CN114644771A - Polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions and preparation method thereof - Google Patents

Polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions and preparation method thereof Download PDF

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CN114644771A
CN114644771A CN202210395268.4A CN202210395268A CN114644771A CN 114644771 A CN114644771 A CN 114644771A CN 202210395268 A CN202210395268 A CN 202210395268A CN 114644771 A CN114644771 A CN 114644771A
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ngo
tio
pvc
stirring
sheet
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赵义平
朱林
张继生
徐向阳
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Shandong Golden Sunshine Pharmaceutical Packaging Co ltd
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Shandong Golden Sunshine Pharmaceutical Packaging Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

A preparation method of a polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions is prepared by the following steps: step (1): preparing GO; step (2): preparing NGO; and (3): NGO-TiO2Preparing; and (4): and (3) preparing the anti-fouling and antibacterial PVC sheet. The invention uses the existing commonly used photocatalytic material TiO2The nano material is introduced into PVC medicine bag sheet material, and TiO is used2The anti-pollution performance of the PVC medicine bag sheet is improved by the photocatalysis of the nano material, and TiO is utilized2PVC (polyvinyl chloride) medicine bag endowed with antibacterial and bacteriostatic functions of nano materialThe sheet has antibacterial and bacteriostatic functions. By using Graphene Oxide (GO) on TiO2Preparation of NGO-TiO series by nano material amino modification method2Nano composite photocatalyst for increasing TiO content2The photocatalysis efficiency under the sun illumination is improved, and the pollution resistance of the PVC medicine bag sheet is further improved.

Description

Polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a polyvinyl chloride medicine package sheet with antifouling and antibacterial functions and a preparation method thereof.
Background
With the rapid increase of the demand of the medicine market and the continuous improvement of the medicine packaging requirement, the functional requirement on the medical medicine packaging material is higher and higher, and the novel functional medical packaging material is more and more the key point of the research and development of the medical medicine packaging field. At present, plastic polymer materials in medical drug packaging materials have a very high market share, and polyvinyl chloride (PVC) drug packaging materials have a very high proportion.
However, the traditional PVC medical drug bag sheet does not have the function of resisting organic pollutant pollution and has no antibacterial and bacteriostatic effects in the using process. After the sheet is used for packaging medicines, pollutants, bacteria and the like in the environment can be adhered to the surface of the sheet when contacting with the sheet in the using process. When people take the medicine, the medicine bag sheet or the container is touched by hands and then the medicine is taken, and the medicine is polluted. Therefore, the PVC medicine packaging material has important functions of anti-fouling, antibiosis and bacteriostasis.
The photocatalytic degradation technology can effectively degrade organic matters by converting light energy into chemical energy, has the advantages of high efficiency, low energy consumption, simple operation, no secondary pollution and the like, and can effectively convert organic pollutants into inorganic molecules or micromolecular substances. Therefore, the photocatalysis technology can be applied to the modification of the medicine packaging material. The photocatalytic material that is currently being extensively studied is titanium dioxide (TiO)2) And zinc oxide (ZnO) and the like. Wherein, TiO2The antibacterial agent is widely concerned, has an antibacterial function and is one of the commonly used antibacterial agents in the plastic industry. Thus, TiO can be utilized2Modified PVC medicine bag material.
At present, for TiO2Photocatalytic research of nano materials has been greatly advanced, but TiO2There are still many problems in the application of catalysis, among which the regulation of TiO2The forbidden band width of the photocatalyst widens the spectral response range and reduces the recombination rate of photon-generated carriers, so that the improvement of the photocatalytic efficiency is a key problem to be solved in the application process, especially under the solar illumination condition.
Thus, use of TiO2Modified PVC medicine bag material, improveTiO2The photocatalytic efficiency under solar illumination and the improvement of the anti-fouling performance are the problems to be solved at present. Meanwhile, how to avoid direct contact between the PVC medicine package sheet and the medicine is also a difficult problem to be solved.
Disclosure of Invention
Aiming at the problems that the PVC sheet material in the existing PVC medicine packaging field does not have the functions of pollution resistance, bacteria resistance and the like, and the PVC sheet material is in direct contact with medicines, the invention aims to solve the technical problem of providing the polyvinyl chloride medicine package sheet material with the functions of pollution resistance and bacteria resistance and the preparation method thereof.
The invention provides a preparation method of a polyvinyl chloride medicine package sheet with an anti-fouling and antibacterial function, which is prepared by the following steps:
step (1): preparation of GO:
slowly adding 200-250 mL of concentrated sulfuric acid into a 1L three-neck flask in an ice-water bath, sequentially adding 10-15 g of graphite and 3-5 g of sodium nitrate, slowly adding the graphite and the sodium nitrate, repeatedly grinding the graphite and the sodium nitrate, stirring for 1-1.5 h, then slowly adding 25-35 g of potassium permanganate, mechanically stirring for 1.5-2 h in the ice-water bath, heating to 30-40 ℃, reacting for 2-2.5 h, then slowly adding 200-250 mL of 30-40 ℃ deionized water, heating the reaction system to 80-90 ℃, stirring for 10-20 min, then slowly adding 400-500 mL of deionized water into the system, stirring for 2min, adding 20-25 mL of hydrogen peroxide to stop the reaction, continuously stirring the reactant for 10-20 min, performing centrifugal separation, repeatedly washing with dilute hydrochloric acid and deionized water for many times, until the pH value of the product is 7, obtaining the graphene oxide GO required by the invention;
step (2): preparation of NGO:
1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) are used as cross-linking agents and synthesized through the polycondensation reaction of GO and EDTA, GO is ultrasonically dispersed in DMF for 2-3 h, the ultrasonically treated suspension is transferred into a three-neck flask, the temperature of a reaction kettle is controlled to be not more than 5 ℃, EDC and NHS are added in the stirring process, the reaction is carried out for 4-5 h at the rotating speed of 200-300 r/min, DETA is dropwise added into the three-neck flask, then the quick stirring is carried out for 6 h at the rotating speed of 500-600 r/min to obtain a NGO mixture, the NGO mixed solution is washed with deionized water for three times to remove impurities, the product is placed in a culture dish and is freeze-dried by a vacuum drier, and the obtained product is hermetically stored;
and (3): NGO-TiO2The preparation of (1):
putting a certain amount of NGO in deionized water, performing ultrasonic treatment for 1h to uniformly disperse the NGO, and preparing TiO2Dispersing the mixture in a toluene solution by using the same treatment method, wherein the mass ratio of NGO to TiO2 is 5-10: 95-90, and mixing the suspension of NGO and the dispersed TiO2Mixing the toluene solution together, stirring for 4-5 h to prepare NGO-TiO2A composite catalyst;
and (4): preparing an anti-fouling and antibacterial PVC sheet:
according to PVC with NGO-TiO2According to the mass ratio of 100: 0.02-0.5, adding NGO-TiO2Adding into PVC medicine packaging sheet formula system, and producing according to conventional PVC medicine packaging sheet calendering process.
Preferably, TiO in the step (3)2The grain diameter is 20 nm-300 nm.
The invention also provides the polyvinyl chloride medicine bag sheet prepared by the preparation method of the polyvinyl chloride medicine bag sheet.
The invention has the beneficial effects that:
the invention has the functions of photocatalysis removal and antibiosis and bacteriostasis, and the medicine packaging sheet not only can effectively resist the pollution of organic matters adhered to the surface on the basis of the traditional polyvinyl chloride medicine packaging function, but also has the functions of antibiosis and bacteriostasis, and can be applied to the field of medical medicine packaging.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
A preparation method of a polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions is prepared by the following steps:
step (1) GO is prepared:
slowly adding 200mL of concentrated sulfuric acid into a 1L three-neck flask in an ice water bath, sequentially adding 10g of graphite and 3g of sodium nitrate, slowly adding the graphite and the sodium nitrate, repeatedly grinding the graphite and the sodium nitrate before adding, stirring for 1h, then slowly adding 25g of potassium permanganate, mechanically stirring for 1.5h in the ice water bath, then heating to 30 ℃, reacting for 2h, then slowly adding 200mL of 30 ℃ deionized water, then heating the reaction system to 80 ℃, stirring for 10min, then slowly adding 400mL of deionized water into the system, stirring for 2min, adding 20mL of hydrogen peroxide to terminate the reaction, continuously stirring the reactants for 10min, carrying out centrifugal separation, and repeatedly washing with dilute hydrochloric acid and deionized water for multiple times until the pH of a product is 7 to obtain the GO required by the invention;
step (2) preparation of NGO:
carrying out synthesis by taking 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) as cross-linking agents through a polycondensation reaction of GO and EDTA, carrying out ultrasonic treatment for 2h to disperse GO in DMF, transferring the suspension after ultrasonic treatment into a three-neck flask, controlling the temperature of a reaction kettle to be not more than 5 ℃, adding EDC and NHS during stirring, reacting for 4h at the rotating speed of 200r/min, dropwise adding DETA into the three-neck flask, rapidly stirring for 6 h at the rotating speed of 500r/min to obtain a NGO mixture, washing the NGO mixture solution with deionized water for three times to remove impurities, placing the product in a culture dish, carrying out freeze drying by using a vacuum drier, and sealing and storing the obtained product;
step (3) NGO-TiO2The preparation of (1):
putting a certain amount of NGO in deionized water, performing ultrasonic treatment for 1h to uniformly disperse the NGO, and preparing TiO2Dispersing in toluene solution by the same treatment method according to NGO and TiO2And (2) mass ratio of 5: 95, mixing the suspension of NGO and dispersed TiO2The toluene solution is mixed together and stirred for 4 hours to prepare NGO-TiO2A composite catalyst;
preparing an antifouling antibacterial functional PVC sheet material:
according to PVC with NGO-TiO2In a mass ratio of 100:0.02 proportion of NGO-TiO2Adding into PVC medicine packaging sheet formula system, and producing according to conventional PVC medicine packaging sheet calendering process.
Example 2
A preparation method of a polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions is prepared by the following steps:
step (1) GO is prepared:
in an ice-water bath, slowly adding 250mL of concentrated sulfuric acid into a 1L three-neck flask, sequentially adding 15g of graphite and 5g of sodium nitrate, slowly adding the graphite and the sodium nitrate, repeatedly grinding the graphite and the sodium nitrate before adding, stirring for 1.5h, then slowly adding 35g of potassium permanganate, mechanically stirring for 2h in the ice-water bath, then heating to 40 ℃, reacting for 2.5h, then slowly adding 250mL of 40 ℃ deionized water, then heating the reaction system to 90 ℃, stirring for 20min, then slowly adding 500mL of deionized water into the system, stirring for 2min, adding 25mL of hydrogen peroxide to terminate the reaction, continuously stirring the reactant for 20min, carrying out centrifugal separation, and repeatedly washing with dilute hydrochloric acid and deionized water for multiple times until the pH of the product is 7 to obtain the GO required by the invention;
step (2) preparation of NGO:
carrying out synthesis by taking 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) as cross-linking agents through a polycondensation reaction of GO and EDTA, carrying out ultrasonic treatment for 3h to disperse GO in DMF, transferring the suspension after ultrasonic treatment into a three-neck flask, controlling the temperature of a reaction kettle to be not more than 5 ℃, adding EDC and NHS during stirring, reacting for 4h at the rotating speed of 300r/min, dropwise adding DETA into the three-neck flask, rapidly stirring for 6 h at the rotating speed of 600 r/min to obtain a NGO mixture, washing the NGO mixture solution with deionized water for three times to remove impurities, placing the product in a culture dish, carrying out freeze drying by using a vacuum drier, and sealing and storing the obtained product;
step (3) NGO-TiO2The preparation of (1):
putting a certain amount of NGO in deionized water, performing ultrasonic treatment for 1h to uniformly disperse the NGO, and preparing TiO2Dispersing in toluene by the same treatment methodIn solution according to NGO with TiO2The mass ratio is 6: 94, mixing the suspension of NGO and dispersed TiO2The toluene solution is mixed together and stirred for 4 hours to prepare NGO-TiO2A composite catalyst;
preparing an antifouling antibacterial functional PVC sheet material:
according to PVC with NGO-TiO2According to the mass ratio of 100:0.05, adding NGO-TiO2Adding into PVC medicine packaging sheet formula system, and producing according to conventional PVC medicine packaging sheet calendering process.
Example 3
A preparation method of a polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions is prepared by the following steps:
step (1) GO is prepared:
slowly adding 200mL of concentrated sulfuric acid into a 1L three-neck flask in an ice water bath, sequentially adding 15g of graphite and 5g of sodium nitrate, slowly adding the graphite and the sodium nitrate, repeatedly grinding the graphite and the sodium nitrate before adding, stirring for 1.5h, then slowly adding 25g of potassium permanganate, mechanically stirring for 2h in the ice water bath, then heating to 30 ℃, reacting for 2h, then slowly adding 250mL of 30 ℃ deionized water, then heating the reaction system to 80 ℃, stirring for 10min, then slowly adding 500mL of deionized water into the system, stirring for 2min, adding 25mL of hydrogen peroxide to terminate the reaction, continuously stirring the reactant for 20min, carrying out centrifugal separation, and repeatedly washing with dilute hydrochloric acid and deionized water for multiple times until the pH of the product is 7 to obtain the GO required by the invention;
step (2) preparation of NGO:
synthesizing 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) serving as cross-linking agents through a polycondensation reaction of GO and EDTA, ultrasonically treating GO for 2.5h to disperse the GO in DMF, transferring the suspension after ultrasonic treatment into a three-neck flask, controlling the temperature of a reaction kettle to be not more than 5 ℃, adding EDC and NHS during stirring, reacting for 4h at the rotating speed of 250r/min, dropwise adding DETA into the three-neck flask, rapidly stirring for 6 h at the rotating speed of 600 r/min to obtain a NGO mixture, washing the NGO mixture solution with deionized water for three times to remove impurities, placing the product in a culture dish vacuum drier for freeze drying, and sealing and storing the obtained product;
step (3) NGO-TiO2The preparation of (1):
putting a certain amount of NGO in deionized water, performing ultrasonic treatment for 1h to uniformly disperse the NGO, and preparing TiO2Dispersing in toluene solution by the same treatment method according to NGO and TiO2The mass ratio is 10: 90, mixing the suspension of NGO and the dispersed TiO2The toluene solution is mixed together and stirred for 5 hours to prepare NGO-TiO2A composite catalyst;
preparing an antifouling antibacterial functional PVC sheet material:
according to PVC with NGO-TiO2The mass ratio of NGO-TiO is 100: 0.12Adding into PVC medicine packaging sheet formula system, and producing according to conventional PVC medicine packaging sheet calendering process.
Example 4
A preparation method of a polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions is prepared by the following steps:
step (1) GO is prepared:
in an ice-water bath, slowly adding 220mL of concentrated sulfuric acid into a 1L three-neck flask, sequentially adding 12g of graphite and 4g of sodium nitrate, slowly adding the graphite and the sodium nitrate, repeatedly grinding the graphite and the sodium nitrate before adding, stirring for 1.5h, then slowly adding 25g of potassium permanganate, mechanically stirring in the ice-water bath for 1.5h, then heating to 35 ℃, reacting for 2.5h, then slowly adding 230mL of 35 ℃ deionized water, then heating the reaction system to 80 ℃, stirring for 10min, then slowly adding 400mL of deionized water into the system, stirring for 2min, adding 20mL of hydrogen peroxide to terminate the reaction, continuously stirring the reactant for 10min, performing centrifugal separation, and repeatedly washing with dilute hydrochloric acid and deionized water for multiple times until the pH of the product is 7 to obtain the GO product required by the invention;
step (2) preparation of NGO:
synthesizing 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) serving as cross-linking agents through a condensation polymerization reaction of GO and EDTA, ultrasonically treating GO for 3h to disperse in DMF, transferring the suspension after ultrasonic treatment into a three-neck flask, controlling the temperature of a reaction kettle to be not more than 5 ℃, adding EDC and NHS during stirring, reacting for 4.5h at the rotating speed of 300r/min, dropwise adding DETA into the three-neck flask, rapidly stirring for 6 h at the rotating speed of 400 r/min to obtain a mixture of NGO, washing the mixed solution of NGO with deionized water for three times to remove impurities, placing the product in a culture dish vacuum drier for freeze drying, and sealing and storing the obtained product;
step (3) NGO-TiO2The preparation of (1):
putting a certain amount of NGO in deionized water, performing ultrasonic treatment for 1h to uniformly disperse the NGO, and preparing TiO2Dispersing in toluene solution by the same treatment method according to NGO and TiO2The mass ratio of (7): 93, mixing the suspension of NGO and dispersed TiO2The toluene solution is mixed together and stirred for 4.5h to prepare the NGO-TiO2A composite catalyst;
step (4) preparation of the anti-fouling and antibacterial PVC sheet:
according to PVC and NGO-TiO2According to the mass ratio of 100:0.2, adding NGO-TiO2Adding into PVC medicine packaging sheet formula system, and producing according to conventional PVC medicine packaging sheet calendering process.
Example 5
A preparation method of a polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions is prepared by the following steps:
step (1) GO is prepared:
in an ice-water bath, slowly adding 220mL of concentrated sulfuric acid into a 1L three-neck flask, sequentially adding 14g of graphite and 3g of sodium nitrate, slowly adding the graphite and the sodium nitrate, repeatedly grinding the graphite and the sodium nitrate, stirring for 1.25h, then slowly adding 30g of potassium permanganate, mechanically stirring in the ice-water bath for 1.5h, then heating to 38 ℃, reacting for 2h, then slowly adding 220mL of 30 ℃ deionized water, heating the reaction system to 85 ℃, stirring for 10min, then slowly adding 500mL of deionized water into the system, stirring for 2min, adding 25mL of hydrogen peroxide to terminate the reaction, continuously stirring the reactants for 10min, performing centrifugal separation, repeatedly washing with dilute hydrochloric acid and deionized water for many times until the pH of a product is 7, and obtaining the GO product required by the invention;
step (2) preparation of NGO:
carrying out synthesis by taking 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) as cross-linking agents through a polycondensation reaction of GO and EDTA, carrying out ultrasonic treatment for 3h to disperse GO in DMF, transferring the suspension after ultrasonic treatment into a three-neck flask, controlling the temperature of a reaction kettle to be not more than 5 ℃, adding EDC and NHS during stirring, reacting for 5h at the rotating speed of 300r/min, dropwise adding DETA into the three-neck flask, rapidly stirring for 6 h at the rotating speed of 550 r/min to obtain a NGO mixture, washing the NGO mixture solution with deionized water for three times to remove impurities, placing the product in a culture dish, carrying out freeze drying by using a vacuum drier, and sealing and storing the obtained product;
step (3) NGO-TiO2The preparation of (1):
putting a certain amount of NGO in deionized water, and performing ultrasonic treatment for 1h to uniformly disperse the NGO and TiO2Dispersing in toluene solution by the same treatment method according to NGO and TiO2The mass ratio is 8: 92, mixing the suspension of NGO and dispersed TiO2The toluene solution is mixed together and stirred for 4.5h to prepare the NGO-TiO2A composite catalyst;
step (4) preparation of the anti-fouling and antibacterial PVC sheet:
according to PVC with NGO-TiO2According to the mass ratio of 100: 0.4, adding NGO-TiO2Adding into PVC medicine packaging sheet formula system, and producing according to conventional PVC medicine packaging sheet calendering process.
Example 6
A preparation method of a polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions is prepared by the following steps:
step (1) GO is prepared:
in an ice-water bath, slowly adding 240mL of concentrated sulfuric acid into a 1L three-neck flask, sequentially adding 13g of graphite and 3.5g of sodium nitrate, slowly adding the graphite and the sodium nitrate, repeatedly grinding the graphite and the sodium nitrate before adding, stirring for 1.5h, then slowly adding 32g of potassium permanganate, mechanically stirring for 1.8h in the ice-water bath, then heating to 38 ℃, reacting for 2.5h, then slowly adding 250mL of deionized water at 36 ℃, then heating the reaction system to 82 ℃ and stirring for 15min, then slowly adding 450mL of deionized water into the system, stirring for 2min, adding 22mL of hydrogen peroxide to terminate the reaction, continuously stirring the reactants for 15min, carrying out centrifugal separation, and repeatedly washing with dilute hydrochloric acid and deionized water for multiple times until the pH of the product is 7, thus obtaining the GO product required by the invention;
step (2) preparation of NGO:
carrying out synthesis by taking 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) as cross-linking agents through a polycondensation reaction of GO and EDTA, carrying out ultrasonic treatment for 2h to disperse GO in DMF, transferring the suspension after ultrasonic treatment into a three-neck flask, controlling the temperature of a reaction kettle to be not more than 5 ℃, adding EDC and NHS during stirring, reacting for 4.5h at the rotating speed of 200r/min, dropwise adding DETA into the three-neck flask, rapidly stirring for 6 h at the rotating speed of 580 r/min to obtain a NGO mixture, washing the NGO mixture solution with deionized water for three times to remove impurities, placing the product in a petri dish vacuum drier for freeze drying, and sealing and storing the obtained product;
step (3) NGO-TiO2The preparation of (1):
putting a certain amount of NGO in deionized water, performing ultrasonic treatment for 1h to uniformly disperse the NGO, and preparing TiO2Dispersing in toluene solution by the same treatment method according to NGO and TiO2The mass ratio is 10: 90, mixing the suspension of NGO and the dispersed TiO2Mixing the toluene solution and stirring for 5h to obtain NGO-TiO2A composite catalyst;
preparing an antifouling antibacterial functional PVC sheet material:
according to PVC with NGO-TiO2According to the mass ratio of 100:0.5, adding NGO-TiO2Adding into PVC medicine packaging sheet formula system, and producing according to conventional PVC medicine packaging sheet calendering process.
The invention has the beneficial effects that:
the invention uses the existing commonly used photocatalytic material TiO2The nano material is introduced into PVC medicine bag sheet material, and TiO is used2The photocatalysis of the nano material improves the pollution resistance of the PVC explosive package sheet, and TiO is utilized2The antibacterial and bacteriostatic functions of the nano material are endowed with the antibacterial and bacteriostatic functions of the PVC medicine bag sheet. By using Graphene Oxide (GO) on TiO2Preparation of NGO-TiO series by nano material amino modification method2Nano composite photocatalyst for increasing TiO content2The photocatalysis efficiency under the sun illumination is improved, and the pollution resistance of the PVC medicine bag sheet is further improved.
The invention takes the traditional PVC medicine bag material as the raw material, and synthesizes the NGO-TiO2The nano composite photocatalyst is added into a PVC formula system, and the calendered sheet production is directly carried out according to the traditional PVC medicine bag sheet calendering and forming process.
NGO-TiO2The composite nano-catalyst has simple preparation process and is easy for industrial production. NGO-TiO2Has high-efficiency photocatalytic anti-fouling capability to sunlight and has spectral antibacterial and bacteriostatic functions. The NGO-TiO of the invention2The photocatalysis removal rate of the composite nano photocatalyst on organic dyes such as methylene blue and the like under the natural light action reaches over 90 percent, the photocatalysis removal rate of the medicine bag sheet on the methylene blue reaches over 70 percent, and the antibacterial rate reaches over 50 percent.
Compared with the prior art, the medical medicine packaging sheet material with the anti-fouling and antibacterial functions is prepared by the invention, and the production process does not need special equipment and is easy to implement industrially. The product of the invention has low cost and good compatibility among materials.
The product is synthesized into aminated graphene oxide (NGO) by condensation of Graphene Oxide (GO) and Diethylenetriamine (DETA), and then series NGO-TiO are prepared by a toluene and water two-phase system self-assembly method2A nano composite photocatalyst. The TiO of the present invention2The particle size is 20-300 nm, and the GO is a GO product prepared by adopting an improved Hummers method.
The invention has the photocatalysis removal function and the antibacterial and bacteriostatic functions, and the medicine packaging sheet can effectively resist the pollution of organic matters adhered to the surface on the basis of the traditional polyvinyl chloride medicine packaging function, has the antibacterial and bacteriostatic functions and can be applied to the field of medical medicine packaging.

Claims (3)

1. A preparation method of a polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions is characterized by comprising the following steps:
step (1): preparation of GO:
slowly adding 200-250 mL of concentrated sulfuric acid into a 1L three-neck flask in an ice-water bath, sequentially adding 10-15 g of graphite and 3-5 g of sodium nitrate, slowly adding the graphite and the sodium nitrate, repeatedly grinding the graphite and the sodium nitrate, stirring for 1-1.5 h, then slowly adding 25-35 g of potassium permanganate, mechanically stirring for 1.5-2 h in the ice-water bath, heating to 30-40 ℃, reacting for 2-2.5 h, then slowly adding 200-250 mL of 30-40 ℃ deionized water, heating the reaction system to 80-90 ℃, stirring for 10-20 min, then slowly adding 400-500 mL of deionized water into the system, stirring for 2min, adding 20-25 mL of hydrogen peroxide to stop the reaction, continuously stirring the reactant for 10-20 min, performing centrifugal separation, repeatedly washing with dilute hydrochloric acid and deionized water for many times, until the pH value of the product is 7, obtaining the graphene oxide GO required by the invention;
step (2): preparation of NGO:
1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) are used as cross-linking agents and synthesized through the polycondensation reaction of GO and EDTA, GO is ultrasonically dispersed in DMF for 2-3 h, the ultrasonically treated suspension is transferred into a three-neck flask, the temperature of a reaction kettle is controlled to be not more than 5 ℃, EDC and NHS are added in the stirring process, the reaction is carried out for 4-5 h at the rotating speed of 200-300 r/min, DETA is dropwise added into the three-neck flask, then the quick stirring is carried out for 6 h at the rotating speed of 500-600 r/min to obtain a NGO mixture, the NGO mixed solution is washed with deionized water for three times to remove impurities, the product is placed in a culture dish and is freeze-dried by a vacuum drier, and the obtained product is hermetically stored;
step (ii) of（3）：NGO-TiO2The preparation of (1):
putting a certain amount of NGO in deionized water, performing ultrasonic treatment for 1h to uniformly disperse the NGO, and preparing TiO2Dispersing the mixture in a toluene solution by using the same treatment method, wherein the mass ratio of NGO to TiO2 is 5-10: 95-90, and mixing the suspension of NGO and the dispersed TiO2Mixing the toluene solution together, stirring for 4-5 h to prepare NGO-TiO2A composite catalyst;
and (4): preparing an anti-fouling and antibacterial PVC sheet:
according to PVC and NGO-TiO2According to the mass ratio of 100: 0.02-0.5, adding NGO-TiO2Adding into PVC medicine packaging sheet material formula system, and rolling according to conventional PVC medicine packaging sheet material rolling process.
2. The method for preparing anti-fouling and antibacterial polyvinyl chloride (PVC) drug package sheet according to claim 1, wherein the TiO in step (3) is TiO2The grain diameter is 20 nm-300 nm.
3. A polyvinyl chloride drug pack sheet obtained by the method for producing a polyvinyl chloride drug pack sheet according to any one of claims 1 to 2.
CN202210395268.4A 2022-04-15 2022-04-15 Polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions and preparation method thereof Pending CN114644771A (en)

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