CN111793340B - Fluorescent antibacterial polycarbonate composite material and preparation method and application thereof - Google Patents
Fluorescent antibacterial polycarbonate composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a fluorescent antibacterial polypropylene material and a preparation method and application thereof, belonging to the field of high polymer materials. The fluorescent antibacterial polycarbonate composite material comprises blended polycarbonate resin and a fluorescent antibacterial high polymer material, wherein the polycarbonate resin accounts for 0.1-20 parts by weight of 100 parts by weight of the fluorescent antibacterial high polymer material; the fluorescent antibacterial high polymer material is a maleic anhydride copolymer zinc salt derivative. The exciting light range of the fluorescent antibacterial polycarbonate composite material is 300-600nm, and the emission light range is 300-700nm. The antibacterial rate of the fluorescent antibacterial polycarbonate composite material to escherichia coli and staphylococcus aureus is more than 99%. The fluorescent antibacterial polycarbonate composite material has the advantages of low price of raw materials, simple preparation method, low environmental pollution, excellent fluorescence performance, high safety and lasting antibacterial effect, and is suitable for industrial application.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and further relates to an antibacterial polycarbonate composite material with fluorescence property and a preparation method and application thereof.
Background
With the continuous development of society, the social economy and the living standard of people are continuously improved, and the sanitary safety problem is more and more emphasized by people. In nature, there are many microbes such as harmful bacteria, fungi and viruses, which cause serious harm to human health, and some of them may even endanger human life. Therefore, in order to meet the increasing demand of people for environmental sanitation and the like, researchers in various countries are developing efficient antibacterial materials.
Most antimicrobial materials are made by adding an antimicrobial agent to the matrix, and conventional antimicrobial agents typically achieve the antimicrobial effect of the entire material by printing or killing bacteria. Compared with the conventional physical and chemical sterilization means, the method is simple and convenient. The traditional antibacterial agents can be mainly divided into inorganic and organic antibacterial agents, but the traditional antibacterial agents are added in a large amount, and can also have a precipitation phenomenon and influence the performance of products.
Polycarbonate is a thermoplastic material which is the fastest in demand among five engineering plastics, has excellent mechanical and thermal properties, is widely applied to the fields of electronic and electric appliances, sheet films, the automobile industry, optical storage media, medical instruments, protective equipment and the like, and is rapidly expanded to emerging fields of aerospace, optical elements, photoelectric information and the like. In these fields, many of them require an antibacterial function to improve the existing hygienic safety, and therefore, it is very important to develop a novel antibacterial polycarbonate material.
At present, most of antibacterial polycarbonate materials realize the antibacterial effect by adding traditional inorganic or organic micromolecular antibacterial agents, chinese patent CN102827469A discloses antibacterial polycarbonate, the technology realizes the antibacterial effect of the polycarbonate materials by adding inorganic antibacterial agents such as nano silver oxide and nano titanium oxide and organic micromolecular antibacterial agents such as polyhexamethylene guanidine phosphate, and the inorganic antibacterial agents and the micromolecular antibacterial agents are easy to separate out, so that the service life and the antibacterial effect of products are influenced. Chinese patent CN107459802A discloses an antibacterial polycarbonate plastic, which is prepared by dispersing nano silver oxide and nano zinc oxide in ceramic powder and sodium silicate, mixing the nano silver oxide and nano zinc oxide with a compound organic quaternary ammonium salt solution to be used as a composite antibacterial agent, and simultaneously adding a large amount of film-forming agents. However, a large amount of additives can affect other properties of the product, and the silver-based antibacterial agent can be discolored under the irradiation of sunlight, so that the appearance and the antibacterial effect of the product are affected.
The zinc element is a trace element necessary for human bodies, the antibacterial agent prepared from the zinc element has the advantages of high efficiency, safety, broad bactericidal spectrum and the like, and Chinese patent CN104072644B discloses a polymer with antibacterial activity. However, the traditional inorganic zinc antibacterial agent has the problem of compatibility with polymers such as polycarbonate and the like, and needs surface modification; the organic zinc antibacterial agent has low decomposition temperature and easy precipitation, and has important application significance if the organic zinc antibacterial agent with high heat resistance and lasting antibacterial effect can be prepared.
Fluorescence is a special material property, which means that when a material is irradiated with light having energy, electrons of the material absorb the energy of the light and undergo transition into an excited state, and when the electrons return from the excited state to a ground state, emitted light having a wavelength different from that of the irradiated light is emitted. The fluorescent material has wide application in the fields of anti-counterfeiting, probes, marks and the like. If a high molecular polymer material endowed with fluorescent and antibacterial properties is applied to polycarbonate, the polycarbonate material has great industrial value.
So far, the research on polycarbonate with fluorescent and antibacterial functions is less, so that the development of fluorescent antibacterial polycarbonate materials with low cost and lasting antibacterial effect and the production process thereof have extremely important market value and economic significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a fluorescent antibacterial polycarbonate composite material and a preparation method thereof. The fluorescent antibacterial polycarbonate composite material used in the invention has low price of raw materials and auxiliary agents in the process, and the production process is mature. The fluorescent antibacterial polycarbonate composite material disclosed by the invention has both a fluorescent effect and an antibacterial property, is high in antibacterial efficiency and long in antibacterial aging, and is extremely easy to industrially popularize.
One of the purposes of the invention is to provide a fluorescent antibacterial polycarbonate composite material.
The fluorescent antibacterial polycarbonate composite material comprises 0.1-20 parts by weight of blended polycarbonate resin and a fluorescent antibacterial high polymer material, preferably 0.1-10 parts by weight of the polycarbonate resin. The fluorescent antibacterial high polymer material is a maleic anhydride copolymer zinc salt derivative.
In the fluorescent antibacterial polycarbonate composite material, the polycarbonate resin is selected from various existing polycarbonate resins in the prior art, and can be at least one of polycarbonate resin prepared by an interfacial phosgene method or polycarbonate resin prepared by a non-interfacial phosgene method. The polycarbonate prepared by the non-interfacial phosgene method comprises polycarbonate resin prepared by ester exchange, ring opening, solid phase polycondensation and other process methods, and the polycarbonate resin prepared by the ester exchange method is preferred.
The zinc salt derivative of the maleic anhydride copolymer in the fluorescent antibacterial polycarbonate composite material is the maleic anhydride copolymer with zinc ions bonded on carboxylic acid groups. Wherein the weight fraction of the zinc element is 10-70%, preferably 20-60%.
The maleic anhydride copolymer may be various maleic anhydride copolymers known in the art, and preferably is a maleic anhydride alternating copolymer including at least one of a linear alternating copolymer and a cross-linked alternating copolymer.
The maleic anhydride alternating copolymer is preferably at least one alternating copolymer obtained by copolymerizing maleic anhydride and a monomer containing isolated carbon-carbon double bonds; more preferably maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer, maleic anhydride-1-butene alternating copolymer, maleic anhydride-2-butene alternating copolymer, maleic anhydride-isobutylene alternating copolymer, maleic anhydride-butadiene alternating copolymer, maleic anhydride-1-pentene alternating copolymer, maleic anhydride-vinylpyrrolidone alternating copolymer, maleic anhydride-itaconic acid alternating copolymer; most preferably at least one of maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methyl styrene alternating copolymer and maleic anhydride-isobutylene alternating copolymer.
The molecular structure of the fluorescent antibacterial high polymer material is characterized in that: divalent zinc ions in the maleic anhydride copolymer zinc salt derivative are connected with two carboxylic acid groups obtained by ring opening of maleic anhydride in the maleic anhydride copolymer, and the two connected carboxylic acid groups can be from the same molecular chain or from two molecular chains.
One preferred scheme of the fluorescent antibacterial high polymer material is as follows:
the zinc salt derivative of the maleic anhydride copolymer of the fluorescent antibacterial polymer material of the present invention preferably has the following general formula:
wherein x, y and z are natural numbers, x is more than or equal to 1, y + z is more than or equal to 0;
the group R 1 、R 2 、R 4 、R 5 Is at least one of H and alkyl, preferably at least one of H, methyl and ethyl;
the group R 3 、R 6 Is H, hydroxy, CH 3 COO-, phenyl and/or alkyl, preferably H, hydroxy and CH 3 COO-, phenyl, methyl and ethyl;
the zinc ions of the zinc salt derivative of the maleic anhydride copolymer are combined (connected) with any two of the carboxyl groups designated by (1), (2), (3) and (4), and the carboxyl group combined (connected) with one zinc ion is the same molecular chain or two molecular chains.
The fluorescent antibacterial high molecular material maleic anhydride copolymer zinc salt derivative has the strongest fluorescence emission range of 400-550 nm under the excitation wavelength of 330-430 nm.
The fluorescent antibacterial high polymer material is prepared by adding a maleic anhydride copolymer into an aqueous solution of alkali metal hydroxide for full reaction, and then adding zinc salt and/or a zinc salt aqueous solution for full reaction.
The fluorescent antibacterial polycarbonate composite material contains a fluorescent antibacterial high polymer material, so that the range of excitation light is 300-600nm, preferably 300-500nm, and the range of emission light is 300-700nm, preferably 350-700nm.
The invention also aims to provide a preparation method of the fluorescent antibacterial polycarbonate composite material.
The preparation method of the fluorescent antibacterial polycarbonate composite material comprises the step of melting and blending the components containing the polycarbonate resin and the fluorescent antibacterial high polymer material according to the amount to obtain the fluorescent antibacterial polycarbonate composite material.
The preparation of the fluorescent antibacterial high polymer material does not use an organic solvent, and the preparation of the fluorescent antibacterial high polymer material comprises the steps of directly adding a maleic anhydride copolymer solid into an aqueous solution of alkali metal hydroxide for full reaction, and then adding a zinc salt and/or a zinc salt aqueous solution for full reaction to obtain the fluorescent antibacterial high polymer material. Specifically, the preparation method of the fluorescent antibacterial polymer material can comprise the following steps:
a. taking alkali metal hydroxide, adding the alkali metal hydroxide into water for dissolving to obtain an alkali metal hydroxide aqueous solution; wherein the weight ratio of the alkali metal hydroxide to the water is (0.1-100): 100, preferably (0.5 to 50): 100, respectively;
b. b, adding the maleic anhydride copolymer into the alkali metal hydroxide aqueous solution prepared in the step a, and fully mixing for reaction; wherein the weight ratio of the maleic anhydride copolymer to the alkali metal hydroxide is in the range of (0.1 to 20): 1, preferably (0.1 to 10): 1; the reaction is acid-base neutralization reaction of carboxylic acid groups of the maleic anhydride copolymer and alkali metal hydroxide;
c. directly adding zinc salt solid into the mixed solution obtained in the step b, fully mixing and reacting, and separating suspended matters to obtain the fluorescent antibacterial high polymer material;
or taking zinc salt solid, adding the zinc salt solid into water for dissolving to obtain a zinc salt water solution, then adding the zinc salt water solution into the mixed solution obtained in the step b, fully mixing and reacting, and separating suspended matters to obtain the fluorescent antibacterial high polymer material;
and c, ion replacement is carried out in the reaction process of the step b, and the alkali metal ions on the reaction product of the alkali metal hydroxide and the maleic anhydride copolymer obtained in the step b are replaced by divalent zinc ions.
Wherein the weight ratio of the zinc salt (solid) to the maleic anhydride copolymer is (0.1-20): 1, preferably (0.1 to 10): 1.
the concentration of the aqueous solution of zinc salt is not required as long as the amount of zinc salt in water is within the solubility range of zinc salt.
Further, the air conditioner is provided with a fan,
in step a, the alkali metal hydroxide is preferably at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, and more preferably at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
In the step b, the maleic anhydride copolymer may be any maleic anhydride copolymer known in the prior art, preferably a maleic anhydride alternating copolymer, more preferably at least one selected from alternating copolymers obtained by copolymerizing maleic anhydride and a monomer containing an isolated carbon-carbon double bond, preferably at least one of a maleic anhydride-vinyl acetate alternating copolymer, a maleic anhydride-styrene alternating copolymer, a maleic anhydride- α -methylstyrene alternating copolymer, a maleic anhydride-1-butene alternating copolymer, a maleic anhydride-2-butene alternating copolymer, a maleic anhydride-isobutylene alternating copolymer, a maleic anhydride-butadiene alternating copolymer, a maleic anhydride-1-pentene alternating copolymer, a maleic anhydride-vinylpyrrolidone alternating copolymer, a maleic anhydride-itaconic acid alternating copolymer, more preferably at least one of a maleic anhydride-vinyl acetate alternating copolymer, a maleic anhydride-styrene alternating copolymer, a maleic anhydride- α -methylstyrene alternating copolymer, and a maleic anhydride-isobutylene alternating copolymer.
In general, the maleic anhydride copolymers described can be prepared by methods known in the art, preferably according to the literature: a new family of thermoplastic photoluminescent polymers, polymer, chem.,2016,7,6250-6256; polymer compositions with a high haze and high transmittance, polymer. Chem.,2015,6,6632-6636, and patent CN 107722177A.
In the step c, the zinc salt can be selected from various zinc salts in the prior art, preferably at least one of water-soluble zinc salts, and more preferably at least one of zinc acetate, zinc lactate, zinc chloride, zinc bromide, zinc nitrate, zinc sulfate and zinc gluconate.
In the preparation of the fluorescent antibacterial polymer material, the reaction speed of the maleic anhydride copolymer in the step b and the alkali metal hydroxide is high, and the reaction can be stopped as long as a uniform solution is formed in principle; the time for the sufficient mixing reaction is preferably 0.1 to 12 hours, and more preferably 0.2 to 6 hours. The reaction temperature and the reaction pressure in the step b are not particularly limited, the reaction temperature is preferably 5 to 95 ℃, more preferably room temperature, and the reaction pressure is preferably normal pressure; the apparatus used for the reaction is also not particularly limited, and solution reaction apparatuses in the prior art can be used. The adding speed of the zinc salt in the step c is not particularly limited, and can be fast or slow; the adding process and the stirring speed after adding are not particularly limited, and the stirring speed can be fast or slow or not; the reaction time is not particularly limited since the precipitation is generated in the system immediately after the zinc salt is added, but the reaction time affects the yield, and the reaction time is preferably 0.1 to 1 hour, preferably 0.1 to 0.5 hour. The precipitated product may be separated from the aqueous solution (separation of suspended matter) by methods known in the art, including filtration, centrifugation, and the like; the separated fluorescent antibacterial polymer material can be dried due to containing a little water, the drying temperature and time are not particularly limited as long as the water is removed, and the drying method can be various drying methods in the prior art, including freeze drying, drying and the like.
In the preparation of the fluorescent antibacterial polymer material, various mixing methods and mixing equipment which are commonly used in the prior art can be adopted for the sufficient mixing, and preferably, a common stirring mode and stirring equipment are adopted for the sufficient mixing. Such as mechanical stirring and mixing, centrifugal mixing, magnetic stirring and mixing, and the like, so that the mixture is fully mixed.
The melt blending in the preparation method of the fluorescent antibacterial polycarbonate composite material adopts the common melt blending process and equipment in polycarbonate processing, such as injection molding, extrusion molding, calendaring molding, blow molding and other melt processing methods. The blending temperature of the melt blending is 230-270 ℃, and the preferred blending temperature is 240-265 ℃. The fluorescent antibacterial agent and the polycarbonate also comprise the auxiliary agents commonly used in the polycarbonate processing field, such as an antioxidant, a plasticizer and other processing auxiliary agents when being melted and blended, and the addition amount of the commonly used auxiliary agents is the conventional amount or is properly adjusted according to the actual situation.
In the process of preparing the fluorescent antibacterial high polymer material, after the maleic anhydride copolymer solid is mixed with an aqueous solution of alkali metal hydroxide, the maleic anhydride and the alkali metal hydroxide undergo acid-base neutralization reaction to generate maleic acid alkali metal salt through ring opening. The same group is easy to aggregate to generate interaction, and the maleic acid alkali metal salt is provided with a large amount of C = O, C-O, and the groups belong to typical secondary fluorescent groups, so that the prepared maleic anhydride copolymer alkali metal derivative has fluorescent property. When zinc salt is added to the above aqueous solution of the alkali metal salt derivative of the maleic anhydride copolymer, the alkali metal ions are replaced with zinc ions. The zinc ions are divalent, and can react with two alkali metal carboxylates on the same polymer molecular chain and also can react with the alkali metal carboxylates on the two polymer molecular chains, and as a result, the cross-linking reaction in the molecular chains and among the molecular chains occurs in the polymer, so that a product (namely, the fluorescent antibacterial high polymer material) is precipitated and separated out from water. Although the alkali metal ions on the alkali metal salt derivative of the maleic anhydride copolymer are replaced by zinc ions, the secondary fluorescent group in the obtained product is still in an aggregation state, and the cross-linking reaction in a molecular chain and among molecular chains can further enhance the aggregation effect, so that the prepared zinc salt derivative of the maleic anhydride copolymer still has the fluorescence property.
Furthermore, the obtained fluorescent antibacterial high polymer material has strong absorption in ultraviolet and visible light regions of a spectrum, so that fluorescence group electrons are subjected to excitation transition, excited state electrons interact with zinc element in the process of returning to the ground state, the zinc element is activated, and the binding capacity of zinc and bacterial cell membranes is enhanced, so that the fluorescent antibacterial high polymer material with high safety and lasting antibacterial effect is generated.
After the fluorescent antibacterial high polymer material and the polycarbonate resin are melted and blended, a large number of ester groups contained in a polycarbonate molecular chain can interact with carboxylic acid groups in the fluorescent antibacterial high polymer material to form space conjugation. Under the action of the conjugated structure, the dispersibility of the fluorescent antibacterial high polymer material in the polycarbonate material can be improved, and the formed space conjugated structure enables the release of the zinc element to be more stable. The space conjugation also changes the photoluminescence performance of the material, so that the fluorescence emission range of the fluorescent antibacterial polymer is changed, the polycarbonate material has the antibacterial performance and the fluorescence performance, and meanwhile, the higher transparency can be kept. Compared with other antibacterial polycarbonate materials, the fluorescent antibacterial polycarbonate material prepared by the invention has more functions, longer antibacterial action time and higher safety.
The invention also aims to provide the application of the fluorescent antibacterial polycarbonate composite material in polycarbonate antibacterial products such as display materials, sunlight plates, lampshades, spectacle lenses, packaging boxes and the like.
The applicant of the invention finds in research that the two-step modification treatment of the maleic anhydride copolymer can obtain the polymer antibacterial agent with fluorescent property; the obtained fluorescent antibacterial high polymer material is blended with polycarbonate resin to obtain the antibacterial polycarbonate composite material with fluorescent property. The main advantages of the invention are:
(1) the maleic anhydride copolymer is a byproduct of industrial polyolefin synthesis, raw materials are easy to obtain, and an industrial production process is mature;
(2) the preparation process of the fluorescent antibacterial high polymer material is simple and easy to implement, materials involved in the process are all cheap conventional materials, and involved equipment is all common equipment in industrial production;
(3) the fluorescent antibacterial polycarbonate composite material has high safety, durable antibacterial effect and various application ways, can meet the application requirements under different conditions, has low production cost and mature process flow, and is easy to realize industrial production;
(4) the fluorescent antibacterial polycarbonate composite material is non-toxic, so the fluorescent antibacterial polycarbonate composite material can be contacted with food, medicines and the like;
(5) the fluorescent antibacterial polycarbonate composite material has special fluorescent property, and can be rapidly distinguished from other polypropylene materials through the fluorescent property, so that the fluorescent antibacterial polycarbonate composite material has an excellent anti-counterfeiting effect.
(6) The fluorescent antibacterial polycarbonate composite material still keeps higher light transmittance and lower haze, and can be applied to the field of traditional polycarbonate.
Drawings
FIG. 1 is a three-dimensional fluorescence spectrum of the fluorescent antibacterial polymer material prepared in example 1; wherein the ordinate is the excitation interval and the abscissa is the emission interval.
FIG. 2 is an elemental energy spectrum of the fluorescent antibacterial polymer material prepared in example 1; the ordinate is intensity, the abscissa is the energy value of the element, can find the corresponding element in the manual according to the energy value.
FIG. 3 is a three-dimensional spectrum of a zinc salt derivative of maleic anhydride copolymer prepared in example 2;
FIG. 4 is a three-dimensional spectrum of a zinc salt derivative of maleic anhydride copolymer prepared in example 3
FIG. 5 is a three-dimensional spectrum of a zinc salt derivative of maleic anhydride copolymer prepared in example 4
FIG. 6 is a three-dimensional fluorescence spectrum of the fluorescent antimicrobial polycarbonate composite prepared in example 5;
FIG. 7 is a three-dimensional fluorescence spectrum of a fluorescent antimicrobial polycarbonate composite prepared in example 6;
FIG. 8 is a three-dimensional fluorescence spectrum of polycarbonate prepared in comparative example 3;
FIG. 9 is a three-dimensional fluorescence spectrum of a fluorescent antimicrobial polycarbonate composite prepared in example 7;
FIG. 10 is a three-dimensional fluorescence spectrum of polycarbonate prepared in comparative example 4;
FIG. 11 is a three-dimensional fluorescence spectrum of the fluorescent antimicrobial polycarbonate composite material prepared in example 8.
FIG. 12 is a three-dimensional fluorescence spectrum of the polycarbonate prepared in comparative example 5.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
1. The experimental data in the examples were determined using the following instruments and methods:
(1) Fluorescence spectroscopy data samples were analyzed using a JY FL3 fluorescence spectrometer from Horiba, japan, using a 450W xenon lamp light source.
(2) Powder antibacterial test standard: GB/T21510-2008; detection bacteria: escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6538).
The antibacterial testing step refers to the GB/T21510-2008 standard for testing, and comprises the following specific steps: 1.0g of the sample to be tested was weighed and 5.0mL of the pre-formed bacterial suspension was added. Pouring 1.0mL of inoculation liquid into an agar culture medium, then culturing for 48 hours in a constant temperature box at the temperature of 37 ℃, and finally counting viable bacteria on a sample to calculate the antibacterial rate. The blank control group was prepared without the test sample and the other operations were as above.
Testing of antibacterial durability: firstly, a sample to be tested is soaked in distilled water at 50 ℃ for 16 hours, and then the test is carried out according to the GB/T21510-2008 standard.
(3) Antibacterial article test standard: GB/T31402-2015; detection bacteria: escherichia coli (ATCC 8739), staphylococcus aureus (ATCC 6538P).
The antibacterial testing step refers to GB/T31402-2015 standard for testing, and comprises the following specific steps: the samples to be tested were prepared as 50X 50mm samples and the bacterial suspension was diluted with 1/500 of the nutrient broth for use. 0.4mL of inoculation liquid is dripped on the surface of a sample, a film with the size of 40 multiplied by 40mm is covered, then the sample is covered with a culture dish cover and cultured for 24 hours under the conditions of the temperature of 35 ℃ and the humidity of 90 percent, and finally the viable bacteria on the sample are counted to calculate the antibacterial rate. The blank control group was replaced with a sample without the addition of the fluorescent antibacterial polymer material, and the other operations were the same as above.
Testing of antibacterial durability: a sample to be tested is soaked in distilled water at 50 ℃ for 16 hours, and then the test is carried out according to the GB/T31402-2015 standard.
(4) Light transmittance haze test standard: GB/T2410-2008; testing an instrument: WGT-S light transmittance haze tester of Shanghai precision instruments and meters Limited.
(5) Element energy spectrum analysis: element energy spectrum analysis is carried out by using a TEAM electric refrigeration energy spectrometer of EDAX company, corresponding elements can be found in a manual according to energy values, and element content can be measured.
2. Raw materials for examples and comparative examples:
the maleic anhydride-vinyl acetate linear alternating copolymers (MVL) used in the examples are prepared according to the methods described in the publication A new family of thermoplastic photoluminescent polymers, under the main conditions and parameters: the molar ratio of the reaction monomer maleic anhydride and vinyl acetate is 1:1, the medium is isoamyl acetate, the initiator is azobisisobutyronitrile, and the reaction is carried out at 70 ℃ for 6 hours.
The maleic anhydride-alpha-methylstyrene crosslinked alternating copolymers (MASC) used in the examples are prepared according to the methods described in the publications Polymer composites with high haze and high transmittance, under the main preparation conditions and parameters: the molar ratio of the reaction monomer maleic anhydride and alpha-methyl styrene is 1:1, the crosslinking agent is divinylbenzene, the medium is isoamyl acetate, the initiator is azobisisobutyronitrile, and the reaction is carried out at 70 ℃ for 6 hours.
Maleic anhydride-carbon four-linear alternating copolymer (MC) used in the examples 4 L), the preparation method described in example 1 in chinese patent publication No. CN107722177a is referred to, and the main preparation conditions and parameters are as follows: the reaction monomers are maleic anhydride (20 kg) and mixed carbon four A (14 kg), the medium is isoamyl acetate (100L), an initiator is azobisisobutyronitrile (2.4 kg), and the reaction is carried out at 70 ℃ for 6 hours, wherein the mixed carbon four A comprises the following components in percentage by weight: 1,2-butadiene, 8.92%;1,3-butadiene, 14.14%; 1-butene, 8.38%; trans-2-butene, 5.84%; cis-2-butene, 31.7%; vinyl acetylene, 10.99%; isobutane, 1.3%; isobutene, 12.78%; n-butane, 2.58%, others, 3.37%.
The maleic anhydride-styrene linear alternating copolymers (MSL) used in the examples are prepared by the method described in the publication A new family of thermoplastic photoluminescent polymers, under the main conditions and parameters: the molar ratio of the reaction monomer maleic anhydride and styrene is 1:1, the medium is isoamyl acetate, the initiator is azobisisobutyronitrile, and the reaction is carried out at 70 ℃ for 6 hours.
Other raw materials are all obtained from the market.
Preparation of fluorescent antibacterial high polymer material
Example 1
Dissolving 5g of sodium hydroxide in 100g of water; weighing 5g of MVL and putting into a sodium hydroxide aqueous solution; and after the MVL is completely dissolved, adding 0.5g of zinc chloride solid, stirring for 10 minutes, then centrifugally separating suspended matters, drying and precipitating to obtain the fluorescent antibacterial high polymer material, wherein a three-dimensional fluorescence spectrogram is shown in figure 1, and when the excitation range is 360-400 nm, the strongest emission range is 500-550 nm. The element energy spectrum analysis data of the fluorescent polymer material is shown in fig. 2 (the gold element sprayed on the surface of the sample at the position of 2.15 eV), the zinc element exists in the product, the weight fraction of the zinc element is measured to be 20%, and no sodium element exists, which indicates that the sodium element is completely replaced by the zinc.
The fluorescent antibacterial high polymer material is subjected to antibacterial test according to the standard GB/T21510-2008, and the antibacterial result is as follows: the antibacterial rate to escherichia coli before water boiling is more than 99%, and the antibacterial rate to staphylococcus aureus is more than 99%; the antibacterial rate to colibacillus after water boiling is more than 99 percent, and the antibacterial rate to staphylococcus aureus is more than 99 percent.
Comparative example 1
Dissolving 5g of sodium hydroxide in 100g of water; weighing 5g of MVL and putting the MVL into a sodium hydroxide aqueous solution; and after the MVL is completely dissolved, drying the solution to obtain a comparison product. The comparative product was tested for antibacterial activity according to standard GB/T21510-2008.
And (3) antibacterial results: the antibacterial rate to Escherichia coli is 0, and the antibacterial rate to Staphylococcus aureus is 0.
Comparative example 2
5g of MVL was weighed out and dissolved in 100g of water, 0.5g of zinc chloride solid was added and mixed thoroughly over 10 minutes without precipitate forming in the solution.
Example 2
0.5g of lithium hydroxide is dissolved in 100g of water; weighing 5g of MASC and putting the MASC into a lithium hydroxide aqueous solution; and after the MASC is completely dissolved, adding the prepared zinc nitrate solution (50 g of zinc nitrate is dissolved in 50g of water), stirring for 10 minutes, centrifugally separating suspended matters, drying and precipitating to obtain the fluorescent antibacterial high polymer material, wherein a three-dimensional fluorescence spectrum of the fluorescent antibacterial high polymer material is shown in figure 3, and when the excitation range is 360-425 nm, the strongest emission range is 420-490 nm. The weight percentage of the zinc element of the fluorescent antibacterial polymer material is 60 percent by element energy spectrum analysis.
The fluorescent antibacterial high polymer material is subjected to antibacterial test according to the standard GB/T21510-2008, and the antibacterial result is as follows: the antibacterial rate to colibacillus before water boiling is more than 99 percent, and the antibacterial rate to staphylococcus aureus is more than 99 percent; the antibacterial rate to colibacillus after boiling is more than 99%, and the antibacterial rate to staphylococcus aureus is more than 99%.
Example 3
Dissolving 50g of potassium hydroxide in 100g of water; weighing 5g of MC4L and putting into the potassium hydroxide aqueous solution; and after the MC4L is completely dissolved, adding a zinc lactate solution (5 g of zinc lactate is dissolved in 50g of water), stirring for 10 minutes, centrifuging, drying and precipitating to obtain the fluorescent antibacterial high polymer material, wherein a three-dimensional fluorescence spectrum of the fluorescent antibacterial high polymer material is shown in figure 4, and when the excitation range is 350-380 nm, the strongest emission range is 400-450 nm. The weight fraction of the zinc element in the fluorescent antibacterial polymer material is 47 percent as measured by element energy spectrum analysis.
The fluorescent antibacterial high polymer material is subjected to antibacterial test according to the standard GB/T21510-2008, and the antibacterial result is as follows: the antibacterial rate to escherichia coli before water boiling is more than 99%, and the antibacterial rate to staphylococcus aureus is more than 99%; the antibacterial rate to colibacillus after water boiling is more than 99 percent, and the antibacterial rate to staphylococcus aureus is more than 99 percent.
Example 4
50g of sodium hydroxide is dissolved in 100g of water; weighing 5g of MSL and putting into a sodium hydroxide aqueous solution; and after the MSL is completely dissolved, adding a zinc chloride solution (20 g of zinc chloride is dissolved in 50g of water), stirring for 10 minutes, centrifugally separating suspended matters, drying and precipitating to obtain the fluorescent antibacterial high polymer material, wherein a three-dimensional fluorescence spectrum is shown in figure 5, and when the excitation range is 380-430 nm, the strongest emission range is 460-520 nm. The weight fraction of the zinc element of the fluorescent antibacterial polymer material is 50 percent as measured by element energy spectrum analysis,
the fluorescent antibacterial high polymer material is subjected to antibacterial test according to the standard GB/T21510-2008. And (3) antibacterial results: the antibacterial rate to colibacillus before water boiling is more than 99 percent, and the antibacterial rate to staphylococcus aureus is more than 99 percent; the antibacterial rate to colibacillus after water boiling is more than 99 percent, and the antibacterial rate to staphylococcus aureus is more than 99 percent.
Preparation of fluorescent antibacterial polycarbonate composite material
Example 5
100 parts by weight of polycarbonate (China petrochemical Beijing Yanshan division, brand B102 7025L2, prepared by transesterification), 1 part by weight of the fluorescent antibacterial polymer material described in example 1, 0.1 part by weight of antioxidant 168 (Switzerland carbaryl) and 0.1 part by weight of antioxidant 1010 (Switzerland carbaryl) are respectively weighed, stirred and mixed uniformly, and then the mixture is put into a Haake double-screw extruder, the temperature is set to be 240-265 ℃, and the mixture is extruded by screws for granulation. Then, fluorescence test is carried out, the range of exciting light is 375-475nm, the range of emitting light is 450-680nm, and the main emission peak is 500-540nm. The light transmittance is 85.9 percent, and the haze is 6.72 percent.
The resulting fluorescent antibacterial polycarbonate composite was injection molded into 60X 2mm specimens for antibacterial testing according to standard GB/T31402-2015. And (3) antibacterial results: the antibacterial rate to escherichia coli before water boiling is more than 99%, and the antibacterial rate to staphylococcus aureus is more than 99%; the antibacterial rate to colibacillus after water boiling is more than 99 percent, and the antibacterial rate to staphylococcus aureus is more than 99 percent.
Example 6
Respectively weighing 100 parts by weight of polycarbonate (same as example 5), 1 part by weight of the fluorescent antibacterial polymer material described in example 4, 0.1 part by weight of antioxidant 168 (Ciba Geigy Switzerland) and 0.1 part by weight of antioxidant 1010 (Ciba Geigy Switzerland), uniformly stirring, putting the mixture into a Haake double-screw extruder, setting the temperature to 240-265 ℃, and extruding and granulating by a screw. Then, a fluorescence test is carried out, wherein the range of excitation light is 375-450nm, the range of emission light is 420-550nm, and the main emission peak is positioned at 440-520nm. The light transmittance is 85.1 percent, and the haze is 7.47 percent.
The resulting fluorescent antibacterial polycarbonate composite was injection molded into 60X 2mm specimens for antibacterial testing according to standard GB/T31402-2015. And (3) antibacterial results: the antibacterial rate to escherichia coli before water boiling is more than 99%, and the antibacterial rate to staphylococcus aureus is more than 99%; the antibacterial rate to colibacillus after boiling is more than 99%, and the antibacterial rate to staphylococcus aureus is more than 99%.
Comparative example 3
100 parts by weight of polycarbonate (same as in example 5), 0.1 part by weight of antioxidant 168 (Ciba Geigy, switzerland) and 0.1 part by weight of antioxidant 1010 (Ciba Geigy, switzerland) are weighed respectively, stirred and mixed uniformly, the mixture is put into a Haake double screw extruder, the temperature is set to be 240-265 ℃, and the mixture is extruded by a screw to be granulated. Thereafter, fluorescence was measured, and as shown in FIG. 5-2, no significant fluorescence was observed. The light transmittance is 87.6 percent, and the haze is 2.36 percent.
The antibacterial tests were carried out according to standard GB/T31402-2015 on samples of fluorescent antibacterial polycarbonate composite injection moulded to 60X 2 mm. And (3) antibacterial results: the antibacterial rate to escherichia coli is 0, and the antibacterial rate to staphylococcus aureus is 0.
Compared with the fluorescence spectrograms of the polycarbonate materials prepared in comparative examples 3, the fluorescence spectra of the fluorescent antibacterial polycarbonate composites in examples 5 and 6 show that due to the introduction of the fluorescent antibacterial polymer material, a fluorescence peak which does not exist in comparative example 3 appears in examples 5 and 6, and the fluorescent antibacterial polycarbonate composites obtained in examples 5 and 6 respectively show that the fluorescence emission ranges of the fluorescent antibacterial polymers in examples 1 and 4 are changed, which indicates that the fluorescent antibacterial polymer material is dispersed in the polycarbonate material, and the ester group in the polycarbonate resin molecular chain and the fluorescent material maleic anhydride copolymer zinc salt interact to form a conjugated structure, so that the excitation range and the emission range of fluorescence are changed.
In addition, comparative example 3 is a blank of polycarbonate resin, and examples 5 and 6 have little influence on transparency and can still maintain good transparency although fluorescent antibacterial high molecular materials are added respectively.
Example 7
Respectively weighing 100 parts by weight of polycarbonate (prepared by Makrolon3103, produced by an interfacial phosgene method, corsia), 0.1 part by weight of the fluorescent antibacterial polymer material described in example 2, 0.1 part by weight of antioxidant 168 (Ciba Geigy, switzerland) and 0.1 part by weight of antioxidant 1010 (Ciba Geigy, switzerland), uniformly stirring, putting the mixture into a Haake double-screw extruder, setting the temperature to 240-265 ℃, and extruding and granulating by screws. Then, a fluorescence test is carried out, wherein the range of excitation light is 375-500nm, the range of emission light is 460-670nm, and the main emission peak is 500-530nm. Light transmittance of 86.1 percent and haze of 5.06 percent
The resulting fluorescent antibacterial polycarbonate composite was injection molded into 60X 2mm specimens for antibacterial testing according to standard GB/T31402-2015. And (3) antibacterial results: the antibacterial rate to escherichia coli before water boiling is more than 99%, and the antibacterial rate to staphylococcus aureus is more than 99%; the antibacterial rate to colibacillus after water boiling is more than 99 percent, and the antibacterial rate to staphylococcus aureus is more than 99 percent.
Comparative example 4
100 parts by weight of polycarbonate (same as in example 7), 0.1 part by weight of antioxidant 168 (Ciba Geigy, switzerland) and 0.1 part by weight of antioxidant 1010 (Ciba Geigy, switzerland) were weighed, stirred and mixed, and the mixture was fed into a Haake twin screw extruder, set to a temperature of 240-265 ℃ and pelletized by screw extrusion. Thereafter, fluorescence was measured, and as shown in FIG. 5-2, no significant fluorescence was observed. The light transmittance is 86.8 percent, and the haze is 3.88 percent.
The extruded samples were injection moulded into 60X 1mm test specimens for antibacterial testing according to standard GB/T31402-2015. And (3) antibacterial results: the antibacterial rate to escherichia coli is 0, and the antibacterial rate to staphylococcus aureus is 0.
Compared with the fluorescence spectrum of the polycarbonate material prepared in comparative example 4, in example 7, due to the introduction of the fluorescent antibacterial polymer material, a fluorescence peak which does not exist in comparative example 4 appears in example 5, and the fluorescence emission range of the fluorescent antibacterial polymer in comparative example 2 changes, which indicates that the fluorescent antibacterial polymer material is dispersed in the polycarbonate material and forms a conjugated structure.
In addition, comparative example 4 is a blank of polycarbonate resin, and example 7 has little influence on transparency and can maintain good transparency despite the addition of a fluorescent antibacterial polymer material.
Example 8
100 parts by weight of polycarbonate (prepared by a Saybolt base, lexan101 interface phosgene method), 10 parts by weight of the fluorescent antibacterial polymer material described in example 3, 0.1 part by weight of antioxidant 168 (Ciba Geigy, switzerland) and 0.1 part by weight of antioxidant 1010 (Ciba Geigy, switzerland) are respectively weighed, stirred and mixed uniformly, the mixture is put into a Haake double screw extruder, the temperature is set to 240-265 ℃, and the mixture is extruded by a screw and granulated. Then, a fluorescence test is carried out, wherein the range of excitation light is 375-500nm, the range of emission light is 460-670nm, and the main emission peak is 500-530nm.
The resulting fluorescent antibacterial polycarbonate composite was injection molded into 60X 2mm specimens for antibacterial testing according to standard GB/T31402-2015. And (3) antibacterial results: the antibacterial rate to escherichia coli before water boiling is more than 99%, and the antibacterial rate to staphylococcus aureus is more than 99%; the antibacterial rate to colibacillus after water boiling is more than 99 percent, and the antibacterial rate to staphylococcus aureus is more than 99 percent.
Comparative example 5
100 parts by weight of polycarbonate (same as in example 8), 0.1 part by weight of antioxidant 168 (Ciba Geigy, switzerland) and 0.1 part by weight of antioxidant 1010 (Ciba Geigy, switzerland) were weighed, mixed, and the mixture was fed into a Haake twin screw extruder, set at 240-265 ℃, pelletized by screw extrusion, and then subjected to fluorescence test, as shown in FIG. 5-2, no significant fluorescence was observed. The light transmittance is 87.3 percent, and the haze is 3.30 percent.
The extruded samples were injection moulded into 60X 2mm test specimens for antibacterial testing according to standard GB/T31402-2015. And (3) antibacterial results: the antibacterial rate to Escherichia coli is 0, and the antibacterial rate to Staphylococcus aureus is 0.
Compared with the fluorescence spectrum of the polycarbonate material prepared in comparative example 5, in example 8, due to the introduction of the fluorescent antibacterial polymer material, a fluorescence peak which does not exist in comparative example 5 appears, and the fluorescence emission range of the fluorescent antibacterial polymer changes compared with that of the fluorescent antibacterial polymer in example 3, which indicates that the fluorescent antibacterial polymer material is dispersed in the polycarbonate material and forms a conjugated structure.
In addition, comparative example 5 is a blank of polycarbonate resin, and example 8 has little influence on transparency and can maintain good transparency although a fluorescent antibacterial polymer material is added.
Claims (24)
1. A fluorescent antibacterial polycarbonate composite material comprises blended polycarbonate resin and a fluorescent antibacterial high polymer material, wherein the polycarbonate resin accounts for 0.1-20 parts by weight of 100 parts by weight of the fluorescent antibacterial high polymer material; the fluorescent antibacterial high polymer material is a maleic anhydride copolymer zinc salt derivative; the zinc salt derivative of the maleic anhydride copolymer is a maleic anhydride copolymer with zinc ions bonded on carboxylic acid groups.
2. The fluorescent antimicrobial polycarbonate composite of claim 1, wherein:
wherein the polycarbonate resin accounts for 0.1 to 10 parts by weight of the fluorescent antibacterial high polymer material based on 100 parts by weight.
3. The fluorescent antimicrobial polycarbonate composite of claim 1, wherein:
the weight percentage of zinc element in the maleic anhydride copolymer zinc salt derivative is 10-70%.
4. A fluorescent antimicrobial polycarbonate composite as claimed in claim 3, wherein:
the weight percentage of zinc element in the maleic anhydride copolymer zinc salt derivative is 20-60%.
5. The fluorescent antimicrobial polycarbonate composite of claim 1, wherein:
divalent zinc ions in the zinc salt derivative of the maleic anhydride copolymer are connected with two carboxylic acid groups obtained by ring opening of maleic anhydride in the maleic anhydride copolymer, and the two connected carboxylic acid groups are the same molecular chain and/or two molecular chains.
6. The fluorescent antimicrobial polycarbonate composite of claim 1, wherein:
the strongest fluorescence emission range of the maleic anhydride copolymer zinc salt derivative is 400-550 nm under the excitation wavelength of 330-430 nm.
7. The fluorescent antimicrobial polycarbonate composite of claim 1, wherein:
the exciting light range of the fluorescent antibacterial polycarbonate composite material is 300-600nm, and the emission light range is 300-700nm.
8. A fluorescent antimicrobial polycarbonate composite as in claim 7, wherein:
the exciting light range of the fluorescent antibacterial polycarbonate composite material is 300-500nm, and the emission light range is 350-700nm.
9. The fluorescent antibacterial polycarbonate composite material as claimed in any one of claims 1 to 8, wherein the fluorescent antibacterial polymer material is prepared by adding a maleic anhydride copolymer into an aqueous solution of an alkali metal hydroxide to react sufficiently, and then adding a zinc salt and/or an aqueous solution of a zinc salt to react sufficiently.
10. The method for preparing the fluorescent antibacterial polycarbonate composite material according to any one of claims 1 to 9, comprising the step of melt blending the components including the polycarbonate resin and the fluorescent antibacterial high polymer material according to the amount to obtain the fluorescent antibacterial polycarbonate composite material.
11. The method for preparing fluorescent antibacterial polycarbonate composite material according to claim 10, wherein the preparation of the fluorescent antibacterial polymer material comprises adding maleic anhydride copolymer into an aqueous solution of alkali metal hydroxide for sufficient reaction, and then adding zinc salt and/or an aqueous solution of zinc salt for sufficient reaction to generate the zinc salt derivative of maleic anhydride copolymer.
12. The method according to claim 10, wherein the method for preparing the fluorescent antibacterial polymer material comprises the following steps:
a. taking alkali metal hydroxide, adding the alkali metal hydroxide into water for dissolving to obtain an alkali metal hydroxide aqueous solution; wherein the weight ratio of the alkali metal hydroxide to the water is (0.1-100): 100, respectively;
b. b, adding the maleic anhydride copolymer into the alkali metal hydroxide aqueous solution prepared in the step a, and fully mixing and reacting; wherein the weight ratio of the maleic anhydride copolymer to the alkali metal hydroxide is in the range of (0.1 to 20): 1;
c. directly adding zinc salt solid into the mixed solution obtained in the step b, fully mixing and reacting, and separating suspended matters to obtain the fluorescent antibacterial high polymer material;
or taking zinc salt solid, adding the zinc salt solid into water for dissolving to obtain a zinc salt water solution, then adding the zinc salt water solution into the mixed solution obtained in the step b, fully mixing and reacting, and separating suspended matters to obtain the fluorescent antibacterial high polymer material;
wherein the weight ratio of the zinc salt to the maleic anhydride copolymer is (0.1-20): 1.
13. the production method according to claim 12,
the weight ratio of the alkali metal hydroxide to the water in the step a is (0.5-50): 100, respectively; and/or the presence of a gas in the atmosphere,
the weight ratio of the maleic anhydride copolymer to the alkali metal hydroxide in the step b is (0.1-10): 1; and/or the presence of a gas in the gas,
the weight ratio of the zinc salt to the maleic anhydride copolymer in the step c is (0.1-10): 1.
14. the method of manufacturing according to claim 12, wherein:
in the step a of the preparation method of the fluorescent antibacterial high polymer material, the alkali metal hydroxide is at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.
15. The method of claim 14, wherein:
the alkali metal hydroxide is at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
16. The method of manufacturing according to claim 12, wherein:
in the step b of the preparation method of the fluorescent antibacterial high polymer material, the maleic anhydride copolymer is selected from maleic anhydride alternating copolymers.
17. The method of manufacturing according to claim 16, characterized in that:
the maleic anhydride copolymer is at least one of alternating copolymers obtained by copolymerizing maleic anhydride and monomers containing isolated carbon-carbon double bonds.
18. The method of manufacturing according to claim 16, wherein:
the maleic anhydride alternating copolymer is selected from maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer, maleic anhydride-1-butene alternating copolymer, maleic anhydride-2-butene alternating copolymer, maleic anhydride-isobutylene alternating copolymer, maleic anhydride-butadiene alternating copolymer, maleic anhydride-1-pentene alternating copolymer, maleic anhydride-vinyl pyrrolidone alternating copolymer and maleic anhydride-itaconic acid alternating copolymer.
19. The method for preparing a polycarbonate resin composition according to claim 18, wherein:
the maleic anhydride alternating copolymer is at least one selected from maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methyl styrene alternating copolymer and maleic anhydride-isobutylene alternating copolymer.
20. The method of manufacturing according to claim 12, wherein:
in the step c of the preparation method of the fluorescent antibacterial high polymer material, the zinc salt is at least one of water-soluble zinc salts.
21. The method of claim 20, wherein:
the zinc salt is at least one of zinc acetate, zinc lactate, zinc chloride, zinc bromide, zinc nitrate, zinc sulfate and zinc gluconate.
22. The production method according to any one of claims 10 to 21, characterized in that:
the blending temperature of the melt blending is 230-270 ℃.
23. The method of manufacturing according to claim 22, wherein:
the blending temperature of the melt blending is 240-265 ℃.
24. Use of the fluorescent antimicrobial polycarbonate composite material according to any one of claims 1 to 9 or the fluorescent antimicrobial polycarbonate composite material prepared by the preparation method according to any one of claims 10 to 23 in display materials, sunlight panels, lamp covers, spectacle lenses, packaging boxes, antimicrobial articles.
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