A polyester with antibacterial and antiviral functions, its preparation method and application

Abstract

This invention relates to a polyester with antibacterial and antiviral functions, its preparation method, and its application. The polyester with antibacterial and antiviral functions is a cationic polymer guanidine salt-supported antibacterial and antiviral polyester. The preparation method includes the following steps: modifying the cationic polymer guanidine salt with a compound containing multiple functional groups to obtain a reactive antibacterial and antiviral adjuvant; during the polymerization of the polyester, adding the reactive antibacterial and antiviral adjuvant, terephthalic acid, diol, and catalyst in a single batch to a polyester reactor to obtain an antibacterial and antiviral random copolyester; or, copolymerizing the reactive antibacterial and antiviral adjuvant with diethyl terephthalate (BHET) to obtain an antibacterial and antiviral copolyester. Compared with the prior art, the polyester obtained by this invention exhibits no dissolution of the antibacterial and antiviral components, uniform dispersion, excellent durability, and good color value in the resulting fiber product.

Description

Technical Field

[0001] This invention relates to the field of functional polyester materials technology, and in particular to a polyester with antibacterial and antiviral functions, its preparation method, and its application. Background Technology

[0002] Protective clothing and masks, as personal protective equipment (PPE) materials, protect wearers from threats posed by harmful microorganisms in public environments. Typically, these protective devices prevent biohazards by providing physical barriers and delaying the penetration of contaminants. However, in recent years, due to the rapid spread of infectious diseases and the increasing threat of harmful organisms, the development of active protective clothing has become crucial.

[0003] Materials used in protective clothing fall into two categories: one is completely impermeable materials, such as butyl rubber and other elastomers, which excel at blocking harmful liquids and aerosols, but suffer from poor water vapor permeability; the other is fiber-based protective clothing, which provides both barrier properties and breathability and comfort to the skin. Among fiber materials, polyester fiber, as the most widely used synthetic polymer, plays a crucial role in the medical textile industry. Developing durable, stable, efficient, and broad-spectrum antibacterial / antiviral polyester fiber protective clothing to meet both medical and civilian needs has become an urgent task.

[0004] The most in-depth research method for manufacturing antibacterial and antiviral PPE is combining PPE with antibacterial agents. The preparation of antibacterial and antiviral fabrics mainly includes surface coating, melt blending, and in-situ polymerization methods. First, antibacterial agents are physically adsorbed onto the fabric through impregnation, coating, sputtering, etc., giving the fabric antibacterial and antiviral functions. This method is simple and low-cost; however, it has disadvantages such as affecting the fabric's hand feel and poor wash resistance. Chemical bonding imparts antibacterial / antiviral properties to fibers or fabrics; compared to physical surface modification, it has better wash resistance and durability, but it also suffers from significant changes in fabric hand feel, color, and mechanical properties before and after finishing. Second, inorganic powders or organic auxiliaries are added during the melt spinning stage, blended with polymers, and then spun to obtain antibacterial / antiviral fibers. The blending process is simple, and the antibacterial and antiviral effects can be maintained for a long time, but the process can lead to additive agglomeration and migration of antibacterial and antiviral auxiliaries into the matrix. Third, in-situ polymerization is a method of copolymerizing polymeric antibacterial and antiviral components with polymer monomers and then spinning them. The difficulty lies in the high technical development requirements. Summary of the Invention

[0005] The purpose of this invention is to solve the above-mentioned problems by providing a polyester with antibacterial and antiviral functions, its preparation method and application. The obtained polyester has no leaching of antibacterial and antiviral components, is uniformly dispersed, has good durability, and the obtained fiber product has good color value.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] The first aspect of this invention provides a method for preparing a polyester with antibacterial and antiviral functions, wherein the polyester with antibacterial and antiviral functions is a cationic polymer guanidine salt-supported antibacterial and antiviral polyester, and the preparation method includes the following steps:

[0008] S1: The cationic polymer guanidine salt is modified with a compound containing multiple functional groups to obtain a reactive antibacterial and antiviral adjuvant.

[0009] S2: During the polymerization of polyester, the reactive antibacterial and antiviral auxiliaries, terephthalic acid, diol, and catalyst are added to the polyester reactor in one pot to obtain an antibacterial and antiviral random copolyester.

[0010] or,

[0011] The reactive antibacterial and antiviral adjuvant was copolymerized with bis(hydroxyethyl) terephthalate (BHET) to obtain an antibacterial and antiviral copolyester.

[0012] Further, in S1, the reactive antibacterial and antiviral adjuvant is prepared by a cationic polymer guanidine salt and a compound A, B with multifunctional groups through a melt reaction or a solution reaction, wherein the molar ratio of the cationic polymer guanidine salt to the compound A, B with multifunctional groups is 0.5-6.

[0013] Furthermore, in S1, the structure of the reactive antibacterial and antiviral adjuvant is as follows:

[0014]

[0015] Where m contains 3-12 methylene segments, X is hydrochloric acid, phosphoric acid, nitric acid, carbonic acid or benzenesulfonic acid, and n is 2-50.

[0016] Furthermore, in S1, the compounds A and B with multifunctional groups are compounds with multifunctional groups;

[0017] The functional group is one or more epoxy groups, or an acid anhydride group, or a polyhydroxy or carboxyl group, or an ester group.

[0018] Furthermore, in S2, the solvent used is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, water, isopropanol, or ethanol;

[0019] Further, in S2, the diol is selected from at least one of ethylene glycol, propylene glycol, butanediol, or pentanediol.

[0020] Further, in S2, the antibacterial and antiviral adjuvant accounts for 0.1%-8% of the mass fraction of terephthalic acid, and the molar ratio of terephthalic acid to diol is 1:1-1:1.6;

[0021] The catalyst is antimony acetate or antimony glycolate, and the amount of catalyst added is 0.01%-0.5% of the mass of terephthalic acid.

[0022] Furthermore, in S2, the esterification reaction temperature is controlled between 180-260℃, and the polycondensation reaction temperature is controlled between 200-290℃.

[0023] A second aspect of the present invention provides an antibacterial and antiviral polyester prepared by the method described above.

[0024] Furthermore, the antibacterial and antiviral polyester has a number-average molecular weight of 15,000-30,000, an intrinsic viscosity of 0.5-1.1 dL / g, and a melting point of 150-250℃.

[0025] A third aspect of the present invention provides an application of the antibacterial and antiviral polyester as described above, wherein the antibacterial and antiviral polyester is used in the preparation of antibacterial and antiviral fibers, the specific process being as follows:

[0026] The antibacterial and antiviral polyester fiber is prepared by pre-crystallization, drying, melt spinning and stretching of the antibacterial and antiviral polyester.

[0027] The antibacterial and antiviral fiber has a single filament fineness of 0.3-10 dtex and a breaking strength of 1.5-7.0 cN / dtex;

[0028] The antibacterial and antiviral fibers have an antibacterial and antiviral effect of greater than 99%.

[0029] Compared with existing technologies, this technical solution has the following technical advantages:

[0030] 1. In this invention, a cationic polymer guanidine salt is attached to a functional group and polymerized in situ in a polyester matrix by covalent bonding, thereby achieving intrinsic antibacterial and antiviral effects.

[0031] 2. The antibacterial and antiviral adjuvants used in this invention are non-irritating to the skin, do not easily induce bacterial resistance, and are suitable for widespread use;

[0032] 3. The antibacterial and antiviral polyester obtained by this invention can effectively improve the problem of poor interfacial compatibility and mechanical properties of fibers prepared with high amounts of antibacterial and antiviral additives.

[0033] 4. The antibacterial and antiviral fiber prepared by this invention can effectively inhibit bacteria and viruses, with long-lasting effects, significant wash resistance, and no leaching of antibacterial and antiviral additives. It is green and environmentally friendly, has no harm to the environment, and has broad application prospects. Detailed Implementation

[0034] The specific steps of the preparation method of the cationic polymer guanidine salt-loaded antibacterial and antiviral polyester fiber in this invention include:

[0035] Step 1: Modify the cationic polymer guanidine salt with compounds containing multifunctional groups to obtain a reactive antibacterial and antiviral adjuvant;

[0036] Step 2: During the polymerization of polyester, the above-mentioned reactive antibacterial and antiviral auxiliaries, terephthalic acid, diol, catalyst, etc. are added to the polyester reactor in proportion to obtain an antibacterial and antiviral random copolyester; or it is copolymerized with diethyl terephthalate (BHET) to obtain an antibacterial and antiviral copolyester.

[0037] The third step involves pre-crystallizing, drying, melt spinning, and stretching the prepared antibacterial and antiviral copolyester to obtain antibacterial and antiviral polyester fibers.

[0038] The first step of the preparation method for reactive antibacterial and antiviral adjuvants involves the preparation of a cationic polymer guanidine salt and a compound A and B with multiple functional groups through a melt reaction or solution reaction, with the molar ratio of the two being 0.5-6.

[0039] The reactive cationic polymer guanidine salt has the following structure:

[0040] or

[0041] Where m can contain 3-12 methylene segments, X can be hydrochloric acid, phosphoric acid, nitric acid, carbonic acid or benzenesulfonic acid, and n is 2-50.

[0042] A and B are compounds containing multiple functional groups. The functional groups can be one or more epoxy groups, an acid anhydride group, multiple hydroxyl or carboxyl groups, or ester groups.

[0043] Compounds containing epoxy functional groups include one or more of epichlorohydrin, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and glycerol triglycidyl ether. Compounds containing anhydride groups include one or more of maleic anhydride, phthalic anhydride, furanyl anhydride, succinic anhydride, and glutaric anhydride. Compounds containing carboxyl functional groups can be 6-chlorohexanoic acid or 5-chlorovalerate. Polyhydroxyl or carboxyl groups refer to hydrolysis products containing both epoxy functional groups and anhydride groups, or compounds containing both carboxyl and hydroxyl groups, such as glycolic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxyvalerate, and 6-hydroxyhexanoic acid. Ester groups can be methyl terephthalate or methyl isophthalate.

[0044] In the preparation of reactive antibacterial and antiviral adjuvants, the solvent used can be one or more of dimethyl sulfoxide, N,N-dimethylformamide, water, isopropanol, or ethanol.

[0045] The diol in the second step is at least one of ethylene glycol, propylene glycol, butanediol, or pentanediol.

[0046] In the second step, the antibacterial and antiviral adjuvant accounts for 0.1%-8% of the mass of terephthalic acid, the molar ratio of terephthalic acid to diol is 1:1-1:1.6, and the catalyst is antimony acetate or antimony glycol, with the amount of catalyst added being 0.01%-0.5% of the mass of terephthalic acid.

[0047] During the polymerization reaction, the esterification reaction temperature is controlled between 180-260℃, and the polycondensation reaction temperature is controlled between 200-290℃.

[0048] The number average molecular weight of antibacterial and antiviral polyester is 15,000-30,000, the intrinsic viscosity is 0.5-1.1 dL / g, and the melting point is 150-250℃.

[0049] The monofilament fineness of the antibacterial and antiviral fibers is 0.3-10 dtex, and the breaking strength is 1.5-7.0 cN / dtex. The antibacterial and antiviral efficacy of the fibers is greater than 99%.

[0050] The present invention will now be described in detail with reference to specific embodiments, but this is by no means a limitation thereof. Any preparation methods, materials, structures, or compositional ratios not explicitly described in this technical solution are considered common technical features disclosed in the prior art.

[0051] Method for determining antibacterial rate: The antibacterial properties of the fibers were tested according to GB / T 20944.3-2008-T Evaluation of Antibacterial Properties of Textiles Part 3: Shaking Method. The sample is considered to have antibacterial effect when the inhibition rate against Staphylococcus aureus and Escherichia coli is ≥70%. For AAA grade products, after 50 washes, the inhibition rate against Staphylococcus aureus is ≥80%, and the inhibition rate against Escherichia coli is ≥70%. The antiviral properties of the fibers were tested according to ISO 18184:2014.

[0052] Example 1

[0053] In this embodiment, intrinsic antibacterial and antiviral polyester fibers are prepared according to the following steps:

[0054] 1) First, polyhexamethylene guanidine hydrochloride was prepared by melt polycondensation. Guanidine hydrochloride in a molar ratio of 1.0-1.5 was reacted with 1,6-hexanediamine at 120°C for 2 h, and then the temperature was raised to 160°C for 14 h to obtain polyhexamethylene guanidine hydrochloride (PHMG).

[0055] 2) Epoxy groups were introduced into PHMG by reacting it with ethylene glycol diglycidyl ether in dimethyl sulfoxide, wherein the molar ratio of amino to epoxy groups was maintained at 1.0. The reaction was carried out at 50 °C for 4 h, and the product was precipitated with acetone to remove unreacted substrate. After vacuum drying at 25 °C for 12 h, the finally purified modified antibacterial and antiviral adjuvant PHMG-EGDE was obtained.

[0056] 3) Terephthalic acid (PTA) and ethylene glycol were added to a reactor at a molar ratio of 1:1.4. Antimony glycolate (0.5% of PTA by mass) was added, and the mixture was heated to 230℃ for esterification for 2 hours to obtain an oligomeric polyester. After esterification, the antibacterial and antiviral adjuvant PHMG-EGDE obtained in step 2 was added, with the amount of PHMG-EGDE being 1% of the PTA by mass. A polycondensation reaction was then carried out at 270℃, under slow vacuum for 1 hour, followed by polymerization under high vacuum for 2 hours. The product was then discharged, pelletized, and the antibacterial and antiviral polyester PET-I was obtained. PET-I polyester has a number-average molecular weight of 15000, an intrinsic viscosity of 0.55 dL / g, and a melting point of 240℃.

[0057] 4) Antibacterial and antiviral polyester PET-I is pre-crystallized, dried, spun, and drawn to obtain fibers. The fiber has a single filament fineness of 2.0 dtex and a breaking strength of 2.0 cN / dtex. It exhibits a 99% inhibition rate against Staphylococcus aureus and Escherichia coli. After 50 washes, it maintains a 99% inhibition rate against Staphylococcus aureus and Escherichia coli, and a 99% antiviral activity against H1N1 influenza A virus.

[0058] Example 2

[0059] In this embodiment, intrinsic antibacterial and antiviral polyester fibers are prepared according to the following steps:

[0060] 1) First, PHMG was prepared according to the method in Example 1; PHMG (5 mmol) was dissolved in 50 ml of ethanol, and 10 mmol of succinic anhydride ethanol solution (50 ml) was added. The reaction was carried out at 70 °C for 2 h. The solvent was removed by rotary evaporation. Then, acetone was added to remove unreacted substrate, the precipitate was centrifuged, and the precipitate was dried thoroughly in a vacuum drying oven to obtain the antibacterial and antiviral adjuvant PHMG-SA.

[0061] 2) Place the PHMG-SA obtained in step 1 into a vacuum drying oven and dry it at 60°C for 12 hours to fully remove water; prepare the oligomeric polyester according to Example 1; after esterification, add PHMG-SA, the amount of PHMG-SA added is 1% of the mass of PTA; carry out polycondensation reaction, the reaction temperature is 275°C, slowly vacuum for 1 hour, and polymerize under high vacuum for 2 hours; discharge, granulate, and obtain antibacterial and antiviral polyester PET-II. The number average molecular weight of PET-II polyester is 19000, the intrinsic viscosity is 0.67 dL / g, and the melting point is 243°C.

[0062] 3) Antibacterial and antiviral polyester PET-II is pre-crystallized, dried, spun, and drawn to obtain fibers. The fiber has a single filament fineness of 1.2 dtex, a breaking strength of 2.3 cN / dtex, and exhibits a 99% inhibition rate against Staphylococcus aureus and Escherichia coli. After 50 washes, the inhibition rate against Staphylococcus aureus reaches 92%, against Escherichia coli 90%, and the antiviral activity against H1N1 influenza A virus is 99%.

[0063] Example 3

[0064] In this embodiment, intrinsic antibacterial and antiviral polyester fibers are prepared according to the following steps:

[0065] 1) First, PHMG was prepared according to the method in Example 1 and cooled to 80°C. Then, methyl terephthalate (molar ratio of 2:1 to PHMG) was added to a round-bottom flask, and nitrogen gas was fully introduced to melt it with PHMG. The mixture was first mixed at 90°C for 1 hour. Then, the temperature was raised to 130°C and the reaction was stirred for 4 hours. The product was discharged to obtain the antibacterial and antiviral adjuvant PHMG-DMT.

[0066] 2) Place the PHMG-DMT obtained in step 1 into a vacuum drying oven and dry it at 60°C for 12 hours to remove moisture completely; prepare the oligomeric polyester according to Example 1; after esterification, add PHMG-DMT, the amount of PHMG-DMT added is 1% of the mass of PTA; carry out polycondensation reaction, the reaction temperature is 280°C, slowly vacuum for 1 hour, and polymerize under high vacuum for 2 hours; discharge, granulate, and obtain antibacterial and antiviral polyester PET-Ⅲ. The number average molecular weight of PET-Ⅲ polyester is 19500, the intrinsic viscosity is 0.69 dL / g, and the melting point is 244°C.

[0067] 3) Antibacterial and antiviral polyester PET-III was pre-crystallized, dried, spun, and drawn to obtain fibers. The fiber's monofilament fineness was 1.8 dtex, its breaking strength was 3.0 cN / dtex, and it exhibited a 99% inhibition rate against Staphylococcus aureus and Escherichia coli. After 50 washes, the inhibition rate against Staphylococcus aureus and Escherichia coli reached 95%, and the antiviral activity against H1N1 influenza A virus was 99%.

[0068] Example 4

[0069] In this embodiment, intrinsic antibacterial and antiviral polyester fibers are prepared according to the following steps:

[0070] 1) First, PHMG was prepared according to the method in Example 1, and the resulting product was thoroughly dried. Terephthalic acid (PTA) and ethylene glycol were added to a reactor at a molar ratio of 1:1.2, along with PHMG at 1% PTA mass ratio, phthalic anhydride at 2% PTA mass ratio, and antimony glycolate catalyst at 0.5% PTA mass ratio. The mixture was heated to 250°C for esterification for 2 hours to obtain an oligomeric polyester. A polycondensation reaction was then carried out at a temperature between 265°C and 265°C, with slow vacuuming for 1 hour, followed by polymerization under high vacuum for 2 hours. The product was then discharged, pelletized, and the antibacterial and antiviral polyester PET-Ⅳ was obtained. PET-Ⅳ polyester had a number-average molecular weight of 15500, an intrinsic viscosity of 0.57 dL / g, and a melting point of 227°C.

[0071] 3) Antibacterial and antiviral polyester PET-Ⅳ is pre-crystallized, dried, spun, and drawn to obtain fibers. The fiber has a single filament fineness of 1.5 dtex, a breaking strength of 1.9 cN / dtex, and exhibits a 99% inhibition rate against Staphylococcus aureus and Escherichia coli. After 50 washes, the inhibition rate against Staphylococcus aureus is 90%, against Escherichia coli is 85%, and the antiviral activity against H1N1 influenza A virus is 99%.

[0072] Example 5

[0073] In this embodiment, intrinsic antibacterial and antiviral polyester fibers are prepared according to the following steps:

[0074] 1) Terephthalic acid (PTA) and ethylene glycol were added to a reactor at a molar ratio of 1:1.4, along with antimony glycolate catalyst at 0.5% of the PTA mass. The mixture was heated to 250°C for esterification for 2 hours to obtain an oligomeric polyester. Polycondensation was then carried out at a temperature between 280°C and 280°C, with slow vacuuming for 1 hour, followed by polymerization under high vacuum for 2 hours. The product was then discharged, granulated, and PET-0 was obtained. PET-0 was placed in a vacuum drum oven and dried at 130°C for 2 hours, followed by further drying at 150°C for 14 hours.

[0075] 2) The antibacterial and antiviral adjuvant PHMG-E was prepared according to Example 2 and dried thoroughly in a vacuum drying oven for 24 hours. The above-mentioned PET-0 and PHMG-E were blended and granulated at a mass ratio of 90:10 at 270°C to obtain the antibacterial and antiviral polyester PET-VI. The number-average molecular weight of PET-VI polyester was 24,500, the intrinsic viscosity was 0.69 dL / g, and the melting point was 245°C.

[0076] 3) Antibacterial and antiviral polyester PET-V is pre-crystallized, dried, spun, and drawn to obtain fibers. The fiber has a single filament fineness of 2.5 dtex, a breaking strength of 3.2 cN / dtex, and exhibits a 90% inhibition rate against Staphylococcus aureus and Escherichia coli. After 50 washes, the inhibition rate against Staphylococcus aureus reaches 80%, against Escherichia coli 85%, and the antiviral activity against H1N1 influenza A virus is 90%.

[0077] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing a polyester with antibacterial and antiviral functions, characterized in that, The polyester with antibacterial and antiviral functions is a cationic polymer guanidine salt-supported antibacterial and antiviral polyester, and its preparation method includes the following steps: S1: The cationic polymer guanidine salt is modified with a compound containing multiple functional groups to obtain a reactive antibacterial and antiviral adjuvant. S2: During the polymerization of polyester, the reactive antibacterial and antiviral auxiliaries, terephthalic acid, diol, and catalyst are added to the polyester reactor in one pot to obtain an antibacterial and antiviral random copolyester. or, The reactive antibacterial and antiviral adjuvant was copolymerized with diethyl terephthalate to obtain an antibacterial and antiviral copolyester. In S1, the reactive antibacterial and antiviral adjuvant is prepared by a cationic polymer guanidine salt and a compound with multiple functional groups through a melt reaction or a solution reaction, wherein the molar ratio of the cationic polymer guanidine salt to the compound with multiple functional groups is 1:0.5-6. In S1, the compound with multifunctional groups is selected from ethylene glycol diglycidyl ether, succinic anhydride, methyl terephthalate, or phthalic anhydride.

2. The method for preparing a polyester with antibacterial and antiviral functions according to claim 1, characterized in that, In S1, the structure of the reactive antibacterial and antiviral adjuvant is as follows: or Where m contains 3-12 methylene segments, X is hydrochloric acid, phosphoric acid, nitric acid, carbonic acid or benzenesulfonic acid, and n is 2-50.

3. The method for preparing a polyester with antibacterial and antiviral functions according to claim 1, characterized in that, In S2, the solvent used is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, water, isopropanol or ethanol; The diol is selected from at least one of ethylene glycol, propylene glycol, butanediol, or pentanediol.

4. The method for preparing a polyester with antibacterial and antiviral functions according to claim 1, characterized in that, In S2, the antibacterial and antiviral adjuvant accounts for 0.1%-8% of the mass fraction of terephthalic acid, and the molar ratio of terephthalic acid to diol is 1:1-1:1.6; The catalyst is antimony acetate or antimony glycolate, and the amount of catalyst added is 0.01%-0.5% of the mass of terephthalic acid.

5. The method for preparing a polyester with antibacterial and antiviral functions according to claim 1, characterized in that, In S2, the esterification reaction temperature is controlled between 180-260℃, and the polycondensation reaction temperature is controlled between 200-290℃.

6. An antibacterial and antiviral polyester prepared by the method according to any one of claims 1 to 5.

7. A polyester with antibacterial and antiviral functions according to claim 6, characterized in that, The antibacterial and antiviral polyester has a number-average molecular weight of 15,000-30,000, an intrinsic viscosity of 0.5-1.1 dL / g, and a melting point of 150-250℃.

8. An application of the antibacterial and antiviral polyester as described in claim 6, characterized in that, The antibacterial and antiviral polyester is used in the preparation of antibacterial and antiviral fibers, and the specific process is as follows: The antibacterial and antiviral polyester fiber is prepared by pre-crystallization, drying, melt spinning and stretching of the antibacterial and antiviral polyester. The antibacterial and antiviral fiber has a single filament fineness of 0.3-10 dtex and a breaking strength of 1.5-7.0 cN / dtex; The antibacterial and antiviral fibers have an antibacterial and antiviral effect of greater than 99%.

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