.15 (br s, 1H, OH), 3.58 (t, 2H, CH ₂ ), 2.19 (t, 2H, CH ₂ ). The 1 H-NMR data confirmed that this product was 3-hydroxypropioamide.
Synthesis of poly (^ -alanine) [00112] In a round bottom flask, 1.2 g of 3-hydroxypropioamide and 0.10 g of sodium carbonate were added. The bottle was connected to a distillation head and a collection bottle. The mixture was heated to about 200 ° C under nitrogen for 5 h. The residual solid was analyzed by 1 H NMR.
[00113] ^Χ Η NMR (D ₂ O, 10% HFIP) ô (ppm), 3.39 (m, CH ₂ ), 2.39 (m, CH ₂ ). The Î ± -H NMR data showed about 70% conversion of 3-hydroxypropioamide to poly (β-alanine).

权利要求:
Claims (20)
[1]
1. Method of producing a polymer, characterized by the fact that it comprises:
combining a compound of formula (3-a) with a weak base to produce the polymer, where:
OR ^1a _R 1b
R ² ^
H / ° ^M the compound of formula (3-a) is R ^1c R ^1d (3-a) wherein each R ^la, R ^lb, R ^lc R ^ld and R ² is independently H or alkyl, and the polymer comprises formula repetition units
OR ^1b R ^1a
1 _C / 'i _d I
RRR ² , or a salt thereof where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-a).
[2]
2. Method of producing a polymer characterized by the fact that it comprises:
a) combining a compound of formula (1) with a nitrogen-containing compound of formula (2) under aqueous conditions to produce a compound of formula (3-a), in which:
the compound of formula (D

[3]
Method according to claim 2, characterized in that it further comprises isolating the compound of formula (3-a) before combining with the weak base to produce the polymer.
[4]
Method according to any one of claims 1 to 3, characterized in that the nitrogen-containing compound of formula (2) is an aqueous nitrogen-containing compound of formula (2).
[5]
Method according to any one of claims 1 to 4, characterized in that the weak base has a pKb value between 7.2 and 10.4.
[6]
Method according to any one of claims 1 to 4, characterized in that the weak base is a carbonate salt or a bicarbonate salt, or a combination thereof.
[7]
Method according to any one of claims 1 to 4, characterized in that the weak base is sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium bicarbonate calcium, or magnesium bicarbonate or any combinations thereof.
[8]
8. Method according to any one of claims 1 to 7, characterized by the fact that the
Petition 870190092849, of 9/17/2019, p. 15/22
3/8 polymer is produced from the compound of formula (3-a) at a temperature of at least 70 ° C.
[9]
Method according to any one of claims 1 to 7, characterized in that the polymer is produced from the compound of formula (3-a) at a temperature between 80 ° C to 160 ° C.
[10]
10. Method of producing a polymer, characterized by the fact that it comprises:
a) combining a compound of formula (3-b) with an alcohol of formula (4) and a compound agent of formula (5), in the compound of formula which each R ^la , R ^lb , R ^lc , R ^ld alkyl, the alcohol of formula (4) the compound of formula R ^lb , R ^lc , R ^ld and R ^{1 2} are as halogenating ce to produce one that:
R ^1a , R ^1b O
R <X n yç OH | _ | / (3-b) is R ^1c R ^1d (3-b) in and R ² is independently H or and in which R ^{3 is} alkyl, and
R ^1a > R ^1b O
R ² ^ 3
N - OR ³ (5) R ^1c R ^1d is wherein R ^la, efinidos above for formula (3b), and R ³ is as defined above for formula (4); and
b) condensing the compound of formula (5) to produce the polymer, wherein the polymer comprises repeat units of OR ^1b R ^1a
1 '' 1d 'formula ^R RR ² where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3-b).
[11]
11. Method of producing a polymer, characterized by the fact that it comprises:
Petition 870190092849, of 9/17/2019, p. 16/22
4/8
a) combining a compound of formula (1) with a nitrogen-containing compound of formula (2) and an organic solvent, or combining a compound of formula (1) with a nitrogen-containing compound of formula (2) under non-aqueous conditions, for produce a compound of formula (3-b), in which:
.0
ç
the compound of formula (1) is o1b old k in what each R ^la , R ^lb , Rlc _{and R} ld independently H or alkyl, the compound containing nitrogen of formula (2)_is r ² -h ₂ in that R ² is H or alkyl; and the compound of formula (3-b) is R ^1a , R ^1b 0 R <x4 JL N ^H _R i / id '' OH (3-b) in what R ^la , R ^lb , R ¹ ^z and R ^ld are as defined above for formula
(1), and R ² is as defined above for formula (2);
b) combining the compound of formula (3-b) with an alcohol of formula (4) and a halogenating agent to produce a compound of formula (5), wherein:
the alcohol of formula (4) and wherein R ^{3 is} alkyl; and
R ^1a > R ^1b O
R ² ^ 3
H / ° ^R the compound of formula (5) is R ^1c R ^1d where R ^la , R ^lb , R ^lc , R ^ld and R ² are as defined above for formula (3b), and R ³ is as defined above for formula (4); and
c) condensing the compound of formula (5) to produce the polymer, wherein the polymer comprises repeat units of OR ^1b R ^1a
1 '' 1d 'formula RRR ² where R ^la , R ^lb , R ^lc , R ^ld and R ² are as
Petition 870190092849, of 9/17/2019, p. 17/22
5/8 defined above for formula (3-b).
[12]
12. Method according to claim 10 or 11, characterized in that R ³ is C1-6 alkyl.
[13]
13. Method according to claim 10 or 11, characterized by the fact that R ³ is methyl or ethyl.
[14]
Method according to any one of claims 10 to 13, characterized in that it further comprises isolating the compound of formula (5) before condensing to produce the polymer.
[15]
Method according to any one of claims 11 to 14, characterized in that it further comprises isolating the compound of formula (3b) before combining with the alcohol of formula (4) and the halogenating agent to produce the compound of formula (5).
[16]
16. Method according to any one of claims 10 to 15, characterized in that the halogenating agent is a chlorinating agent.
[17]
17. Method according to any one of claims 10 to 15, characterized by the fact that the halogenating agent is SOCI2, POCI3, PCI3, SOBr2, POBrs, or PBrs, or any combination thereof.
[18]
18. Method according to any one of claims 10 to 17, characterized in that the method is carried out under anhydrous conditions.
[19]
19. Method according to any one of claims 10 to 17, characterized in that the compound of formula (3-b) is combined with the alcohol of formula (4) and the halogenating agent under anhydrous conditions to produce the compound of formula (5).
[20]
20. Method, according to any of the
Petition 870190092849, of 9/17/2019, p. 18/22
6/8
claims 10 to 17, characterized by the fact that the compound of formula (3-b), the alcohol of formula (4), and the halogenating agent has each independently less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% by weight of water.21. Method, according to any of the claims 1 to 20, characterized by the fact that R ^la is H.22. Method, according to any of the claims 1 to 20, characterized by the fact that R ^la is alkyl.23. Method, according to claim 22, characterized by fact that R ^la is C1-6 alkyl. 24. Method, according to claim 22, characterized by fact that R ^la is methyl, ethyl or propyl.25. Method, according to any of the claims 1 to 24, characterized by the fact that R ^lb is H.26. Method, according to any of the claims 1 to 24, characterized by the fact that R ^lb is alkyl.27. Method, according to claim 26, characterized by fact that R ^lb is C1-6 alkyl. 28. Method, according to claim 26, characterized by fact that R ^lb is methyl, ethyl or propyl.29. Method, according to any of the claims 1 to 28, characterized by the fact that R ^lc is
Η.
Petition 870190092849, of 9/17/2019, p. 19/22
7/8
30. Method, in a deal with any an of claims 1 to 28, featured by the fact that what R ^lc is alkyl. 31. Method, in a deal with the claim 30, characterized by fact that R ^lc is C 1-6 alkyl.32. Method, in a deal with the claim 30, characterized by fact that R ^lcit's methyl, ethyl or propyl. 33. Method, in a deal with any an of claims 1 to 32, featured by the fact that what R ^ld is H. 34. Method, in a deal with any an of claims 1 to 32, featured by the fact that what R ^ld is alkyl. 35. Method, in a deal with the claim 34, characterized by fact that R ^ld is C 1-6 alkyl.36. Method, in a deal with the claim 34,
characterized by the fact that R ^ld is methyl, ethyl or propyl.
37. Method according to any one of claims 1 to 36, characterized in that R ² is H.
38. Method according to any one of claims 1 to 36, characterized in that R ² is alkyl.
39. Method according to claim 38, characterized in that R ² is C1-6 alkyl.
40. Method according to claim 38, characterized by the fact that R ² is methyl, ethyl, propyl or butyl.
Petition 870190092849, of 9/17/2019, p. 20/22
8/8
41. Method according to any one of claims 1 to 40, characterized in that the polymer has a bio-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% or about 100%.
42. Method according to any one of claims 1 to 9 and 21 to 41, characterized by the fact that the compound of formula (3-a) is obtained from renewable feed charge.
43. Method according to any one of claims 10 to 41, characterized in that the compound of formula (3-a) is obtained from renewable feed charge.
44. Method according to any one of claims 2, 4, and 11 to 43, characterized by the fact that the compound of formula (1) is obtained from renewable feed charge.
45. Method according to any one of claims 2, 4, and 11 to 44, characterized in that the compound of formula (2) is obtained from renewable feed charge.
46. Polymer, characterized in that it is produced according to the method as defined in any one of claims 1 to 45.

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US10676426B2|2017-06-30|2020-06-09|Novomer, Inc.|Acrylonitrile derivatives from epoxide and carbon monoxide reagents|

US10590099B1|2017-08-10|2020-03-17|Novomer, Inc.|Processes for producing beta-lactone with heterogenous catalysts|

法律状态:
2021-06-22| B11A| Dismissal acc. art.33 of ipl - examination not requested within 36 months of filing|

2021-09-08| B11Y| Definitive dismissal - extension of time limit for request of examination expired [chapter 11.1.1 patent gazette]|

2021-10-19| 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

US201762473008P| true| 2017-03-17|2017-03-17|

PCT/US2018/022248|WO2018170006A1|2017-03-17|2018-03-13|Polyamides, and methods of producing thereof|

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