Glycerol ether polymers

Abstract

The present disclosure relates to polymers comprising glycerol ethers, foams, gels, thermoplastics or elastomers comprising the polymers, and methods of making such polymers.

Description

Technical Field

[0001] The present invention relates to polymers prepared from glycerol ethers such as glycerol monoether and glycerol diether. Background Art

[0002] Bottlebrush polymers (BBPs) are a special class of polymers with relatively short pendant chains attached to the polymer backbone. The development of new bottlebrush polymers prepared from polyesters has attracted much attention because they can be a sustainable alternative to traditional petroleum-based polymers. Currently, BBPs are suitable as material platforms for ultrasoft interfaces, sensing, lubricants and delivery applications due to their unique tangle-free rheology. However, most of the existing BBPs do not exhibit tangle-free rheology in the low temperature range. In addition, the existing polyester-based BBPs are highly cross-linked polymers that are not easy to fine-tune the thermomechanical properties and viscoelasticity. In addition, known polyester BBPs are generally hydrophilic in nature, and the hydrophobicity / hydrophilicity ratio cannot be precisely fine-tuned. In addition, traditional polyester BBPs are prone to ester exchange reactions, which limits their applications.

[0003] Therefore, there is an urgent need to develop polymers that overcome or at least improve one or more of the above disadvantages. Summary of the Invention

[0004] In one aspect, a polymer having the following general structure (I) is provided:

[0005]

[0006] in:

[0007] x, y and z are each independently 0 or an integer from 1 to 5;

[0008] n is an integer from 1 to 24;

[0009] v is an integer from 1 to 2000; and

[0010] R 1 Is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl, linear or branched C2-C 30 Alkynyl, or a substituent having the following general structure (II):

[0011]

[0012] in:

[0013] p, q and r are each independently 0 or an integer from 1 to 5;

[0014] R 2 and R 3 Each independently is H, linear or branched C1-C30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 alkynyl; and

[0015] This is the position where the substituent having the general structure (II) is linked to the polymer having the general structure (I).

[0016] Advantageously, monoglycerol ether (MGE) or diglycerol ether (DGE), having an aliphatic chain attached to a glycerol backbone via an ether linkage, may be a suitable bio-based monomer for the synthesis of highly tunable polyester polymers such as bottle brush polymers (BBP).

[0017] Advantageously, various segments of the polymer can contain a variety of aliphatic chains, and increasing the chain length within the aliphatic polyester repeating unit can favorably adjust the thermomechanical properties of BBP toward a softer and more elastic end point. For example, the introduction of longer alkyl chains can increase the overall hydrophobicity of the polymer, while the presence of poly(ethylene glycol) side chains can effectively increase the overall hydrophobicity of the polymer. By designing the polymer, bifunctional groups can be introduced into the side chains, thereby incorporating a variety of functional groups into the polymer. Furthermore, the ether groups on the pendant chains of BBP can impart higher thermal stability to the polymer.

[0018] Advantageously, unlike conventional BBPs that are highly cross-linked and hydrophilic in nature, the hydrophobicity / hydrophilicity ratio and viscoelasticity of the disclosed polymers can be easily fine-tuned to prepare softer, elastic polymers.

[0019] In view of this, the BBP disclosed herein may advantageously have enhanced chemical stability. The enhanced chemical stability can ensure that the BBP forms a well-defined structure that is less susceptible to transesterification.

[0020] Advantageously, the polymers of the present disclosure can be biodegradable due to the biocompatibility and biodegradability of the constituent monomers. The polymers of the present disclosure can be degraded through enzymatic and hydrolytic degradation reactions while exhibiting suitable physical and mechanical properties for a wide variety of applications. Advantageously, the polymers of the present disclosure can have properties comparable to non-biodegradable commercial plastics such as polypropylene or polyethylene, while being biodegradable and having significantly less environmental impact.

[0021] In another aspect, there is provided a foam, gel, thermoplastic or elastomer comprising a polymer as defined above.

[0022] In another aspect, a method for preparing a polymer having the general structure (I) is provided,

[0023]

[0024] The steps include:

[0025] Provided is a glycerol ether having the following general structure (III):

[0026] and

[0027] A glycerol ether having the general structure (III) is contacted with a dicarboxylic acid having the following general structure (IVa) or a diacid chloride having the following structure (IVb) under polymerization reaction conditions:

[0028]

[0029] wherein L is CH2 or aryl;

[0030] in:

[0031] x, y and z are each independently 0 or an integer from 1 to 5;

[0032] n is an integer from 1 to 24; and

[0033] R 1 and R 1’ Each independently is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl, linear or branched C2-C 30 Alkynyl, or a substituent having the following general structure (II):

[0034]

[0035] in:

[0036] p, q and r are each independently 0 or an integer from 1 to 5;

[0037] R 2 and R 3 Each independently is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 alkynyl; and

[0038] is the position where the substituent having the general structure (II) is connected to the glycerol ether having the general structure (III),

[0039] where R 1 or R 1’ In the glycerol ether having the general structure (III), R 1 and R 1’ Both are not H.

[0040] The method defined above can include a direct polycondensation reaction followed by a curing step, thereby efficiently preparing the polymer. The method also allows the synthesis of a variety of BBPs and the fine-tuning of their properties by varying 1) the length of the alkyl chain on the monoglycerol ether / diglycerol ether (MGE / DGE), 2) the length of the alkyl chain on the diacid, and 3) the position of the alkyl chain on the MGE / DGE diol.

[0041] In another aspect, there is provided the use of a polymer as defined above, or a foam, gel, thermoplastic or elastomer as defined above, in nanocapsules, in sensing and delivery applications, as a soft tissue substitute, lubricant, surface coating, motion control grease, ultra-soft surface.

[0042] Due to the biocompatibility and biodegradability of the constituent monomers, the polymers of the present disclosure may be suitable for use in biological systems, for example, as soft tissue replacements.

[0043] definition

[0044] As used herein, the following words and terms shall have the meanings indicated:

[0045] "Acyl" refers to a RC(=O)- group, where the R group can be an optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl, or optionally substituted heteroaryl, as defined herein. Examples of acyl groups include acetyl, benzoyl, and aminoacyl groups derived from amino acids. The group can be a terminal group or a bridging group. If the group is a terminal group, it is bonded to the rest of the molecule through the carbonyl carbon.

[0046] "Alkenyl," as a group or part of a group, refers to an aliphatic hydrocarbon group containing at least one carbon-carbon double bond in the normal chain, which may be straight or branched, and preferably has 2-30 carbon atoms, more preferably 2-20 carbon atoms, and most preferably 2-10 carbon atoms. The group may contain multiple double bonds in the normal chain, and the orientations of each are independently E or Z. Exemplary alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, and nonenyl. The group may be a terminal group or a bridging group.

[0047] Unless otherwise specified, "alkyl" as a group or part of a group refers to a straight-chain or branched aliphatic hydrocarbon group, preferably C1-C 30 Alkyl, more preferably C1-C 20 Alkyl, most preferably C1-C 10 Examples of suitable linear and branched C1-C6 alkyl substituents include methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, tert-butyl, hexyl, etc. The group may be a terminal group or a bridging group.

[0048] "Alkynyl," as a group or part of a group, refers to an aliphatic hydrocarbon group containing a carbon-carbon triple bond in the normal chain, which may be straight or branched, and preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 19 carbon atoms. Exemplary structures include, but are not limited to, ethynyl and propynyl. The group may be a terminal group or a bridging group.

[0049] "Aryl" as a group or part of a group means (i) an optionally substituted monocyclic or fused polycyclic aromatic carbocyclic ring (a cyclic structure in which the ring atoms are all carbon), preferably having 5 to 12 atoms per ring, examples of which include phenyl, naphthyl, etc.; (ii) an optionally substituted partially saturated bicyclic aromatic carbocyclic ring moiety in which the phenyl and C 5-7 Cycloalkyl or C 5-7 Cycloalkenyl groups are fused together to form a ring structure, such as tetrahydronaphthyl, indenyl or indanyl. This group can be a terminal group or a bridge group. Aryl groups are usually C6-C 18 Aryl.

[0050] In the context of this application "biobased" means that the material is derived in whole or in part from materials of biological origin, such as plants, animals, enzymes and microorganisms, including bacteria, fungi and yeasts.

[0051] The word "substantially" does not exclude "completely", for example, a composition "substantially free of" Y may completely be free of Y. If necessary, the word "substantially" may be omitted from the present invention.

[0052] Unless otherwise stated, the terms "include" and "comprising" and their grammatical variations are intended to represent "open" or "inclusive" language such that they include both the listed elements and permit the inclusion of additional, non-listed elements.

[0053] As used herein, the term "about," in the context of concentrations of formulation ingredients, typically refers to + / - 5% of the stated value, more typically refers to + / - 4% of the stated value, more typically refers to + / - 3% of the stated value, more typically refers to + / - 2% of the stated value, more typically refers to + / - 1% of the stated value, and more typically refers to + / - 0.5% of the stated value.

[0054] In this disclosure, certain embodiments may be disclosed in the format of a range. It should be understood that describing in range format is for convenience and brevity only and should not be construed as a rigid limitation on the disclosed range. Therefore, the description of a range should be considered to have specifically disclosed all possible subranges within that range, as well as individual numerical values. For example, a description of a range such as 1-6 should be considered to have specifically disclosed subranges within that range, such as 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, and individual numerical values ​​within that range, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the size of the range.

[0055] This paper may also have carried out a broad and general description of certain embodiments. Each narrower category and sub-general grouping that falls within the general disclosure also forms a part of this disclosure. This includes the general description of the embodiment carried out under the situation of proviso or negative limitation, and this proviso or negative limitation deletes any subject matter from this general concept, no matter whether this paper specifically narrates the material of this deletion. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] The accompanying drawings illustrate the disclosed embodiments and are used to explain the principles of the disclosed embodiments. However, it should be understood that the accompanying drawings are only for illustration purposes and are not intended to limit the scope of the present invention.

[0058] [ Figure 1 ]

[0059] Figure 1 is a set of images showing: (a) a schematic representation of a branched bottlebrush polyester formed from a monoglycerol ether with pendant ether side chains (1002) and a polyester backbone (1004); (a') a schematic representation of a branched bottlebrush polyester formed from a diglycerol ether with pendant ether side chains R1 and R2 and a polyester backbone (1004), wherein R1 and R2 independently represent C3, C 8-14 、C 16 or C 18 Alkyl groups; (b) Chemical scheme showing the synthesis of MGEs; (c) Chemical scheme showing the A2+B2 polymerization of 1-O-MGE with a diacid. The R group is variable, thus allowing a large number of permutations to form a variety of polymers with different thermomechanical properties and viscoelasticity; (d) Chemical scheme showing the A2+B2 polymerization of 2-O-MGE with a diacid. The R group is variable, thus allowing a large number of permutations to form a variety of polymers with different thermomechanical properties and viscoelasticity; (e) Illustration of MGE-based polyesters with different alkyl chain lengths in the backbone n and chain m.

[0060] [ Figure 2 ]

[0061] Figure 2 is a set of schemes showing details of the synthesis of (a) 1-O-MGE, (b) 2-O-MGE, (c) 1,2-O-DGE 1',2'diol, (d) 1,3-O-DGE 1',2'diol, and (e) 1,2-O-DGE 1',3'diol via Williamson ether synthesis and acid-catalyzed hydrolysis.

[0062] [ Figure 3 ]

[0063] Figure 3Some schematic diagrams of monomers prepared in the present disclosure are shown, showing monoglycerol ether (MGE) (3002) and diglycerol ether (DGE) (3004). R1 ​​and R2 independently represent C3, C 8-14 、C 16 or C 18 alkyl.

[0064] [ Figure 4 ]

[0065] Figure 4 (a) Schematic diagram of the formation of BBP from the monoglycerol ether monomers from commercially available glycerol acetone acetal and 2-phenyl-1,3-dioxane-5-ol in three steps, where R independently represents C3, C 8-14 、C 16 or C 18 (b) Schematic diagram of the formation of BBP by diglyceryl ether monomers prepared by the present disclosure, R1 and R2 represent C3, C 8-14 、C 16 or C 18 alkyl.

[0066] [ Figure 5 ]

[0067] Figure 5 Some schematic diagrams of BBP prepared in the present disclosure are shown, showing monoglycerol polyester (6002) and diglycerol polyester (6004). R, R1 and R2 independently represent C3, C 8-14 、C 16 or C 18 alkyl.

[0068] [ Figure 6 ]

[0069] Figure 6 The following graphs of the degree of reaction versus time are shown, as well as the M n and Relationship diagram with reaction degree: m=9, 1-O-MGE / n=10, diacid / Sn(1 / 1 / 0.1), m=10, 1-O-MGE / n=10, diacid / Sn(1 / 1 / 0.1), m=11, 1-O-MGE / n=10, diacid / Sn(1 / 1 / 0.1), m=12, 1-O-MGE / n=10, diacid / Sn(1 / 1 / 0.1), m=13, 1-O-MGE / n=10, diacid / Sn(1 / 1 / 0.1), m=14, 1-O-MGE / n=10, diacid / Sn(1 / 1 / 0.1) system (Table 1(entries 1-6)). Figure 1. (a) Reaction extent vs. time, (b) Mw / Mn vs. reaction extent p (%), and (c) Mn vs. reaction extent p (%) (bottom) for the 1-O-MGE / diacid / Sn (1 / 1 / 0.1) system (180°C) (Table 1, entry 3). The solvent for all systems was diphenyl ether. Symbols are as shown.

[0070] [ Figure 7 ]

[0071] Figure 7 is a group of the following 1 H NMR spectra: (a) 1-O MGE (m = 18) / diacid (n = 9) BBP and its starting materials; (b) 2-O MGE (m = 18) / diacid (n = 9) BBP and its starting materials; (c) 1-O MAG (m = 18) / diacid (n = 9) BBP and its starting materials; (d) polymerization of monomers with branches; (e) polymerization of monomers with branches (zoomed in); (f) polymerization of 1-O-MGE diol with saturated side chains; (g) polymerization of 1-O-MGE diol with unsaturated side chains; (h) comparison of 1-O-MGE, 1-O-MAG, and 2-O-MGE monomers and polymers; (i) 1,2-O-DGE 1',2' diol (m = 4) / diacid (n = 10); and (j) 1,2-O-DGE 1',3'-diol (m=4) / diacid (n=10).

[0072] [ Figure 8 ]

[0073] Figure 8 is T showing 1-O-MGE BBP m Plot of values ​​where m = 9-14 and 18, n = 10 (Table 2 (entries 1-6 and 16)).

[0074] [ Figure 9 ]

[0075] Figure 9 is a set of graphs showing (a) T of ethylene glycol, 1-O-MGE BBP mvalues, where m = 12, 16 and 18, n = 7-12; (b) T of 2-O-MGE BBP m values, where m = 3, n = 4-12; (c) T of 1-O-MGE BBP m values, where m=16, n=4-14, 18 and 22.

[0076] [ Figure 10 ]

[0077] Figure 10 Schematic diagram of MGE BBP arrangements with (a) even and (b) odd carbon numbers between ester groups. Arrows indicate polarization directions.

[0078] [ Figure 11 ]

[0079] Figure 11 A set of figures showing the effects of ester and ether bonds. (a) shows the structures of 1-O-MGEBBP and 1-O-MAG BBP; (b) shows the T of 1-O-MGE BBP (circles) and 1-O-MAG BBP (squares). m (c) is a diagram showing the values ​​of 1-O-MGE BBP (side chain ether linkage) and 1-O-MAG BBP (side chain ester linkage). The arrows below each figure indicate that different alkyl chain lengths of MGE and α, ω diacids lead to different thermomechanical properties and viscoelastic properties of BBP.

[0080] [ Figure 12 ]

[0081] Figure 12 Comparison of T between 1-O-MGE BBP (circle) and 2-O-MGE BBP (square) m Plot of values ​​where m=18, n=7-12 (Table 2 (entries 13-24)).

[0082] [ Figure 13 ]

[0083] Figure 13 is a graph showing the effect of double bonds on diacids and comparing the T values ​​of 1-O-MGE BBP (m=16, n=4) prepared from saturated diacids (e.g., succinic acid) and unsaturated diacids (e.g., fumaric acid and itaconic acid). m Value. T of C16 diol succinate (square) m The highest value is 42.7 ° C. The introduction of a double bond in the chain of C16 diol fumaric acid (circular) leads to T m is lower, at 34.2 °C, while the introduction of a double bond outside the chain of C16 diol fumaric acid (circular) will result in T mEven lower, at 27.7℃.

[0084] [ Figure 14 ]

[0085] Figure 14 Graphs showing TGA curves of (a) 1-O-MGE BBP (m=9-14, n=10) and (b) 1-O-MGE BBP (m=18, n=7-12).

[0086] [ Figure 15 ]

[0087] Figure 15 is a set of TGA graphs, which (a) compare the values ​​of 1-O-MGE BBP and 1-O-MAG BBP, and (b) compare the values ​​of 1-O-MGE BBP and 2-O-MGE BBP. Figure 15 (a) shows that the introduction of an ester bond into the BBP side chain (1-O-MAG BBP) generally decreases T at large m values ​​compared to 1-O-MGE BBP. m . Figure 15 (b) shows that the T of 1-O-MGEBBP is higher than that of 2-O-MGE BBP. m Usually higher.

[0088] [ Figure 16 ]

[0089] Figure 16 Schematic diagrams showing gel permeation chromatography (GPC) methods, demonstrating that MGE BBP can undergo hydrolytic degradation to form MGE and α- and ω-diacids, followed by polycondensation to reform MGE BBP. a) Chromatogram of 1-O-MGE BBP (Mn = 20291, D = 1.32) in 60% THF / 40% NaOH (aq) undergoing hydrolysis conditions. b) Chromatogram showing efficient degradation of the polyester to 1-O-MGE diol and diacid monomers after 1 hour. c) and d) chromatograms showing that the polymer can be reformed under repolymerization conditions: Mn = 1521, D = 2.11 after 6 hours (c) and Mn = 8089, D = 1.72 after 18 hours (d) respectively.

[0090] [ Figure 17 ]

[0091] Figure 17 is a schematic diagram showing the scalability of preparing 1-O-MGE monomer from epichlorohydrin in a 10 L reactor.

[0092] [ Figure 18 ]

[0093] Figure 18 Is a series of display from t = 0 to t = 24 hours period used1 H NMR spectrum of the reaction monitoring of the formation of 1-O-MGE BBP from 1-O-MGE diol m=18 and n=12 diacid. 1 Proton signals from substances (a), (b), (c), and (d) were detected in H NMR.

[0094] [ Figure 19 ]

[0095] Figure 19 This graph shows the relationship between the ratio of substances (A), (B), (C), and (D) over time. The A-axis represents time in minutes, and the B-axis represents relative percentages. DETAILED DESCRIPTION

[0096] The present invention provides a polymer having the following general structure (I):

[0097]

[0098] in:

[0099] x, y and z are each independently 0 or an integer from 1 to 5;

[0100] n is an integer from 1 to 24;

[0101] v is an integer from 1 to 2000; and

[0102] R 1 Is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl, linear or branched C2-C 30 Alkynyl, or a substituent having the following general structure (II):

[0103]

[0104] in:

[0105] p, q and r are each independently 0 or an integer from 1 to 5;

[0106] R 2 and R 3 Each independently is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 alkynyl; and

[0107] This is the position where the substituent having the general structure (II) is linked to the polymer having the general structure (I).

[0108] x, y, and z may each independently be 0 or an integer from 1 to 5, or an integer of 1, 2, 3, 4, or 5. x may be 0 or 1. y may be 1. z may be 0 or 1.

[0109] n can be an integer of 1-24, 1-4, 1-8, 1-12, 1-16, 1-20, 4-8, 4-12, 4-16, 4-20, 4-24, 8-12, 8-16, 8-20, 8-24, 12-16, 12-20, 12-24, 16-20, 16-24, or 20-24.

[0110] v may be an integer of 1-2000, 1-100, 1-200, 1-500, 1-1000, 100-200, 100-500, 100-1000, 100-2000, 200-500, 200-1000, 200-2000, 500-1000, 500-2000, or 1000-2000.

[0111] R 1 It can be H.

[0112] R 1 Can be linear or branched C1-C 30 Alkyl. Linear or branched C1-C 30 The alkyl group can contain 1-30, 1-5, 1-10, 1-15, 1-20, 1-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0113] Linear or branched C1-C 30 The alkyl group may include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, and any combination thereof.

[0114] R 1 Can be linear or branched C2-C 30 Alkenyl. Linear or branched C2-C 30 An alkenyl group can contain 2-30, 2-5, 2-10, 2-15, 2-20, 2-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0115] R 1Can be linear or branched C2-C 30 Alkynyl. Linear or branched C2-C 30 An alkynyl group can contain 2-30, 2-5, 2-10, 2-15, 2-20, 2-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0116] R 1 It may be selected from 2-ethylhexyl, 3,7-dimethyloctan-1-yl, geranyl, neryl, citronellyl, phytyl, farnesyl, and any combination thereof. 1 May contain monoterpenes.

[0117] R 1 It may be a substituent having the following general structure (II):

[0118]

[0119] p, q, and r may each independently be 0 or an integer from 1 to 5, or an integer of 1, 2, 3, 4, or 5. p may be 0 or 1. q may be 0 or 1. r may be 0 or 1.

[0120] R 2 and R 3 can be independently H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl.

[0121] R 2 and R 3 can be H independently of each other.

[0122] R 2 and R 3 Can be independently linear or branched C1-C 30 Alkyl. Linear or branched C1-C 30 The alkyl group can contain 1-30, 1-5, 1-10, 1-15, 1-20, 1-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0123] R 2 and R 3 Can be independently linear or branched C2-C 30Alkenyl. Linear or branched C2-C 30 An alkenyl group can contain 2-30, 2-5, 2-10, 2-15, 2-20, 2-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0124] R 2 and R 3 Can be independently linear or branched C2-C 30 Alkynyl. Linear or branched C2-C 30 An alkynyl group can contain 2-30, 2-5, 2-10, 2-15, 2-20, 2-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0125] R 2 and R 3 R may be independently selected from 2-ethylhexyl, 3,7-dimethyloctan-1-yl, geranyl, neryl, citronellyl, phytyl, farnesyl, and any combination thereof. 2 and R 3 Monoterpenes may be included independently.

[0126] It may be a position where the substituent having the general structure (II) is linked to the polymer having the general structure (I).

[0127] x may be 0 or 1, y may be 1, z may be 0 or 1, p may be 0 or 1, q may be 0 or 1, or r may be 0 or 1.

[0128] x may be 0 or 1, y may be 1, z may be 0 or 1, p may be 0 or 1, q may be 0 or 1, and r may be 0 or 1.

[0129] x can be 0, y can be 1, z can be 1, and R 1 It can be a linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl.

[0130] x can be 1, y can be 1, z can be 0, and R 1 It can be a linear or branched C1-C 30 Alkyl, linear or branched C2-C 30Alkenyl or linear or branched C2-C 30 Alkynyl.

[0131] x can be 0, y can be 1, z can be 1, R 1 may be a substituent having the general structure (II), r may be 0, p may be 1, and q may be 1.

[0132] x can be 0, y can be 1, z can be 1, R 1 may be a substituent having the general structure (II), r may be 1, p may be 1, and q may be 0.

[0133] x can be 1, y can be 1, z can be 0, R 1 may be a substituent having the general structure (II), r may be 1, p may be 1, and q may be 0.

[0134] When x is 1, y is 1, and z is 0, R 1 It may not be a linear or branched C1-C6 alkyl group.

[0135] The polymer may have the following structure:

[0136]

[0137]

[0138] where R 2 、R 3 and R 4 Can be independently linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl.

[0139] R 2 and R 3 may be independently as defined above.

[0140] R 4 It can be H.

[0141] R 4 Can be linear or branched C1-C 30 Alkyl. Linear or branched C1-C 30 The alkyl group can contain 1-30, 1-5, 1-10, 1-15, 1-20, 1-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0142] R 4 Can be linear or branched C2-C 30 Alkenyl. Linear or branched C2-C 30 An alkenyl group can contain 2-30, 2-5, 2-10, 2-15, 2-20, 2-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0143] R 4 Can be linear or branched C2-C 30 Alkynyl. Linear or branched C2-C 30 An alkynyl group can contain 2-30, 2-5, 2-10, 2-15, 2-20, 2-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0144] R 4 It may be selected from 2-ethylhexyl, 3,7-dimethyloctan-1-yl, geranyl, neryl, citronellyl, phytyl, farnesyl, and any combination thereof. 4 May contain monoterpenes.

[0145] The polymer may be bottlebrush polyester.

[0146] The bottlebrush polyester may be a branched bottlebrush polyester.

[0147] The polymer may be a biodegradable polymer.

[0148] The molecular weight of the polymer can be from about 7,000 to about 100,000, from about 7,000 to about 8,000, from about 7,000 to about 9,000, from about 7,000 to about 10,000, from about 7,000 to about 20,000, from about 7,000 to about 50,000, from about 8,000 to about 9,000, from about 8,000 to about 10,000, from about 8,000 to about 20,000, from about 8,000 to about 50,000, from about 8,000 to about 100 ,000, about 9,000 to about 10,000, about 9,000 to about 20,000, about 9,000 to about 50,000, about 9,000 to about 100,000, about 10,000 to about 20,000, about 10,000 to about 50,000, about 10,000 to about 100,1000, about 20,000 to about 50,000, about 20,000 to about 100,000 or about 50,000 to about 100,000.

[0149] The intrinsic viscosity of the polymer can be in the range of about 0.2 dL / g to about 2.5 dL / g, about 0.2 dL / g to about 0.5 dL / g, about 0.2 dL / g to about 1 dL / g, about 0.2 dL / g to about 1.5 dL / g, about 0.2 dL / g to about 2 dL / g, about 0.5 dL / g to about 1 dL / g, about 0.5 dL / g to about 1.5 dL / g, about 0.5 dL / g to about 2 dL / g, about 0.5 dL / g to about 2.5 dL / g, about 1 dL / g to about 1.5 dL / g, about 1 dL / g to about 2 dL / g, about 1 dL / g to about 2.5 dL / g, about 1.5 dL / g to about 2 dL / g, about 1.5 dL / g to about 2.5 dL / g, or about 2 dL / g to about 2.5 dL / g.

[0150] The melting temperature of the polymer may be from about -40°C to about 100°C, from about -40°C to about -20°C, from about -40°C to about 0°C, from about -40°C to about 20°C, from about -40°C to about 40°C, from about -40°C to about 60°C, from about -40°C to about 80°C, from about -20°C to about 0°C, from about -20°C to about 20°C, from about -20°C to about 40°C, from about -40°C to about 60°C, from about -40°C to about 80°C, from about -40°C to about 100°C. , about 0°C to about 20°C, about 0°C to about 40°C, about 0°C to about 60°C, about 0°C to about 80°C, about 0°C to about 100°C, about 20°C to about 40°C, about 20°C to about 60°C, about 20°C to about 80°C, about 20°C to about 100°C, about 40°C to about 60°C, about 40°C to about 80°C, about 40°C to about 100°C, about 60°C to about 80°C, about 60°C to about 100°C, or about 80°C to about 100°C.

[0151] The degradation temperature of the polymer may be above 300° C. The degradation temperature of the polymer may be in the range of about 300° C. to about 500° C., about 300° C. to about 350° C., about 300° C. to about 400° C., about 300° C. to about 450° C., about 350° C. to about 400° C., about 350° C. to about 450° C., about 350° C. to about 500° C., about 400° C. to about 450° C., about 400° C. to about 500° C., or about 450° C. to about 500° C.

[0152] There is also provided a foam, gel, thermoplastic or elastomer comprising a polymer as defined above.

[0153] Also provided is a method for preparing a polymer having the following general structure (I):

[0154]

[0155] The steps include:

[0156] Provided is a glycerol ether having the following general structure (III):

[0157] and

[0158] A glycerol ether having the general structure (III) is contacted with a dicarboxylic acid having the following general structure (IVa) or a diacid chloride having the following structure (IVb) under polymerization reaction conditions:

[0159]

[0160] Wherein L is -CH2- or aryl;

[0161] in:

[0162] x, y and z are each independently 0 or an integer from 1 to 5;

[0163] n is an integer from 1 to 24; and

[0164] R 1 and R 1’ Each independently is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl, linear or branched C2-C 30 Alkynyl, or a substituent having the following general structure (II):

[0165]

[0166] in:

[0167] p, q and r are each independently 0 or an integer from 1 to 5;

[0168] R2 and R 3 Each independently is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 alkynyl; and

[0169] is the position where the substituent having the general structure (II) is connected to the glycerol ether having the general structure (III),

[0170] In the glycerol ether having the general structure (III), R 1 or R 1’ It is H, but R 1 and R 1’ Both are not H.

[0171] R 1 、R 2 、R 3 , x, y, z, n, p, q, r can be defined as above.

[0172] L can be -CH2- or aryl. Aryl can be furyl, phenyl, naphthyl or any combination thereof.

[0173] R 1’ It can be H.

[0174] R 1’ Can be linear or branched C1-C 30 Alkyl. Linear or branched C1-C 30 The alkyl group can contain 1-30, 1-5, 1-10, 1-15, 1-20, 1-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-3 carbon atoms.

[0175] R 1’ Can be linear or branched C2-C 30 Alkenyl. Linear or branched C2-C 30 An alkenyl group can contain 2-30, 2-5, 2-10, 2-15, 2-20, 2-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0176] R 1’ Can be linear or branched C2-C 30Alkynyl. Linear or branched C2-C 30 An alkynyl group can contain 2-30, 2-5, 2-10, 2-15, 2-20, 2-25, 5-10, 5-15, 5-20, 5-25, 5-30, 10-15, 10-20, 10-25, 10-30, 15-20, 15-25, 15-30, 20-25, 20-30, or 25-30 carbon atoms.

[0177] R 1’ It may be selected from 2-ethylhexyl, 3,7-dimethyloctan-1-yl, geranyl, neryl, citronellyl, phytyl, farnesyl, and any combination thereof. 1’ May contain monoterpenes.

[0178] The providing step may comprise reacting a compound of the following structure with a linear or branched C1-C 30 Alkyl halides, linear or branched C2-C 30 Alkenyl halides or linear or branched C2-C 30 Alkynyl halides react under glycerol ether reaction conditions:

[0179]

[0180] The halide may be bromide, chloride, iodide or fluoride.

[0181] The alkyl halide may be an alkyl bromide, an alkyl chloride, an alkyl iodide or an alkyl fluoride. The alkyl halide may be an alkyl bromide.

[0182] The glycerol ether reaction conditions may include Williamson ether synthesis, which includes contacting a compound of the following structure with an alkali metal or alkali metal hydride in a solvent at a temperature of -4°C to 4°C, adding a linear or branched C1-C 30 Alkyl halide, linear or branched C2-C 30 Alkenyl halide or linear or branched C2-C 30 Alkynyl halide to form a mixture, and stirring the mixture at a temperature of 60°C to 80°C for a duration of 3 hours to 24 hours:

[0183]

[0184] The compound of the following structure can be

[0185] contacting with an alkali metal or alkali metal hydride at a temperature of about -4°C to about 4°C, about -4°C to about -2°C, about -4°C to about 0°C, about -4°C to about 2°C, about -2°C to about 0°C, about -2°C to about 2°C, about -2°C to about 4°C, about 0°C to about 2°C, about 0°C to about 4°C, or about 2°C to about 4°C:

[0186]

[0187] The alkali metal may be metallic sodium.

[0188] The alkali metal hydride may be NaH or KH.

[0189] The solvent may be toluene, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, diethyl ether, or a polar deactivating solvent such as dimethyl sulfoxide (DMSO).

[0190] The mixture may be stirred at a temperature of about 60°C to about 80°C, about 60°C to about 70°C, or about 70°C to about 80°C.

[0191] The mixture can be stirred for a duration of about 3 hours to about 24 hours, about 3 hours to about 9 hours, about 3 hours to about 15 hours, about 3 hours to about 21 hours, about 9 hours to about 15 hours, about 9 hours to about 21 hours, about 9 hours to about 24 hours, about 15 hours to about 21 hours, about 15 hours to about 24 hours, or about 21 hours to about 24 hours.

[0192] The contacting step of the Williamson ether synthesis can be followed by acidification, wherein the acidification step can be carried out in a solvent comprising 1 M aqueous HCl and ethanol in a volume ratio of about 5:1 to about 2:1, about 5:1 to about 4:1, about 5:1 to about 3:1, about 4:1 to about 3:1, about 4:1 to about 2:1, or about 3:1 to about 2:1.

[0193] In the glycerol ether having the general structure (III), R 1 or R 1’ It can be H, but R 1 and R 1’ Both cannot be H.

[0194] x can be 0, y can be 1, z can be 1, R 1 Can be linear or branched C1-C 30 Alkyl, and R 1’ It can be H.

[0195] x can be 0, y can be 1, z can be 1, R 1’ Can be linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl, and R 1 It can be H.

[0196] x can be 1, y can be 1, z can be 0, R 1 Can be linear or branched C1-C 30Alkyl, and R 1’ It can be H.

[0197] x can be 1, y can be 1, z can be 0, R 1’ Can be linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl, and R 1 It can be H.

[0198] x can be 0, y can be 1, z can be 1, R 1 It can be a substituent having the general structure (II), r can be 0, p can be 1, q can be 1, and R 1’ It can be H.

[0199] x can be 0, y can be 1, z can be 1, R 1’ It can be a substituent having the general structure (II), r can be 0, p can be 1, q can be 1, and R 1 It can be H.

[0200] x can be 0, y can be 1, z can be 1, R 1 It can be a substituent having the general structure (II), r can be 1, p can be 1, q can be 0, and R 1’ It can be H.

[0201] x can be 0, y can be 1, z can be 1, R 1’ It can be a substituent having the general structure (II), r can be 1, p can be 1, q can be 0, and R 1 It can be H.

[0202] x can be 1, y can be 1, z can be 0, R 1 It can be a substituent having the general structure (II), r can be 1, p can be 1, q can be 0, and R 1’ It can be H.

[0203] x can be 1, y can be 1, z can be 0, R 1’ It can be a substituent having the general structure (II), r can be 1, p can be 1, q can be 0, and R 1 It can be H.

[0204] x can be 0, y can be 1, z can be 1, R 1 It can be a substituent having the general structure (II), r can be 0, p can be 1, q can be 1, and R 1’ It can be H.

[0205] x can be 0, y can be 1, z can be 1, R 1’ is a substituent having the general structure (II), r can be 0, p can be 1, q can be 1, and R 1 It can be H.

[0206] When x is 1, y is 1, and z is 0, R 1 It may not be a linear or branched C1-C6 alkyl group, and R 1’ It can be H.

[0207] Glyceryl ethers having the general structure (III) may have the following structures:

[0208]

[0209] where R 2 、R 3 and R 4 Can be each independently linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl.

[0210] R 2 、R 3 and R 4 May be as defined above.

[0211] The dicarboxylic acid having the general structure (IVa) can be selected from 1,3-propanedioic acid, 1,4-butanedioic acid, 1,5-pentanedioic acid, 1,6-hexanedioic acid, 1,7-heptanedioic acid, 1,8-octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanedioic acid , 1,16-hexadecanedioic acid, 1,17-heptadecanedioic acid, 1,18-octadecanedioic acid, 1,19-nonadecanedioic acid, 1,20-eicosanedioic acid, 1,21-heneicosanedioic acid, 1,22-docosanedioic acid, 1,23-tricosanedioic acid, 1,24-tetracosanedioic acid, furan-2,5-dicarboxylic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, and any mixture thereof.

[0212] The diacyl chloride having the general structure (IVb) can be selected from 1,3-malonyl dichloride, 1,4-succinoyl dichloride, 1,5-glutaryl dichloride, 1,6-adipoyl dichloride, 1,7-heptanedioyl dichloride, 1,8-octanedioyl dichloride, 1,9-azelaoyl dichloride, 1,10-decanedioyl dichloride, 1,11-undecanediyl dichloride, 1,12-dodecanediyl dichloride, 1,13-tridecanediyl dichloride, 1,14-tetradecanediyl dichloride, 1,15-pentadecanedioyl dichloride, chlorine, 1,16-hexadecandioyl dichloride, 1,17-heptadecanedioyl dichloride, 1,18-octadecandioyl dichloride, 1,19-nonadecanedioyl dichloride, 1,20-eicosanedioyl dichloride, 1,21-heneicosanedioyl dichloride, 1,22-docosandioyl dichloride, 1,23-tricosandioyl dichloride, 1,24-tetracosanedioyl dichloride, furan-2,5-dicarbonyl dichloride, terephthaloyl dichloride, naphthalene-2,6-dicarbonyl dichloride, and any mixture thereof.

[0213] The polymerization reaction conditions can be any conditions that allow the glycerol ether of the general structure (III) to react with the dicarboxylic acid of the general structure (IVa) or the diacid chloride of the general structure (IVb).

[0214] The glycerol ether having the general structure (III) can be contacted with a dicarboxylic acid having the general structure (IVa) or a diacid chloride having the general structure (IVb) in a molar ratio of about 3:1 to about 1:2, about 3:1 to about 2:1, about 3:1 to about 1:1, about 2:1 to about 1:1, about 2:1 to about 1:2, or about 1:1 to about 2:1.

[0215] The contacting step of polymer reaction conditions may include a first heating step conducted at a temperature of about 150°C to about 220°C, about 150°C to about 170°C, about 150°C to about 200°C, about 170°C to about 200°C, about 170°C to about 220°C, or about 200°C to about 220°C.

[0216] The contacting step of polymer reaction conditions may include a first heating step conducted under an inert atmosphere. The inert atmosphere may include nitrogen, argon, and any mixtures thereof.

[0217] The first heating step may also include a catalyst.

[0218] The catalyst may be selected from chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, p-toluenesulfonic acid monohydrate, and any mixture thereof.

[0219] The catalyst may comprise tin. The catalyst may be elemental tin.

[0220] The molar ratio of catalyst to glyceryl ether having the general structure (III) can be from about 1:8 to about 1:100, from about 1:8 to about 1:10, from about 1:8 to about 1:20, from about 1:8 to about 1:50, from about 1:10 to about 1:20, from about 1:10 to about 1:50, from about 1:10 to about 1:100, from about 1:20 to about 1:50, from about 1:20 to about 1:100, or from about 1:50 to about 1:100.

[0221] The contacting step of polymer reaction conditions may further comprise a second heating step carried out at a temperature of about 150°C to about 250°C, about 150°C to about 170°C, about 150°C to about 200°C, about 150°C to about 220°C, about 170°C to about 200°C, about 170°C to about 220°C, about 170°C to about 250°C, about 200°C to about 220°C, about 200°C to about 250°C, or about 220°C to about 250°C.

[0222] The contacting step of polymer reaction conditions may further comprise a second heating step conducted for a duration of about 12 hours to about 36 hours, about 12 hours to about 18 hours, about 12 hours to about 24 hours, about 12 hours to about 30 hours, about 18 hours to about 24 hours, about 18 hours to about 30 hours, about 18 hours to about 36 hours, about 24 hours to about 30 hours, about 24 hours to about 36 hours, or about 30 hours to about 36 hours.

[0223] The contacting step of polymer reaction conditions may further comprise a second heating step carried out under an inert atmosphere. The inert atmosphere may be as defined above.

[0224] Also provided is the use of a polymer as defined above or a foam, gel, thermoplastic or elastomer as defined above in nanocapsules, as a soft tissue substitute, lubricant, surface coating, motion control grease, ultra-soft surface in sensing and delivery applications.

[0225] In an embodiment, the ultra-soft surface can be a surface with ultra-soft compliance and low outgassing. They can be used to provide an effective thermal interface between a heat sink and an electronic device. They can be used on uneven surfaces, air gaps, or rough surface textures, helping to provide superior thermal performance and long-term stability compared to traditional thermal pads. They are typically used in telecommunications equipment, PC boards, chassis applications, thermally enhanced ball grid arrays (BGAs), memory modules, graphics processing units (GPUs) / central processing units (CPUs) applications, and a large number of other industrial equipment. Generally, increasing the alkyl chain length of the polyester backbone can increase the flexibility of the polyester chain. This can make the polymer more flexible.

[0226] In another example, delivery applications can involve the delivery of molecular cargo. Polyester BBPs can have varying hydrophilic / hydrophobic ratios and can exhibit various shape-changing behaviors depending on the type of solvent they are in. This allows for the entrapment of molecular cargo under appropriate conditions and subsequent site-specific activation and release.

[0227] Example

[0228] Non-limiting examples of the present invention will be described in further detail by referring to specific examples, but these examples should not be construed as limiting the scope of the present invention in any way.

[0229] Monoglycerol ethers (MGEs), which have an aliphatic chain attached to the glycerol backbone via an ether bond, can exist in the form of a diol and can have variable alkyl chain lengths. MGEs can be broadly divided into 1-O-monoglycerol ether (1-O-MGE) and 2-O-monoglycerol ether (2-O-MGE), depending on whether the alkyl chain is located at the Sn-1 or Sn-2 position. They can be synthesized by reacting commercially available alkyl bromides with acetone acetal and the Williamson ether of 2-phenyl-1,3-dioxan-5-ol, respectively, followed by an acidification step ( Figure 1 (b)), 1-O-MGE and 2-O-MGE were obtained.

[0230] In nature, hyperthermophilic archaea have membranes with enhanced thermal stability due to ether linkages compared to ester-linked membranes of non-thermophilic eukaryotes and bacteria. Although this may seem like a minor difference from a chemical perspective, replacing ester groups with ether groups on the pendant chains of BBPs has been shown to result in higher thermal stability compared to their fatty acyl counterparts.

[0231] In the present disclosure, a series of 1-O-MGE and 2-O-MGE diols ( Figure 1 (b)). These diols were combined with a series of commercially available diacids with different alkyl chain lengths (carbon number (n) = 7-16, 18 and 22), and a series of MGE-based BBPs with polyester backbones and pendant ether chains (sidechains) were synthesized ( Figure 1 (a) Figure 1 (c) Figure 1 (d) and Figure 1 (e)), these polyester backbones and pendant ether chains (branches) have different m and n values ​​and different ether positions (1 or 2) in the MGE, thus seeking the diversity of MGE-based BBPs with different polymer properties.

[0232] The synthesized MGE-based polyester backbone, BBP, was characterized, and its thermal, mechanical, and hydrolytic degradation properties were studied. BBPs typically have a molecular weight exceeding 10,000, a melting point between -20°C and 40°C, and a degradation temperature above 350°C, making them suitable lubricants for low-temperature applications. The polymer can be broken down into shorter chains under physiological conditions through macromolecular cleavage reactions, ultimately forming non-toxic byproducts.

[0233] The synthesized DGE-based polyester backbone BBP was characterized and its thermal properties were studied. The molecular weight of BBP is typically over 6000. DGE diols differ from MGE diols in that they have an additional glycerol moiety. The introduction of an additional glycerol moiety generally increases the hydrophilicity of DGE BBP polymers. DGE BBP polymers offer the synthetic advantage of dual tunability on their dialiphatic arms, according to which R 2 and R 3 Different glycidyl ethers and alkyl bromides can be linked. The polymer can be decomposed into shorter chains through macromolecular cleavage reactions under physiological conditions, ultimately forming non-toxic byproducts.

[0234] Hyperbranched polyethers (not polyesters) with ether-linked branches have been reported previously. However, there are no reports of synthesizing polyesters using 1-O-MGE and 2-O-MGE or other diglycerol ethers (DGE) as monomers.

[0235] Material

[0236] All chemicals used were either synthesized or commercially available. Silica gel column chromatography was performed using a 230–400 nm mesh from Merck (Rahway, NJ, USA); alkyl bromides (97%–99%, Sigma Aldrich (St. Louis, MN, USA)), glycidyl ethers (97%–99%, Sigma Aldrich (St. Louis, MN, USA)), C4 diacid succinic acid (99%, Sigma Aldrich (St. Louis, MN, USA)), C5 diacid glutaric acid (99%, Sigma Aldrich (St. Louis, MN, USA)), C6 diacid adipic acid (99%, Sigma Aldrich (St. Louis, MN, USA)), C7 diacid pimelic acid (98%, Sigma Aldrich (St. Louis, MN, USA)), C8 diacid suberic acid (98% Sigma Aldrich (St. Louis, MN, USA)), C9 diacid azelaic acid (98% Sigma Aldrich (St. Louis, MN, USA)) were used as the precipitants. Aldrich (St. Louis, Minnesota, USA), C 10 Diacid Sebacic acid (99%, Wilmar International (Singapore)), C 11Diacid undecanedioic acid (99% Sigma Aldrich (St. Louis, MN, USA)), C 12 Diacid dodecanedioic acid (99% Sigma Aldrich (St. Louis, MN, USA)), α,ω-diacid with 10-16 carbon atoms (99%, Wilmar International (Singapore)), high-density polyethylene (HDPE, Sinopec Qilu Petrochemical Co., Ltd. (Shandong, China)), poly(butylene adipate-co-terephthalate) (PBAT, Yifan Pharmaceutical Technology Co., Ltd. (Hangzhou, Zhejiang, China)), and chloroform (AR grade, Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China)) were used as received.

[0237] method

[0238] Characterization

[0239] 1 H NMR spectra were recorded on a JEOL ECA400 UltraShield 400 MHz instrument (Tokyo, Japan). CDCl3 was used as the solvent and tetramethylsilane was used as the internal reference. Chemical shifts (δ) are expressed in parts per million downfield from tetramethylsilane (TMS δ = 0.00 ppm). 13 C NMR was recorded on a JEOL ECA400 UltraShield 70 MHz spectrometer (Tokyo, Japan). CDCl3 was used as the solvent and tetramethylsilane was used as the internal reference. Chemical shifts (δ) are expressed in parts per million downfield from tetramethylsilane (TMS δ = 0.00 ppm).

[0240] GPC analysis was performed on a Shodex GPC-101 liquid chromatograph (Tokyo, Japan) equipped with a Shodex KD-806M mixed gel column (300×8.0 mm; particle size=10 μm) (THF). The eluent was THF at a flow rate of 0.6 mL / min (40° C.). Samples were analyzed using a Shodex differential refractometer RI-101. The column system was calibrated using poly(methyl methacrylate) and polystyrene standards.

[0241] Thermal analysis of the cocrystals was performed using a QSeries differential scanning calorimeter (DSC) Q50 and a thermogravimetric analyzer (TGA) Q500 (TA Instruments, New Castle, DE, USA). DSC analysis was performed using aluminum sample pans under flowing nitrogen at a flow rate of 50 mL / min. Samples were cooled to -80°C and then heated to 70-100°C (depending on the sample) at a heating rate of 10°C / min. TGA analysis was performed on platinum pans under flowing air at a flow rate of 60 mL / min at a heating rate of 10°C / min over a temperature range of 26-600°C.

[0242] Thermal transitions were recorded using a differential scanning calorimeter (DSC, Q200, TA Instruments, New Castle, DE, USA) under a nitrogen flow. Approximately 8-10 mg of sample was tested under a standard heating-cooling-heating cycle with a heating and cooling rate of 10°C / min.

[0243] Thermogravimetric (TG) measurements were performed by a thermal analyzer (TGA, Q500, TA Instrument (New Castle, DE, USA)) from 30°C to 550°C under a nitrogen environment with a heating rate of 10°C / min.

[0244] Synthesis of 1-O-MGE

[0245] like Figure 2 As shown in (a), NaH (60% dispersion in mineral oil, 3.02 g, 0.0756 mol) (2 equivalents) is added to a stirred solution of acetone acetal (1a, 5 g, 0.0378 mol) (1 equivalent) in anhydrous toluene at 0°C and the reaction is allowed to proceed for 30 minutes. Alkyl bromide (0.0378 mol) (1 equivalent) is added dropwise to the reaction mixture. The reaction mass is stirred at reflux for 6-20 hours. The reaction is monitored using gas chromatography mass spectrometry (GCMS) until the consumption of acetone acetal is observed. After completion of the reaction, the reaction mixture is quenched with saturated ammonium chloride solution, the toluene is removed in vacuo, the crude reaction mass is extracted with ethyl acetate (2 x 20 ml), and washed with deionized water (1 x 20 ml). The organic layer is removed in vacuo, and the resulting intermediate (2a) is acidified to form (3a). Typically, for C3, C8, C9 1-O-MGE, purification is performed by flash column chromatography, while for C 10 -C 14 、C 16 and C 18 1-O-MGE is purified by vacuum distillation or recrystallization. The typical yield is 60-80 mol%.

[0246] Synthesis of 2-O-MGE

[0247] like Figure 2 As shown in (b), NaH (60% dispersion in mineral oil, 2.22 g, 0.0556 mol (2 equivalents)) was added to a stirred solution of 2-phenyl-1,3-dioxane-5-ol (1b, 5 g, 0.0278 mol) (1 equivalent) in anhydrous toluene at 0 ° C. The reaction was allowed to proceed for 30 minutes. Alkyl bromide (0.0278 mol) (1 equivalent) was added dropwise to the reaction mixture. The reaction mass was stirred at reflux for 6-20 hours. The reaction was monitored using gas chromatography mass spectrometry (GCMS) until the consumption of 2-phenyl-1,3-dioxane-5-ol was observed. After completion of the reaction, the reaction mixture was quenched with saturated ammonium chloride solution, toluene was removed in vacuo, the crude reaction mass was extracted with ethyl acetate (2 x 20 ml), and washed with deionized water (1 x 20 ml). The organic layer was removed in vacuo, and the resulting intermediate (2b) was acidified to form (3b). Typically, C3, C8, and C9 2-O-MGE were purified by flash column chromatography, whereas C 10 -C 14 、C 16 and C 18 2-O-MGE is purified by vacuum distillation or recrystallization. Typical yields are 60 to 80 mol%.

[0248] Synthesis of 1-O-MGE BBP

[0249] Tin powder (catalyst) (0.1 eq) was added to a mixture of 1-O-MGE diol (1 eq) and diacid (1 eq). The reaction mixture was heated at 180°C for 24 h with magnetic stirring. The monomers melted at the study temperature of 180°C and the polymerization was a melt polycondensation. The tin powder (diameter of about 150 μm) was not completely dissolved in the reaction mixture and the surface of the powder particles catalyzed the esterification (polymerization). The reactor was not capped with a water stopcock and the water generated during the polymerization evaporated from the reaction mixture at the polymerization temperature of 180°C, causing the equilibrium of the esterification to shift from the reactants (alcohol and carboxylic acid) to the products (esters). By using 1 H NMR, the extent of the reaction was determined by the consumption of CH protons of the glycerol backbone. n and The values ​​are PMMA-calibrated gel permeation chromatography (GPC) values, where PMMA is poly(methyl methacrylate). n Values ​​and molecular weight calculations of diols and diacids. M n The values ​​are not absolute values ​​but PMMA calibration values, so the DP values ​​are considered as estimates. For 1-O-MGE, a relatively high molecular weight (M n >10,000) of the polymer, and the degree of reaction was relatively high (>90%).

[0250] Synthesis of 2-O-MGE BBP

[0251] To a mixture of 2-O-MGE diol (1 eq) and diacid (1 eq) was added tin powder (catalyst) (0.1 eq). The reaction mixture was heated at 180°C for 24 h with magnetic stirring. The monomers melted at the study temperature of 180°C and the polymerization was a melt polycondensation. The tin powder (approximately 150 μm in diameter) was not completely dissolved in the reaction mixture and the surface of the powder particles catalyzed the esterification (polymerization). The reactor was not capped with a water stopcock and the water generated during the polymerization evaporated from the reaction mixture at the polymerization temperature of 180°C, causing the equilibrium of the esterification to shift from the reactants (alcohol and carboxylic acid) to the products (esters). By using 1 H NMR, the extent of the reaction was determined based on the consumption of CH groups in the glycerol backbone. n and The values ​​are PMMA-calibrated gel permeation chromatography (GPC) values, where PMMA is poly(methyl methacrylate). n Values ​​and molecular weight calculations of diols and diacids. M n The values ​​are not absolute values ​​but PMMA calibrated values, so the DP values ​​are considered estimates. For 2-O-MGE, a polymer with a relatively high molecular weight (Mn>15,000) and a relatively high degree of reaction (>95%) was obtained after 6 hours of stirring.

[0252] Synthesis of 1,2-O-DGE 1',2'-diol

[0253] like Figure 2As shown in (c), NaH (60% dispersion in mineral oil, 3.02 g, 0.0756 mol (2 equivalents)) was added to a stirred solution of acetone glycerol (1a, 5 g, 0.0378 mol) (1 equivalent) in anhydrous toluene at 0°C and reacted for 30 minutes. Glycidyl ether (0.0378 mol) (1 equivalent) was added dropwise to the reaction mixture. The reaction mass was stirred at reflux for 20 hours. The reaction was monitored using gas chromatography mass spectrometry (GCMS) until the consumption of acetone glycerol or glycidyl ether was observed. After completion of the reaction, the reaction mixture was quenched with saturated ammonium chloride solution, the toluene was removed in vacuo, the crude reaction mass was extracted with ethyl acetate (2 x 20 ml), and washed with deionized water (1 x 20 ml). The organic layer was removed in vacuo, and the resulting intermediate (4a) was obtained. Typically, purification can be performed by flash column chromatography at this stage to prevent the appearance of complex mixtures in subsequent steps. Intermediate 4a is reconstructed in anhydrous toluene and NaH (60% dispersion in mineral oil, 3.02g, 0.0756mol (about 2 equivalents)) is added. The mixture is stirred for 30 minutes. Alkylated bromide (0.0378mol) (1 equivalent) is added dropwise to the reaction mixture. The reaction mass is stirred under reflux for 20 hours. The reaction is monitored using gas chromatography-mass spectrometry (GCMS) until the consumption of intermediate 4a is observed. Typically, 1,2-O-DEG-1', 2' diol is obtained by purification by flash column chromatography.

[0254] Synthesis of 1,2-O-DGE 1',3'-diol

[0255] like Figure 2As shown in (d), NaH (60% dispersion in mineral oil, 2.22 g, 0.0556 mol (2 equivalents)) was added to a stirred solution of 2-phenyl-1,3-dioxane-5-ol (1b, 5 g, 0.0278 mol) (1 equivalent) in anhydrous toluene at 0 ° C. The reaction was allowed to proceed for 30 minutes. Glycidyl ether (0.0278 mol) (1 equivalent) was added dropwise to the reaction mixture. The reaction mass was stirred at reflux for 72 hours. The reaction was monitored using gas chromatography-mass spectrometry (GCMS) until the consumption of 2-phenyl-1,3-dioxane-5-ol or glycidyl ether was observed. After completion of the reaction, the reaction mixture was quenched with saturated ammonium chloride solution, toluene was removed in vacuo, the crude reaction mass was extracted with ethyl acetate (2 x 20 ml), and washed with deionized water (1 x 20 ml). The organic layer was removed in vacuo, and the resulting intermediate (4b) was obtained. Typically, at this stage, purification can be performed by flash column chromatography to prevent the appearance of complex mixtures in subsequent steps. Intermediate 4b is reconstructed in anhydrous toluene and NaH (60% dispersion in mineral oil, 2.22 g, 0.0556 mol (about 2 equivalents)) is added. The mixture is stirred for 30 min. Alkylated bromide (0.0378 mol) (1 equivalent) is added dropwise to the reaction mixture. The reaction mass is stirred at reflux for 20 hours. The reaction is monitored using gas chromatography mass spectrometry (GCMS) until the consumption of intermediate 4b is observed. Typically, purification is performed by flash column chromatography to obtain 1,2-O-DEG-1', 3' diol.

[0256] Synthesis of 1,3-O-DGE 1',2'-diol

[0257] like Figure 2As shown in (e), at 0 ° C, NaH (60% dispersion in mineral oil, 3.02g, 0.0756mol (2 equivalents)) was added to a stirred solution of aliphatic alcohol (0.0378mol) (1 equivalent) in anhydrous toluene and reacted for 30 minutes. Epichlorohydrin (0.0189mol) (0.5 equivalents) was added dropwise to the reaction mixture. The reaction mass was stirred under reflux for 6-20 hours. The reaction was monitored using gas chromatography mass spectrometry (GCMS) until the consumption of the aliphatic alcohol was observed. After the reaction was completed, the reaction mixture was quenched with saturated ammonium chloride solution, toluene was removed in vacuo, the crude reaction mass was extracted with ethyl acetate (2x 20ml), and washed with deionized water (1x 20ml). The organic layer was removed in vacuo to obtain the intermediate (4c). NaH (60% dispersion in mineral oil, 3.02g, 0.0756mol (about 2 equivalents)) was added to the intermediate 4c obtained and reacted for 30 minutes. 3-chloropropane-1,2-diol (0.0378 mol) (1 equivalent) was added dropwise to the reaction mixture. The reaction mixture was stirred at reflux for 6-20 hours. The reaction was monitored using gas chromatography-mass spectrometry (GCMS) until the consumption of intermediate 4c was observed. Typically, 1,3-O-DEG-1', 2' diol was obtained by flash column chromatography.

[0258] Synthesis of 1,2-O-DGE 1',2'BBP, 1,2-O-DGE 1',3'BBP, 1,3-O-DGE 1',2'BBP

[0259] Tin powder (catalyst) (0.1 eq) was added to a mixture of DGE diol (1 eq) and diacid (1 eq). The reaction mixture was heated at 180°C for 24 h under magnetic stirring. The monomers melted at the study temperature of 180°C and polymerized by melt polycondensation. The tin powder (approximately 150 μm in diameter) was not completely dissolved in the reaction mixture and the surface of the powder particles catalyzed the esterification (polymerization). The reactor was not capped with a water stopcock and the water generated during the polymerization evaporated from the reaction mixture at the polymerization temperature of 180°C, causing the equilibrium of the esterification to shift from the reactants (alcohol and carboxylic acid) to the product (ester). Use 1 H NMR, the extent of the reaction was determined based on the consumption of CH groups in the DGE unit. n and The values ​​are PMMA-calibrated gel permeation chromatography (GPC) values, where PMMA is poly(methyl methacrylate). DP values ​​are based on the M n The molecular weight of diols and diacids is calculated. nThe values ​​are not absolute values ​​but PMMA calibration values, so the DP values ​​are considered as estimates. For 1,2-O-DEG 1',2'BBP, 1,2-O-DEG1',3'BBP, and 1,3-O-DEG 1',2'BBP, M was obtained after stirring for 24 hours. n Typical molecular weights are >6,000, and the degree of reaction is relatively moderate (>80%).

[0260] Example 1: Synthesis of Monomers

[0261] 1-O-MGE diol monomer and 2-O-MGE diol monomer

[0262] Ten 1-O-MGE diol monomers and ten 2-O-MGE diol monomers with different alkyl chain lengths (m = 3, 8-14, 16, and 18) were synthesized ( Figure 2 1-O-MGE and 2-O-MGE were synthesized in anhydrous toluene (30 mL) using NaH (60% dispersion in mineral oil, 2 equivalents) via commercially available acetone acetal and Williamson ether of 2-phenyl-1,3-dioxan-5-ol (1 equivalent). After stirring at 0°C for 30 minutes, alkyl bromides (R = C3, C8-C 14 、C 16 and C 18 The reaction was monitored by gas chromatography mass spectrometry (GCMS), and the reaction conversion was generally 70-80%. After quenching the reaction with saturated ammonium chloride solution, the intermediate 2a or 2b ( Figure 2 ) was extracted twice with ethyl acetate, combined, and concentrated to dryness. Subsequent acid-catalyzed hydrolysis (3:1 1 M HCl / EtOH solution) yielded the desired compound 1-O-MGE (3a) or 2-O-MGE (3b) ( Figure 2 ), by flash column chromatography (short alkyl chain, R = C3, C8-C9) or recrystallization (medium alkyl chain, R = C 10-14 、C 16 and C 18 ) Purified compounds. Some examples of synthetic monomers are Figure 3 R1 and R2 independently represent C3, C 8-14 、C 16 or C 18 alkyl.

[0263] 1,2-O-DGE 1',2'diol monomer and 1,2-O-DGE 1',3'diol monomer

[0264] 1,2-O-DGE 1',2'diol monomers and 1,2-O-DEG 1',3'diol monomers were synthesized, and their alkyl chain lengths (m = 4) were as follows. Figure 2 (c) and Figure 2 (d) As shown. In anhydrous toluene (30 mL), NaH (60% dispersion in mineral oil, 2 equivalents) was used to synthesize 1,2-O-DGE 1',2' diol and 1,2-O-DEG 1',3' diol monomers from commercially available starting materials acetone glycerol acetal and Williamson ether of 2-phenyl-1,3-dioxane-5-ol (1 equivalent), respectively. After stirring at 0°C for 30 minutes, glycidyl ether (R=C4) in anhydrous toluene (1 mL) was added dropwise. The reaction was monitored using gas chromatography mass spectrometry (GCMS), and the reaction conversion was typically 70-80%. After quenching the reaction with saturated ammonium chloride solution, the mixture containing intermediate 4a ( Figure 2 (c)) or 4b( Figure 2 (d)) The resulting mixture was extracted twice with ethyl acetate, combined, and concentrated to dryness. Typically, purification is performed by flash column chromatography at this stage to prevent the appearance of complex mixtures in subsequent steps. Intermediates 4a and 4b are reconstituted in anhydrous toluene, followed by the addition of NaH (60% (about 2 equivalents)). After stirring at 0°C for 30 minutes, alkyl bromide (R=C4) (1 mL) in anhydrous toluene is added dropwise. The reaction is monitored using gas chromatography-mass spectrometry (GCMS), and the reaction conversion is typically 70%. After quenching the reaction with saturated ammonium chloride solution, the resulting mixture is extracted twice with ethyl acetate, combined, and concentrated to dryness. Subsequent acid-catalyzed hydrolysis (3:1 1M HCl / EtOH solution) produces the desired compound 1,2-O-DGE-1', 2' diol or 1,2-O-DEG-1', 3' diol, which is purified by flash column chromatography.

[0265] Synthesis of 1,3-O-DEG 1',2'diol Monomer

[0266] An example of a 1,3-O-DEG 1',2' diol monomer was synthesized using NaH (60% dispersion in mineral oil, 2 eq) in anhydrous toluene (30 mL) via Williamson ether synthesis of a commercially available aliphatic alcohol (1 eq). After stirring at 0°C for 30 min, epichlorohydrin (0.5 eq) in anhydrous toluene (1 mL) was added dropwise. The reaction was monitored using gas chromatography mass spectrometry (GCMS) with reaction conversions typically >85%. After quenching the reaction with saturated ammonium chloride solution, the mixture containing intermediate 4c ( Figure 2e) The resulting mixture was extracted twice with ethyl acetate, combined, and concentrated to dryness. Typically, purification can be performed by flash column chromatography at this stage to prevent the appearance of complex mixtures in subsequent steps. Intermediate 4c was reconstructed in anhydrous toluene and NaH (60% (about 2 equivalents)) was added. After stirring at 0°C for 30 minutes, 3-chloropropane-1,2-diol (1 mL) in anhydrous toluene was added dropwise. The reaction was monitored using gas chromatography-mass spectrometry (GCMS), and the reaction conversion was typically 60%. After quenching the reaction with saturated ammonium chloride solution, the resulting mixture was extracted twice with ethyl acetate, combined, and concentrated to dryness, and purified by flash column chromatography to obtain 1,3-O-DEG-1',2'diol monomer.

[0267] Example 2: Synthesis of polymer

[0268] like Figure 4 As shown, 30 BBPs were synthesized using a series of 1-O-MGE and 2-O-MGE, where m = 3, 8-14, 16 and 18 (all integers), and a series of diacids, where n = 4-14, 18 and 22 (all integers). Figure 4 As shown in (a), a mixture of MGE diol (1 equivalent), diacid (1 equivalent), diphenyl ether (DPE, 30% wt), and tin powder (catalyst) (0.1 equivalent) was heated at 180°C for 24 hours with magnetic stirring. The monomers melt at the study temperature of 180°C, and the polymerization is a melt polycondensation. The tin powder (approximately 150 μm in diameter) does not completely dissolve in the reaction mixture, and the surface of the powder particles catalyzes esterification (polymerization). The reactor is not capped with a water stopcock, and the water produced during the polymerization evaporates from the reaction mixture at the polymerization temperature of 180°C, shifting the esterification equilibrium from the reactants (alcohol and carboxylic acid) to the products (ester).

[0269] Figure 4 (b) shows how some BBPs are synthesized from diglycerol ether (DGE). Figure 1 a'.

[0270] Some examples of synthetic BBP polymers include Figure 5 R, R1 and R2 independently represent C3, C 8-14 、C 16 or C 18 alkyl.

[0271] like Figure 4 As shown in (b), a series of 1,2-O-DGE 1',2'diol monomers and 1,2-O DGE 1',3'diol monomers, wherein m=4 (all integers), and diacids, wherein n=10 (all integers), were used to synthesize DGE BBP. Figure 4As shown in (b), a mixture of DGE diol (1 equivalent), diacid (1 equivalent), diphenyl ether (DPE, 30% wt), and tin powder (catalyst) (0.1 equivalent) was heated at 180°C for 24 hours with magnetic stirring. The monomers melt at the study temperature of 180°C, and the polymerization is a melt polycondensation. The tin powder (approximately 150 μm in diameter) does not completely dissolve in the reaction mixture, and the surface of the powder particles catalyzes esterification (polymerization). The reactor is not capped with a water stopcock, and the water generated during the polymerization evaporates from the reaction mixture at the polymerization temperature of 180°C, shifting the esterification equilibrium from the reactants (alcohol and carboxylic acid) to the products (esters).

[0272] Table 1 shows the polymerization results of 30 representative BBPs prepared from 1-O-MGE.

[0273]

[0274] For example, the polymerization of 1-O-MGE with m=9 and diacid with n=10 (Table 1 (entry 1)) reached 95% reaction degree after 24 hours (using 1 H NMR, consumption of CH protons of the glycerol backbone), and generation of M n =12000(DP=29) and (=M w / M n ) = 1.16 (after purification by precipitation in ethanol) of BBP, where M n and M n are the number average molecular weight and weight average molecular weight respectively. DP is the degree of polymerization, is the dispersion. The degree of reaction (p) is expressed as 1 H NMR is determined based on the consumption of CH protons in the glycerol backbone. n and The values ​​are PMMA-calibrated gel permeation chromatography (GPC) values, where PMMA is poly(methyl methacrylate). The DP values ​​are based on the M n Values ​​and molecular weight calculations of diols and diacids. M n The values ​​are not absolute values ​​but PMMA calibration values, so the DP values ​​are considered as estimates. Therefore, a polymer with a relatively high molecular weight (M n =12000 (DP=29)), while the degree of reaction was relatively high (95%).

[0275] Figure 6Table 1 (entries 1-6) shows the polymerization results of 1-O-MGE diol (m is a constant value of 9-14) in combination with a diacid (n is a constant value of 10). Table 1 (entries 7-12) shows the polymerization results of 1-O-MGE diol (m is a constant value of 12) in combination with a diacid (n is a constant value of 7-12). Table 1 (entries 13-18) shows the results of 1-O-MGE diol (m is a constant value of 18) in combination with a diacid (n is a constant value of 7-12).

[0276] A different MGE, 2-O-MGE, was also investigated instead of 1-O-MGE. Table 1 (entries 19-24) shows the results of combining 2-O-MGE diol (m is a constant value of 18) with diacids (n is different values ​​from 7 to 12). Due to the structural differences between 2-O-MGE and 1-O-MGE, in most cases (n = 7-12), the M of 2-O-MGE (m = 18) is higher than that of 1-O-MGE. n 10,000 after 6 hours, while in all cases studied (n=7-12), the M of 1-O-MGE (m=18) n It took 24 hours to reach 10,000. This may be due to the increased reactivity of 2-O-MGE with two primary alcohols compared to 1-O-MGE with a primary alcohol and a secondary alcohol.

[0277] Figure 7 Some of the synthesized monomers and their respective BBPs are shown 1 H NMR spectroscopy.

[0278] Figure 7 (a) shows the mixture of 1-O-MGE (m=18) diol and diacid (n=9) before polymerization (top spectrum) and after polymerization (bottom spectrum). 1H NMR spectrum. The CH protons (proton c) and CH2 protons adjacent to the OH group (proton b) in 1-O-MGE appear at 3.89-3.84 ppm and 3.74 ppm, respectively. The CH2 protons adjacent to the COOH group in the diacid (proton j) appear at 2.37 ppm. After polymerization, these peaks for the polymer backbone shift to 5.22-5.17 ppm (CH2 protons (proton c')), 4.33-4.16 ppm (CH2 protons adjacent to the -OC(=O) bond (proton b')), and 2.31-2.38 ppm (CH2 protons adjacent to the -(C=O)O bond (proton j')). The p-value was determined based on the attenuation of the monomer peak (peak at 3.89-3.84 ppm) and the increase in the polymer peak (the sum of the integrated ratios of the peaks at 5.22-5.17 ppm, 5.01-4.99 ppm, and 4.02-3.98 ppm). At the same time, the peaks b' (CH), c' (HOCH2CH), and f' (CH2COO), corresponding to the protons in the polymer converted from the monomer, reappeared at 5.17 ppm, 4.11-4.3 ppm4, and 2.31-2.38 ppm, respectively, confirming the formation of the polymer.

[0279] Figure 7 (b) shows the mixture of 2-O-MGE (m=18) diol and diacid (n=9) before polymerization (top spectrum) and after polymerization (bottom spectrum). 1 H NMR spectrum: CH protons (proton c) in 2-O-MGE appear at 3.49-3.44 ppm. Figure 7 (b) shows the spectral distribution of a mixture of 2-O-MGE (m=18) diol and diacid (n=9) before (top spectrum) and after (bottom spectrum) polymerization. 1 H NMR spectroscopy. After polymerization, the peaks of CH protons (proton c) at 3.49-3.44 ppm and CH protons (proton b) adjacent to OH in 2-O-MGE, as well as the peak of CH protons (proton h) adjacent to COOH in the diacid at 2.37-2.33 ppm, shifted to 3.70-3.65 ppm (CH protons (proton c')), 4.20-4.09 ppm (CH protons (proton b') adjacent to -OC(=O) bonds), and 2.34-2.30 ppm (CH protons (proton h') adjacent to -(C=O)O bonds) for the polymer backbone, confirming polymer formation. The p-value was determined based on the attenuation of the monomer peak (peak at 3.49-3.44 ppm) and the increase in the polymer peak (3.79-3.66 ppm).

[0280] Figure 7(c) shows the mixture of 1-O-MAG (m=18) diol and diacid (n=9) before polymerization (top spectrum) and after polymerization (bottom spectrum). 1 H NMR spectrum, where MAG stands for monoacylglycerol. The CH protons (proton c) and CH2 protons adjacent to the OH group (proton b) in 1-O-MGE appear at 3.94-3.89 ppm, 3.79-3.66, and 3.64 ppm, respectively. The CH2 protons adjacent to the COOH group in the diacid (proton j) appear at 2.37 ppm. After polymerization, these peaks of the polymer backbone shift to 5.28-5.24 ppm (CH2 protons (proton c')), 4.31-4.08 ppm (CH2 protons adjacent to the -OC(=O) bond (proton b')), and 2.36-2.29 ppm (CH2 protons adjacent to the -(C=O)O bond (proton j')), confirming polymer formation. The p-value was determined based on the attenuation of the monomer peak (peak at 3.94-3.89 ppm) and the increase in the polymer peak (5.28-5.24 ppm).

[0281] Figure 7 (d) shows the formation of 2-ethylhexyl 1-O-MGE diol from 2-(((2-ethylhexyl)oxy)methyl)oxirane. This is a representative example of the formation of a BBP with branched alkyl side chains. This BBP can be formed in a one-pot synthesis from the glycidyl ether 2-(((2-ethylhexyl)oxy)methyl)oxirane.

[0282] Figure 7 (e) shows Figure 7 (d) Amplification 1 H NMR spectra show the conversion of 2-ethylhexyl glycidyl ether (bottom spectrum) to 2-ethylhexyl 1-O-MGE diol (middle spectrum) and then to 2-ethylhexyl 1-O-MGE BBP (top spectrum, n=9). The CH protons in the 2-ethylhexyl glycidyl group (proton c, bottom spectrum) appear at 3.14-3.10 ppm. After hot water-promoted epoxy ring opening, the CH protons (proton c, middle spectrum) appear at 3.89-3.84 ppm, indicating the formation of 2-ethylhexyl 1-O-MGE. Upon application of polymerization conditions, the CH protons shift to 5.22-5.17 ppm (proton c', top spectrum), indicating successful polymerization.

[0283] Figure 7 (f) shows the mixture of 1-O-MGE (m=18) diol and diacid (n=9) monitored from 1 hour to 24 hours. 1 H NMR spectra. The enlarged spectrum from 6.0 ppm to 3.0 ppm shows the 1-O-MGE BBP before and after polymerization. 1Comparison of H' NMR Spectra This example demonstrates the successful formation of BBP with saturated side chains.

[0284] Figure 7 (g) shows the 1H NMR spectrum of a mixture of 1-O-MGE (m=18, with cis double bonds) diol and diacid (n=9) monitored from 1 hour to 24 hours. The zoomed spectrum from 6.0 ppm to 3.0 ppm shows the 1-O-MGE BBP before and after polymerization. 1 Comparison of H' NMR spectra. Double bond signal is shown at 5.3 ppm. This example demonstrates the successful formation of BBP with unsaturated side chains.

[0285] Figure 7 (h) shows the mixture of 1-O-MGE (m=18) diol and diacid (n=9) before polymerization (top spectrum) and after polymerization (bottom spectrum). 1 H NMR spectrum. The CH protons (proton c) and CH protons adjacent to the OH group (proton b) in 1-O-MGE appear at 3.89-3.84 ppm and 3.74 ppm, respectively. The CH protons (proton j) adjacent to the COOH group in the diacid appear at 2.37 ppm. After polymerization, these peaks for the polymer backbone shift to 5.22-5.17 ppm (CH protons (proton c')), 4.33-4.16 ppm (CH protons adjacent to the -O-C(=O) bond (proton b')), and 2.31-2.38 ppm (CH protons adjacent to the -(C=O)O bond (proton j')). The p-value was determined based on the attenuation of the monomer peak (peak at 3.89-3.84 ppm) and the increase in the polymer peak (sum of the integrated ratios of the peaks at 5.22-5.17 ppm, 5.01-4.99 ppm, and 4.02-3.98 ppm). Simultaneously, the b' (CH), c' (HOCH2CH), and f' (CH2COO) peaks of the corresponding protons in the polymer converted from the monomer reappeared at 5.17 ppm, 4.11-4.34 ppm, and 2.31-2.38 ppm, respectively, confirming polymer formation. The enlarged spectrum shows a comparison of the H' NMR spectra of 1-O-MGE BBP before and after polymerization. This example demonstrates the successful one-pot synthesis of a BBP with branched side chains from 2-(((2-ethylhexyl)oxy)methyl)oxirane.

[0286] Figure 7 (i) shows the mixture of 1,2-O-DGE 1',2' diol (m = 4) and diacid (n = 10) before polymerization (top spectrum) and after polymerization (bottom spectrum). 1H NMR spectrum. The CH protons (proton c) in 1,2-O-DGE 1',2' appear at 3.87-3.84 ppm. The CH2 protons (proton l) adjacent to the COOH group in the diacid appear at 2.36-2.32 ppm. After polymerization, these peaks of the polymer backbone shift to 5.21 ppm (CH2 protons (proton c')) and 2.34-2.28 ppm (CH2 protons adjacent to the -(C=O)O bond (proton j')). The p-value was determined based on the attenuation of the monomer peak (peak at 3.87-3.84 ppm) and the increase in the polymer peak (sum of the integrated ratios of the peak at 5.21 ppm). This example demonstrates the successful implementation of a DGE BBP.

[0287] Figure 7 (j) shows the mixture of 1,2-O-DGE 1',3' diol (m = 4) and diacid (n = 10) before polymerization (top spectrum) and after polymerization (bottom spectrum). 1 H NMR spectrum. The CH protons (proton c) in the 1,2-O-DGE 1',3' diol appear at 3.82-3.44 ppm, overlapping with other glycerol protons. The CH2 protons (proton k) adjacent to the COOH group in the diacid appear at 2.35-2.32 ppm. After polymerization, the CH peak becomes discernible, shifting to 3.79-3.75 ppm (CH2 protons (proton c')), while the CH2 protons (proton k') adjacent to the -(C=O)O bond become distinct at 2.34-2.30 ppm. Furthermore, the c' (CH2) and k' (CH2COO) peaks of the corresponding protons in the polymer derived from the monomer confirm polymer formation. This example demonstrates the successful implementation of DGE BBP.

[0288] Example 3: Melting Temperature

[0289] The melting temperature (T m )( Figure 8 、 Figure 9 and Table 2 ).

[0290] Figure 8 The effect of varying the alkyl chain length of the diol on T m In the case of n being a fixed value of 10 (the length of the main chain alkyl chain derived from the diacid), as the value of m (the length of the branched alkyl chain) increases from 9 to 14, T m The value also increases ( Figure 8 A difference of 94.7°C was observed between m = 0 (linear polyester) and m = 9 (bottlebrush polyester).

[0291] Table 2. Thermal properties of BBP.

[0292]

[0293]

[0294] a. Esterification conditions: diol / diacid 1:1 mol / mol, tin powder (based on diol, 10 mol%), temperature / time (T / t): 180°C / 6-24 hours

[0295] b. Melting temperature (second scan) The entries in Table 2 correspond to the entries in Table 1.

[0296] Interestingly, it was observed that the values ​​of m and n had no significant effect on T m The "odd" effect of the value ( Figure 8 ). “Odd-even” (odd m and even n) T of polyester m The value is lower than the T value of the adjacent "even-even" (even m and even n) polyester m value. Figure 8 Examples of polyesters formed when m = 9 and 11 are shown, where T m The values ​​are -21.7℃ and -15.9℃, respectively, which are lower than the -9.0℃ T of m=10 polyester. m Previous reports have only demonstrated the “odd-even” effect caused by changes in the polyester backbone, while reports on the “odd-even” effect caused by the pendant chains of bottlebrush polymers have never been reported before.

[0297] Figure 9 (a) shows that the melting temperature of the linear polymer is very high compared to BBP, indicating that the side chains of BBP disrupt the chain stacking, resulting in a lower melting point. Comparison of ethylene glycol and 1-O-MGE (when m = 12) shows an average decrease of about 50°C for n = 7-12. Figure 9 (a) also shows that the melting point of the polymer tends to increase with increasing length of the side alkyl chain.

[0298] For the sake of completeness, Figure 9 (b) shows the T of 2-O-MGE BBP when m = 3 and n = 4-12 m This represents the case where the alkyl side chain is shorter (m=3), where the odd-even effect is the dominant factor in the T of BBP. m It is still common in China. Figure 9 (c) shows the T of 1-O-MGE BBPs with m = 16 and n = 4-14, 18, and 22 m , indicating that when n value changes from 4-14 and m=16, T m In addition, when m = 16 and n = 4, 18 or 22, BBP can be an ideal candidate material for automotive grease.

[0299] In general, polyesters derived from dicarboxylic acids containing an even number of carbon atoms have higher melting temperatures than polyesters derived from diacids containing an odd number of carbon atoms. This observation is attributed to the fact that the crystalline phase of aliphatic polyesters with an even number of carbon atoms between the ester groups contains tight dipole layers with opposite orientations (effectively canceling out local polarization), while the crystals of polyesters derived from dicarboxylic acids with an odd number of carbon atoms have tight carbonyl groups with the same orientation ( Figure 10 Since the local polarization of the stacked polyester chains is offset, greater hydrophobic interactions are generated between the aliphatic segments, resulting in a higher T m .

[0300] Figure 11 The T values ​​of BBPs prepared from 1-O-MGE BBP (circles) and 1-O-MAG BBP (squares) (m=18 and n=7-12) are shown. m The curve shows that when the n value is low (n<7), the T m It is usually lower than that of 1-O-MAG BBP. However, when n is higher (usually n>7), the T of 1-O-MGE BBP is m This indicates that MGEs and α- and ω-diacids with different alkyl chain lengths can produce BBPs with different thermomechanical properties and viscoelasticity.

[0301] Figure 12 is a graph showing how the position of the ether bond affects the melting point, and is the T of BBP prepared from 1-O-MGE BBP (circles) and 2-O-MGE BBP (squares) (m=18 and n=7-12). m The curve shows that the T of 1-O-MGE BBP is m The 2-carbon diol backbone of 1-O-MGE BBP is more rigid than the 3-carbon diol backbone of 2-O-MGE BBP, so its T m higher.

[0302] Figure 13 The T values ​​of 1-O-MGE BBP prepared from 1-O-MGE diol (m=16) and various diacids (n=4) are shown. m Graph of T of C16 diol succinate (squares) m The highest is 42.7 ° C. The introduction of double bonds in the C16 diol fumaric acid (circular) chain will lead to T m The lower one is 34.2℃; the introduction of double bond outside the C16 diol fumaric acid (circular) chain will result in T m Even lower, at 27.7 °C. This shows that the introduction of double bonds in the main chain usually leads to a m reduce.

[0303] Example 4: Decomposition Temperature

[0304] Table 3 shows the 5%-decomposition temperatures (T) of 1-O-MGE BBPs with m=9-14 and n=10 determined by thermogravimetric analysis (TGA). d,5 ) and 50%-decomposition temperature (T d,50 ). In general, the T of all studied BBPs d,50 The values ​​are all above 350℃. This group of data does not show that T d,5 and T d,50 Significant changes related to the m-value of 1-O-MGE.

[0305] Table 3. Thermal degradation properties of 1-O-MGE BBP with m = 9-14 and n = 10

[0306] <![CDATA[Entry a > MGE (diol) m / n of polymer Mn <![CDATA[T d,5 b (℃)]]> <![CDATA[T d,50 c (℃)]]> 1 1-O-MGE 9 / 10 12000 327 378 2 1-O-MGE 10 / 10 15000 333 380 3 1-O-MGE 11 / 10 13000 295 378 4 1-O-MGE 12 / 10 10000 324 375 5 1-O-MGE 13 / 10 12000 324 380 6 1-O-MGE 14 / 10 11000 329 381

[0307] a. Esterification conditions: diol / diacid 1:1 mol / mol, tin powder (based on diol, 10 mol%), temperature / time (T / t): 180°C / 18-24 hours

[0308] bT d,5 is the temperature at which the sample loses 5% of its weight.

[0309] cT d,50 is the temperature at which the sample loses 50% of its weight.

[0310] Figure 14 The percentage weight loss of 1-O-MGE BBP with m = 9-14 and n = 10 with respect to temperature is shown in (a) and Table 4. The results show that changing the alkyl chain length of the BBP side chain has no significant effect on the decomposition temperature of the polymer.

[0311] Figure 14 (b) and Table 5 show the percent weight loss versus temperature for 1-O-MGE BBP with m = 18 and n = 7-11. The results indicate that varying the alkyl chain length of the BBP diacid backbone generally does not significantly affect the decomposition temperature of the polymer.

[0312] Table 4. Thermal degradation properties of 1-O-MGE BBP with m = 9-14 and n = 10

[0313] <![CDATA[Entry a > MGE (diol) m / n of polymer Mn <![CDATA[T d,5 b (℃)]]> <![CDATA[T d,50 c (℃)]]> 1 1-O-MGE 9 / 10 12000 327 378 2 1-O-MGE 10 / 10 15000 333 380 3 1-O-MGE 11 / 10 13000 295 378 4 1-O-MGE 12 / 10 10000 324 375 5 1-O-MGE 13 / 10 12000 324 380 6 1-O-MGE 14 / 10 11000 329 381

[0314] a. Esterification conditions: diol / diacid 1:1 mol / mol, tin powder (based on diol, 10 mol%), temperature / time (T / t): 180°C / 18-24 hours

[0315] bT d,5 is the temperature at which the sample loses 5% of its weight.

[0316] cT d,50 is the temperature at which the sample loses 50% of its weight.

[0317] Table 5. Thermal degradation properties of 1-O-MGE BBP with m = 18 and n = 7-11

[0318] <![CDATA[Entry a > MGE (diol) m / n of polymer Mn <![CDATA[T d,5 b (℃)]]> <![CDATA[T d,50 c (℃)]]> 1 1-O-MGE 18 / 7 12000 307 376 2 1-O-MGE 18 / 8 15000 313 387 3 1-O-MGE 18 / 9 17000 313 385 4 1-O-MGE 18 / 10 12000 333 380 5 1-O-MGE 18 / 11 15000 266 386

[0319] a. Esterification conditions: diol / diacid 1:1 mol / mol, tin powder (based on diol, 10 mol%), temperature / time (T / t): 180°C / 18-24 hours

[0320] bT d,5 is the temperature at which the sample loses 5% of its weight.

[0321] cT d,50 is the temperature at which the sample loses 50% of its weight.

[0322] Figure 15 (a) and Table 6 compare the weight loss percentages of 1-O-MGE BBP and 1-O-MAG BBP with m=18 and n=7-11 with respect to temperature. The results show that the introduction of ether groups into the side chains of BBP tends to increase the T of the polymers compared to ester groups. d,5 and T d,50 , thereby improving the thermal stability of the polymer.

[0323] Figure 15 (b) and Table 7 compare the weight loss percentages of 1-O-MGE BBP and 2-O-MGE BBP with m=18 and n=7-11 with respect to temperature. The results show that compared with 2-O-MGE BBP, 1-O-MGE BBP has a higher T d,5 The T values ​​of these two types of polymers tend to be higher. d,50 The values ​​are relatively similar.

[0324] Table 6. Thermal degradation properties of 1-O-MGE BBP and 1-O-MAG BBP

[0325] <![CDATA[Item a > MGE (diol) m / n of polymer <![CDATA[M n ]]> <![CDATA[T d,5 b (℃)]]> <![CDATA[T d,50 b (℃)]]> 1 1-O-MGE 18 / 7 12000 306.7 376.4 2 1-O-MGE 18 / 8 15000 313.2 386.7 3 1-O-MGE 18 / 9 17000 312.8 384.5 4 1-O-MGE 18 / 10 12000 332.5 380.2 5 1-O-MGE 18 / 11 15000 265.5 385.5 6 1-O-MAG (ester) 18 / 7 15000 313.4 360.2 7 1-O-MAG (ester) 18 / 8 14000 198.5 376.8 8 1-O-MAG (ester) 18 / 9 12000 247.1 375.4 9 1-O-MAG (ester) 18 / 10 20000 176.6 375.8 10 1-O-MAG (ester) 18 / 11 19000 172.9 372.8

[0326] Table 7. Thermal degradation properties of 1-O-MGE BBP and 2-O-MGE BBP

[0327] <![CDATA[Entry a > MGE (diol) m / n of polymer <![CDATA[M n ]]> <![CDATA[T d,5 b (℃)]]> <![CDATA[T d,50 b (℃)]]> 1 1-O-MGE 18 / 7 12000 306.7 376.4 2 1-O-MGE 18 / 8 15000 313.2 386.7 3 1-O-MGE 18 / 9 17000 312.8 384.5 4 1-O-MGE 18 / 10 12000 332.5 380.2 5 1-O-MGE 18 / 11 15000 265.5 385.5 6 2-O-MGE 18 / 7 12000 192.7 388.7 7 2-O-MGE 18 / 8 14000 232.5 367.7 8 2-O-MGE 18 / 9 15000 297.3 389.1 9 2-O-MGE 18 / 10 14000 188.9 390.0 10 2-O-MGE 18 / 11 10000 211.3 399.2

[0328] Figure 16Shown is a gel permeation chromatogram of 1-O-MGE BBP undergoing hydrolytic degradation. Figure 16 a) shows the chromatogram of 1-O-MGE BBP (Mn=20291, D=1.32) undergoing hydrolysis conditions (60% THF / 40% NaOH(aq)). Figure 16 b) shows that after 1 hour, the polyester is effectively degraded to form 1-O-MGE diol and diacid monomer. Figure 16 c) and 16d) show that the polymer can be reformed under repolymerization conditions, and after 6 hours, Mn = 1521, D = 2.11, and after 18 hours, Mn = 8089, D = 1.72.

[0329] Figure 17 The key steps required to synthesize 1-O-MGE diol from epichlorohydrin are shown. The reaction was carried out in a 10 L reactor with an overall reaction yield of 87%.

[0330] Figure 18 The results show the mixture of 1-O-MGE (m=18) diol and diacid (n=9) monitored from 0 minutes to 24 hours. 1 H NMR spectrum. The spectrum from 6.0 ppm to 3.0 ppm was zoomed in to observe the appearance and disappearance of species A, B, C, and D during the polymerization process.

[0331] Figure 19 Table 8 shows that intermediate B is generally present in solution in greater amounts than intermediate C. Due to the presence of the known more reactive primary alcohol, intermediate C likely exists as a more transient intermediate and forms product D more quickly.

[0332]

[0333] Table 8. Ratios of substances (A), (B), (C), and (D) relative to time

[0334] Time (min) (A)％ (B)％ (C)％ (D)％ 0 100 0 0 0 10 81.81 13.29 4.91 0 20 61.46 30.33 8.21 0 30 40.78 40.24 10.75 8.23 40 28.58 45.27 12.76 13.4 50 21.54 46.95 12.69 18.82 60 17.37 45.37 11.99 25.27 70 14.73 44.90 11.06 29.32 80 14.44 42.54 10.39 32.63 90 13.57 41.71 11.33 33.39 100 12.17 41.41 11.27 35.15 110 12.38 41.06 11.56 35 120 11.95 41.02 11.30 35.73 130 11.61 40.65 11.50 36.25 140 11.68 39.86 11.38 37.07 150 10.04 40.44 11.43 38.10 160 10.43 40.78 10.80 37.99 170 9.42 39.55 11.82 39.21 180 10.49 39.61 10.87 39.03 240 6.41 38.41 9.71 45.47 300 0 35.47 11.38 53.15 360 0 33.83 8.89 57.29 420 0 30.66 9.72 59.62 480 0 29.35 8.72 61.93 1440 0 0 7.41 92.6

[0335] Industrial Applicability

[0336] Polymers as defined herein can be used as substitutes for petroleum-based polymers. Polymers as defined herein can be used as soft tissue substitutes, lubricants, surface coatings, motion control greases, or ultra-soft surfaces in nanocapsules, in sensing and delivery applications. Polymers as defined herein can also be used as thermoplastic vulcanizates, which can be used in 3D printing, packaging materials, fiber technology, self-cleaning surfaces, self-repairing surfaces, shape memory polymers, and antifouling polyester films.

[0337] The process for preparing a polymer as defined herein may be used to prepare a polymer as defined above.

[0338] Obviously, various other modifications and adaptations of the present invention will be apparent to those skilled in the art after reading the above disclosure without departing from the spirit and scope of the invention, and all such modifications and adaptations are intended to be within the scope of the appended claims.

Claims

1. A polymer having the following general structure (I): in: x, y and z are each independently 0 or an integer from 1 to 5; n is an integer from 1 to 24; v is an integer from 1 to 2000; and R 1 H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl, linear or branched C2-C 30 Alkynyl, or a substituent having the following general structure (II): in: p, q and r are each independently 0 or an integer from 1 to 5; R 2 and R 3 Each independently is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 alkynyl; and This is the position where the substituent having the general structure (II) is linked to the polymer having the general structure (I).

2. The polymer according to claim 1, characterized in that: x is 0 or 1; y is 1; z is 0 or 1; p is 0 or 1; q is 0 or 1; or r is 0 or 1.

3. The polymer according to claim 1 or 2, characterized in that: i) x is 0, y is 1, z is 1, and R 1 Is linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl; ii) x is 1, y is 1, z is 0, and R 1 Is linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl; iii) x is 0, y is 1, z is 1, R 1 is the substituent having the general structure (II), r is 0, p is 1 and q is 1; iv) x is 0, y is 1, z is 1, R 1 is the substituent having the general structure (II), r is 1, p is 1 and q is 0; or v) x is 1, y is 1, z is 0, R 1 is the substituent having the general structure (II), r is 1, p is 1 and q is 0.

4. The polymer according to claim 3, characterized in that When x is 1, y is 1, and z is 0, R 1 Not a linear or branched C1-C6 alkyl group.

5. A polymer according to any one of the preceding claims, characterized in that The polymer has the following structure: Where R 2 , R 3 and R 4 Each independently is a linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl.

6. A polymer according to any one of the preceding claims, characterized in that The polymer is bottle brush polyester.

7. The polymer according to claim 6, characterized in that The bottle brush polyester is a branched bottle brush polyester.

8. A polymer according to any one of the preceding claims, characterised in that The polymer is a biodegradable polymer.

9. A polymer according to any one of the preceding claims, characterised in that The molecular weight of the polymer is 7,000-100,000.

10. The polymer according to any one of the preceding claims, characterized in that The polymer has an intrinsic viscosity of 0.2 dL / g to 2.5 dL / g, or a melting temperature of -40°C to 100°C, or a degradation temperature of 300°C or above.

11. A foam, gel, thermoplastic or elastomer comprising a polymer as claimed in any one of the preceding claims.

12. A method for preparing a polymer having the following general structure (I): The steps include: Provided is a glycerol ether having the following general structure (III): and A glycerol ether having the general structure (III) is contacted with a dicarboxylic acid having the following general structure (IVa) or a diacyl chloride having the following general structure (IVb) under polymerization reaction conditions: Wherein L is CH2 or aryl; in: x, y and z are each independently 0 or an integer from 1 to 5; n is an integer from 1 to 24; and R 1 and R 1’ Each independently is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl, linear or branched C2-C 30 Alkynyl, or a substituent having the following general structure (II): in: p, q and r are each independently 0 or an integer from 1 to 5; R 2 and R 3 Each independently is H, linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 an alkynyl group; and is the position where the substituent having the general structure (II) is connected to the glycerol ether having the general structure (III), Where R 1 or R 1’ In the glycerol ether having the general structure (III), R 1 and R 1’ Both are not H.

13. The method according to claim 12, characterized in that The providing step comprises making a compound of the following structure: With linear or branched C1-C 30 Alkyl halides, linear or branched C2-C 30 Alkenyl halides or linear or branched C2-C 30 Alkynyl halides react under glycerol ether reaction conditions.

14. The method according to claim 13, characterized in that The halide is bromide.

15. The method according to claim 13 or 14, characterized in that The glycerol ether reaction conditions include Williamson ether synthesis, including making a compound of the following structure: reacting with an alkali metal or an alkali metal hydride at a temperature of -4°C to 4°C in a solvent, wherein the solvent is preferably toluene, adding the linear or branched C1-C30 alkyl halide, linear or branched C2-C30 alkenyl halide or linear or branched C2-C30 alkynyl halide to form a mixture, and stirring the mixture at a temperature of 60°C to 80°C for a duration of 3 hours to 24 hours.

16. The method according to claim 15, characterized in that The method is followed by acidification, wherein the acidification step is carried out in a solvent comprising 1 M aqueous hydrochloric acid solution and ethanol, wherein the volume ratio of the two in the solvent is 5:1 to 2:

1.

17. The method according to any one of claims 12 to 16, characterized in that: i) x is 0, y is 1, z is 1, R 1 Is linear or branched C1-C 30 Alkyl and R 1’ It is H; ii) x is 0, y is 1, z is 1, R 1’ Is linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl and R 1 It is H; iii) x is 1, y is 1, z is 0, R 1 Is linear or branched C1-C 30 Alkyl and R 1’ It is H; iv) x is 1, y is 1, z is 0, R 1’ Is linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl and R 1 It is H; v) x is 0, y is 1, z is 1, R 1 is the substituent having the general structure (II), r is 0, p is 1, q is 1 and R 1’ It is H; vi) x is 0, y is 1, z is 1, R 1’ is the substituent having the general structure (II), r is 0, p is 1, q is 1 and R 1 It is H; vii) x is 0, y is 1, z is 1, R 1 is the substituent having the general structure (II), r is 1, p is 1, q is 0 and R 1’ It is H; viii) x is 0, y is 1, z is 1, R 1’ is the substituent having the general structure (II), r is 1, p is 1, q is 0 and R 1 It is H; ix) x is 1, y is 1, z is 0, R 1 is the substituent having the general structure (II), r is 1, p is 1, q is 0 and R 1’ It is H; x)x is 1, y is 1, z is 0, R 1’ is the substituent having the general structure (II), r is 1, p is 1, q is 0 and R 1 It is H; xi) x is 0, y is 1, z is 1, R 1 is the substituent having the general structure (II), r is 0, p is 1, q is 1 and R 1’ is H; or xii) x is 0, y is 1, z is 1, R 1’ is the substituent having the general structure (II), r is 0, p is 1, q is 1 and R 1 It's H.

18. The method according to claim 17, characterized in that When x is 1, y is 1, and z is 0, R 1 is not a linear or branched C1-C6 alkyl group and R 1’ It's H.

19. The method according to any one of claims 12 to 18, characterized in that: The glycerol ether having the general structure (III) has the following structure: Where R 2 , R 3 and R 4 Each independently is a linear or branched C1-C 30 Alkyl, linear or branched C2-C 30 Alkenyl or linear or branched C2-C 30 Alkynyl.

20. The method according to any one of claims 12 to 19, characterized in that The dicarboxylic acid having the general structure (IVa) is selected from 1,3-propanedioic acid, 1,4-succinic acid, 1,5-pentanedioic acid, 1,6-hexanedioic acid, 1,7-pimelic acid, 1,8-octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanedioic acid, 1,16-hexadecanedioic acid, 1,17-heptadecanedioic acid, 1,18-octadecanedioic acid, 1,19-nonadecanedioic acid, 1,20-eicosanedioic acid, 1,21-heneicosanedioic acid, 1,22-docosanedioic acid, 1,23-tricosanedioic acid, 1,24-tetracosanedioic acid, furan-2,5-dicarboxylic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid and any mixture thereof, or the diacid chloride having the general structure (IVb) is selected from 1,3-propanedioic acid dichloro, 1,4-succinoyl dichloride, 1,5-glutaryl dichloride, 1,6-hexadecanoyl dichloride, 1,7-pimeloyl dichloride, 1,8-octanedioyl dichloride, 1,9-azelayl dichloride, 1,10-decanedioyl dichloride, 1,11-undecanoyl dichloride, 1,12-dodecanoyl dichloride, 1,13-tridecanoyl dichloride, 1,14-tetradecanoyl dichloride, 1,15-pentadecanedioyl dichloride, 1,16-hexadecanoyl dichloride dichloride, 1,17-heptadecanedioyl dichloride, 1,18-octadecanediyl dichloride, 1,19-nonadecanedioyl dichloride, 1,20-eicosanedioyl dichloride, 1,21-heneicosanedioyl dichloride, 1,22-docosanedioyl dichloride, 1,23-tricosanediyl dichloride, 1,24-tetracosanedioyl dichloride, furan-2,5-dicarbonyl dichloride, terephthaloyl dichloride, naphthalene-2,6-dicarbonyl dichloride, and any mixture thereof.

21. The method according to any one of claims 12 to 20, characterized in that The glycerol ether having the general structure (III) is contacted with the dicarboxylic acid having the general structure (IVa) or the diacyl chloride having the general structure (IVb) at a molar ratio of 3:1 to 1:

2.

22. The method according to any one of claims 12 to 21, characterized in that The contacting step includes a first heating step performed at a temperature of 150° C. to 220° C. or under an inert atmosphere.

23. The method according to claim 22, characterized in that The first heating step also includes a catalyst.

24. The method according to claim 23, characterized in that The catalyst is selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, p-toluenesulfonic acid monohydrate and any mixture thereof.

25. The method according to claim 23 or 24, characterized in that The molar ratio of the catalyst to the glycerol ether having the general structure (III) is 1:8 to 1:

100.

26. The method according to any one of claims 23 to 25, characterized in that The contacting step further comprises a second heating step carried out at a temperature of 150° C. to 250° C. or for a duration of 12 hours to 36 hours or under an inert atmosphere.

27. Use of a polymer according to any one of claims 1 to 10 or a foam, gel, thermoplastic or elastomer according to claim 11 in nanocapsules, as a soft tissue substitute, lubricant, surface coating, motion control grease or ultra-soft surface in sensing and delivery applications.

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