阅读说明：本技术 一种抗菌聚氨酯树脂及其制备方法 (Antibacterial polyurethane resin and preparation method thereof ) 是由 吴谦 俞涛 尚永华 孙淑常 李建峰 朱付林 史培猛 王鹏 刘岩 于 2020-11-16 设计创作，主要内容包括：本发明提供一种抗菌聚氨酯树脂及其制备方法,该树脂包括抗菌聚合物,所述抗菌聚合物由甲基丙烯酰胍单体和乙烯基苯磺酰胺单体共聚而成,所述树脂中还包括异氰酸酯、多元硫醇化合物等原料。本发明的聚氨酯树脂能有效抑制微生物的吸附和生长,对大肠杆菌和金黄色葡萄球菌的抗菌率达99％,具有较强抗菌性能,而且改善了树脂的玻璃化转变温度,同时未对光学树脂的透射比和产品合格率产生负面影响。(The invention provides an antibacterial polyurethane resin and a preparation method thereof, wherein the resin comprises an antibacterial polymer, the antibacterial polymer is prepared by copolymerizing a methacrylylguanidine monomer and a vinyl benzene sulfonamide monomer, and the resin also comprises raw materials such as isocyanate, a polythiol compound and the like. The polyurethane resin can effectively inhibit the adsorption and growth of microorganisms, has 99 percent of antibacterial rate to escherichia coli and staphylococcus aureus, has strong antibacterial performance, improves the glass transition temperature of the resin, and does not have negative influence on the transmittance of optical resin and the product percent of pass.)

1. The antibacterial polyurethane resin is characterized by comprising an antibacterial polymer, wherein the antibacterial polymer is formed by copolymerizing a methacrylylguanidine monomer containing a guanidyl unit and a vinylbenzenesulfonamide monomer.

2. The polyurethane resin according to claim 1, wherein the antibacterial polymer is prepared by a method comprising: dissolving a methacrylylylguanidine monomer containing a guanidyl unit and a vinylbenzenesulfonamide monomer in an organic solvent, and then carrying out free radical polymerization under the condition of a free radical initiator; wherein the molar ratio of the methacrylylylguanidine to the vinylbenzenesulfonamide monomer is 1:1 to 9:1, preferably 2:1 to 7:1, more preferably 3:1 to 6: 1.

3. The polyurethane resin according to claim 1, wherein the radical initiator is an organic peroxy compound initiator or azo compound initiator or redox system initiator or photoinitiator, the organic peroxy compound initiator is selected from dibenzoyl peroxide or dicarbonate peroxide, the azo compound initiator is selected from azobisisobutyronitrile or azobisisoheptonitrile, the redox system initiator is selected from organic oil-soluble redox system formed by acyl peroxide compound and tertiary amine compound, and the photoinitiator is selected from photoinitiator IRGACURE-2959;

further preferably, the free radical initiator is a dibenzoyl peroxide and N, N-dimethylaniline composite initiator, and the addition amount of the free radical initiator and the N, N-dimethylaniline composite initiator is 1% -3%, preferably 1.5-2.5% of the total weight of the monomers of the methacrylylylguanidine and the vinylbenzenesulfonamide.

4. The polyurethane resin of claim 1, wherein the methacrylylylylguanidine monomer has the following structural formula:

the vinylbenzenesulfonamide monomers include 2-vinylbenzenesulfonamide, 3-vinylbenzenesulfonamide and 4-vinylbenzenesulfonamide, preferably 4-vinylbenzenesulfonamide.

5. The polyurethane resin according to claim 1, further comprising an isocyanate component, a polythiol compound, optionally a catalyst, optionally an optical resin release agent, and optionally an ultraviolet absorber.

6. Resin according to claim 1, characterized in that the isocyanate is selected from aliphatic, cycloaliphatic or aromatic isocyanates, preferably toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, dimethylbiphenyl diisocyanate, 1, 4-cyclohexane diisocyanate, p-phenylene diisocyanate, tetramethyl m-xylylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, xylylene diisocyanate, cyclohexane dimethylene diisocyanate, norbornane diisocyanate, or a combination of two or more thereof, with xylylene diisocyanate or cyclohexane dimethylene diisocyanate being more preferable, and xylylene diisocyanate being more preferable;

preferably, the polythiol compound is selected from the group consisting of ethylene glycol dimercaptoacetate, 1, 2-bis (2-mercaptoethoxy) ethane, bis (mercaptoacetic acid) -1, 4-butanediol, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), pentaerythritol tetramercaptoacetate, 2, 3-dithio (2-mercapto) -1-propanethiol, pentaerythritol tetrakis (3-mercaptopropionate), and combinations of one or two or more thereof, preferably 2, 3-dithio (2-mercapto) -1-propanethiol or pentaerythritol tetrakis (3-mercaptopropionate), more preferably 2, 3-dithio (2-mercapto) -1-propanethiol.

7. Resin according to claim 5 or 6, characterized in that the isocyanate and the polythiol compound are used in a molar ratio NCO groups/SH groups of 0.8 to 1.5, preferably in a molar ratio of 0.9 to 1.1.

8. The polyurethane resin according to claim 5, wherein the antimicrobial polymer is added in an amount of 0.1 to 10 wt%, preferably 1 to 8 wt%, more preferably 3 to 6 wt%, based on the total weight of the isocyanate and the polythiol compound required for preparing the polyurethane optical resin.

9. The polyurethane resin according to claim 5, wherein the catalyst is selected from the group consisting of catalysts commonly used in the art, preferably organotin compounds, and is added in an amount of 0 to 2.0% by weight, preferably 0.005 to 2.0% by weight, preferably 0.01 to 1.5% by weight, based on the total mass of the isocyanate component and the polythiol compound;

preferably, the ultraviolet absorber is a benzophenone-based, triazine-based, and benzotriazole-based ultraviolet absorber, and is added in an amount of 0 to 3.0% by weight, preferably 0.01 to 3.0% by weight, preferably 0.03 to 1% by weight, based on the total mass of the isocyanate component and the polythiol compound;

preferably, the optical resin mold release agent is a phosphate-based mold release agent, and is added in an amount of 0 to 3.0% by weight, preferably 0.01 to 3.0% by weight, preferably 0.08 to 1.5% by weight, based on the total mass of the isocyanate component and the polythiol compound.

10. A method for producing a polyurethane resin according to any one of claims 1 to 9, characterized in that the polyurethane resin is produced by mixing a cyanate ester component, a polythiol compound, an antibacterial polymer, an optional catalyst, an optional optical resin release agent, and an optional ultraviolet absorber, and then carrying out a polymerization reaction.

Technical Field

The invention relates to the field of optical resin, in particular to antibacterial polyurethane resin and a preparation method thereof.

Background

Optical materials are widely used for spectacle lenses, windshields of airplanes and automobiles, and optical elements such as lenses, prisms, and the like. The development of the resin lens mainly takes safety, high definition and protection as three basic starting points, wherein the protection is to research and prepare an optical resin material with multiple functions. Polyurethane type optical resins, which are obtained by polymerizing an isocyanate and a polythiol compound, are an important development direction of new optical resins in recent years.

In daily life, the contact between the two hands of a person and the lenses is the most, when the two hands contact the lenses, sweat stains or excrement of the two hands are easy to adhere to the lenses, and then bacteria are easy to nourish on the lenses, so that the lenses become bacteria growing hotbeds, and the lenses are easy to become dirty after long-term storage. When two hands contact the lens, the lens can contact other articles again, so that bacteria or pollutants are stuck to the articles through the two hands, and the human health is easily damaged. Especially for special post personnel such as medical care workers, it is especially important to develop a lens which has good antibacterial property and is not easy to breed bacteria.

At present, in the field of optical materials, the antibacterial property of resin lenses can be improved mainly by means of blending and adding silver ions or coating an antibacterial agent coating film on the surface of resin.

In patent CN 111499809 a, polypropylene glycol plasticizer, nano-silica reinforcing agent, silver ions, zinc ions, and glass microparticles are added into propenyl diglycol carbonate, and then mixed uniformly, and melt-extruded by a twin-screw extruder to prepare the antibacterial spectacle lens, which has a certain antibacterial property against escherichia coli, salmonella, staphylococcus aureus, and the like.

In patent CN 111158165A, the titanium dioxide-silver nano antibacterial agent is coated on the surface of the lens to prepare the multifunctional medical protective glasses, so that the problems of ocular pathogenic bacteria infection and pollen allergy are solved, and the eyes are kept moist. The titanium dioxide-silver nano antibacterial agent commonly used in the market at present comprises titanium dioxide, silver and other metal elements, the titanium dioxide-silver has the functions of sterilizing and resisting viruses under visible light and ultraviolet light, degrading bacteria, decomposing pollen and other organic matters, and the titanium dioxide-silver can also keep strong antibacterial and virus killing functions under the action of silver ions without a light source.

In patent CN 108070828A, a first film layer, namely a nano titanium dioxide layer, a second film layer, namely a nano silver layer, and a third film layer, namely an ITO layer (nano indium tin metal oxide) are symmetrically and sequentially coated on the inner and outer surfaces of the substrate from inside to outside, so as to realize the antibacterial effect of the lens.

The optical resin material generally has a three-dimensional network structure inside and relatively good light transmission, but a general resin lens has no antibacterial property, and the light transmission of the general resin lens is greatly influenced after some wear-resistant agents or antibacterial agents are added. In addition, the antibacterial layer plated on the surface of the lens has an unstable structure, and poor film bonding is likely to occur, so that the compatibility between the antibacterial agent and the resin should be improved as much as possible, and the light transmittance of the resin should be improved. In addition, in the medical field, resin lenses are required to have good heat resistance due to the operation requirements such as high-temperature sterilization.

Disclosure of Invention

In view of the above problems, the present invention provides the following technical solutions:

the invention aims to provide an antibacterial polyurethane resin and a preparation method thereof, so that the prepared polyurethane resin has excellent antibacterial performance and heat resistance, has excellent optical performance and can be used for optical resin lenses.

In order to solve the problems, the invention provides an antibacterial polyurethane resin which comprises an antibacterial polymer, wherein the antibacterial polymer is formed by copolymerizing a methacrylylguanidine monomer containing a guanidyl unit and a vinylbenzenesulfonamide monomer.

Among them, the synthesis of methacryloylguanidine monomer was carried out according to the method described in the reference (Pubchem CID: 12413805) or patent CN 109569331A.

The preparation method of the antibacterial polymer comprises the following steps: methacrylylylylguanidine Monomer (MAG) containing a guanidino unit and vinylbenzenesulfonamide monomer (SS) are dissolved in an organic solvent, followed by radical polymerization under the condition of a radical initiator.

Preferably, the free radical initiator is an organic peroxide initiator or an azo initiator or a redox system initiator or a photoinitiator, the organic peroxide initiator is selected from dibenzoyl peroxide (BPO) or peroxydicarbonates, the azo initiator is selected from Azobisisobutyronitrile (AIBN) or Azobisisoheptonitrile (ABVN), the redox system initiator is selected from an organic oil-soluble redox system formed by a peroxyacyl compound and a tertiary amine compound, and the photoinitiator is selected from a photoinitiator IRGACURE-2959(CAS number: 106797-53-9) and the like.

Further preferably, the free radical initiator is a dibenzoyl peroxide (BPO) and N, N-Dimethylaniline (DMA) complex initiator, both added in an amount of 1% to 3%, preferably 1.5% to 2.5% of the total weight of the monomers Methacrylylylylylguanidine (MAG) and vinylbenzenesulfonamide (SS).

Preferably, the reaction temperature is 0-50 ℃, and the reaction time is 1-12 h. Further preferably, the reaction temperature is room temperature (25 ℃ +/-5 ℃), and the reaction time is 2-4 h.

The structural formula of the methacrylylylguanidine monomer is as follows:

the vinylbenzenesulfonamide monomers include ortho-2-vinylbenzenesulfonamide, meta-3-vinylbenzenesulfonamide and para-4-vinylbenzenesulfonamide, and 4-vinylbenzenesulfonamide is preferable in view of steric hindrance during polymerization.

The guanidino is introduced into the application, and is applied to the bactericide due to the advantages of good thermal stability and durable antibacterial performance. The inhibition or killing of microorganisms is usually achieved by influencing the growth and division of bacteria or fungi, the germination of spores and the occurrence of phenomena such as cell swelling, cytoplasm disintegration, respiratory depression and cell wall destruction.

The monomer molar ratio of Methacrylylylguanide (MAG) to vinylbenzenesulfonamide is 1:1 to 9:1, preferably 2:1 to 7:1, more preferably 3:1 to 6: 1.

The organic solvent is an organic solvent which can fully dissolve two monomers of the methacrylylguanidine and the vinyl benzene sulfonamide, can stably exist and does not generate chemical reaction. Specifically, there are included, but not limited to, organic solvents such as hydrocarbons such as toluene, halogenated hydrocarbons such as chlorobenzene, ketones such as acetone, ethers such as methyl t-butyl ether, alcohols such as ethanol, amides such as dimethylformamide, sulfones such as dimethyl sulfoxide, etc., preferably dimethyl sulfoxide.

The antibacterial polyurethane resin comprises an isocyanate component, a polythiol compound, an antibacterial polymer, a catalyst, an optional optical resin release agent and an optional ultraviolet absorbent.

The isocyanate component used in the raw materials is not particularly limited, and as a specific example of the isocyanate component, such as but not limited to toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, dimethylbiphenyl diisocyanate, 1, 4-cyclohexane diisocyanate, p-phenylene diisocyanate, tetramethylm-xylylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, xylylene diisocyanate, cyclohexane dimethylene diisocyanate, norbornane diisocyanate, or a combination of two or more thereof, preferably xylylene diisocyanate or cyclohexane dimethylene diisocyanate, more preferably xylylene diisocyanate.

The polythiol compound used in the starting material is not particularly limited, and as specific examples of the polythiol compound, for example, but not limited to, the polythiol compound is selected from one or a combination of two or more of ethylene glycol dimercaptoacetate, 1, 2-bis (2-mercaptoethoxy) ethane, bis (mercaptoacetic acid) -1, 4-butylene ester, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), pentaerythritol tetramercaptoacetate, 2, 3-dithio (2-mercapto) -1-propanethiol, pentaerythritol tetrakis (3-mercaptopropionate) ester, preferably 2, 3-dithio (2-mercapto) -1-propanethiol or pentaerythritol tetrakis (3-mercaptopropionate), more preferably 2, 3-dithio (2-mercapto) -1-propanethiol.

In order to increase the degree of reaction of the functional groups, the ratio of the two monomers of the isocyanate and the polythiol compound is required to be controlled so that the molar ratio of NCO groups/SH groups is in the range of 0.8 to 1.5, preferably 0.9 to 1.1.

The antibacterial polymer is the antibacterial polymer of the present invention, and is added in an amount of 0.1 to 10 wt%, preferably 1 to 8 wt%, more preferably 3 to 6 wt%, based on the total mass of the isocyanate component and the polythiol compound.

The antibacterial polymer is added into polyurethane resin, so that the polyurethane optical resin has antibacterial property, amide groups and NCO groups in the antibacterial agent with large molecular weight are effectively bonded, the compatibility of the auxiliary agent and the matrix resin is enhanced, the thermal stability of the resin is improved, and the increase of the fraction defective of resin lenses, such as easiness in foaming, caused by the direct addition of a guanidino monomer is prevented.

The polyurethane resin may further contain a catalyst, an ultraviolet absorber, a release agent, and the like.

As the catalyst, there can be used those commonly used in the art, for example, organotin compounds, and specific examples thereof include dialkyltin halides such as dibutyltin dichloride and dimethyltin dichloride, dialkyltin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctoate and dibutyltin dilaurate, and dibutyltin dichloride is preferable. The catalyst may be added in an amount of 0 to 2.0% by weight, preferably 0.005 to 2.0% by weight, preferably 0.01 to 1.5% by weight, based on the total mass of the isocyanate component and the polythiol compound.

The ultraviolet absorber is selected from organic products mainly including benzophenones, triazines, benzotriazoles and the like, wherein the benzophenones have weak absorption effect and the triazines have poor stability, so benzotriazoles are mostly selected for industrial production, and the benzotriazole ultraviolet absorber is specifically selected from UV49, UV326, UV 327, UV 360, UV 380 and UV 329, preferably UV 329 (trade name Tinuvin 329) by taking the benzotriazoles as an example, and the addition amount of the ultraviolet absorber can be 0-3.0 wt%, preferably 0.01-3.0 wt%, preferably 0.03-1 wt% based on the total mass of the isocyanate component and the polythiol compound.

In view of the special requirement for light transmittance of the optical resin, an internal mold release agent of the phosphoric ester-based mold release agent trade name Zelec UN (manufactured by Sigma-Aldrich or Stepan corporation) is selected as the optical resin mold release agent, and the amount added may be, for example, 0 to 3.0% by weight, preferably 0.01 to 3.0% by weight, preferably 0.08 to 1.5% by weight, based on the total mass of the isocyanate component and the polythiol compound.

The invention also provides a preparation method of the polyurethane resin, which is prepared by mixing the isocyanate component, the polythiol compound, the antibacterial polymer, the optional catalyst, the optional optical resin release agent and the optional ultraviolet absorbent and then carrying out polymerization reaction. The antimicrobial polymer is preferably ground to a powder and added to the reaction.

The antibacterial polyurethane resin disclosed by the invention can be applied to optical resin.

The present invention can adopt the existing preparation process for preparing the polyurethane optical resin by using the polymerization reaction of isocyanate and polythiol compound, which is well known in the art, and the preparation process mainly comprises the steps of stirring and mixing the components in the raw material composition, degassing and curing to obtain the polyurethane optical resin. The curing process needs to be slowly heated from low temperature to high temperature, for example, from room temperature to 100-120 ℃, so that the polymerization curing is performed, and then the optical material is obtained after secondary curing and demolding.

The antibacterial polyurethane optical resin prepared by the preparation method has 99% of antibacterial rate on escherichia coli and staphylococcus aureus, has strong antibacterial performance, improves the glass transition temperature Tg of resin materials, has good heat resistance, and does not have negative effects on the transmittance and the product qualification rate of the optical resin. Therefore, according to the preparation method of the invention, the antibacterial polyurethane optical material with excellent performance can be prepared.

Drawings

FIG. 1: example 1 preparation of copolymer (PMAG-PSS)¹H-NMR chart.

FIG. 2: the absorption spectrum of the antibacterial polyurethane optical resin of example 1.

Detailed Description

The present invention is further illustrated by the following examples, which do not limit the scope of the invention as claimed.

The following examples of the invention will be characterized analytically using the following instruments.

Gel permeation chromatography analysis: gel permeation chromatography characterization of copolymer macromolecules was performed by means of an Agilent model 1260 high performance liquid gel permeation chromatograph. The samples were dissolved in Tetrahydrofuran (THF) to prepare a 5mg/mL solution, which was tested on a GPC instrument at a elution rate of 1mL/min and room temperature.

Hydrogen nuclear magnetic resonance spectrogram analysis: the hydrogen NMR spectra of the copolymers were characterized by means of a Varian INOVA hydrogen NMR spectrometer (500 MHz). And (3) dissolving 5-10 mg of sample solvent in deuterated dimethyl sulfoxide (DMSO), uniformly mixing the solution, and performing 1H-NMR test by using an NMR spectrometer.

Optical resin application index analysis: the light transmittance is a Hunterlab USVIS 1839 color difference meter, the test light source is C/2 light source, the test mode is total transmittance, and the average value of transmittance in the wavelength range of 380 nm-780 nm is taken as the sample transmittance. In addition, the yellowness index (YI value) of the sample was tested in the same mode. For optical lenses, the higher the transmittance, the smaller the reflection and absorption, and the clearer the optical material. Meanwhile, the smaller the YI value, the better the hue of the plastic lens, and the larger the YI value, the worse the hue becomes. GB 10810.3-2006 section 3 of spectacle lenses and related spectacle products: the transmittance specification and measurement method requires uniform transmittance of 80% or more in a visible light spectrum region (380 nm-780 nm). GB 2506-: when the refractive index of the lens is more than or equal to 1.56, the YI is less than or equal to 2.20; when the refractive index of the lens is less than 1.56, the YI is less than or equal to 1.20.

The glass transition temperature Tg is measured by adopting a high-pressure differential scanning calorimeter (METTLER HPDSC 1) of Mettler-Torledo company, and the DSC measuring method comprises the steps of heating and scanning at the temperature of 30-300 ℃, the heating rate is 10 ℃/min, and the nitrogen flow is 50ml/min in a nitrogen atmosphere; each sample was tested in parallel 3 times and the average was taken.

The antibacterial performance of the optical resin is characterized by the antibacterial rate to bacteria such as escherichia coli, staphylococcus aureus and the like, and the specific implementation method refers to the national standard GB/T30706-2014.

The synthesis of methacrylylguanide was prepared according to the reference (PubChem CID: 12413805) and patent CN 109569331A. The preparation method comprises the following steps: preparing 1 wt% methyl methacrylate solution with ethanol, eluting guanidine hydrochloride with ethanol, and passing through ion exchange resin column (OH)^-) Converting into free guanidine, evaporating eluate, adding ethanol to obtain 1% ethanol solution of guanidine. Then adding the ethanol solution of guanidine into an ethanol solution of equimolar methyl methacrylate, heating to 100 ℃, and stirring and refluxing for reaction for 4 hours. After the reaction is finished, evaporating the ethanol to be dry and recrystallizing in ethanol/diethyl ether (1:2) to obtain the target product of the methacrylylylguanidine.

Nuclear magnetic analysis data were as follows 1H-NMR (DMSO-d 6): 8.56(s, 4H), 6.04(s, 1H),5.98(s, 1H), 2.43(s, 3H).

In the following examples, the methacrylylylguanidine monomers synthesized by the above method were used, and then copolymers (PMAG-PSS) of Methacrylguanidine (MAG) and 4-vinylbenzenesulfonamide (SS) were prepared in different monomer molar ratios. PMAG-PSS with different contents is added subsequently to prepare the blue light-proof polyurethane optical resin. Polyurethane optical resin preparation samples were all prepared from a fixed mold (the fixed mold was a flat-bottomed glass cup having a bottom surface of 500mm in diameter and 800mm in height).

The main raw materials are as follows: m-xylylene diisocyanate (XDI, NCO content 44.7%, purity not less than 99.5%, Wanhua chemical, trade name XR-2005), cyclohexanedimethyleneMethyl diisocyanate (H)₆XDI, NCO content 43.3%, purity 99.7% or more, Vanhua chemical, trade name XR-2006), hexamethylene diisocyanate (HDI, NCO content 49.8%, purity 99.5% or more, Vanhua chemical), isophorone diisocyanate (IPDI, NCO content 37.8%, purity 99.5% or more, Vanhua chemical) and polythiol compound selected from 2, 3-dithio (2-mercapto) -1-propanethiol (trade name polythiol 504, purity 98% or more, Kyobo chemical), tetrakis (3-mercaptopropionic acid) pentaerythritol ester (trade name polythiol 405, purity 98% or more, Kyobo chemical), dibutyltin dichloride (DBC, purity 96%, Sigma-Aldrich) as catalyst, internal mold release agent (trade name Zelec UN, Sigma-Aldrich, purity 98%), UV-absorbent (trade name TINUVIN 329, purity 98%, shanghai Aladdin Biotechnology Ltd).

Example 1

An antimicrobial polyurethane optical resin containing 4 wt% of PMAG-PSS copolymer (monomer molar ratio of MAG to SS 5:1) was prepared.

(1) Synthesis of PMAG-PSS polymers.

31.75g of Methacryloylguanidine (MAG) and 9.15g of 4-vinylbenzenesulfonamide (SS) were sequentially added to a reaction vessel, and then 81.8g of dimethyl sulfoxide (DMSO) was added thereto, followed by stirring at room temperature to completely dissolve the monomers. Then, 0.82g of dibenzoyl peroxide (BPO) was added to the mixture, and after completely dissolving the mixture by stirring, 0.82g of N, N-Dimethylaniline (DMA) was added dropwise thereto, followed by stirring and mixing, followed by reaction at room temperature for 3 hours. The amounts of BPO and DMA added were 2% by weight based on the total mass of methacrylylylguanide and 4-vinylbenzenesulfonamide. After the reaction was completed, the mixture was filtered to collect a filter cake, and the filter cake was washed with toluene three times (50 ml each time). And finally, drying the filter cake at room temperature in vacuum to obtain the PMAG-PSS. The number average molecular weight Mn of the PMAG-PSS copolymer was about 45000 and the polydispersity index PID was 1.62 as measured by Gel Permeation Chromatography (GPC), indicating that polymerization of the monomer occurred. Further, a hydrogen nuclear magnetic resonance instrument is adopted to test the structural composition of macromolecules (deuterated DMSO is used as a solvent), and as shown in figure 1, the existence of two structural units in a molecular chain is verified, so that the successful copolymerization of two monomers is shown.

(2) Preparation of antibacterial polyurethane optical resin

0.015g of dibutyltin dichloride as a catalyst, UV-3290.05 g of an ultraviolet absorber, 0.1g of an internal mold release agent, 52g of m-Xylylene Diisocyanate (XDI) and 4g of a PMAG-PSS copolymer were placed in a reaction vessel with stirring at room temperature, mixed and dissolved. Further, 48g of 2, 3-dithio (2-mercapto) -1-propanethiol was added and mixed to form a raw material composition. Filtering the raw material composition with filter membrane, injecting into a special mold for lens processing (the liquid level of the raw material composition in the mold is about 7mm), degassing at 25 deg.C under 2kPa for 1 hr, and the pore diameter of the filter membrane is 1 μm.

After degassing, it was cured by polymerization by programmed heating from 25 ℃ to 120 ℃ in an oven set at a heating rate of 0.2 ℃/min. And when the temperature of the oven reaches 120 ℃, maintaining for 2 hours to obtain a cured sample, naturally cooling the subsequent sample to room temperature, performing secondary curing at the room temperature for 48 hours, and demolding to obtain the optical resin material.

Example 2

An antimicrobial polyurethane optical resin containing 9 wt% of PMAG-PSS copolymer (monomer molar ratio of MAG to SS was 2:1) was prepared.

(1) Synthesis of PMAG-PSS polymers.

25.4g of Methacryloylguanidine (MAG) and 18.3g of 4-vinylbenzenesulfonamide (SS) were sequentially added to a reaction vessel, and 87.4g of dimethyl sulfoxide (DMSO) was further added as a solvent, and the mixture was stirred at room temperature to completely dissolve the monomers. Then, 1.09g of dibenzoyl peroxide (BPO) was added to the mixture, and after completely dissolving the mixture by stirring, 1.09g of N, N-Dimethylaniline (DMA) was added dropwise thereto, followed by stirring and mixing, followed by reaction at room temperature for 3 hours. The amounts of BPO and DMA added were 2.5% by weight based on the total mass of methacrylylylguanidine and 4-vinylbenzenesulfonamide. After the reaction was completed, the mixture was filtered to collect a filter cake, and the filter cake was washed with toluene three times (50 ml each time). And finally, drying the filter cake at room temperature in vacuum to obtain the PMAG-PSS.

(2) Preparation of antibacterial polyurethane optical resin

0.015g of dibutyltin dichloride as a catalyst, UV-3290.05 g of an ultraviolet absorber, 0.1g of an internal mold release agent, 52g of m-Xylylene Diisocyanate (XDI) and 9g of a PMAG-PSS copolymer were placed in a reaction vessel with stirring at room temperature, mixed and dissolved. Further, 48g of 2, 3-dithio (2-mercapto) -1-propanethiol was added and mixed to form a raw material composition. Filtering the raw material composition with filter membrane, injecting into a special mold for lens processing (the liquid level of the raw material composition in the mold is about 7mm), degassing at 25 deg.C under 2kPa for 1 hr, and the pore diameter of the filter membrane is 1 μm.

After degassing, it was cured by polymerization by programmed heating from 25 ℃ to 120 ℃ in an oven set at a heating rate of 0.2 ℃/min. And when the temperature of the oven reaches 120 ℃, maintaining for 2 hours to obtain a cured sample, naturally cooling the subsequent sample to room temperature, performing secondary curing at the room temperature for 48 hours, and demolding to obtain the optical resin material.

Example 3

An antimicrobial polyurethane optical resin containing 0.2 wt% of PMAG-PSS copolymer (monomer molar ratio of MAG to SS 8:1) was prepared.

(1) Synthesis of PMAG-PSS polymers.

40.64g of Methacryloylguanidine (MAG) and 7.32g of 4-vinylbenzenesulfonamide (SS) were sequentially added to a reaction vessel, and 95.92g of dimethyl sulfoxide (DMSO) was further added thereto, followed by stirring at room temperature to completely dissolve the monomers. Then, 0.72g of dibenzoyl peroxide (BPO) was added to the mixture, and after completely dissolving the mixture by stirring, 0.72g of N, N-Dimethylaniline (DMA) was added dropwise thereto, followed by stirring and mixing, followed by reaction at room temperature for 3 hours. The amounts of BPO and DMA added were 1.5% by weight based on the total mass of methacrylylylguanidine and 4-vinylbenzenesulfonamide. After the reaction was completed, the mixture was filtered to collect a filter cake, and the filter cake was washed with toluene three times (50 ml each time). And finally, drying the filter cake at room temperature in vacuum to obtain the PMAG-PSS.

(2) Preparation of antibacterial polyurethane optical resin

0.015g of dibutyltin dichloride as a catalyst, UV-3290.05 g of an ultraviolet absorber, 0.1g of an internal mold release agent, 52g of m-Xylylene Diisocyanate (XDI) and 0.2g of a PMAG-PSS copolymer were added to a reaction vessel with stirring at room temperature, and mixed and dissolved. Further, 48g of 2, 3-dithio (2-mercapto) -1-propanethiol was added and mixed to form a raw material composition. Filtering the raw material composition with filter membrane, injecting into a special mold for lens processing (the liquid level of the raw material composition in the mold is about 7mm), degassing at 25 deg.C under 2kPa for 1 hr, and the pore diameter of the filter membrane is 1 μm.

After degassing, it was cured by polymerization by programmed heating from 25 ℃ to 120 ℃ in an oven set at a heating rate of 0.2 ℃/min. And when the temperature of the oven reaches 120 ℃, maintaining for 2 hours to obtain a cured sample, naturally cooling the subsequent sample to room temperature, performing secondary curing at the room temperature for 48 hours, and demolding to obtain the optical resin material.

Example 4

An antimicrobial polyurethane optical resin containing 5 wt% of PMAG-PSS copolymer (monomer molar ratio of MAG to SS was 4:1) was prepared.

(1) Synthesis of PMAG-PSS polymers.

30.48g of Methacryloylguanidine (MAG) and 10.98g of 4-vinylbenzenesulfonamide (SS) were sequentially added to a reaction vessel, and 82.92g of dimethyl sulfoxide (DMSO) was further added thereto, followed by stirring at room temperature to completely dissolve the monomers. Then, 0.83g of dibenzoyl peroxide (BPO) was added to the mixture, and after completely dissolving the mixture by stirring, 0.83g of N, N-Dimethylaniline (DMA) was added dropwise thereto, followed by stirring and mixing, followed by reaction at room temperature for 3 hours. The amounts of BPO and DMA added were 2% by weight based on the total mass of methacrylylylguanide and 4-vinylbenzenesulfonamide. After the reaction was completed, the mixture was filtered to collect a filter cake, and the filter cake was washed with toluene three times (50 ml each time). And finally, drying the filter cake at room temperature in vacuum to obtain the PMAG-PSS.

(2) Preparation of antibacterial polyurethane optical resin

0.05g of dibutyltin Dichloride (DBS) as a catalyst, UV-3290.05 g of an ultraviolet absorber, 0.1g of an internal mold release agent and cyclohexanedimethylene diisocyanate (H) as a catalyst were placed in a reaction vessel with a stirrer at room temperature₆XDI)47.8g and PMAG-PSS copolymer 5g were mixed and dissolved. Further, 28.4g of 2, 3-dithio (2-mercapto) -1-propanethiol and 23.8g of pentaerythritol tetrakis (3-mercaptopropionate) were added in this order and mixed to form a raw material composition. Filtering with filter membrane, injecting into special mold for processing lens (the liquid level of the raw material composition in the mold is about 7mm), and sealingDegassing at 25 deg.C under 2kPa for 1 hr, and the pore diameter of the filter membrane is 1 μm.

After degassing, it was cured by polymerization by programmed heating from 25 ℃ to 120 ℃ in an oven set at a heating rate of 0.1 ℃/min. And when the temperature of the oven reaches 120 ℃, maintaining for 2 hours to obtain a cured sample, naturally cooling the subsequent sample to room temperature, performing secondary curing at the room temperature for 48 hours, and demolding to obtain the optical resin material.

Example 5

An antimicrobial polyurethane optical resin containing 5 wt% of PMAG-PSS copolymer (monomer molar ratio of MAG to SS 5:1) was prepared.

(1) Synthesis of PMAG-PSS polymers.

31.75g of Methacryloylguanidine (MAG) and 9.15g of 4-vinylbenzenesulfonamide (SS) were sequentially added to a reaction vessel, and then 81.8g of dimethyl sulfoxide (DMSO) was added thereto, followed by stirring at room temperature to completely dissolve the monomers. Then, 0.82g of dibenzoyl peroxide (BPO) was added to the mixture, and after completely dissolving the mixture by stirring, 0.82g of N, N-Dimethylaniline (DMA) was added dropwise thereto, followed by stirring and mixing, followed by reaction at room temperature for 3 hours. The amounts of BPO and DMA added were 2% by weight based on the total mass of methacrylylylguanide and 4-vinylbenzenesulfonamide. After the reaction was completed, the mixture was filtered to collect a filter cake, and the filter cake was washed with toluene three times (50 ml each time). And finally, drying the filter cake at room temperature in vacuum to obtain the PMAG-PSS.

(2) Preparation of antibacterial polyurethane optical resin

0.05g of dibutyltin Dichloride (DBS) as a catalyst, UV-3290.05 g of an ultraviolet absorber, 0.1g of an internal mold release agent, 23g of Hexamethylene Diisocyanate (HDI) and cyclohexanedimethylene diisocyanate (H) were placed in a reaction vessel with a stirrer at room temperature₆XDI)15.5g, isophorone diisocyanate (IPDI)11.5g, and PMAG-PSS copolymer 5g, mixed and dissolved. Further, 38g of 2, 3-dithio (2-mercapto) -1-propanethiol and 12g of pentaerythritol tetrakis (3-mercaptopropionate) were added in this order and mixed to form a raw material composition. Filtering with filter membrane, injecting into a special mold for processing lens (the liquid level of the raw material composition in the mold is about 7mm), degassing at 25 deg.C under 2kPa for 1 hr, filteringThe pore diameter of the filtration pores of the membrane was 1 μm.

After degassing, it was cured by polymerization by programmed heating from 25 ℃ to 120 ℃ in an oven set at a heating rate of 0.1 ℃/min. And when the temperature of the oven reaches 120 ℃, maintaining for 2 hours to obtain a cured sample, naturally cooling the subsequent sample to room temperature, performing secondary curing at the room temperature for 48 hours, and demolding to obtain the optical resin material.

Comparative example 1: and preparing the PMAG-PSS-free polyurethane optical resin material. In comparison with example 1, no home-made PMAG-PSS copolymer was added in this comparative example, and the types of the remaining samples and the amounts thereof, the experimental procedures and the reaction time were the same as those in example 1.

Comparative example 2: and preparing the PMAG-PSS-free polyurethane optical resin material. In comparison with example 4, no home-made PMAG-PSS copolymer was added in this comparative example, and the types of the remaining samples and the amounts thereof, the experimental procedures and the reaction time were the same as those of example 4.

To further illustrate the technical advancement of the present invention, experimental tests were now conducted on the indices of the various examples and comparative examples.

And (3) testing antibacterial performance: antibacterial experiments are respectively carried out on the optical resin lens materials of the embodiments 1-5 and the comparative examples 1-2 thereof, so as to represent the antibacterial performance of the optical resin by the antibacterial rate to bacteria such as escherichia coli, staphylococcus aureus and the like, and the specific implementation method refers to the national standard GB/T30706-2014. The above test data are shown in Table 1.

And (3) testing optical performance: the optical resin lens materials of examples 1 to 5 and comparative examples 1 to 2 were subjected to light transmittance (transmittance) and YI value tests, respectively, and the above test data are shown in Table 2.

Thermal performance testing: the glass transition temperatures Tg of the optical resin lens materials of examples 1 to 5 and comparative examples 1 to 2 were measured by differential scanning calorimetry (DSC method), respectively, and each sample was tested in parallel 3 times and averaged. The Tg test data for the samples are shown in table 2.

TABLE 1 antimicrobial Properties of optical resin lenses in examples 1-5 and comparative examples 1-2

TABLE 2 transmittance and Tg values of optical resin lens materials in examples 1 to 5 and comparative examples 1 to 2

According to the results of the examples 1-5 and the comparative examples 1-2, the antibacterial polyurethane optical resin obtained by the preparation method disclosed by the invention not only has 99% antibacterial rate on escherichia coli and staphylococcus aureus, but also has strong antibacterial performance, the glass transition temperature Tg of the resin material is improved, the heat resistance is good, and meanwhile, the transmittance and the product yield of the optical resin are not negatively influenced by the addition of the PMAG-PSS. Therefore, according to the preparation method of the present invention, an antibacterial polyurethane resin having excellent properties can be prepared.

The embodiments described above are some, but not all embodiments of the invention. Modifications or adaptations of the present invention may occur to those skilled in the art in light of the present disclosure. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.