CN116556055A - Quaternary ammonium salt modification of polyester substrate by solution post-grafting method - Google Patents
Quaternary ammonium salt modification of polyester substrate by solution post-grafting method Download PDFInfo
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- CN116556055A CN116556055A CN202310476056.3A CN202310476056A CN116556055A CN 116556055 A CN116556055 A CN 116556055A CN 202310476056 A CN202310476056 A CN 202310476056A CN 116556055 A CN116556055 A CN 116556055A
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 25
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 53
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 26
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 24
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- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052760 oxygen Inorganic materials 0.000 claims description 2
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- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 70
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M14/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/418—Cyclic amides, e.g. lactams; Amides of oxalic acid
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a solution post-grafting method for modifying a terylene base material by quaternary ammonium salt, which relates to the technical field of modified non-woven fabric preparation and comprises the steps of pretreatment of a PET non-woven fabric of S1, fixation of a photoinitiator of S2, dropwise addition of grafting reaction liquid of S3, ultraviolet irradiation grafting reaction of S4, modification of an antibacterial active ingredient of S5 and acquisition of PET-g-PAA@As of S6. According to the invention, by using a more effective surface grafting modification technology and taking polyester PET fibers as a base material, adopting a solution post-treatment method, olefin groups containing free carboxyl groups on PET macromolecular links are made in advance, and then quaternary ammonium salt is used for replacing hydrogen ions on part of carboxyl groups, so that the PET fibers with good antibacterial performance are obtained, and the antibacterial fibers with the inherent excellent performance of the PET fibers are maintained, so that the polyester sleeve of the semi-permanent central venous catheter with the antibacterial function, which can be used for long-term, safe, mass production and cost saving, is constructed.
Description
Technical Field
The invention relates to the technical field of preparation of modified non-woven fabrics, in particular to a solution post-grafting method for modifying a terylene base material by quaternary ammonium salt.
Background
With aging population and rising diabetes incidence rate, the autologous veins of a patient subjected to long-term dialysis are difficult to meet the requirement of constructing a vascular access, the catheter becomes a new 'life line' for saving the life of the patient until the last 80 years, under the effort of medical material specialists, a central venous semi-permanent catheter with PET-CUFF is developed, a deep venous catheter with a dacron sleeve is 2-3 cm away from a skin tunnel portal, the dacron sleeve can be fused with tissue reaction, the catheter is fixed in position and does not leak blood, but the catheter is an exogenous implantable medical material and has unavoidable complications, and although various improvements are made on the catheter materials in the prior researches, an antibacterial coating is designed, the catheter has long service time, more open operation opportunities, the patient has easy infection factors, and the improved antibacterial material has no definite curative effect. Wherein, dacron cover (Cuff) is a part of pipe, is the netted fibrous structure of making by dacron, dacron material, i.e. polyethylene terephthalate, also known as PET. After the catheter is placed, PET-CUFF is quickly adhered to subcutaneous tissue, so that the catheter is fixed, the spread of microorganisms is prevented, and the terylene material is elastic and has the characteristics of high strength, heat resistance, deflection resistance, corrosion resistance, low water absorption, good biocompatibility and the like. However, in clinical applications, the disadvantages of anti-infection, anti-inflammation and insufficient anti-complications are still exhibited. Most of the antibacterial material modifications are currently directed to the catheter itself, while the antibacterial modification with PET-CUFF is less studied.
Through research, radiation grafting is a grafting method which is developed faster in recent years, and has the advantages of advanced technology, energy conservation, high efficiency, no pollution and the like compared with the common chemical grafting. The commonly used radiation sources are Co60 gamma rays, electron beams and ultraviolet light, the former two are more ways of researching earlier, for example, patent CN102108112A, a polypropylene resin is pre-irradiated by a Co60 radiation source or a high-frequency high-voltage electron accelerator in air, and then the pre-irradiated polypropylene resin is added into a monomer to carry out grafting reaction to prepare the graft copolymer, the way is that the high-energy radiation is utilized to enable the surface of a polymer substrate to generate active free radicals so as to promote grafting reaction, but the high-energy radiation energy is too high, the interior of the substrate is often changed, the grafting rate is improved, but the mechanical property of the material is influenced, so that the service life is influenced, and the radiation method has high cost and great environmental hazard and is not suitable for industrial utilization.
Compared with chemical methods and high-energy irradiation widely used at home and abroad, ultraviolet irradiation is similar to the high-energy irradiation method in principle, and is similar to the chemical method initiated by initiator heat in the process flow. Meanwhile, the ultraviolet light energy is low, the penetrability of the material is lower than that of other high-energy radiation, the material can be basically strictly limited to the shallow surface of the material, the mechanical property of the material is not excessively damaged, and the reaction degree is easy to control. For example, in the patent CN1607213a, ultraviolet light is not directly irradiated on the surface of a polymer material but irradiated on a photosensitizer, and the polymer material is placed in volatile gas of the photosensitizer or immersed in an inert organic solution or aqueous solution of the photosensitizer to perform free radical reaction for grafting modification; the two-step method of the patent CN1607214A comprises the steps of irradiating ultraviolet light on volatile gases of a photosensitizer or on an inert organic solution of the photosensitizer, carrying out free radical reaction on the surface of a polymer material to introduce dormant radicals, and carrying out graft polymerization reaction with a grafting monomer in a second step, wherein the polymer material with dormant free radicals on the surface is contacted with the grafting monomer in a small reaction space in the mode, so that the grafting rate is improved, but the grafting rate is still lower than that of the one-step method, the operation is complex, the dormant radicals on the surface are easy to be lost in air, and the actual application is not facilitated.
Disclosure of Invention
The invention aims to provide a solution post-grafting method for modifying a quaternary ammonium salt of a polyester substrate so as to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: a solution post-grafting method for modifying the quaternary ammonium salt of a polyester substrate comprises the following operation steps:
s1, pretreatment of PET non-woven fabrics:
the PET is cleaned and dried, then is extracted by acetone, and is taken out for drying.
S2, fixing a photoinitiator:
the extracted PET is sprayed on one side by using acetone solution of Benzophenone (BP) with a certain concentration, and naturally dried in the dark.
S3, dropwise adding grafting reaction liquid:
and (3) putting the dried PET into a quartz glass reaction tank, and dripping grafting reaction liquid on the PET. Introducing nitrogen to remove oxygen in the reaction tank.
S4, ultraviolet irradiation grafting reaction:
and (3) reacting for 10-50 min under ultraviolet irradiation, then taking out, washing with water, extracting with acetone, and drying to obtain the PET fiber (PET-g-PAA) with the surface grafted with carboxyl functional groups.
S5, modifying antibacterial active ingredients:
an amount of PET-g-PAA was added to an aqueous solution containing 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and reacted at room temperature for 2 hours, after which an amount of aminopolysaccharide quaternary ammonium salt (Amino polysaccharide quaternary ammonium salt, hereinafter abbreviated As As) and N-hydroxysuccinimide (NHS) were added and stirring was continued for 24 to 48 hours.
S6, obtaining PET-g-PAA@As:
after the reaction, the mixture was washed with deionized water to obtain PET-g-PAA@As.
In the step S1, a commercially available PET nonwoven fabric is selected as a raw material for experiments based on PET-Cuff actually used in the catheter, and the pretreatment method of the PET nonwoven fabric is to extract the PET nonwoven fabric with acetone, take out and dry the PET nonwoven fabric, and in the photo-grafting experiment of the present item, the selected photosensitizer is Benzophenone (BP), and the monomer Acrylic Acid (AA) is a modified material to which carboxyl groups are added.
Further, in the step S2, the photosensitizer selected in the experiment is hydrogen abstraction type photosensitizer Benzophenone (BP), the photosensitizer BP is transited from a singlet state to a triplet state under the irradiation of ultraviolet light UV, then active hydrogen atoms are abstracted from an organic chain on the surface of mps@pg, so that free radicals are generated on the surface of a substrate, and BP itself generates half pinacol after abstracting hydrogen ions, so that the free radical initiation activity of the half pinacol is very low, and monomer self polymerization is difficult to initiate after the half pinacol is separated from the surface of the substrate, so that the efficiency of grafting reaction initiated by the type of the photosensitizer of BP is high.
In the step S3, the size of the quartz tank matched with the ultraviolet grafting experimental condition is the most suitable size area after cutting the PET non-woven fabric used in preparation due to the specificity of the ultraviolet grafting experimental condition; the selection of the organic monomer is extremely important in the photo-grafting reaction, the experiment starts according to the experimental conditions and the characteristics of the PET substrate, the PET substrate is a hydrophobic material, and after BP is loaded, if the reaction liquid is an organic solvent system, BP is very easy to dissolve in the solvent, and can not be effectively initiated on the surface of the fiber. Therefore, the reaction needs to be carried out in an aqueous solution containing a certain lipophilic solute, and the comprehensive analysis of the conditions shows that the property of the water-soluble acrylic monomer completely meets the requirement of the grafting experiment, so that the acrylic acid is used as the grafting monomer for the experiment to carry out the photo-grafting study.
In the step S4, placing the PET non-woven fabric loaded with BP into AA aqueous solution with a certain concentration to perform Ultraviolet (UV) illumination grafting reaction, and attacking the "-C-H" site of the hydrocarbon chain on the surface of the PET fiber by BP through photochemical hydrogen extraction reaction; thereby forming a 'C.cndot.' active free radical, and then initiating the Graft polymerization of the AA monomer from the substrate surface by a 'Graft from' method. In addition, the "-C-H" sites on the PAA chain are triggered by irradiation, thereby creating more grafting sites and, therefore, a degree of PAA polymer layer.
Further, in the step S4, the grafting rate can be obviously increased by adding an inorganic acid or an organic acid into the co-irradiation grafting system, and for the reason that the acid affects the grafting reaction, it is generally believed that the sensitization of the acid is a synergistic effect of various actions, such as the acid increases the H atom concentration in the reaction, the solubility of the grafting monomer in the solution, and the viscosity of the system, and at the same time, the acid can also cause the increase of a monomer-solvent reaction intermediate, which tends to cause more grafting reaction active sites, in addition, the chain length of the oligomer becomes shorter and the amount of the oligomer increases due to the presence of the acid, the short chain oligomer diffuses more easily into the swelling substrate, more effective chain termination is obtained in the reaction active region, resulting in an increase in the viscosity of the grafting solution and the solution swelled in the substrate, and a great difference in monomer concentration in different regions of the grafting system.
Furthermore, in the step S4, in the ultraviolet grafting reaction, ultraviolet light is taken as a precondition of the reaction, the influence of the illumination time on the grafting rate is also obvious, when the dosage of the PET fiber is fixed, 15wt.% of photosensitizer BP is loaded, and 25 vol.% of acrylic acid monomer and H in the reaction solution are added + The concentration is 0.2mol/L, and the product of the polyacrylic acid pre-modified PET fiber with larger grafting rate can be obtained by illumination for 30 min. Therefore, PET-g-PAA prepared by the experimental parameters is selected, extracted and washed by acetone and then used for carrying out subsequent modification experiments of antibacterial components.
Furthermore, in the step S5, aminopolysaccharide quaternary ammonium salt (As) is selected in the project, so that the antibacterial agent has a broad-spectrum antibacterial function, and can obviously inhibit and kill common pathogenic microorganisms such As staphylococcus aureus, escherichia coli and the like in intestinal tracts; meanwhile, the method can regulate fibroblast proliferation and keratinization, accelerate wound healing, reduce scar formation, and provide a safe and effective method for crosslinking amino bonds by taking 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) as a water-soluble, non-cytotoxic and biocompatible carbodiimide as a coupling agent and n-hydroxysuccinimide (NHS) as a stabilizer, thereby improving crosslinking efficiency. Unlike conventional crosslinkers, EDC and NHS introduce "zero length" amide crosslinking between carboxyl and amino groups, and furthermore EDC and NHS are only catalysts, which can be removed by dialysis. However, EDC and NHS above a certain concentration may risk cytotoxicity, and thus the maximum EDC/NHS concentration required for use in the experiment should be less than 0.3mol/L, which can be considered safe in biological materials.
Further, in the step S5, PET-g-PAA@As is prepared through EDC/NHS mediated polymerization, 4-morpholinoethanesulfonic acid (MES) solution (pH=3.61+/-0.01) with the concentration of 0.1mol/L is prepared in deionized water, PET-g-PAA and As are respectively added into the 0.1mol/L MES solution, the solution is stirred uniformly and is moved into an ice/water bath, a solution for mixing PET-g-PAA and As is prepared, a certain amount of NHS is added into the mixed solution, a certain amount of EDC is then added, and the stirring reaction is continued for 6 hours, so that PET-g-PAA@As can be obtained.
The invention provides a solution post-grafting method for modifying a terylene base material by quaternary ammonium salt, which is used for constructing a terylene sleeve of a semi-permanent central venous catheter with an antibacterial function, and the terylene sleeve has the advantages of long-acting, safety, batch production and cost saving and has the following advantages:
1. according to the invention, by using a more effective surface grafting modification technology, polyester PET fibers are used as a base material, a solution post-treatment method is adopted, free carboxyl-containing olefin groups on PET macromolecular links are made in advance, and then quaternary ammonium salt is used for replacing hydrogen ions on partial carboxyl groups, so that the PET fibers with good antibacterial performance are obtained, and the inherent excellent performance of the PET fibers is maintained.
Drawings
Fig. 1-1 is an SEM photograph: (a) on-catheter PET-Cuff; (B) schematic drawing of commercially available PET nonwoven fabric;
FIGS. 1-2 are schematic representations of FT-IR analysis of PET-Cuff on a catheter and commercially available PET nonwoven fabrics;
FIG. 2 is a schematic representation of the effect of photosensitizer loading on PET grafted PAA;
FIG. 3-1 is a schematic diagram of a one-factor condition;
FIG. 3-2 is a schematic representation of the effect of monomer AA concentration on PET grafted PAA;
FIG. 4-1 is a schematic diagram of a technical scheme of ultraviolet light initiated grafting;
FIG. 4-2 shows solution H + Schematic representation of the effect of concentration on PET grafted PAA;
FIG. 4-3 is a schematic illustration of the effect of illumination time on PET grafted PAA;
FIG. 5 is a schematic diagram of the preparation route of PET-g-PAA@As.
Detailed Description
The invention provides a technical scheme that: a solution post-grafting method for modifying the quaternary ammonium salt of a polyester substrate comprises the following operation steps:
s1, pretreatment of PET non-woven fabrics:
cleaning and drying PET, extracting with acetone, taking out and drying, wherein in the step S1, a commercially available PET non-woven fabric is selected as a raw material for experiments based on the PET-Cuff actually used on a catheter, the pretreatment method of the PET non-woven fabric is that the PET non-woven fabric is extracted with acetone, taken out and dried, in addition, in the photo-grafting experiment of the item, the selected photosensitizer is Benzophenone (BP), and the monomer Acrylic Acid (AA) is a modified material endowed with carboxyl groups;
the original morphology of PET-Cuff can be seen in SEM photographs (as shown in FIGS. 1-1), as well as the substrates identified for use in this project, i.e., commercially available PET nonwoven fabrics. As can be seen from SEM pictures, the two base materials have basically consistent shapes and are of a non-woven fabric structure with certain thickness, and the diameters of the fiber filaments are very close and basically between 18 and 20 mu m. However, the surface of the commercially available PET fibers was found to be extremely smooth, while the filaments of PET-Cuff were somewhat messy. Therefore, to further confirm whether the materials are consistent, we performed analytical identification by infrared test characterization;
as shown in figures 1-2, the infrared test analysis results show that the infrared light of the two materialsThe spectral absorption peaks are substantially identical and contain all the characteristic absorption peaks of PET: 1090cm -1 And 1240cm -1 Belongs to C-O telescopic vibration peak, 1470cm -1 And 1504cm -1 A vibration absorption peak of C=C on benzene ring, 1712cm -1 A C=O stretching vibration peak of 2965cm -1 And 2910cm -1 Then all belong to the C-H vibration absorption peak. Therefore, it was confirmed that both materials were PET fibers, and the commercial PET nonwoven fabric was selected for the present project for the subsequent experiments.
S2, fixing a photoinitiator:
the method comprises the steps of (1) obtaining extracted PET, spraying an acetone solution of Benzophenone (BP) with a certain concentration on one side, naturally airing the PET in a dark place, wherein in the step S2, the selected photosensitizer is hydrogen-abstracted photosensitizer Benzophenone (BP), the photosensitizer BP is transited to a triplet state from a singlet state channeling state under the irradiation of ultraviolet light UV, then active hydrogen atoms are abstracted from an organic chain on the surface of MPS@PG, so that free radicals are generated on the surface of a base material, and BP per se generates half pinacol after abstracting hydrogen ions, the free radical initiation activity of the half pinacol is very low, so that the self polymerization of monomers is difficult to initiate after the BP is separated from the surface of the base material, the efficiency of grafting reaction initiated by the type of photosensitizer is high, in the experiment, BP is firstly dissolved in acetone, the BP acetone solution with 25% of the process concentration is prepared, and then sprayed on the surface of PET fibers, and the BP can be crystallized and separated on the surface of the fiber due to rapid volatilization of the acetone, so that the photoinitiator is effectively fixed;
in the experiment, the AA concentration was 20vol%, and the solution contained H + The reaction solution with the concentration of 0.2mol/L is respectively loaded with 0wt percent, 5wt percent, 10wt percent, 15wt percent, 20wt percent and 25wt percent of photosensitizer on the surface of the PET fiber, and is irradiated for 30min by UV, then the grafting product is obtained according to the experimental steps, the grafting rate of the product is calculated by a weighing method after the product is cleaned and dried, and the result is shown as figure 2, and the result shows that when the loading of the photosensitizer is increased from 0wt percent to 25wt percent under the condition that the adding amount of the base material PET is a fixed value, the grafting rate of PAA on the surface is gradually increased from 0 percent to 58.9 percent, and the grafting rate of the PAA on the surface is reduced as the loading of BP is continuously increased. This also proves that when there is no photosensitivityWhen the agent exists, the grafting reaction cannot be realized; when the photosensitizer is insufficient, the effective active sites in the PET cannot be fully utilized, and the surface can be fully grafted along with the increase of the dosage of the photosensitizer. However, when the added amount of BP exceeds a certain value, H on the graft chain structure of polyacrylic acid is abstracted after BP which is partially separated from the surface of the substrate is excited, so that the graft chain is branched to form crosslinking, and too much branched crosslinking is too early to stop the chain, so that the grafting rate is reduced, and too much semipinacol can initiate monomer homopolymerization after entering the solution, and the grafting effect is also affected.
S3, dropwise adding grafting reaction liquid:
and (3) putting the dried PET into a quartz glass reaction tank, and dripping grafting reaction liquid on the PET. In the S3 step, the size of the quartz tank matched with the special ultraviolet grafting experimental conditions is the most suitable size and area after cutting the PET non-woven fabric used in preparation; the selection of the organic monomer is extremely important in the photo-grafting reaction, the experiment starts according to the experimental conditions and the characteristics of the PET substrate, the PET substrate is a hydrophobic material, and after BP is loaded, if the reaction liquid is an organic solvent system, BP is very easy to dissolve in the solvent, and can not be effectively initiated on the surface of the fiber. Therefore, the reaction is required to be carried out in an aqueous solution containing a certain lipophilic solute, and the comprehensive analysis of the conditions shows that the property of the water-soluble acrylic acid monomer completely meets the requirement of the grafting experiment, so that the acrylic acid is used as the grafting monomer for the experiment to carry out the photo-grafting study;
the PET in the item only needs to carry out single-sided illumination grafting and related modification due to the application specificity. And the solid-liquid ratio used in the experiment, namely the PET dosage and the volume of the reaction solution are set to be constant values, so that the influence of other key factors in the experiment on the grafting rate of the material is inspected on the basis. According to the material preparation scheme, a photosensitizer and a solution containing H are selected in the photo-grafting reaction + The concentration, the monomer consumption and the illumination time are used as experimental factors to design single-factor experiments, and the experimental factors are selected in a range (shown in the figure 3-1);
in the experiment, the loading of the photosensitizer is 15wt.%, and H in the reaction solution is contained + The concentration of AA is 0.2mol/L, the concentration of AA is respectively 10vol%, 15vol%, 20vol%, 25vol%, 30vol% and 35vol%, and the grafting is carried out for 30min under UV irradiation, then the grafting product is obtained according to the experimental steps, the grafting rate of the product is calculated by a weighing method after the product is washed and dried, and the result (shown in the figure 3-2) shows that the effect of the use amount of the acrylic acid monomer on grafting is large. When the monomer content was increased from 10 to 35vol%, the grafting ratio of the product was increased from 13.7 to 241.2%. This is due to the special reaction conditions adopted in the present experiment, since a certain amount of the reaction liquid was directly dropped into the PET fiber film after supporting BP, the fiber film to be reacted locked the reaction liquid in its fiber structure, and the reaction was started after the irradiation of ultraviolet light. Therefore, the higher the monomer concentration, the more reactive species. And too much H on the polypropylene grafted chain structure, so that the grafted chain is branched to form crosslinking, and too much byproducts, namely ineffective grafting, are generated. At a concentration of 25vol% it was possible to react the monomers sufficiently and completely and the grafted surface of the PET substrate was relatively uniform and smooth.
S4, ultraviolet irradiation grafting reaction:
reacting for 10-50 min under ultraviolet irradiation, then taking out, washing with water, extracting with acetone, and drying to obtain PET fiber (PET-g-PAA) with carboxyl functional groups grafted on the surface;
s4, placing the PET non-woven fabric loaded with BP into AA aqueous solution with a certain concentration for Ultraviolet (UV) illumination grafting reaction, and attacking the "-C-H" site of hydrocarbon chain on the surface of the PET fiber by BP through photochemical hydrogen extraction reaction; thereby forming a 'C.cndot.' active free radical, and then initiating the Graft polymerization of the AA monomer from the substrate surface by a 'Graft from' method. In addition, the "-C-H" sites on the PAA chain are triggered under irradiation, so that more grafting sites are generated, and therefore, a certain PAA polymer layer is formed, the project starts on the basis of the previous related research, and the interaction and influence among key preparation factors are inspected and evaluated by a single factor condition aiming at the PET basis, so that the preparation condition is optimized, and the grafting degree is improved (as shown in fig. 4-1);
in the step S4, the grafting rate can be obviously increased by adding inorganic acid or organic acid into the co-irradiation grafting system, and for the reason that the acid affects the grafting reaction, it is widely believed that the sensitization of the acid is a synergistic effect of various actions, such as the acid increases the H atom concentration in the reaction, the dissolution degree of the grafting monomer in the solution and the viscosity of the system, and at the same time, the acid can lead to the increase of monomer-solvent reaction intermediates, which often lead to more grafting reaction active points, in addition, the chain length of the oligomer becomes shorter and the number of the oligomer increases due to the existence of the acid, the short chain oligomer is easier to diffuse into a swelling substrate, more effective chain termination is obtained in a reaction active region, the solution viscosity of the grafting solution and the swelling in the substrate increases, and the monomer concentration in different regions of the grafting system is greatly different;
in the experiment, the reaction solution contains H at an AA concentration of 20 vol.% and a photosensitizer loading of 15wt.% + The concentrations of the grafting products were 0mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L and 0.5mol/L, respectively, and were irradiated with UV for 30 minutes, and the grafting products were obtained by the experimental procedures, and the grafting rates of the products were calculated by a weighing method after washing and drying the products to obtain results (as shown in FIG. 4-2), from which it was found that the grafting degree to PET was greatly different although acid was added and not added, but H + The variation in concentration (0.1-0.5M) appears to have no significant effect on the efficiency of the reception. The results show that the addition of the inorganic acid promotes the hydrogen extraction reaction of the polymer molecules, improves the hydrogen extraction efficiency of the polymer molecules, and the monomers diffuse through the polymer matrix to produce a lower viscosity solution. Thus, the addition of acid can increase the degree of grafting. The highest grafting rate is H + The concentration is 0.2mol/L to 0.3mol/L, and then the concentration is reduced along with the increase of the acid concentration;
in the S4 step, in the ultraviolet grafting reaction, ultraviolet light is taken as a precondition of the reaction, the influence of illumination time on the grafting rate is obvious, when the dosage of the PET fiber is fixed, 15wt.% of photosensitizer BP is loaded, and 25 vol.% of acrylic acid monomer and H in the reaction solution are added + The concentration is 0.2mol/L, and the grafting rate can be higher by illumination for 30minThe product of polyacrylic acid pre-modified PET fiber. Therefore, PET-g-PAA prepared by the experimental parameters is selected, extracted and cleaned by acetone and then used for carrying out subsequent modification experiments of antibacterial components;
in the experiment, the loading of the photosensitizer is 15wt.%, and H in the reaction solution is contained + The concentration is 0.2mol/L, the AA concentration is 25vol%, the UV irradiation time is 1min, 10min, 20min, 30min, 40min and 50min respectively, the experimental steps are carried out again to obtain a grafted product, the grafted product is obtained by washing and drying the product, and the grafting rate of the product is calculated by a weighing method, so that the result (shown in fig. 4-3) is obtained, the irradiation time is increased, the grafting rate is only 21.6% when the irradiation time is 1min, and the grafting rate reaches the maximum value and is 159.8% when the irradiation time is 30 min. Indicating that the photografting reaction is a continuous reaction process, the excitation of the photosensitizer is also continuously performed during the reaction, so that a proper illumination time is necessary. However, the effect of grafting gain caused by the excessively long illumination time is not obvious, and the effective initiator in the system is completely reacted along with the extension of the reaction time, so that the aggravation of side reaction brings unnecessary trouble to the treatment of subsequent products. Therefore, the illumination time is limited to 30 min.
S5, modifying antibacterial active ingredients:
adding a certain amount of PET-g-PAA into an aqueous solution containing 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) to react for 2 hours at room temperature, adding a certain amount of aminopolysaccharide quaternary ammonium salt (Amino polysaccharide quaternary ammonium salt, hereinafter referred to As) and N-hydroxysuccinimide (NHS), and continuously stirring for 24-48 hours;
in the step S5, aminopolysaccharide quaternary ammonium salt (As) is selected in the project, so that the antibacterial agent has a broad-spectrum antibacterial function, and can obviously inhibit and kill common pathogenic microorganisms such As staphylococcus aureus, escherichia coli and the like in intestinal tracts; meanwhile, the method can regulate fibroblast proliferation and keratinization, accelerate wound healing, reduce scar formation, and provide a safe and effective method for crosslinking amino bonds by taking 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) as a water-soluble, non-cytotoxic and biocompatible carbodiimide as a coupling agent and n-hydroxysuccinimide (NHS) as a stabilizer, thereby improving crosslinking efficiency. Unlike conventional crosslinkers, EDC and NHS introduce "zero length" amide crosslinking between carboxyl and amino groups, and furthermore EDC and NHS are only catalysts, which can be removed by dialysis. However, EDC and NHS above a certain concentration may risk cytotoxicity, so the maximum EDC/NHS concentration required for use in the experiment should be less than 0.3mol/L, which can be considered safe in biological materials;
in the S5 step, PET-g-PAA@As is prepared through EDC/NHS mediated polymerization (shown in FIG. 5), 4-morpholinoethanesulfonic acid (MES) solution (pH=3.61+/-0.01) with the concentration of 0.1mol/L is prepared in deionized water, PET-g-PAA and As are respectively added into the 0.1mol/L MES solution, the solution is stirred uniformly and is moved into an ice/water bath, a solution for mixing PET-g-PAA and As is prepared, a certain amount of NHS is added into the mixed solution, a certain amount of EDC is then added, and the stirring reaction is continued for 6 hours, so that the PET-g-PAA@As can be obtained.
S6, obtaining PET-g-PAA@As:
after the reaction, the mixture was washed with deionized water to obtain PET-g-PAA@As.
The solution post-grafting method is used for carrying out quaternary ammonium salt modification on the polyester base material, the polyester PET fiber is used as the base material by a more effective surface grafting modification technology, the solution post-treatment method is adopted, the olefin group containing free carboxyl on the PET macromolecular chain is pre-treated, and then the quaternary ammonium salt is used for replacing the hydrogen ion on part of the carboxyl, so that the PET fiber with good antibacterial performance is obtained, and the inherent excellent antibacterial fiber of the PET fiber is maintained.
Claims (9)
1. The method for modifying the quaternary ammonium salt of the polyester base material by a solution post-grafting method is characterized by comprising the following operation steps of:
s1, pretreatment of PET non-woven fabrics:
the PET is cleaned and dried, then is extracted by acetone, and is taken out for drying.
S2, fixing a photoinitiator:
the extracted PET is sprayed on one side by using acetone solution of Benzophenone (BP) with a certain concentration, and naturally dried in the dark.
S3, dropwise adding grafting reaction liquid:
and (3) putting the dried PET into a quartz glass reaction tank, and dripping grafting reaction liquid on the PET. Introducing nitrogen to remove oxygen in the reaction tank.
S4, ultraviolet irradiation grafting reaction:
and (3) reacting for 10-50 min under ultraviolet irradiation, then taking out, washing with water, extracting with acetone, and drying to obtain the PET fiber (PET-g-PAA) with the surface grafted with carboxyl functional groups.
S5, modifying antibacterial active ingredients:
an amount of PET-g-PAA was added to an aqueous solution containing 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and reacted at room temperature for 2 hours, after which an amount of aminopolysaccharide quaternary ammonium salt (Amino polysaccharide quaternary ammonium salt, hereinafter abbreviated As As) and N-hydroxysuccinimide (NHS) were added and stirring was continued for 24 to 48 hours.
S6, obtaining PET-g-PAA@As:
after the reaction, the mixture was washed with deionized water to obtain PET-g-PAA@As.
2. The method for modifying a polyester substrate by post-solution grafting according to claim 1, wherein in the step S1, a commercially available PET nonwoven fabric is selected as a raw material for experiments based on PET-Cuff actually used in a catheter, the pretreatment method of the PET nonwoven fabric is extraction with acetone, extraction and drying, and in the photo-grafting experiment of the present item, the selected photosensitizer is Benzophenone (BP), and the monomer Acrylic Acid (AA) is a modified material for imparting a carboxyl group.
3. The method for modifying the quaternary ammonium salt of the polyester substrate by the post-solution grafting method according to claim 1, wherein in the step S2, the selected photosensitizer is hydrogen-abstracting photosensitizer Benzophenone (BP), the photosensitizer BP is transited to a triplet state from a singlet state channeling state under the irradiation of ultraviolet light UV, then active hydrogen atoms are abstracted from an organic chain on the surface of MPS@PG, so that free radicals are generated on the surface of the substrate, and BP itself generates half pinacol after abstracting hydrogen ions, the free radical initiation activity of the half pinacol is very low, so that the self polymerization of monomers is difficult to initiate after the half pinacol is removed from the surface of the substrate, the efficiency of initiating grafting reaction of the BP type photosensitizer is high, in the experiment, BP is firstly dissolved in acetone, the BP acetone solution with 25% of the process concentration is prepared, and then the BP is sprayed on the surface of PET fiber, and the BP can be crystallized and separated on the surface of the fiber due to rapid volatilization of the acetone, so that the photoinitiator is effectively fixed.
4. The method for modifying the quaternary ammonium salt of the polyester substrate by the post-solution grafting method according to claim 1, wherein in the step S3, the size of the quartz tank matched with the method is the most suitable size area after cutting the PET non-woven fabric used in the preparation due to the specificity of the ultraviolet grafting experimental condition; the selection of the organic monomer is extremely important in the photo-grafting reaction, the experiment starts according to the experimental conditions and the characteristics of the PET substrate, the PET substrate is a hydrophobic material, and after BP is loaded, if the reaction liquid is an organic solvent system, BP is very easy to dissolve in the solvent, and can not be effectively initiated on the surface of the fiber. Therefore, the reaction needs to be carried out in an aqueous solution containing a certain lipophilic solute, and the comprehensive analysis of the conditions shows that the property of the water-soluble acrylic monomer completely meets the requirement of the grafting experiment, so that the acrylic acid is used as the grafting monomer for the experiment to carry out the photo-grafting study.
5. The method for modifying the quaternary ammonium salt of the polyester substrate by the post-solution grafting method according to claim 1, wherein in the step S4, the PET non-woven fabric loaded with BP is put into an AA aqueous solution with a certain concentration for Ultraviolet (UV) illumination grafting reaction, and BP attacks the "-C-H" site of the hydrocarbon chain on the surface of the PET fiber by photochemical hydrogen extraction reaction; thereby forming a 'C.cndot.' active free radical, and then initiating the Graft polymerization of the AA monomer from the substrate surface by a 'Graft from' method. In addition, the "-C-H" sites on the PAA chain are triggered by irradiation, thereby creating more grafting sites and, therefore, a degree of PAA polymer layer.
6. The post-solution grafting method for modifying a polyester substrate according to claim 1, wherein in the step S4, the grafting rate is remarkably increased by adding an inorganic acid or an organic acid to the co-irradiation grafting system, and for reasons that the acid affects the grafting reaction, it is widely believed that the sensitization effect of the acid is a synergistic effect of various effects, such as the acid increases the H atom concentration in the reaction, the dissolution degree of the grafting monomer in the solution, and the viscosity of the system, and at the same time, the acid can cause an increase in monomer-solvent reaction intermediate, which tends to cause more grafting reaction active sites, and in addition, the chain length of the oligomer becomes shorter and the number of the oligomer increases, the short chain oligomer diffuses more easily to the swelling substrate, the chain ends more effectively in the reaction active region, the viscosity of the grafting solution and the solution swelling in the substrate increases, and the monomer concentration in different regions of the grafting system greatly differs.
7. The method for modifying the quaternary ammonium salt of the polyester substrate by the post-solution grafting method according to claim 1, wherein in the step S4, the ultraviolet light is used as a precondition of the reaction in the ultraviolet light grafting reaction, the effect of the illumination time on the grafting rate is also obvious, when the dosage of the PET fiber is constant, 15wt.% of photosensitizer BP is loaded, and 25 vol.% of acrylic acid monomer and H in the reaction solution are added + The concentration is 0.2mol/L, and the product of the polyacrylic acid pre-modified PET fiber with larger grafting rate can be obtained by illumination for 30 min. Therefore, PET-g-PAA prepared by the experimental parameters is selected, extracted and washed by acetone and then used for carrying out subsequent modification experiments of antibacterial components.
8. The method for modifying the quaternary ammonium salt of the polyester substrate by the post-grafting solution method according to claim 1, wherein in the step S5, aminopolysaccharide quaternary ammonium salt (As) is selected in the project, so that the method has a broad-spectrum antibacterial function and can remarkably inhibit and kill common pathogenic microorganisms such As staphylococcus aureus, escherichia coli and the like in intestinal tracts; meanwhile, the method can regulate fibroblast proliferation and keratinization, accelerate wound healing, reduce scar formation, and provide a safe and effective method for crosslinking amino bonds by taking 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) as a water-soluble, non-cytotoxic and biocompatible carbodiimide as a coupling agent and n-hydroxysuccinimide (NHS) as a stabilizer, thereby improving crosslinking efficiency. Unlike conventional crosslinkers, EDC and NHS introduce "zero length" amide crosslinking between carboxyl and amino groups, and furthermore EDC and NHS are only catalysts, which can be removed by dialysis. However, EDC and NHS above a certain concentration may risk cytotoxicity, and thus the maximum EDC/NHS concentration required for use in the experiment should be less than 0.3mol/L, which can be considered safe in biological materials.
9. The post-solution grafting method for modifying a polyester substrate with a quaternary ammonium salt according to claim 1, wherein in the step S5, a solution of PET-g-paa@as is prepared by EDC/NHS mediated polymerization, a solution of 4-morpholinoethanesulfonic acid (MES) with a concentration of 0.1mol/L is prepared in deionized water (ph=3.61±0.01), PET-g-PAA and As are respectively added to the 0.1mol/L MES solution, the solution is stirred uniformly and transferred into an ice/water bath to prepare a solution of mixed PET-g-PAA and As, a certain amount of NHS is added to the mixed solution, a certain amount of EDC is then added, and the stirring reaction is continued for 6 hours, thereby obtaining PET-g-paa@as.
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