CN116135907A - Intrinsic antibacterial nylon and preparation method and application thereof - Google Patents
Intrinsic antibacterial nylon and preparation method and application thereof Download PDFInfo
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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Abstract
The invention provides an intrinsic antibacterial nylon which is prepared by homopolymerization and polymerization and has a structural formula of
Wherein R is 1 A linear hydrocarbon group of 1 to 10 carbon atoms; r is R 2 Is furan ring, benzene ring, pyrazine ring, C1-C3 straight-chain hydrocarbon group; n is 50-200. By adopting the technical scheme of the invention, the Schiff base structure with antibacterial activity is designed in the main chain of the polyamide material, so that the broad-spectrum antibacterial performance of the nylon material is realized, the problems of reduced antibacterial performance, pollution of the antibacterial agent and the like caused by precipitation of the antibacterial agent are solved, the production method is simple, the cost is low, and the application forms are flexible and various.
Description
Technical Field
The invention relates to the technical field of functional nylon preparation, in particular to an intrinsic antibacterial nylon, and a preparation method and application thereof.
Background
Polyamide (nylon) is one of the most widely used engineering plastics in terms of yield, variety and use. The modified polyurethane has the excellent physical and chemical properties of high mechanical strength, good electrical property, wear resistance, oil resistance, weak acid resistance, weak base, weak polar organic solvent resistance, good processing fluidity and the like, and is widely applied to the fields of buildings, automobiles, communication, packaging, personal care, fabrics and the like. Along with the development of production technology, various main nylon resins and modification technologies are rapidly developed, and various functional characteristics of nylon besides mechanical properties, such as antibacterial, low temperature resistance, high temperature resistance and the like, are endowed. The application field of the functionalized nylon material is further expanded.
Nylon products are easy to be contaminated and bred with various microorganisms including pathogenic bacteria in the process of processing and using, and cause a certain harm to the health of people. Particularly, in the application of clothing, food packaging and medical fields, the high-efficiency broad-spectrum durable and safe antibacterial performance of nylon materials is highly concerned.
The traditional antibacterial nylon material is mainly realized by adding organic antibacterial agents (quaternary ammonium salts, chitosan, guanidine salts and the like) and inorganic antibacterial agents (zinc oxide, nano silver and the like). For example, chinese patent 113802379A realizes the efficient antibacterial effect of nylon 6 fiber by adding 0.1-1wt% of organic antibacterial agent such as quaternary ammonium salt into nylon 6. And Chinese patent No. CN113802379A realizes the antibacterial property of the nylon composite material by adding inorganic antibacterial agents such as nano silver and the like into the copolymerized nylon. However, this strategy of achieving antimicrobial efficacy of nylon materials by adding antimicrobial agents inevitably suffers from deficiencies in the materials produced due to the deficiencies of the antimicrobial agents themselves. For the organic antibacterial agent, the organic antibacterial agent has relatively good compatibility with nylon matrix resin, can be uniformly dispersed, but is easy to decompose in the high-temperature nylon processing process to cause failure, and meanwhile, the organic antibacterial agent has stronger toxicity and is easy to cause the defect of bacterial drug resistance; while the inorganic antibacterial agent has good high-temperature stability, the inorganic antibacterial agent is easy to separate out in the long-term service process to cause the reduction and even failure of the antibacterial effect, and meanwhile, the antibacterial agent separated out in the fields of implantable articles, food packaging and the like can cause secondary pollution.
Chinese patent No. CN114635292a discloses a polyamide fabric coated with polyurethane having a schiff base network structure and a preparation method thereof, wherein a solution containing polyurethane having a schiff base network structure is subjected to a doctor blading-baking technique to obtain a fabric coating having an antibacterial effect. However, the preparation method of the Schiff base network structure polyurethane is complex, the condition is harsh, the cost is high, and the preparation method can intangibly and greatly improve the raw material cost when the Schiff base network structure polyurethane is applied to common commercial nylon sheets or films.
Therefore, the nylon material which has the advantages of simple production method, low cost, flexible and various application forms and good antibacterial property has positive significance for the production of nylon industry.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention discloses an intrinsic antibacterial nylon and a preparation method and application thereof, wherein a Schiff base structure with antibacterial activity is designed in a main chain of a polyamide material, so that the broad-spectrum antibacterial performance of the nylon material is realized, the problems of reduced antibacterial performance, pollution of the antibacterial agent and the like caused by precipitation of the antibacterial agent are solved, and the production method is simple, low in cost and flexible and various in application form.
In order to achieve the above purpose, the invention provides the following technical scheme, namely the intrinsic antibacterial nylon, the structural formula of which is shown as the formula (I):
R 2 is furan ring, benzene ring, pyrazine ring, C1-C3 straight-chain hydrocarbon group; n is 50-200; the antibacterial rate of the intrinsic antibacterial nylon to the escherichia coli and/or the staphylococcus aureus is 100%.
Preferably, the intrinsic antibacterial nylon is prepared from a raw material A and a raw material B;
wherein the structural formula of the raw material A is shown as a formula (II):
The structural formula of the raw material B is shown as (III):
In some preferred embodiments, feedstock B is any of 2, 5-furandicarboxaldehyde, terephthalaldehyde, 1, 4-pyrazindicarboxaldehyde, malondialdehyde, succinaldehyde, or glutaraldehyde.
Preferably, the intrinsic antimicrobial nylon is a homopolymerized nylon; the number average molecular weight is more than or equal to 5000g/mol; or, more than or equal to 10000g/mol; or, more than or equal to 20000g/mol; and/or the weight average molecular weight is not less than 10kg/mol; or, more than or equal to 20kg/mol; or, at least 50kg/mol; or more than or equal to 100kg/mol.
The antibacterial rate of the intrinsic antibacterial nylon on escherichia coli and/or staphylococcus aureus can reach 100%.
In order to achieve another purpose, the invention also provides a preparation method of the intrinsic antimicrobial nylon, which comprises the steps of respectively dissolving the raw material A and the raw material B in an organic solvent, uniformly mixing, stirring and reacting for 12-24 hours at 50-70 ℃ to perform homopolymerization reaction to obtain the intrinsic antimicrobial nylon; and/or filtering or suction filtering to separate out solid matters in the reaction system after the reaction is finished, namely the intrinsic antibacterial nylon.
Preferably, the organic solvent comprises any one or more of diethyl ether, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol dimethyl ether, anisole, m-nitroanisole, p-chloroanisole, methyl isobutyl ketone, acetophenone, p-chloroacetophenone, o-nitroacetophenone, sulfolane, methylene chloride, chloroform, 1, 2-dichloroethane, chlorobenzene, alpha-naphthalene chloride, acetonitrile, propionitrile, benzene, toluene, benzene cyanide, nitrobenzene, nitrotoluene, ethyl acetate, and methyl benzoate.
Preferably, the feed a and feed B are added in equimolar proportions.
The intrinsic antibacterial nylon provided by the technical scheme is added with other reagents, uniformly mixed, and subjected to injection molding compression molding at 240-260 ℃ by an injection molding machine to prepare the intrinsic antibacterial nylon sheet, molded or molded product. Other include, but are not limited to, adjuvants or modifiers, etc., such as plasticizers, flame retardants, lubricants, ultraviolet absorbers, antioxidants, fillers, etc.
The invention tests and verifies the antibacterial performance of the sheet, film material or coating using the intrinsic antibacterial nylon, and compares the sheet, film material or coating with products such as nylon 6 and nylon 66 sold in the market in the prior art under the same conditions, and the results show that the intrinsic antibacterial nylon prepared by the invention has outstanding antibacterial performance, and particularly has 100% antibacterial rate for Escherichia coli and staphylococcus aureus (Staphylococcus aureus) compared with the prior art.
The technical scheme of the invention has the technical effects that:
1. by adopting the technical scheme of the invention,
(1) The intrinsic antibacterial nylon provided by the technical scheme of the invention is prepared by adopting a homopolymerization method, and the nylon material with excellent antibacterial performance and antibacterial long-acting stability can be obtained without adding an antibacterial agent into the nylon material, so that the problems of precipitation of the antibacterial agent and the like in the material in-service process are avoided, and the antibacterial performance and the antibacterial aging of the formed intrinsic antibacterial nylon material can be effectively ensured.
(2) The preparation method of the intrinsic antibacterial nylon provided by the technical scheme of the invention has the advantages of simple process, high yield, safety, environmental protection and low cost.
(3) The intrinsic antibacterial nylon material provided by the technical scheme of the invention has various processing modes in the application process, can be prepared by methods such as melt extrusion injection molding, solution film forming and the like, is simple to operate and easy to control, and is very suitable for industrial production.
(4) The intrinsic antibacterial nylon product provided by the technical scheme of the invention has long-acting antibacterial performance, and the effective antibacterial time is basically the same as the service life of the intrinsic antibacterial nylon product, and is far higher than that of a nylon product prepared by adding an antibacterial agent in the prior art in the earlier stage of production.
Drawings
FIG. 1 Nuclear magnetic resonance according to example 1 of the present invention 1 H-NMR spectra.
Detailed Description
The objects, technical solutions and advantages of the embodiments of the present invention will be more apparent, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The disclosures of all patent and non-patent documents cited in this invention are incorporated herein by reference in their entirety.
The terms "comprises," "comprising," "includes," "including," "having," "with," or any other variation thereof, as used in the present invention, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or". For example, the condition a or B satisfies any one of the following: a is true (or present) and B is false (or absent), a is false (or absent) and B is true (or present), and a and B are both true (or present). The phrase "one or more" is intended to cover a non-exclusive inclusion. For example, one or more of A, B and C, means any one of the following: a alone, B alone, a combination of C, A and B alone, a combination of B and C, a combination of a and C, or a combination of A, B and C.
In addition, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the invention. This description should be read to include one or at least one, and the singular also includes the plural unless it is obvious that it is meant otherwise.
As used herein, the term "bio-derived" is used interchangeably with "biobased" or "bio-derived" and refers to chemical compounds including monomers and polymers obtained in whole or in any part from any renewable resource, including but not limited to plants, animals, marine materials, or forestry materials. The "biobased content" of any such compound is to be understood as determining the percentage of carbon content of the compound that has been obtained or derived from such renewable resources.
As used herein, the term "furan dicarboxaldehyde" is used interchangeably with 2, 5-diformylfuran, 2, 5-furan dicarboxaldehyde, 2, 4-furan dicarboxaldehyde, 3, 4-furan dicarboxaldehyde, and 2, 3-furan dicarboxylic acid. As used herein, 2, 5-furandicarboxaldehyde (DFF) is an oxidized furan derivative having the structural formula:
Some embodiments of the present invention provide a method for preparing an intrinsically antimicrobial nylon, comprising: respectively dissolving the raw materials A and B in the same solvent system in an equimolar ratio, pouring the raw materials A and B into the same reaction kettle, uniformly mixing the raw materials A and B, stirring the raw materials B at 50-70 ℃ for reaction for 12-24 hours, and performing suction filtration from the reaction system after the reaction is finished to obtain a precipitate, namely the target intrinsic antibacterial nylon product; and/or filtering and separating out solid matters in the reaction system after the reaction is finished, namely the intrinsic antibacterial nylon, wherein the structural general formula of the intrinsic antibacterial nylon is shown as the formula (I):
By regulating R in the raw materials 1 And R is 2 The kind, solvent, reaction temperature and reaction time of the nylon resin are selected to obtain a series of intrinsic antibacterial nylon resins, and products such as sheets, films, coatings and the like are obtained by adopting processing technologies such as casting, melt extrusion, brushing and the like.
In some embodiments, the structural formula of feedstock a is as shown in (II):
wherein R in raw material A 1 Is benzene ring, -CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -any one of them.
In some embodiments, the structural formula of the raw material B is shown in (III):
wherein R in raw material B 2 Is furan ring, pyrazine ring, benzene ring, -CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -any one of them.
In some embodiments, the furandicarboxaldehyde is derived from a biomass material.
In some embodiments, the prepared intrinsic antimicrobial nylon material is also subjected to an antimicrobial property test after an accelerated aging test; wherein the time of the accelerated aging test is 500-1000 hours; the conditions for the accelerated aging test are that the humidity is greater than or equal to 99% and the temperature is 30 ℃.
In some comparative examples, comparative nylon resins selected, including but not limited to nylon 66, nylon 6T66, nylon 6I6T, and nylon 6, were all selected from commercial products purchased from switzerland Ai Mansi, sucarb, dupont, basf, and the like.
In some embodiments, the intrinsic antimicrobial nylon prepared by the technical scheme of the invention is used for preparing nylon material products, and the intrinsic antimicrobial nylon material products are prepared by double-screw melt extrusion and injection molding, and the processing temperature is 240-260 ℃. In some embodiments, the intrinsic antimicrobial nylon material article is formed by dissolving it in Hexafluoroisopropanol (HFIP), then coating the solution onto the surface of a metal substrate such as stainless steel, carbon steel, aluminum, etc., and after the solvent has evaporated, forming an intrinsic antimicrobial nylon coating.
In some embodiments, the intrinsically antimicrobial nylon material article is prepared by dissolving it in Hexafluoroisopropanol (HFIP), casting the solution into polytetrafluoroethylene or glass petri dish, and stripping after the solvent has evaporated.
In some embodiments, the furandicarboxaldehyde can be obtained from a renewable resource.
During processing, processing aids and modifiers conventional in the art, such as plasticizers, flame retardants, lubricants, ultraviolet absorbers, antioxidants, fillers, and the like, may also be used.
Specifically, plasticizers include, but are not limited to: one or more of dioctyl phthalate, didecyl phthalate, liquid paraffin, wax, dimethyl phthalate, diethyl phthalate, phosphate esters, etc.
And/or flame retardants include, but are not limited to: one or more of bis (hexachlorocyclopentadiene), cyclooctane, ammonium polyphosphate, decabromodiphenyl ether, bis (hydroxyethyl) methyl phosphine oxide, cyanuric acid, melamine, and the like.
And/or lubricants including, but not limited to: vinyl bis-stearamide, butyl stearate, and the like.
And/or ultraviolet absorbers include, but are not limited to: one or more of 2-hydroxy-4-methoxybenzophenone, 2-dihydroxy-4-methoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, ethylene-2-cyano-3, 3-diphenylacrylate, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, and the like.
And/or antioxidants include, but are not limited to: 4-hydroxymethyl-2, 6-di-tert-butylphenol, diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1-thiobis- (2-naphthol), 4-butylene-bis (6-tert-butyl-m-cresol), 2-thiobis- (4-methyl-6-tert-butylphenol) and the like.
And/or fillers include, but are not limited to: glass fiber, asbestos, wollastonite, calcium silicate, talc, montmorillonite, etc.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosed composition embodiments, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety unless a particular paragraph is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
The technical scheme, implementation process and principle of the invention will be further explained through specific examples. It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. The described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise indicated, reagents and starting materials used in the following examples were obtained commercially, and test methods in which specific conditions were not noted were generally conducted under conventional conditions or under conditions recommended by the respective manufacturers. Further, unless otherwise indicated, the experimental methods, detection methods, and preparation methods disclosed in the present invention all employ techniques conventional in the art. These techniques are well described in the prior art.
Examples and/or comparative examples relate to detection item criteria or methods:
1. molecular weight test
The number average molecular weight and weight average molecular weight of the product were determined using GPC columns.
Specifically, the size exclusion chromatography system Alliance 2695 (Waters Corporation, milford, MA) was equipped with a Waters 414TM differential refractive index detector, a multi-angle light scattering photometer DAWN Heleos II (Wyatt Technologies, santa barba, CA), and a ViscoStar TM differential capillary viscometer detector (Wyatt). The software for data acquisition and simplification was available from Wyatt, version 5.4. The column used was two Shodex GPC HFIP-806M styrene-divinylbenzene columns having a exclusion limit of 2X 107 and a theoretical plate of 8,000/30cm and an exclusion limit of 2X 10 5 And a Shodex GPC HFIP-804MTM styrene-divinylbenzene column with theoretical plates of 10,000/30 cm.
The sample was dissolved in 1, 3-hexafluoro-2-propanol (HFIP) containing 0.01M sodium trifluoroacetate, mixed with moderate stirring at 50℃for four hours, and then filtered using a 0.45 μm PTFE filter. The concentration of the solution was about 2mg/mL.
Setting the chromatograph to 35 ℃; the flow rate is 0.5mL/min, and data are collected; the injection volume was 100 μl; the run time was 80min. Data is imported from all three detectors to simplify the data. The light scatter detector employs eight scatter angles. The column correction references are not involved in the data processing.
2. 1 H-NMR Spectroscopy
The present prepared in the example was recorded in a 400MHz NMR apparatusDeuterated dimethyl sulfoxide (DMSO-d 6) or deuterated dichloromethane (CD) characterizing polyamides of antimicrobial nylon materials 2 Cl 2 ) In deuterated trifluoroacetic acid (TFA-d) of the polyamides of examples 4-10 1 H-NMR 13 C NMR spectrum. Chemical shifts of protons are recorded in ppm of low magnetic field of TMS using resonance of deuterated solvents as internal standard.
3. Antibacterial test
The antibacterial test method is carried out according to the test method of GBT31402-2015 plastic surface antibacterial property. The test strain selected for the antibacterial test comprises one or two of Escherichia coli (Escherichia coli) and Staphylococcus aureus (Staphylococcus aureus).
Example 1
The intrinsic antimicrobial nylon provided in this example is designated nylon 1#.
In this embodiment, the raw materials are respectively:
the raw material A has the structure as follows
R1 is-CH 2 CH 2 CH 2 CH 2 -。
Raw material B is 2, 5-furan dicarboxaldehyde.
The preparation method comprises the steps of mixing the raw material A and the raw material B in an equimolar manner, and dissolving the mixture in an organic solvent, wherein the organic solvent is a mixed solution of dichloromethane and dimethyl sulfoxide, and the volume ratio of the dichloromethane to the dimethyl sulfoxide is 1:10 The reaction is carried out for 18h at 60 ℃. After the reaction is finished, the reaction system is filtered, and the obtained precipitate is nylon 1# of the embodiment, and the structural formula is
Nylon 1# had a number average molecular weight of 10015 and a weight average molecular weight of 12361 as measured by GPC column chromatography.
And dissolving the prepared nylon 1# in hexafluoroisopropanol, coating the nylon 1# on the surface of metal aluminum by using a coating rod, volatilizing an air-drying solvent at room temperature to obtain an antibacterial coating containing the intrinsic antibacterial nylon, controlling the film thickness to be between 100 and 200 mu m, and testing the antibacterial performance of the antibacterial coating by using GBT 31402-2015.
The antibacterial agent 1# prepared in this example was subjected to structural characterization. Referring to FIG. 1, the nuclear magnetic resonance spectrum of the present embodiment shows two proton peaks a and b on the acylhydrazone structure generated after the reaction, wherein the proton peak a on the acylhydrazone structure generated after the reaction is located at 11-12ppm; the proton peak b on the imine bond linked to the furan ring, generated after the reaction, was located at 8.5ppm. As can be seen from the graph display, the structural formula can be prepared by adopting the technical scheme of the invention
Example 2
The intrinsic antimicrobial nylon provided in this example is designated nylon 2#.
In this embodiment, the raw materials are respectively:
the raw material A has the structure as follows
R 1 Is benzene ring.
Raw material B is 2, 5-furan dicarboxaldehyde.
The preparation method comprises the steps of mixing the raw material A and the raw material B in equal mole, dissolving the mixture in an organic solvent, wherein the organic solvent is a mixed solution of dichloromethane and dimethyl sulfoxide, and reacting for 24 hours at 55 ℃ in a volume ratio of 1:3. After the reaction, the reaction system is filtered, and the obtained precipitate is nylon 2# of the embodiment, and the structural formula is
Nylon 2# had a number average molecular weight of 12816 and a weight average molecular weight of 17687 as determined by GPC column chromatography.
Nylon 2# prepared in the example is dissolved in hexafluoroisopropanol, and is coated on the surface of metal aluminum by a coating rod, after the solvent is volatilized in air drying at room temperature, the antibacterial coating containing the intrinsic antibacterial nylon is obtained, the film thickness is controlled between 100 and 200 mu m, and the antibacterial performance of the antibacterial coating is tested by GBT 31402-2015.
Example 3
The intrinsic antimicrobial nylon provided in this example was designated nylon 3#.
In this embodiment, the raw materials are respectively:
the raw material A has the structure as follows
R1 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
Raw material B is 2, 5-furan dicarboxaldehyde.
The preparation method comprises the steps of mixing the raw material A and the raw material B in an equimolar manner, and dissolving the mixture in an organic solvent, wherein the organic solvent is a mixed solution of dichloromethane and dimethyl sulfoxide, and the volume ratio of the dichloromethane to the dimethyl sulfoxide is 1:10 The reaction is carried out for 20h at 65 ℃. After the reaction is finished, the reaction system is filtered, and the obtained precipitate is nylon No. 3 of the embodiment, and the structural formula is
Nylon 3# had a number average molecular weight of 1689 and a weight average molecular weight of 23211 as determined by GPC column chromatography.
Nylon 3# is dissolved in hexafluoroisopropanol, and is cast in a polytetrafluoroethylene mould, and after the solvent is evaporated in air at room temperature, the antibacterial film material containing the intrinsic antibacterial nylon is obtained, the film thickness is controlled between 300 and 1000 mu m, and the antibacterial performance of the antibacterial film material is tested by GBT 31402-2015.
Example 4
The intrinsic antimicrobial nylon provided in this example was designated nylon 4#.
In this embodiment, the raw materials are respectively:
the raw material A has the structure as follows
R 1 is-CH 2 CH 2 CH 2 CH 2 -。
Raw material B is terephthalaldehyde.
The preparation method comprises the steps of mixing the raw material A and the raw material B in an equimolar manner, and dissolving the mixture in an organic solvent, wherein the organic solvent is a mixed solution of benzene and dimethyl sulfoxide, and the volume ratio of the benzene to the dimethyl sulfoxide is 1:10 The reaction was carried out at 55℃for 24 hours. After the reaction, the reaction system is filtered, and the obtained precipitate is nylon No. 4 in the embodiment, and the structural formula is
Nylon 4# had a number average molecular weight of 12775 and a weight average molecular weight of 17629 as determined by GPC chromatography.
Nylon 4# is dissolved in hexafluoroisopropanol, and is cast in a polytetrafluoroethylene mould, after the solvent is evaporated in air at room temperature, the antibacterial film material containing the intrinsic antibacterial nylon is obtained, the film thickness is controlled between 300 and 1000 mu m, and the antibacterial performance of the antibacterial film material is tested by GBT 31402-2015.
Example 5
The intrinsic antimicrobial nylon provided in this example was designated nylon # 5.
In this embodiment, the raw materials are respectively:
the raw material A has the structure as follows
R 1 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
The raw material B is 1, 4-pyrazine dicarboxaldehyde.
The preparation method comprises the steps of mixing the raw material A and the raw material B in an equimolar manner, and dissolving the mixture in an organic solvent, wherein the organic solvent is a mixed solution of tetrahydrofuran, ethyl acetate and chloroform, and the volume ratio of the three is 1:2: 10 The reaction was carried out at 70℃for 12h. After the reaction is finished, the reaction system is filtered, and the obtained precipitate is nylon No. 5 of the embodiment, and the structural formula is
Nylon 5# has a number average molecular weight of 22090 and a weight average molecular weight of 3084 as determined by GPC chromatography.
After nylon 5# is blended with an antioxidant and a lubricant, the types and the proportions of the selected auxiliary agents such as the antioxidant are all the types commonly used in the common nylon processing process, the addition amount is also the same as that of the common nylon processing, the antioxidant 098 brand is Doverphos-9228, the chemical name is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, produced by Dover company in the United states, and the addition amount is 0.5% of nylon 5# in percentage by mass; the lubricant is pentaerythritol stearate, and the addition amount of the lubricant is 0.5% of nylon 5# by mass percent.
Sheets were extruded through a screw extruder at 250 ℃ with a 6cm x 0.1em gauge and tested for antimicrobial properties through GBT 31402-2015.
Example 6
The intrinsic antimicrobial nylon provided in this example was designated nylon 6#.
In this embodiment, the raw materials are respectively:
the raw material A has the structure as follows
R 1 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
Raw material B is terephthalaldehyde.
The preparation method comprises mixing the raw materials A and B in equal mole, dissolving in organic solvent (chloroform) for 24h at 70deg.C. After the reaction, the reaction system is filtered, and the obtained precipitate is nylon 6# of the embodiment, and the structural formula is
Nylon 6# had a number average molecular weight of 17803 and a weight average molecular weight of 24569 as determined by GPC chromatography.
After nylon 6# is blended with an antioxidant and a lubricant, the types and proportions of the selected auxiliary agents such as the antioxidant and the like are all the types and proportions commonly used in the common nylon processing process, the addition amount is also no different from that of the common nylon processing, and the antioxidant 098 is selected in the embodiment，The chemical name of the catalyst is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, which is manufactured by Dover company in the United states, and the addition amount of the catalyst is 0.5 percent of nylon 5# in percentage by mass; the lubricant is pentaerythritol stearate, and the addition amount of the lubricant is 0.5% of nylon 5# by mass percent.
Sheets were extruded through a screw extruder at 250 ℃ with a 6cm x 0.1cm gauge and tested for antimicrobial properties by GBT 31402-2015.
Example 7
The intrinsic antimicrobial nylon provided in this example is designated nylon # 7.
The raw material A has the structure as follows
R1 is
-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
Raw material B is succinyl aldehyde.
The preparation method comprises the steps of mixing the raw material A and the raw material B in equal mole, dissolving in an organic solvent, and reacting for 24 hours at 70 ℃ under the condition that the organic solvent is dimethyl sulfoxide. After the reaction is finished, the reaction system is filtered, and the obtained precipitate is nylon 7# of the embodiment, and the structural formula is
Nylon # 7 had a number average molecular weight of 35014 and a weight average molecular weight of 48320 as determined by GPC column.
After nylon No. 7 is blended with an antioxidant and a lubricant, the types and proportions of the selected auxiliary agents such as the antioxidant and the like are all the types and proportions commonly used in the common nylon processing process, the addition amount is also no different from that of the common nylon processing, and the antioxidant is selected in the embodiment，098 is Doverphos-9228, the chemical name is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, and the adding amount of the Dover is 0.5% of nylon 5 in percentage by mass; the lubricant is pentaerythritol stearate, and the addition amount of the lubricant is 0.5% of nylon 5# by mass percent.
Sheets were extruded through a screw extruder at 250 ℃ with a 6cm x 0.1cm gauge and tested for antimicrobial properties by GBT 31402-2015.
Comparative example 1
Nylon 66 is selected to be dissolved in hexafluoroisopropanol, and is coated on the surface of metal aluminum by a coating rod, the film thickness is controlled between 100-200 mu m, after the coating is air-dried at room temperature, the intrinsic nylon antibacterial coating is obtained, and the antibacterial performance of the intrinsic nylon antibacterial coating is tested by GBT 31402-2015.
Comparative example 2
Nylon 6T66 is selected and dissolved in hexafluoroisopropanol, and is coated on the surface of metal aluminum by a coating rod, the film thickness is controlled between 100-200 mu m, after the air drying at room temperature, the intrinsic nylon antibacterial coating is obtained, and the antibacterial performance of the intrinsic nylon antibacterial coating is tested by GBT 31402-2015.
Comparative example 3
Nylon 66 is selected to be dissolved in hexafluoroisopropanol, and is coated on the surface of metal aluminum by a coating rod, the film thickness is controlled between 100-200 mu m, after the coating is air-dried at room temperature, the intrinsic nylon antibacterial coating is obtained, and the antibacterial performance of the intrinsic nylon antibacterial coating is tested by GBT 31402-2015.
Comparative example 4
Nylon 6T66 is selected and dissolved in hexafluoroisopropanol, and is coated on the surface of metal aluminum by a coating rod, the film thickness is controlled between 100 and 200 mu m, after the air drying at room temperature, the intrinsic nylon antibacterial coating is obtained, and the antibacterial performance of the intrinsic nylon antibacterial coating is tested by GBT 31402-2015.
Comparative example 5
Nylon 66 is dissolved in hexafluoroisopropanol and is cast in a polytetrafluoroethylene mould, after air drying at room temperature, the intrinsic antibacterial nylon membrane material is obtained, the membrane thickness is controlled between 300 and 1000 mu m, and the antibacterial performance is tested by GBT 31402-2015.
Comparative example 6
Nylon 6T66 is selected and dissolved in hexafluoroisopropanol, and is cast in a polytetrafluoroethylene mould, after air drying at room temperature, the intrinsic antibacterial nylon membrane material is obtained, the membrane thickness is controlled between 300 and 1000 mu m, and the antibacterial performance is tested by GBT 31402-2015.
Comparative example 7
Nylon 66 is dissolved in hexafluoroisopropanol and is cast in a polytetrafluoroethylene mould, after air drying at room temperature, the intrinsic antibacterial nylon membrane material is obtained, the membrane thickness is controlled between 300 and 1000 mu m, and the antibacterial performance is tested by GBT 31402-2015.
Comparative example 8
Nylon 6T66 is selected and dissolved in hexafluoroisopropanol, and is cast in a polytetrafluoroethylene mould, after air drying at room temperature, the intrinsic antibacterial nylon membrane material is obtained, the membrane thickness is controlled between 300 and 1000 mu m, and the antibacterial performance of the material is tested by GBT 31402-2015.
Comparative example 9
After blending nylon 66 with antioxidant and lubricant (the types and the addition ratio of the auxiliary agents are consistent with those of example 5), extruding and injection molding into sheets at 250 ℃ through a screw extruder, wherein the specifications of the sheets are 6cm by 0.1cm, and testing the antibacterial performance of the sheets through GBT 31402-2015.
Comparative example 10
After blending nylon 616T with antioxidants and lubricants (the types and addition ratios of the above auxiliary agents are consistent with those of example 5), an injection molded sheet was extruded through a screw extruder at 250 ℃ with a sheet gauge of 6cm x 0.1em and tested for antimicrobial properties by GBT 31402-2015.
Comparative example 11
After blending nylon 66 with antioxidant and lubricant (the types and addition ratio of the auxiliary agents are consistent with those of example 5), extruding and injecting sheets through a screw extruder at 250 ℃, wherein the specifications of the sheets are 6cm x 0.1cm, and testing the antibacterial performance of the sheets through GBT 31402-2015.
Comparative example 12
After nylon 616T is blended with an antioxidant and a lubricant (the types and the addition proportion of the auxiliary agents are consistent with those of the embodiment 5), an injection molding sheet is extruded by a screw extruder at 250 ℃, the specification of the sheet is 6cm x 0.1cm, and the antibacterial property of the sheet is tested by GBT31402-2015
Comparative example 13
After nylon 6T66 was blended with an antioxidant and a lubricant (the types and addition ratios of the above auxiliary agents were the same as in example 5), a sheet was extrusion-molded by a screw extruder at 260 ℃ and the sheet gauge was 6cm x 0.1cm, and the antibacterial properties thereof were tested by GBT 31402-2015.
Comparative example 14
After blending nylon 10T with antioxidant and lubricant (the types and addition ratios of the above auxiliary agents are consistent with those of example 5), the sheet was extruded and injection molded by a screw extruder at 260 ℃ with a sheet gauge of 6cm x 0.1cm, and the antibacterial properties were tested by GBT 31402-2015.
Comparative example 15
After nylon 6T66 was blended with an antioxidant and a lubricant (the types and addition ratios of the above auxiliary agents were the same as in example 5), a sheet was extrusion-molded by a screw extruder at 260 ℃ and the sheet gauge was 6cm x 0.1cm, and the antibacterial properties thereof were tested by GBT 31402-2015.
Comparative example 16
After blending nylon 10T with antioxidant and lubricant (the types and addition ratios of the above auxiliary agents are consistent with those of example 5), the sheet was extruded and injection molded by a screw extruder at 260 ℃ with a sheet gauge of 6cm x 0.1em and tested for antimicrobial properties by GBT 31402-2015.
Table 1 comparison of antimicrobial properties of example and comparative coatings
| Sample of | Form of material | Antibacterial property of E.coli | Antibacterial property of staphylococcus aureus | |
| Example 1 | Nylon 1# | Coating layer | 100％ | 100％ |
| Example 2 | Nylon 2# | Coating layer | 100％ | 100％ |
| Example 3 | Nylon 3# | Film material | 100％ | 100％ |
| Example 4 | Nylon 4# | Film material | 100％ | 100％ |
| Example 5 | Nylon 5# | Sheet material | 100％ | 100％ |
| Example 6 | Nylon 6# | Sheet material | 100％ | 100％ |
| Example 7 | Nylon 7# | Sheet material | 100％ | 100％ |
| Comparative example 1 | Nylon 66 | Coating layer | 12.5％ | 11.9％ |
| Comparative example 2 | Nylon 6T66 | Coating layer | 0％ | 19.2％ |
| Comparative example 3 | Nylon 66 | Coating layer | 12.5％ | 11.9％ |
| Comparative example 4 | Nylon 6T66 | Coating layer | 0％ | 19.2％ |
| Comparative example 5 | Nylon 66 | Film material | 0％ | 13.9％ |
| Comparative example 6 | Nylon 6T66 | Film material | 5.7％ | 6.2％ |
| Comparative example 7 | Nylon 66 | Film material | 0％ | 13.9％ |
| Comparative example 8 | Nylon 6T66 | Film material | 5.7％ | 6.2％ |
| Comparative example 9 | Nylon 66 | Sheet material | 17.2％ | 10.6％ |
| Comparative example 10 | Nylon 6I6T | Sheet material | 2.9％ | 11.9％ |
| Comparative example 11 | Nylon 66 | Sheet material | 17.2％ | 10.6％ |
| Comparative example 12 | Nylon 6I6T | Sheet material | 2.9％ | 11.9％ |
| Comparative example 13 | Nylon 6T66 | Sheet material | 21.6％ | 14.2％ |
| Comparative example 14 | Nylon 10T | Sheet material | 0 | 9.70％ |
| Comparative example 15 | Nylon 6T66 | Sheet material | 21.6％ | 14.2％ |
| Comparative example 16 | Nylon 10T | Sheet material | 0 | 9.70％ |
The data shown in table 1 are all averages of the samples after testing.
As can be seen from Table 1, the antibacterial properties of the antibacterial articles, such as films, sheets or coatings, prepared from the nylon materials prepared in examples 1-7, against E.coli and Staphylococcus aureus were 100%. Compared with nylon 6, nylon 66, nylon 6T66, nylon 10T and the like in the prior art of comparative examples 1-16, has remarkably excellent antibacterial performance.
The above is only a preferred embodiment of the present invention, which is not to be construed as limiting the scope of the present invention, and various modifications and variations of the present invention will be apparent to those skilled in the art. Variations, modifications, substitutions, integration and parameter changes may be made to these embodiments by conventional means or may be made to achieve the same functionality within the spirit and principles of the present invention without departing from such principles and spirit of the invention.
Claims (10)
1. The intrinsic antibacterial nylon is characterized by having a structural formula shown in a formula (I):
wherein R is 1 Is benzene ring, C1-C10 straight-chain hydrocarbon;
R 2 is furan ring, pyrazine ring, C1-C3 straight-chain hydrocarbon group;
n is 50-200.
2. The intrinsically-antimicrobial nylon of claim 1, wherein the intrinsically-antimicrobial nylon is prepared from raw materials a and B;
the structural formula of the raw material A is shown as a formula (II):
wherein R is 1 Is benzene ring, C1-C10 straight-chain hydrocarbon;
the structural formula of the raw material B is shown as (III):
wherein R is 2 Is furan ring, pyrazine ring, benzene ring, C1-C3 straight-chain hydrocarbon group.
3. The intrinsically-antimicrobial nylon of claim 2, wherein the feedstock B is any of 2, 5-furandicarboxaldehyde, terephthalaldehyde, 1, 4-pyrazindicarboxaldehyde, malondialdehyde, succinaldehyde, or glutaraldehyde.
4. The intrinsically-antimicrobial nylon of claim 1, wherein the intrinsically-antimicrobial nylon is a homopolymerized nylon; the number average molecular weight of the intrinsic antibacterial nylon is more than or equal to 5000g/mol; and/or the weight average molecular weight of the intrinsic antibacterial nylon is more than or equal to 10kg/mol.
5. The intrinsically-antimicrobial nylon of any of claims 1-4, wherein the intrinsically-antimicrobial nylon has a number average molecular weight of greater than or equal to 10000g/mol: or, more than or equal to 20000g/mol; and/or the weight average molecular weight of the intrinsic antibacterial nylon is more than or equal to 20kg/mol; or, at least 50kg/mol; or more than or equal to 100kg/mol.
6. The intrinsically-antimicrobial nylon of any of claims 1-4, wherein the intrinsically-antimicrobial nylon has an antimicrobial efficacy against escherichia coli and/or staphylococcus aureus of 100%.
7. A preparation method for preparing the intrinsic antibacterial nylon according to any one of claims 1 to 6, which is characterized in that raw material A and raw material B are respectively dissolved in organic solvent and uniformly mixed, and then stirred and reacted for 12 to 24 hours at 50 to 70 ℃ for homopolymerization to prepare the intrinsic antibacterial nylon; and/or filtering or suction filtering to separate solid matters in the reaction system after the reaction is finished, namely the intrinsic antibacterial nylon;
the structural formula of the raw material A is shown as a formula (II):
wherein R is 1 Is benzene ring, C1-C10 straight-chain hydrocarbon;
the structural formula of the raw material B is shown as (III):
wherein R is 2 Is furan ring, pyrazine ring, benzene ring, C1-C3 straight-chain hydrocarbon group.
8. The method for preparing the intrinsically-antimicrobial nylon of claim 7, wherein the organic solvent comprises any one or more of diethyl ether, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol dimethyl ether, anisole, m-nitroanisole, p-chloroanisole, methyl isobutyl ketone, acetophenone, p-chloroacetophenone, o-nitroacetophenone, sulfolane, methylene chloride, chloroform, 1, 2-dichloroethane, chlorobenzene, α -naphthalene chloride, acetonitrile, propionitrile, benzene, toluene, benzene cyanide, nitrobenzene, nitrotoluene, ethyl acetate, methyl benzoate.
9. The method for preparing the intrinsically-antimicrobial nylon of claim 7, wherein the raw material a and the raw material B are added in an equimolar ratio.
10. An inherently antimicrobial nylon article comprising the inherently antimicrobial nylon of any of claims 1-6; the article is a film, sheet, coating, shaped or molded article.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3354122A (en) * | 1962-12-21 | 1967-11-21 | Du Pont | Polymers of polyacylhydrazones and process of preparation therefor |
| CN114796184A (en) * | 2022-06-07 | 2022-07-29 | 兰州大学 | Compound containing semi-rigid acylhydrazone ligand and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3354122A (en) * | 1962-12-21 | 1967-11-21 | Du Pont | Polymers of polyacylhydrazones and process of preparation therefor |
| CN114796184A (en) * | 2022-06-07 | 2022-07-29 | 兰州大学 | Compound containing semi-rigid acylhydrazone ligand and preparation method and application thereof |
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