Poly(3-hydroxybutyrate) polymer derivative and preparation thereof, and antimicrobial product

Abstract

Provided in the present invention is a poly(3-hydroxybutyrate) polymer derivative, having a structure as represented by formula (I), wherein A is phenyl or phenyl C1-C4 alkyl, optionally substituted with a substituent selected from hydroxyl, C1-C4 alkyl, and C2-C4 alkenyl, R is saturated C1-C4 alkyl or hydroxyl-substituted saturated C1-C4 alkyl, Z is a polymeric residue of a hydroxy C3-C10 alkanoic acid, x is an integer from 1 to 20, and y is an integer from 0 to 20. Compared with an unmodified 3-hydroxybutyrate polymer, the poly(3-hydroxybutyrate) polymer derivative provided by the present invention has a significantly improved aromatic odor while retaining excellent broad-spectrum antimicrobial / antiviral effects of a poly(3-hydroxybutyrate) polymer, can also degrade under natural conditions, and has no irritation to the skin.

Description

Poly 3-hydroxybutyrate polymer derivatives and their preparation and antimicrobial products Technical Field

[0001] The present invention relates to the technical field of chemical synthesis of functional macromolecules, and in particular to a poly (3-hydroxybutyrate) polymer derivative, a method for preparing the poly (3-hydroxybutyrate) polymer derivative, and an antimicrobial product, such as an antibacterial and / or antiviral product, comprising the poly (3-hydroxybutyrate) polymer derivative. Background Art

[0002] Preventing the spread and infection of pathogenic microorganisms has always been a major public health and safety concern for society. Pathogenic microbial infections, especially viral infections, can not only cause individual infections and illnesses but can also trigger global crises. Furthermore, as pathogenic microorganisms continue to mutate and evolve, their resistance to traditional fungicides continues to increase. Therefore, humanity urgently needs to develop new broad-spectrum fungicides for widespread use in agriculture, the environment, medicine, textiles and apparel, food packaging, and healthcare for personal protection. This is to address the difficulties and challenges caused by the rapid spread and increasing drug resistance of various pathogenic microorganisms.

[0003] Poly (3-hydroxybutyrate) polymer (PHB) is a polyester polymer with excellent biocompatibility and natural degradability. It is widely used in textiles, food packaging, drug delivery, tissue engineering scaffolds and other fields. Currently, there are two main sources of poly (3-hydroxybutyrate) polymer. One is synthesized by microbial fermentation, which extracts, separates and purifies nutrients and energy storage substances synthesized in microorganisms. Microbial fermentation is mostly used to prepare crude poly (3-hydroxybutyrate) polymer products with low purity requirements. The obtained products have natural chirality. The other is synthesized by artificial ring-opening polymerization reaction, using β-butyrolactone as a monomer and an organic metal complex as a catalyst. The synthesized products are mostly racemic.

[0004] Chinese patent CN101297030A discloses a method for producing PHB using genetically engineered microbial fermentation, and extracting and isolating PHB with a medium or high molecular weight from the microbial culture medium. Chinese patent CN110452115A discloses a method for synthesizing low-molecular-weight PHB oligomers via chemical ring-opening polymerization using β-butyrolactone as a monomer, aluminum isopropoxide, and pyridine as catalysts. Chinese patent CN113200849A discloses a method for synthesizing 3-hydroxybutyrate polymers by artificial ring-opening polymerization, as well as a method for isolating and purifying the same. In recent years, due to the high cost of β-butyrolactone as a raw material, the main method for industrially producing poly (3-hydroxybutyrate) polymers has been microbial fermentation.

[0005] However, poly (3-hydroxybutyrate) polymers obtained by microbial fermentation and artificial synthesis, whether chirally regular homopolymers or copolymers or racemates synthesized by ring-opening polymerization, all have a peculiar unpleasant odor, which is produced by PHB oligomers, which are volatile fatty acids (VFA). This odor seriously affects and limits the widespread application of poly (3-hydroxybutyrate) polymers as antibacterial / antiviral active components in textiles such as masks and sanitary napkins, washing and cleaning products, or personal hygiene products.

[0006] Summary of the Invention

[0007] One of the objectives of the present invention is to provide a poly (3-hydroxybutyrate) polymer derivative that overcomes the aforementioned drawbacks of prior art poly (3-hydroxybutyrate) polymers. The poly (3-hydroxybutyrate) polymer derivative provided by the present invention has reduced unpleasant odor concentration and exhibits a certain aromatic odor, while also retaining excellent broad-spectrum antibacterial and antiviral effects and being capable of degradation under natural conditions.

[0008] In the first aspect of the present invention, a poly 3-hydroxybutyrate polymer derivative is provided, which has a structure as shown in formula (I):

[0009] wherein A is phenyl or phenyl C1-C4 alkyl, which is optionally substituted with a substituent selected from hydroxy, C1-C4 alkyl and C2-C4 alkenyl,

[0010] R is a C1-C4 saturated alkyl group or a C1-C4 saturated alkyl group substituted with a hydroxyl group,

[0011] Z is a polymerized residue of a hydroxy C3-C10 alkanoic acid, and

[0012] x is an integer of 1-20, and y is an integer of 0-20.

[0013] According to certain embodiments, in the poly 3-hydroxybutyrate polymer derivative provided by the present invention, the A is selected from the group consisting of p-hydroxyphenyl, o-hydroxyphenyl, m-hydroxyphenyl, dihydroxyphenyl, trihydroxyphenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, benzyl, phenethyl and The group composed of.

[0014] According to certain embodiments, in the poly 3-hydroxybutyrate polymer derivative provided by the present invention, the R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, hydroxyethyl, 2,3-dihydroxypropyl and isobutyl.

[0015] According to certain embodiments, the hydroxy C3-C10 alkanoic acid is selected from the group consisting of 3-hydroxyvaleric acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, and 3-hydroxydecanoic acid.

[0016] According to certain embodiments, the content of 3-hydroxybutyrate monomer units in the poly 3-hydroxybutyrate polymer derivative is not less than 50 wt%, preferably not less than 70 wt%, not less than 90 wt%, or not less than 95 wt%.

[0017] According to certain embodiments, the poly 3-hydroxybutyrate polymer derivative provided by the present invention has a structure as shown in formula (II):

[0018] where the sum of x and y is 1, 2, 3, 4, or 5.

[0019] According to certain embodiments, the poly 3-hydroxybutyrate polymer derivative provided by the present invention has a weight average molecular weight of no more than 10,000; preferably, the poly 3-hydroxybutyrate polymer derivative has a weight average molecular weight in the range of 200-10,000, more preferably in the range of 200-8,000, 200-5,000, 200-3,000 or 250-1,000.

[0020] According to certain embodiments, the poly 3-hydroxybutyrate polymer derivative provided by the present invention has a fragrant odor.

[0021] In a second aspect of the present invention, a method for preparing the poly 3-hydroxybutyrate polymer derivative as described above is provided, wherein the method comprises:

[0022] Providing a compound represented by formula (IV);

[0023] The compound of formula (IV) undergoes a second esterification reaction with a carboxylic acid of formula (III), A-COOH Formula (III)

[0024] Preferably, the second esterification reaction is carried out at a temperature of 55-65°C; and

[0025] Optionally, isolating the poly 3-hydroxybutyrate polymer derivative represented by formula (I) from the product mixture obtained from the second esterification reaction;

[0026] wherein R, A, Z, x and y are as defined above.

[0027] According to certain embodiments, the compound represented by formula (IV) is prepared by the following steps:

[0028] Providing a polymer represented by formula (V) as a starting material;

[0029] The terminal carboxyl group of the polymer represented by formula (V) undergoes a first esterification reaction with an alcohol to obtain an intermediate product represented by formula (IV), wherein the alcohol is a C1-C4 alkyl alcohol. Preferably, the first esterification reaction is carried out at a temperature of 100-150°C.

[0030] According to certain embodiments, the polymer represented by formula (V) is a product obtained by microbial fermentation.

[0031] According to certain embodiments, the first esterification reaction is carried out in the presence of an acid, preferably the acid comprises one or more of sulfuric acid, an organic sulfonic acid or an anhydride thereof, preferably, the organic sulfonic acid comprises one or more of benzenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid and alkylsulfonic acid.

[0032] According to certain embodiments, the reaction solvent for the first esterification reaction includes one or more of dichloromethane and chloroform.

[0033] According to certain embodiments, the carboxylic acid of formula (III) is selected from the group consisting of benzoic acid, p-hydroxybenzoic acid, salicylic acid, gallic acid, and cinnamic acid.

[0034] According to certain embodiments, the C1-C4 alkyl alcohol is selected from the group consisting of monohydric alcohols and polyhydric alcohols. Preferably, the monohydric alcohol includes methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, and the polyhydric alcohol includes ethylene glycol and glycerol.

[0035] According to certain embodiments, the first esterification reaction is performed at a temperature of 100°C to 130°C.

[0036] In a third aspect of the present invention, an antibacterial and / or antiviral product is provided, which comprises the poly 3-hydroxybutyrate polymer derivative according to the first aspect of the present invention or the poly 3-hydroxybutyrate polymer derivative obtained by the method according to the second aspect of the present invention.

[0037] According to certain embodiments, the antibacterial and / or antiviral products provided by the present invention include textiles, personal hygiene products, drug carriers, fabric finishing agents, washing and cleaning products, fragrances or medical products; preferably, the textiles include masks, bedding and clothing.

[0038] According to certain embodiments, the antibacterial and / or antiviral preparation provided herein is in the form of a powder, solution, sol, gel, fiber, yarn or film.

[0039] In a fourth aspect, the present invention further provides use of the 3-hydroxybutyrate polymer derivative according to the first aspect or the 3-hydroxybutyrate polymer derivative obtained according to the method of the second aspect in antibacterial and / or antiviral products.

[0040] The above technical solution of the present invention has at least the following advantages.

[0041] 1. The 3-hydroxybutyrate polymer derivatives provided herein have significantly improved odor compared to prior art 3-hydroxybutyrate polymers. These derivatives generally have reduced levels of unpleasant odor and can exhibit aromatic or fruity aromas similar to those of fragrances, or a rum-like aroma. Due to this improved odor, the 3-hydroxybutyrate polymer derivatives provided herein are widely applicable in various fields, including biopharmaceuticals, textiles and apparel, food packaging, and healthcare.

[0042] 2. The 3-hydroxybutyrate polymer derivative provided by the present invention can retain the excellent broad-spectrum antibacterial / antiviral effects of the 3-hydroxybutyrate polymer, and can be (completely) degraded under natural conditions while being non-irritating to the skin.

[0043] 3. The synthesis method of the 3-hydroxybutyrate polymer derivative provided by the present invention is simple to operate, and the raw materials and reagents used are widely available and inexpensive, making it easy to achieve large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The above and other objects and features of the present disclosure will become apparent from the following description of the present disclosure when taken in conjunction with the accompanying drawings.

[0045] FIG1 is a hydrogen nuclear magnetic resonance spectrum and a carbon nuclear magnetic resonance spectrum of a 3-hydroxybutyrate polymer derivative obtained according to Example 1 of the present invention using deuterated chloroform as a deuterated reagent.

[0046] FIG2 is a Fourier transform infrared absorption spectrum of a sample of the 3-hydroxybutyrate polymer derivative obtained by the potassium bromide tableting method according to Example 2 of the present invention. DETAILED DESCRIPTION

[0047] Although the present invention provides references to various embodiments, those skilled in the art will recognize that changes in form and detail may be made without departing from the spirit and scope of the present application. Reference to various embodiments does not limit the scope of the claims appended hereto. Additionally, any embodiments set forth in this application are not intended to be limiting and merely set forth some of the many possible embodiments of the present invention.

[0048] The methods and materials used in the examples are described below, but methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. It should be understood that if any prior art publication is mentioned herein, such reference does not constitute an admission that the publication forms part of the common general knowledge in the art.

[0049] definition

[0050] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In the event of any inconsistency, the present document (including definitions) will prevail.

[0051] Throughout this application, where an article is described as having, including, or comprising particular components, or a method is described as having, including, or comprising particular steps, it is contemplated that the articles of manufacture taught herein may also consist essentially of, or consist of, the recited components, and that the methods taught herein may also consist essentially of, or consist of, the recited steps.

[0052] In this application, when an element or component is referred to as being included in and / or selected from a list of enumerated elements or components, it should be understood that the element or component can be any one of the enumerated elements or components, or the element or component can be selected from a group consisting of two or more of the enumerated elements or components. In addition, it should be understood that the elements and / or features of the compositions or methods described herein can be combined in various ways, whether explicitly or implicitly herein, without departing from the spirit and scope of the present teachings.

[0053] Should be understood that, as long as can make the teaching of the present invention remain operable, the order of steps or the order of performing certain actions can be changed.In addition, two or more steps or actions can be performed simultaneously.

[0054] Unless otherwise expressly stated, when the term "about" is used before a numerical value, the present invention also includes the specific numerical value itself, unless otherwise specifically stated. As used herein, the term "about" refers to a variation of ±10%, ±7%, ±5%, ±3%, ±1%, or ±0% of the nominal value, unless otherwise stated or inferred.

[0055] In the present invention, the expression "optionally" refers to two embodiments in which the features (eg, components, steps, etc.) defined by the term may or may not be present.

[0056] In the present invention, any range of values ​​includes all values ​​within the range and should be interpreted as including any sub-range of the endpoints of the real values ​​within the range. For example, the disclosure of a range of 1 to 5 in this specification should be considered to mean any of the following ranges: 1-5, 1-4, 1-3, 1-2, 2-5, 2-4, 2-3, 3-5, 3-4, and 4-5.

[0057] As used herein, the term "poly 3-hydroxybutyrate polymer" or "3-hydroxybutyrate polymer" (PHB) is a class of polyhydroxyalkanoate (PHA) polymers. "3-hydroxybutyrate polymer" or "poly 3-hydroxybutyrate polymer" refers to a polymer containing 3-hydroxybutyric acid monomer units, including homopolymers of 3-hydroxybutyric acid and copolymers of 3-hydroxybutyric acid and other hydroxyalkanoic acids, such as those having the structure of formula (V) as defined herein. Other hydroxyalkanoic acids can be, for example, one or more of 3-hydroxyvaleric acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxyvaleric acid, 3-hydroxypentanoic acid, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, and 3-hydroxydecanoic acid.

[0058] The "poly 3-hydroxybutyrate polymer" or "3-hydroxybutyrate polymer" used in the present invention is generally a 3-hydroxybutyrate oligomer or oligomer, and usually has a weight average molecular weight of no more than 10,000.

[0059] In one embodiment, the "3-hydroxybutyrate polymer" or "poly 3-hydroxybutyrate polymer" of the present invention has a weight average molecular weight in the range of 200-10,000, 252-10,000, 200-8,000, 200-5,000, 200-3,000, 250-1,000, 252-700, or 252-525.

[0060] In one embodiment, the "poly 3-hydroxybutyrate polymer" or "3-hydroxybutyrate polymer" of the present invention is a homopolymer or copolymer of 3-hydroxybutyrate, which can generally be a homopolymer or copolymer of (R) 3-hydroxybutyrate obtained by microbial fermentation.

[0061] As used herein, the term "poly 3-hydroxybutyrate polymer derivative" or "3-hydroxybutyrate polymer derivative" refers to a modified product of a poly 3-hydroxybutyrate polymer obtained by esterifying the terminal carboxyl group and / or terminal hydroxyl group of the 3-hydroxybutyrate polymer.

[0062] In the present invention, "microbial fermentation" refers to the process of using microorganisms, under suitable conditions, to convert raw materials into desired products through specific metabolic pathways. The 3-hydroxybutyrate polymer of the present invention can be produced using genetically engineered microorganisms that possess at least one gene related to the metabolism, and particularly, the production, of the 3-hydroxybutyrate polymer.

[0063] In the present invention, the microorganisms that can be used to produce 3-hydroxybutyrate polymers by microbial fermentation can be one or more microorganisms or bacterial groups of Aeromonas, Alcaligenes, Azotobacter, Bacillus, Clostridium, Halonacterium, Nocardia, Rhodospirillum, Pseudomonas, Alcanivorax, Rhodococcus, Ralstonia, Zoogloea, Escherichia, Candida, Saccharomyces, Yarrowia, etc., and their variant microorganisms, and the poly 3-hydroxybutyrate polymer is obtained by fermentation, separation and purification. The resulting poly (3-hydroxybutyrate) polymer can be a poly (3-hydroxybutyrate) polyester homopolymer or a copolymer of poly (3-hydroxybutyrate) and other hydroxyalkanoates. Modification of one or more genes involved in the synthesis of poly (3-hydroxybutyrate) polymers can occur in the aforementioned microorganisms. These modifications can result in the production of PHA synthase, poly (3-hydroxybutyrate) synthase, enoyl-CoA hydratase (ECH), and / or PHB synthase, and / or other enzymes involved in fatty acid metabolism.

[0064] As used herein, the term "C1-C4 alkyl alcohol" refers to a linear or branched alkyl alcohol having 1-4 carbon atoms in the molecular chain. Exemplary C1-C4 alkyl alcohols may be monohydric alcohols or polyhydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, glycerol or isobutanol, etc. Similarly, as used herein, the term "C1-C4 saturated alkyl" or "C1-C4 alkyl" refers to a linear or branched monovalent hydrocarbon group having the corresponding number of carbon atoms in the molecular chain. Exemplary C1-C4 (saturated) alkyl groups may be methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, etc.; hydroxyl-substituted C1-C4 (saturated) alkyl groups may be hydroxyethyl and or 2,3-dihydroxypropyl. The alkyl monohydric alcohol or polyhydric alcohol used in the present invention is preferably a small molecule alcohol having a molecular weight of 1000 or less.

[0065] The term "phenyl C1-C4 alkyl" as used herein refers to "phenyl-(C1 to C4 alkyl)-", and the definition of C1-C4 alkyl is as described above.

[0066] The term "substituted" means that one or more hydrogens on the designated atom or group are replaced with a selected designated group, provided that the normal valency of the designated atom is not exceeded under the circumstances.

[0067] As used herein, the term "hydroxy C3-C10 alkanoic acid" refers to a C3-C10 alkylcarboxylic acid substituted with one or more hydroxy groups, such as 3-hydroxyvaleric acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxyvaleric acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, and 3-hydroxydecanoic acid. The polymerized residue of a hydroxy C3-C10 alkanoic acid refers to a monomer unit remaining in the polymer chain after the hydroxy C3-C10 alkanoic acid is polymerized through an intermolecular esterification reaction between the hydroxyl and carboxyl groups.

[0068] In one embodiment, the copolymer derivative comprising 3-hydroxybutyrate and 3-hydroxyvalerate monomer units may have the following structure:

[0069] wherein R, A, x and y are as defined above.

[0070] Advantages and features of the present invention will become more apparent from the following description of illustrative embodiments.The scope of the present invention is not limited to any specific embodiments described herein.

[0071] The present invention provides a 3-hydroxybutyrate polymer derivative obtained by chemically modifying a 3-hydroxybutyrate polymer biopolyester. This derivative can be used as an antibacterial and / or antiviral active material to impart broad-spectrum antimicrobial properties to related products or articles, while also exhibiting significantly improved aroma and odor. It is also capable of degrading under natural conditions. The 3-hydroxybutyrate polymer derivative provided herein can be included in articles (e.g., medical supplies or personal hygiene products) to provide antibacterial and / or antiviral effects.

[0072] 3-Hydroxybutyrate polymer derivatives

[0073] The 3-hydroxybutyrate polymer derivative provided by the present invention has a structure as shown in formula (I):

[0074] wherein A is phenyl or phenyl C1-C4 alkyl, which is optionally substituted with a substituent selected from hydroxy, C1-C4 alkyl and C2-C4 alkenyl,

[0075] R is a C1-C4 saturated alkyl group or a C1-C4 saturated alkyl group substituted with a hydroxyl group,

[0076] Z is a polymerized residue of a hydroxy C3-C10 alkanoic acid, and

[0077] x is an integer of 1-20, and y is an integer of 0-20.

[0078] In certain embodiments, A is selected from the group consisting of p-hydroxyphenyl, o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxybenzyl, o-hydroxybenzyl, m-hydroxybenzyl, p-hydroxyphenethyl, o-hydroxyphenethyl, m-hydroxyphenethyl, p-hydroxyphenylpropyl, p-hydroxyphenylisopropyl, o-hydroxyphenylpropyl, m-hydroxyphenylpropyl, p-hydroxyphenylbutyl, o-hydroxyphenylbutyl, m-hydroxyphenylbutyl, and polyhydroxyphenyl, benzyl, phenethyl, and The group composed of.

[0079] In a preferred embodiment, A is selected from p-hydroxyphenyl or p-hydroxybenzyl.

[0080] In certain embodiments, R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, hydroxyethyl, 2,3-dihydroxypropyl, and isobutyl. In preferred embodiments, R is selected from methyl or ethyl.

[0081] The C1-C4 alkyl group or the C2-C4 alkenyl group may be substituted by a substituent, and the substituent may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group, preferably a methyl group or an ethyl group.

[0082] In a preferred embodiment of the present invention, x can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; y can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0083] In an embodiment of the present invention, the hydroxy C3-C10 alkanoic acid can be selected from the group consisting of 3-hydroxyvaleric acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxyvaleric acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid and 3-hydroxydecanoic acid. Preferably, the hydroxy C3-C10 alkanoic acid can be 3-hydroxyvaleric acid.

[0084] In the molecular chain of the 3-hydroxybutyrate polymer derivative of the present invention, the 3-hydroxybutyrate monomeric unit is preferably the main monomeric unit. In certain embodiments, the content of the 3-hydroxybutyrate monomeric unit in the 3-hydroxybutyrate polymer derivative is not less than 50% by weight, preferably not less than 70% by weight, not less than 90% by weight, not less than 95% by weight, not less than 98% by weight, or 100% by weight.

[0085] In one embodiment, the 3-hydroxybutyrate polymer derivative of the present invention comprises 3-hydroxybutyrate and 3-hydroxyvalerate monomer units, which have, for example, the structure shown in the following formula (II):

[0086] wherein the sum of x and y is 1, 2, 3, 4 or 5. The 3-hydroxybutyrate polymer derivative having this structure has significantly improved aromatic odor.

[0087] In certain embodiments, the 3-hydroxybutyrate polymer derivative has a weight average molecular weight of no greater than 10,000.

[0088] In preferred embodiments, the 3-hydroxybutyrate polymer derivative has a weight average molecular weight in the range of 200-10,000, 252-10,000, 200-8,000, 200-5,000, 200-3,000, 250-1,000, 252-1,000, 252-700, or 252-525.

[0089] In certain embodiments, the 3-hydroxybutyrate polymer derivatives provided herein have an aromatic odor. For example, the aromatic odor can be a fragrance similar to that of a fragrance or a fruity aroma, or a rum-like aroma. Due to the improved odor, the 3-hydroxybutyrate polymer derivatives provided herein can be widely used in various fields such as biopharmaceuticals, textiles and clothing, food packaging, and medical and health care.

[0090] Preparation method of 3-hydroxybutyrate polymer derivative

[0091] The present invention also provides a method for preparing a 3-hydroxybutyrate polymer derivative, wherein the method comprises:

[0092] Providing a compound represented by formula (IV);

[0093] The intermediate product of formula (IV) undergoes a second esterification reaction with a carboxylic acid of formula (III), A-COOH Formula (III),

[0094] Preferably, the second esterification reaction is carried out at a temperature of 55-65°C; and

[0095] Optionally, isolating the 3-hydroxybutyrate polymer derivative represented by formula (I) from the product mixture obtained from the second esterification reaction;

[0096] wherein A is phenyl or phenyl C1-C4 alkyl, which is optionally substituted with a substituent selected from hydroxy, C1-C4 alkyl and C2-C4 alkenyl,

[0097] R is a C1-C4 saturated alkyl group or a C1-C4 saturated alkyl group substituted with a hydroxyl group,

[0098] Z is a polymerized residue of a hydroxy C3-C10 alkanoic acid,

[0099] x is an integer of 1-20, and y is an integer of 0-20.

[0100] According to one embodiment of the present invention, the compound represented by the above formula IV is prepared by the following steps:

[0101] Providing a poly 3-hydroxybutyrate polymer as shown in formula (V) as a starting material,

[0102] The terminal carboxyl group of the poly (3-hydroxybutyrate) polymer undergoes a first esterification reaction with an alcohol to obtain an intermediate product represented by formula (IV), wherein the alcohol is a C1-C4 alkyl alcohol. Preferably, the first esterification reaction is carried out at a temperature of 100-150°C.

[0103] The C1-C4 alkyl alcohol is selected from the group consisting of monohydric alcohol and polyhydric alcohol. Preferably, the monohydric alcohol includes methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, and the polyhydric alcohol includes ethylene glycol and glycerol.

[0104] As mentioned above, the poly 3-hydroxybutyrate polymer starting material used in the present invention is a product obtained by microbial fermentation, and generally has a weight average molecular weight of less than 10,000.

[0105] The esterification reaction of the present invention can be carried out in a conventional solvent for esterification reactions. However, the preferred esterification reaction solvent can be selected from the group consisting of dichloromethane, ethanol, dimethyl sulfoxide, toluene, ethyl acetate, chloroform, and ionic liquids, deep eutectic solvents, or supercritical fluids. In a preferred embodiment, the esterification reaction solvent can be dichloromethane or chloroform.

[0106] In certain embodiments, dichloromethane or chloroform can be used as a solvent for the first esterification reaction as described above. In a preferred embodiment, the 3-hydroxybutyrate polymer starting material is dissolved in dichloromethane as a solvent to obtain a solution, an acid catalyst and a C1-C4 alkyl alcohol are added to the resulting solution to obtain a reaction mixture, and the reaction mixture is heated to perform the esterification reaction.

[0107] In certain embodiments, the concentration of the reactant in the reaction mixture can be 1 to 30 weight %, preferably 1 to 20 weight %, 1 to 15 weight %, and more preferably 8 to 12 weight %, calculated based on the content of the reactant poly 3-hydroxybutyrate polymer; for example, 1 weight %, 2 weight %, 3 weight %, 4 weight %, 5 weight %, 6 weight %, 7 weight %, 8 weight %, 9 weight %, 10 weight %, 11 weight %, 12 weight %, 13 weight %, 14 weight % or 15 weight % or any range therebetween.

[0108] In certain embodiments, the first esterification reaction can be carried out at 100-150° C., preferably 100-130° C., 110-130° C., more preferably 115-125° C. or about 120° C. Typically, the first esterification reaction can be carried out at a temperature that boils / refluxes the reaction mixture.

[0109] In certain embodiments, the first esterification reaction is conducted for a period of about 100 hours, 90 hours, 80 hours, 70 hours, 60 hours, 50 hours, 40 hours, 30 hours, or any range therebetween.

[0110] In certain embodiments, the first esterification reaction is carried out in the presence of an acid. In certain embodiments, the acid comprises sulfuric acid, an organic sulfonic acid, or an anhydride thereof. For example, the organic sulfonic acid may comprise benzenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid, and an alkylsulfonic acid. Preferred acids may be sulfuric acid or p-toluenesulfonic acid.

[0111] In the present invention, after the first esterification reaction is completed, the unreacted alcohol is removed from the obtained reaction mixture and the resulting mixture can be directly used for the second esterification reaction, thereby simplifying the operation steps.

[0112] In certain embodiments, for the second esterification reaction as described above, the concentration of the reactants in the reaction mixture may be 0 to 20 wt %, preferably 20 wt %, calculated based on the content of the intermediate formula (IV).

[0113] In certain embodiments, the carboxylic acid of formula (III) comprises one or more of benzoic acid, p-hydroxybenzoic acid, salicylic acid, gallic acid, cinnamic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxyphenylacetic acid, o-hydroxyphenylacetic acid, m-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, o-hydroxyphenylpropionic acid, m-hydroxyphenylpropionic acid, p-hydroxyphenylbutyric acid, p-hydroxyphenylisobutyric acid, o-hydroxyphenylbutyric acid, m-hydroxyphenylbutyric acid, p-hydroxyphenylvaleric acid, o-hydroxyphenylvaleric acid, m-hydroxyphenylvaleric acid, dihydroxybenzoic acid, trihydroxybenzoic acid, phenylacetic acid, and phenylpropionic acid.

[0114] In certain embodiments, the second esterification reaction is carried out at a temperature of about 60° C. In a preferred embodiment, the reaction mixture is subjected to reduced pressure distillation during the second esterification reaction to distill off the organic solvent (e.g., dichloromethane) and the generated water from the reaction mixture, thereby facilitating the reaction to proceed toward the formation of esters, thereby increasing the conversion rate of the reactants.

[0115] In certain embodiments, the second esterification reaction is conducted for a period of about 30 hours, 28 hours, 26 hours, 24 hours, 22 hours, 20 hours, 18 hours, 16 hours, or any range therebetween.

[0116] In the present invention, after the second esterification reaction is completed, the reaction mixture can be post-treated to obtain the product 3-hydroxybutyrate polymer derivative. For example, saturated sodium carbonate or saturated sodium bicarbonate aqueous solution / dilute hydrochloric acid solution can be added to the reaction mixture solution obtained from the second esterification reaction. After multiple separation extractions, the mixture can be filtered using an oil-based filter membrane (e.g., 0.22 micron pore size) to remove insoluble matter. Multiple separation extractions using ultrapure water are then performed to remove the acid catalyst. Finally, a transparent liquid 3-hydroxybutyrate polymer derivative with a fruity or rum aroma is obtained.

[0117] Application of 3-hydroxybutyrate polymer derivatives

[0118] The 3-hydroxybutyrate polymer derivative provided by the present invention or the 3-hydroxybutyrate polymer derivative obtained according to the method of the present invention can be used in various antibacterial and / or antiviral products in the fields of biomedicine, textiles and clothing, food packaging, medical care and hygiene.

[0119] In some embodiments, the antibacterial and / or antiviral article can be prepared in the form of a powder, solution, sol, gel, fiber, yarn, or film.

[0120] In some embodiments, the antibacterial and / or antiviral product can be selected from the group consisting of textiles, personal hygiene products, drug carriers, fabric finishing agents, cleaning products, food packaging, fragrances, and medical products.

[0121] In certain embodiments, the textile can be made of a material selected from cotton, linen, silk, woolen cloth, synthetic fabric, and blended fabric. The textile can be selected from the group consisting of, for example, masks, bedding (e.g., bed sheets), and clothing. In certain embodiments, the 3-hydroxybutyrate polymer derivative can be formed into a coating for a textile or personal hygiene product.

[0122] For example, when the terminal groups of 3-hydroxybutyrate polymer derivatives contain phenolic hydroxyl groups, since the phenolic hydroxyl groups are weakly acidic, they can neutralize ammonia in urine and can be used in personal hygiene products such as diapers to eliminate odors to a certain extent.

[0123] In particular, because the 3-hydroxybutyrate polymer derivatives provided by the present invention have a unique aromatic odor, when they are included in a product, the content of the 3-hydroxybutyrate polymer derivative component can be roughly estimated by smell. For example, the 3-hydroxybutyrate polymer derivatives provided by the present invention can be included in the surface coating of a mask. In this case, after the mask has been used for a period of time, the residual content of the 3-hydroxybutyrate polymer derivative in the mask can be determined by smell, thereby determining whether the mask product still has effective antibacterial and / or antiviral effects.

[0124] The antibacterial and / or antiviral preparations provided herein may contain, in addition to the 3-hydroxybutyrate polymer derivative as an active ingredient, other known antibacterial and / or antiviral active ingredients. In certain embodiments, the antibacterial and / or antiviral preparations provided herein may further contain other ingredients, such as additives / adjuvants, solvents, and the like, as long as the active ingredients can be formulated into any form or type of antibacterial and / or antiviral preparation without affecting the antibacterial and / or antiviral activity of the active ingredients. The present invention is not limited thereto.

[0125] In some embodiments, other known antibacterial and / or antiviral active ingredients may be one or more of lactic acid, lactic acid oligomers, 3-hydroxybutyric acid oligomers and esterified derivatives thereof, ethanol, isopropanol, o-cresol, m-cresol, p-cresol, p-chloro-m-xylenol, triclosan, hypochlorous acid and its salts, chlorine dioxide, ozone, hydrogen peroxide or acetic acid.

[0126] In some embodiments, the additive may be a cosolvent such as ethanol or isopropanol or distilled water.

[0127] The following describes specific embodiments of the present invention with reference to the accompanying drawings. It should be understood that various modifications are possible without departing from the scope of the present invention as described above. The following embodiments are provided for illustration only.

[0128] Example

[0129] Material

[0130] The 3-hydroxybutyrate polymer starting material used in the present invention is (3-hydroxybutyric acid)-co-(3-hydroxyvaleric acid) copolymer (PHBV), whose structure is shown in Figures 1A-1B, where x+y = an integer from 1 to 5. This PHBV can be obtained from Ningbo Tianan Biomaterial Co., Ltd. or other suppliers, or by the methods and conditions disclosed in CN101297030A.

[0131] Other reaction reagents, catalysts, solvents and additives used in this example can be obtained commercially.

[0132] Synthesis and Characterization of 3-Hydroxybutyrate Polymer Derivatives

[0133] Example 1

[0134] 1-1. Synthesis of 3-hydroxybutyrate polymer derivatives

[0135] 5 g of (3-hydroxybutyric acid)-co-(3-hydroxyvaleric acid) copolymer (PHBV) powder derived from a microbial fermentation method was weighed and dissolved in 60 ml of dichloromethane solvent to obtain a dichloromethane mixed solution. Then, p-hydroxybenzenesulfonic acid was dissolved in anhydrous ethanol (alcoholysis reagent) to prepare 50 ml of a 10 wt % alcoholysis solution, which was then added to the above dichloromethane mixed solution. The mixture was heated to 120° C. and boiled for about 72 hours. After cooling to room temperature, a reaction solution containing an intermediate product (whose structure is shown in Figures 1C-1D) was obtained.

[0136] After adding distilled water to split the reaction solution, the reaction solution containing the intermediate product was transferred to an eggplant-shaped flask. p-Hydroxybenzoic acid was added to the eggplant-shaped flask containing the reaction solution. After another 24-hour vacuum esterification reaction at 65°C, a saturated aqueous solution of sodium carbonate and a dilute hydrochloric acid solution were added. After multiple extractions, the insoluble matter was removed by filtration using a 0.22-micron oil filter membrane. The final product, a 3-hydroxybutyrate polymer derivative, was obtained as a clear liquid with a fruity or rum aroma. The yield of the final product was 78%.

[0137] Structural Characterization of 1-2,3-Hydroxybutyrate Polymer Derivatives

[0138] The structures of the starting polymer, intermediate, and final product, the 3-hydroxybutyrate polymer derivative, used in Example 1-1, were characterized using proton and carbon nuclear magnetic resonance spectroscopy. Specifically, the aforementioned compounds were dissolved in deuterated chloroform and measured and data collected using a Jeol ECZ500R 500 MHz Solid-State NMR spectrometer. The resulting NMR spectra are shown in Figure 1.

[0139] Figures 1A-1B show the structure of the starting material and its H 1N spectra and C 2N spectra, respectively; Figures 1C-1D show the structure of the intermediate product and its H 1N spectra and C 2N spectra, respectively; and Figures 1E-1F show the structure of the final product and its H 1N spectra and C 2N spectra, respectively. As shown in Figure 1 , the H 1N spectra and C 2N spectra of the starting material, intermediate product, and final product are consistent with the structural formula shown in the figure, with no other functional group changes or by-products.

[0140] The x+y / polymerization degree of the 3-hydroxybutyrate polymer derivative obtained in this example is 2 to 8, and the content of the 3-hydroxybutyrate monomer unit in the 3-hydroxybutyrate polymer derivative exceeds 90%.

[0141] According to the European standard (BS EN13725:2022), the odor concentration of the modified PHBVE oligomer is 25OUE / m 3 In contrast, the odor concentration of unmodified PHBV or PHB oligomers is 40OUE / m 3 , it can be seen that the odor of the modified oligomer is significantly improved.

[0142] Example 2

[0143] 1. The same method as in Example 1-1 was used for synthesis, except that:

[0144] 1) Catalyst

[0145] The catalyst used in this embodiment is anhydrous methanol containing 10% by weight of sulfuric acid.

[0146] 2) Alcoholysis solvent

[0147] In this embodiment, methanol was used as the alcoholysis reagent in the first esterification reaction, and the reaction temperature was controlled at 100°C.

[0148] The product obtained in this example is a transparent or translucent liquid, and the yield of the final product is 82%.

[0149] 2. Fourier Transform Infrared Absorption Spectroscopy The liquid product collected in step 1 of this example was subjected to a potassium bromide pelleting method, and the Fourier transform infrared absorption spectrum of the collected sample was measured using a PerkinElmer Spectrum 100 FT-IR Spectrometer. The spectrum is shown in FIG2 .

[0150] At wave number ~3400cm -1 The absorption peak at is the molecular vibration absorption peak of the hydroxyl group of the 3-hydroxybutyrate polymer and the hydroxyl group of the carboxylic acid, with a wave number of 3000 cm -1 The three moderate intensity characteristic absorption peaks at the 3-hydroxybutyrate oligomer or oligomer correspond to the methyl hydrocarbon, secondary carbon hydrocarbon and tertiary carbon hydrocarbon stretching vibration absorption peaks, with wave numbers of 1700 cm -1 The peak at is the carbonyl stretching vibration absorption peak of the ester bond of the 3-hydroxybutyrate oligomer or oligomer. The infrared spectrum of the product is consistent with that of the corresponding substance, and no other functional group changes or by-products are present.

[0151] Comparative Example

[0152] The synthesis was carried out using the same method as Example 1-1, except that salicylic acid was used as the acid for the second esterification reaction and the reaction temperature was controlled at 62°C. The product obtained in this comparative example was a viscous liquid, and the final product yield was 73%. The odor was not improved compared to the unmodified PHBV or PHB oligomer.

[0153] Odor Testing and Antibacterial / Antiviral Activity Testing of 3-Hydroxybutyrate Polymer Derivatives

[0154] Test Example 1

[0155] According to the European Standard: Air Quality - Dynamic Odor Measurement (BS EN13725:2022), the poly (3-hydroxybutyrate) polymer derivatives obtained in Examples 1-3 and Comparative Examples were subjected to odor tests. The results are summarized in Table 1 below.

[0156] Table 1

[0157] As shown in Table 1 above, the odor concentration (BS EN13725:2022) test results show that the unmodified PHBV or PHB oligomer has an unpleasant sour odor, and the unpleasant odor concentration is 40OU E / m 3 In contrast, the unpleasant odor concentration of the PHBVE derivatives provided in Examples 1-3 of the present invention is significantly reduced, and the odor type exhibited is significantly improved, with a pleasant fruity or rum aroma.

[0158] Test Example 2

[0159] 1) The 3-hydroxybutyrate polymer derivative obtained in Example 1-1 was used as the solute and dissolved in a 30% by mass ethanol aqueous solution to obtain 100 g of a 10% by mass test solution. Using a K-3 spray gun, the initial spray pressure was set to 0.2 MPa, the spray liquid flow rate was set to 40 mg / min, and the spray height was fixed at 20 cm. The fabric to be sprayed was a polypropylene hot air fabric. The spray nozzle spray was appropriately adjusted to evenly spray the test solution onto both sides of a 40 g polypropylene spunbond nonwoven fabric. The fabric was then dried in a 65°C oven to obtain a test sample.

[0160] The same polypropylene hot air cloth without coating treatment was used as a blank control sample.

[0161] 2) Candida albicans (C.albicans ATCC No.10231) was used as the experimental fungal strain. According to the absorption method requirements of the American Association of Textile Chemists and Colorists (AATCC100-2019), the polypropylene hot air cloth sample sprayed with antibacterial active ingredients was cut into 4.8 cm diameter discs. The number of discs was based on the absorption of 1 mL of bacterial solution. 1 mL of the solution with a concentration of (1.4×10 5 cfu / mL) of Candida albicans suspension was inoculated on the sample. After 24 hours of contact culture, the number of surviving bacteria on the sample with a contact time of 0 hour was compared with that on the sample with a contact time of 24 hours, and the bacterial reduction rate was calculated.

[0162] The antibacterial test results are shown in the following table:

[0163] The above antibacterial test results show that the polypropylene hot air cloth with the antibacterial active coating has a bacteria reduction rate of more than 99.99%, indicating that the 3-hydroxybutyrate polymer derivative obtained in the embodiment of the present invention has excellent antibacterial effect.

[0164] Test Example 3

[0165] 1) The 3-hydroxybutyrate polymer derivative obtained in Example 1-1 was used as the solute and dissolved in a 30% by mass ethanol aqueous solution to obtain 100 g of a 10% by mass test solution. A K-3 spray gun was used, with an initial spray pressure of 0.2 MPa, a liquid flow rate of 40 mg / min, and a fixed spray height of 20 cm. The fabric to be sprayed was a polypropylene hot air cloth. The spray nozzle was adjusted appropriately to spray the solution evenly onto both sides of a 40 g polypropylene hot air cloth. The cloth was then dried in an oven at 65°C to obtain a test sample. An uncoated polypropylene hot air cloth was used as a blank control sample.

[0166] 2) H1N1 influenza A virus (ATCC VR-1469) was used as the experimental test virus strain. According to the requirements of ISO 18184:2019(E) for the determination of antiviral activity of textiles, 9 groups of 30 mL sample bottles were prepared. The virus titer was (1×10 7 TCID 50 / mL~5×10 7 TCID 50 / mL) of virus inoculated test suspension.

[0167] 3) The polypropylene hot air cloth samples sprayed with the antibacterial active ingredient of 3-hydroxybutyrate polymer derivative were cut into square specimens of 0.40±0.05 grams each, for a total of 9 samples, of which 6 samples were virus-inoculated experimental samples (including Group I: 3 unsprayed polypropylene hot air cloth blank samples and Group II: 3 groups of sprayed polypropylene hot air cloth samples); 3 samples were blank polypropylene hot air cloth control samples that were not inoculated with the virus and were not sprayed (Group III).

[0168] Accurately take 0.2ml of virus suspension by micropipette and add it dropwise to several points of 6 experimental samples, respectively, and place them in 6 groups of 30ml sample bottles with lids, and then cover the sample bottles. Immediately add 20ml of eluent to 3 of the virus-inoculated and unsprayed polypropylene hot air cloth blank samples (Group I), screw on the lid, vortex mix for 5s, repeat 5 times, and elute the virus from the unsprayed blank samples. After incubation at 25°C for 2h, add 20ml of eluent to 3 sprayed polypropylene hot air cloth test samples (Group II) and 3 groups of uninoculated and unsprayed blank polypropylene hot air cloth samples (Group III), cover the lid and vortex mix for 5s, repeat 5 times, and elute the virus from the two groups of samples.

[0169] 4) Using virus titer TICD 50 The virus titer of the remaining infectious virus was counted and the titer of the infectious virus was calculated. The reduction rate was calculated by comparing the ratio between the sprayed test sample and the unsprayed control sample through the common logarithm to obtain the antiviral activity value, thereby determining the antiviral performance of the test sample.

[0170] The anti-virus test results are shown in the figure:

[0171] As shown in the table above, the antiviral activity value (logarithmic reduction value) of the polypropylene hot air nonwoven fabric with an antiviral coating on its surface is 4.27, and the antiviral rate is greater than 99.99%, indicating that the 3-hydroxybutyrate polymer derivative obtained in this embodiment of the present invention has excellent antiviral effects.

[0172] Although the present invention has been described with reference to specific embodiments thereof, it will be appreciated by those skilled in the art that various changes and modifications may be made without departing from the true spirit and scope of the present invention. In addition, many modifications may be made to adapt specific circumstances, materials, compositions of matter, methods, and process steps to the spirit and scope of the present invention.

Claims

1. A poly 3-hydroxybutyrate polymer derivative having a structure as shown in formula (I): in, A is phenyl or phenyl C1-C4 alkyl, which is optionally substituted with a substituent selected from hydroxy, C1-C4 alkyl and C2-C4 alkenyl, R is a C1-C4 saturated alkyl group or a C1-C4 saturated alkyl group substituted with a hydroxyl group, Z is a polymerized residue of a hydroxy C3-C10 alkanoic acid, and x is an integer of 1-20, and y is an integer of 0-20.

2. The poly 3-hydroxybutyrate polymer derivative according to claim 1, wherein the A is selected from the group consisting of p-hydroxyphenyl, o-hydroxyphenyl, m-hydroxyphenyl, dihydroxyphenyl, trihydroxyphenyl, p-methylphenyl, o-methylphenyl, m-methylphenyl, benzyl, phenethyl and The group composed of.

3. The poly (3-hydroxybutyrate) polymer derivative according to claim 1 or 2, wherein R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, hydroxyethyl, 2,3-dihydroxypropyl and isobutyl.

4. The poly 3-hydroxybutyrate polymer derivative according to any one of claims 1 to 3, wherein the hydroxy C3-C10 alkanoic acid is selected from the group consisting of 3-hydroxyvaleric acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, and 3-hydroxydecanoic acid.

5. The poly 3-hydroxybutyrate polymer derivative according to any one of claims 1 to 4, wherein the content of 3-hydroxybutyrate monomer units in the poly 3-hydroxybutyrate polymer derivative is not less than 50 wt%, preferably not less than 70 wt%, not less than 90 wt% or not less than 95 wt%.

6. The poly 3-hydroxybutyrate polymer derivative according to any one of claims 1 to 5, which has a structure as shown in formula (II): where the sum of x and y is 1, 2, 3, 4, or 5.

7. The poly 3-hydroxybutyrate polymer derivative according to any one of claims 1 to 6, having a weight average molecular weight of no more than 10,000; preferably, the poly 3-hydroxybutyrate polymer derivative has a weight average molecular weight in the range of 200-10,000, more preferably in the range of 200-8,000, 200-5,000, 200-3,000 or 250-1,000. The poly 3-hydroxybutyrate polymer derivative according to any one of claims 1 to 7, which has a fragrant odor.

9. A method for preparing the poly 3-hydroxybutyrate polymer derivative according to any one of claims 1 to 8, wherein the method comprises: Providing a compound represented by formula (IV); The compound of formula (IV) undergoes a second esterification reaction with a carboxylic acid as shown in formula (III), A-COOH Formula (III) Preferably, the second esterification reaction is carried out at a temperature of 55-65°C; and Optionally, isolating the poly 3-hydroxybutyrate polymer derivative represented by formula (I) from the product mixture obtained from the second esterification reaction; wherein R, A, Z, x and y are as defined in claim 1.

10. The method according to claim 9, wherein the compound represented by formula (IV) is prepared by the following steps: Providing a polymer represented by formula (V) as a starting material; The terminal carboxyl group of the polymer represented by formula (V) undergoes a first esterification reaction with an alcohol to obtain an intermediate product represented by formula (IV), wherein the alcohol is a C1-C4 alkyl alcohol. Preferably, the first esterification reaction is carried out at a temperature of 100-150°C. The method according to claim 10 , wherein the polymer represented by formula (V) is a product obtained by microbial fermentation.

12. The method according to any one of claims 10-11, wherein the first esterification reaction is carried out in the presence of an acid, preferably the acid comprises one or more of sulfuric acid, an organic sulfonic acid or an anhydride thereof, preferably the organic sulfonic acid comprises one or more of benzenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid and alkylsulfonic acid.

13. The method according to any one of claims 10 to 12, wherein the reaction solvent of the first esterification reaction comprises one or more of dichloromethane and chloroform.

14. The method according to any one of claims 9 to 13, wherein the carboxylic acid of formula (III) is selected from the group consisting of benzoic acid, p-hydroxybenzoic acid, salicylic acid, gallic acid, and cinnamic acid.

15. The method according to any one of claims 10-14, wherein the C1-C4 alkyl alcohol is selected from the group consisting of monohydric alcohols and polyhydric alcohols, preferably, the monohydric alcohol includes methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, and the polyhydric alcohol includes ethylene glycol and glycerol.

16. The method according to any one of claims 10-15, wherein the first esterification reaction is carried out at a temperature of 100°C to 130°C.

17. An antibacterial and / or antiviral product comprising the poly 3-hydroxybutyrate polymer derivative according to any one of claims 1 to 8 or the poly 3-hydroxybutyrate polymer derivative obtained by the method according to any one of claims 9 to 16.

18. The antibacterial and / or antiviral product according to claim 17, comprising textiles, personal hygiene products, drug carriers, fabric finishing agents, cleaning products, fragrances or medical products; preferably, the textiles comprise masks, bedding and clothing.

19. The antibacterial and / or antiviral article according to any one of claims 17 to 18, which is in the form of a powder, solution, sol, gel, fiber, yarn or film.

20. Use of the 3-hydroxybutyrate polymer derivative according to any one of claims 1 to 8 or the 3-hydroxybutyrate polymer derivative obtained by the method according to any one of claims 9 to 16 in antibacterial and / or antiviral products.

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