CN111349207A - Light-cured resin with antibacterial and anti-fouling functions and preparation method thereof - Google Patents

Light-cured resin with antibacterial and anti-fouling functions and preparation method thereof Download PDF

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CN111349207A
CN111349207A CN202010377208.0A CN202010377208A CN111349207A CN 111349207 A CN111349207 A CN 111349207A CN 202010377208 A CN202010377208 A CN 202010377208A CN 111349207 A CN111349207 A CN 111349207A
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antibacterial
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谢佳武
张冬明
李新雄
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Bonfurt New Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance

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  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention belongs to the technical field of light-cured resin, and particularly relates to light-cured resin with antibacterial and antifouling functions and a preparation method thereof. The invention provides a light-cured resin with antibacterial and antifouling functions, which is characterized by comprising the following raw materials: prepolymer I, prepolymer II, hydroxyl-terminated polydimethylsiloxane and first catalyst; the preparation raw materials of the prepolymer I comprise choline chloride, diisocyanate, a second catalyst and a diluent; the preparation raw materials of the prepolymer II comprise a hydroxy propionate monomer, polyisocyanate 1 and a polymerization inhibitor. The light-cured resin with the antibacterial and antifouling functions can be directly coated on the surface of a base material, and can also be added into other light-cured materials to form a UV coating; the antibacterial technology is combined with the ultraviolet curing technology, so that the surface of the coating has stable and lasting antibacterial effect.

Description

Light-cured resin with antibacterial and anti-fouling functions and preparation method thereof
Technical Field
The invention belongs to the technical field of light-cured resin, and particularly relates to light-cured resin with antibacterial and antifouling functions and a preparation method thereof.
Background
Pathogens such as bacteria and mold have been a great hazard to the health of human or animal bodies, and cause decomposition and damage of materials and deterioration of food, resulting in great health and economic loss. Therefore, how to reduce or even avoid the harm of pathogens such as bacteria to the environment and human bodies becomes a problem which people want to solve, especially since new coronavirus outbreaks in 2019, various industries pay more and more attention to the upgrading and marketization application of antibacterial and antiviral products, so that the rapid development of antibacterial coatings is out of the way.
The development of antibacterial coatings has been accumulated for a long time, and at present, most of organic antibacterial agents such as organic silicon quaternary ammonium salts and organic polyphenols and antibacterial metal ion compounds such as silver ions and tin are added into a coating system together to endow a coating with antibacterial properties. The antibacterial property of the coating is endowed with certain timeliness by the physical adding mode, and the antibacterial effect is gradually lost as the antibacterial property is dissolved and lost on the surface of the coating along with the time. Particularly, the required antibacterial timeliness requirement is higher for furniture, mobile phones, intelligent equipment and the like which are closely contacted with the life of people in corresponding environments. Among organic compound antibacterial agents, quaternary ammonium salt type antibacterial agents have good bactericidal action, and are safe, environment-friendly and nontoxic. However, the chemical activity of the common quaternary ammonium salt is low, the quaternary ammonium salt exists in a basically free state during application, the toxicity is relatively high, and the irritation is strong. Researches find that the performance of the organosilicon quaternary ammonium salt prepared by introducing siloxane into a quaternary ammonium salt structure is greatly changed, and the organosilicon quaternary ammonium salt not only has excellent antibacterial and bacteriostatic properties, but also has no stimulation and carcinogenic effect on human skin. However, after the organosilicon quaternary ammonium salt antibacterial agent is activated in water, the organosilicon quaternary ammonium salt antibacterial agent loses activity and loses long-acting property within 4 to 8 hours. In addition, silver ions are difficult to disperse in a coating system and are easy to dissociate and remove after being activated in the coating, so that the antibacterial durability of the coating is lost.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a photocurable resin with antibacterial and antifouling functions, which is prepared from the following raw materials: prepolymer I, prepolymer II, hydroxyl-terminated polydimethylsiloxane and first catalyst;
the preparation raw materials of the prepolymer I comprise choline chloride, diisocyanate, a second catalyst and a diluent;
the preparation raw materials of the prepolymer II comprise a hydroxy propionate monomer, polyisocyanate 1 and a polymerization inhibitor.
As a preferred technical scheme, the preparation raw materials comprise the following components in parts by weight: 40-80 parts of prepolymer I, 40-100 parts of prepolymer II, 80-180 parts of hydroxyl-terminated polydimethylsiloxane and 0.1-0.4 part of first catalyst;
the preparation raw materials of the prepolymer I comprise choline chloride, diisocyanate, a second catalyst and a diluent; the preparation raw materials of the prepolymer II comprise a hydroxy propionate monomer, polyisocyanate 1 and a polymerization inhibitor.
As a preferable technical scheme, the preparation raw materials of the prepolymer I comprise, by weight, 12.9-15.4 parts of choline chloride, 18.9-25.9 parts of diisocyanate, 0.06-0.1 part of a second catalyst and 33-41 parts of a diluent.
As a preferable technical scheme, the preparation method of the prepolymer I comprises the following steps: adding choline chloride and a diluent into a reactor, and uniformly stirring; then adding diisocyanate, and stirring for 5-15min at 20-30 ℃; adding a second catalyst, raising the temperature to 70-90 ℃, and reacting for 3-5h at constant temperature to obtain a prepolymer I.
As a preferred technical scheme, the diluent is an acrylate reactive diluent.
As a preferable technical scheme, the preparation raw materials of the prepolymer II comprise 50.5-70.9 parts of hydroxy propionate monomer, 18.2-56.6 parts of polyisocyanate 1 and 0.18-0.32 part of polymerization inhibitor.
As a preferable technical scheme, the hydroxyl acrylate monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, pentaerythritol triacrylate, hydroxypropyl methacrylate, 2-hydroxyl n-butyl acrylate and dipentaerythritol pentaacrylate.
As a preferred technical scheme, the preparation method of the prepolymer II comprises the following steps: adding a hydroxyl acrylate monomer, polyisocyanate 1 and a polymerization inhibitor into a reactor, controlling the reaction temperature at 50-70 ℃, and reacting at a constant temperature for 2.5-4h to obtain a prepolymer II.
As a preferable technical scheme, the hydroxyl-terminated polydimethylsiloxane has the molecular formula:
Figure BDA0002480404690000021
(ii) a Wherein n is 5-40.
The second aspect of the present invention provides a method for preparing the photocurable resin, comprising the steps of: adding the prepolymer I, the prepolymer II and the hydroxyl-terminated polydimethylsiloxane into a reaction container, uniformly stirring at 20-30 ℃, adding a first catalyst, raising the temperature to 80-90 ℃, reacting at a constant temperature for 3.5-5.5h, and measuring the content of isocyanate to be below 0.1 wt% to obtain the photocuring resin with the antibacterial and antifouling functions.
Has the advantages that: the light-cured resin with the antibacterial and antifouling functions can be directly coated on the surface of a base material, and can also be added into other light-cured materials to form a UV coating; the antibacterial technology is combined with the ultraviolet curing technology, so that the surface of the coating has stable and lasting antibacterial effect.
Detailed Description
In order to solve the problems, the invention provides a light-cured resin with antibacterial and antifouling functions, which is prepared from the following raw materials: prepolymer I, prepolymer II, hydroxyl-terminated polydimethylsiloxane and first catalyst;
the preparation raw materials of the prepolymer I comprise choline chloride, diisocyanate, a second catalyst and a diluent;
the preparation raw materials of the prepolymer II comprise a hydroxy propionate monomer, polyisocyanate 1 and a polymerization inhibitor.
Preferably, the light-cured resin with the antibacterial and antifouling functions comprises the following preparation raw materials in parts by weight: 40-80 parts of prepolymer I, 40-100 parts of prepolymer II, 80-180 parts of hydroxyl-terminated polydimethylsiloxane and 0.1-0.4 part of first catalyst;
the preparation raw materials of the prepolymer I comprise choline chloride, diisocyanate, a second catalyst and a diluent; the preparation raw materials of the prepolymer II comprise a hydroxy propionate monomer, polyisocyanate 1 and a polymerization inhibitor.
More preferably, the light-cured resin with the antibacterial and antifouling functions comprises the following preparation raw materials in parts by weight: 45.4-70.4 parts of prepolymer I, 47.8-92.1 parts of prepolymer II, 86.3-173.8 parts of hydroxyl-terminated polydimethylsiloxane and 0.11-0.33 part of first catalyst;
the preparation raw materials of the prepolymer I comprise choline chloride, diisocyanate, a second catalyst and a diluent; the preparation raw materials of the prepolymer II comprise a hydroxy propionate monomer, polyisocyanate 1 and a polymerization inhibitor.
The reaction mechanism of the photocuring resin with the antibacterial and antifouling functions is that choline chloride and diisocyanate are reacted to prepare a prepolymer I containing quaternary ammonium salt, a hydroxy propionate monomer is reacted with polyisocyanate 1 to prepare a prepolymer II, and then the prepolymer I, the prepolymer II and hydroxy-terminated polydimethylsiloxane are subjected to chain extension reaction to prepare the photocuring resin with the antibacterial and antifouling functions. The chemical reaction formula is as follows:
Figure BDA0002480404690000031
Figure BDA0002480404690000041
prepolymer I
Preferably, the preparation raw materials of the prepolymer I comprise 12.9-15.4 parts of choline chloride, 18.9-25.9 parts of diisocyanate, 0.06-0.1 part of second catalyst and 33-41 parts of diluent in parts by weight;
the preparation method of the prepolymer I comprises the following steps: adding choline chloride and a diluent into a reactor, and uniformly stirring; then adding diisocyanate, and stirring for 5-15min at 20-30 ℃; adding a second catalyst, raising the temperature to 70-90 ℃, and reacting for 3-5h at constant temperature to obtain a prepolymer I.
The choline chloride is prepared from industrial raw materials with the mass content of more than 99.0%.
Preferably, the diisocyanate is at least one selected from isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate.
Among them, isophorone diisocyanate (IPDI for short), dicyclohexylmethane diisocyanate (HMDI for short), toluene diisocyanate (TDI for short), hexamethylene diisocyanate (HDI for short), and diphenylmethane diisocyanate (MDI for short).
Preferably, the second catalyst is selected from one or more of organic bismuth, organic tin, organic zinc and potassium iodide.
Preferably, the diluent is an acrylate reactive diluent; more preferably, the acrylate reactive diluent is selected from one or more of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, 1, 4-butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate.
Wherein, 1, 6-hexanediol diacrylate is abbreviated as HDDA, tripropylene glycol diacrylate is abbreviated as TPGDA, neopentyl glycol diacrylate is abbreviated as NPGDA, 1, 4-butanediol diacrylate is abbreviated as BDDA, trimethylolpropane triacrylate is abbreviated as TMPTA, pentaerythritol tetraacrylate is abbreviated as PET4A, and ethoxylated trimethylolpropane triacrylate is abbreviated as TMP3 EOTA.
Prepolymer II
Preferably, the preparation raw materials of the prepolymer II comprise, by weight, 50.5-70.9 parts of hydroxy propionate monomer, 18.2-56.6 parts of polyisocyanate 1 and 0.18-0.32 part of polymerization inhibitor.
The preparation method of the prepolymer II comprises the following steps: adding a hydroxyl acrylate monomer, polyisocyanate 1 and a polymerization inhibitor into a reactor, controlling the reaction temperature at 50-70 ℃, and reacting at a constant temperature for 2.5-4h to obtain a prepolymer II.
Preferably, the hydroxy acrylate monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, pentaerythritol triacrylate, hydroxypropyl methacrylate, 2-hydroxy n-butyl acrylate, dipentaerythritol pentaacrylate.
Preferably, the polyisocyanate 1 is one or two selected from isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, HDI trimer polyisocyanate and HDI biuret polyisocyanate. Wherein isophorone diisocyanate is abbreviated as IPDI, dicyclohexylmethane diisocyanate is abbreviated as HMDI, toluene diisocyanate is abbreviated as TDI, and hexamethylene diisocyanate is abbreviated as HDI.
Preferably, the polymerization inhibitor is selected from one or more of p-hydroxyanisole, hydroquinone and BHT.
The BHT refers to dibutyl hydroxy toluene.
Hydroxy-terminated polydimethylsiloxane
Preferably, the hydroxyl-terminated polydimethylsiloxane has the formula:
Figure BDA0002480404690000061
wherein n is 5-40; more preferably, n is 15 to 30.
When n is 5-40, the number average molecular weight of the hydroxyl-terminated polydimethylsiloxane is between 500 and 3000;
when n is 15-30, it represents that the number average molecular weight of the hydroxyl-terminated polydimethylsiloxane is between 1000-2000.
First catalyst
The first catalyst is one or more of organic bismuth, organic tin and organic zinc.
Preferably, the preparation method of the light-cured resin with the antibacterial and antifouling functions comprises the following steps: adding the prepolymer I, the prepolymer II and the hydroxyl-terminated polydimethylsiloxane into a reaction container, uniformly stirring at 20-30 ℃, adding a first catalyst, raising the temperature to 80-90 ℃, reacting at a constant temperature for 3.5-5.5h, and measuring the content of isocyanate to be below 0.1 wt% to obtain the photocuring resin with the antibacterial and antifouling functions.
The isocyanate content test is a test method commonly used in the art. Without particular limitation, for example, the NCO content can be quantitatively calculated by reacting a polymer whose isocyanate content is to be measured with an excess of di-n-butylamine and titrating the excess of di-n-butylamine with hydrochloric acid.
The invention has the beneficial effects that: 1) the quaternary ammonium salt-choline chloride with antibacterial effect is selected, the raw materials are easily available, safe and environment-friendly, the reaction activity with isocyanate is high, and the operation is simple, convenient and safe; 2) the antibacterial molecular structure and the photocuring active group are grafted mutually by adopting hydroxyl-terminated polydimethylsiloxane, the antibacterial structure is introduced into the photocuring resin, and the antibacterial group stably exists after light irradiation, so that the long-term and high-efficiency antibacterial effect is maintained; 3) polydimethylsiloxane is introduced into a molecular structure, the surface energy of the polydimethylsiloxane is low, the polydimethylsiloxane can migrate from the surface of a coating layer to endow resin with a good anti-fouling characteristic, quaternary ammonium salt groups can be dragged to migrate to the surface in the process of migrating the polydimethylsiloxane to the surface so as to further improve the antibacterial property of the resin, the polydimethylsiloxane structure with the molecular weight of 1000-; 4) the quaternary ammonium salt structure in the molecular structure endows the surface of the coating with hydrophilicity, so that the surface of the coating after antibiosis has self-cleaning and self-repairing functions, and repeated high-efficiency antibiosis can be realized; 5) the light-cured resin with the antibacterial and antifouling functions can be directly coated on a base material or added into other UV coating systems, and has good antibacterial durability and antifouling effect on the coating.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
A photocuring resin with antibacterial and antifouling functions is prepared from the following raw materials: 70.4g of prepolymer I, 68.6g of prepolymer II, 86.3g of hydroxyl-terminated polydimethylsiloxane (number average molecular weight of 1000), 0.11g of first catalyst (0.08 g of organic bismuth and 0.03g of organic tin);
the preparation method of the prepolymer I comprises the following steps: adding 14.1g of choline chloride and 41.0g of TMPTA into a reactor, uniformly stirring until the mixture is semitransparent, then adding 25.9g of HMDI, stirring for 10min at room temperature, adding 0.06g of organic bismuth and 0.02g of potassium iodide, heating to 65-68 ℃, reacting for 3.5h at constant temperature, sampling to test that the content of isocyanate is 5.0-5.3%, cooling and sealing to obtain a prepolymer I;
the preparation method of the prepolymer II comprises the following steps: and adding 51.9g of pentaerythritol triacrylate, 26.5g of HMDI and 0.28g of p-hydroxyanisole into another reactor, controlling the temperature to be 58-60 ℃, reacting for 3.0 hours at constant temperature, sampling to test that the content of isocyanate is 5.3-5.5%, cooling and sealing well to obtain a prepolymer II.
The preparation method of the photocuring resin with antibacterial and antifouling functions comprises the following steps: adding the prepolymer I, the prepolymer II and the hydroxyl-terminated polydimethylsiloxane into a reaction container, uniformly stirring at 20-30 ℃, adding a first catalyst, raising the temperature to 82-85 ℃, reacting at a constant temperature for 4 hours, and measuring the content of isocyanate to be below 0.1 wt% to obtain the photocuring resin with the antibacterial and antifouling functions.
Example 2
A photocuring resin with antibacterial and antifouling functions is prepared from the following raw materials: 56.7g of prepolymer I, 89.4g of prepolymer II, 104.2g of hydroxyl-terminated polydimethylsiloxane (number average molecular weight 1500), 0.19g of a first catalyst (0.15 g of organic bismuth and 0.04g of organic tin);
the preparation method of the prepolymer I comprises the following steps: adding 14.1g of choline chloride, 21.0g of TMPTA and 20.0g of HDDA into a reactor, uniformly stirring until the mixture is semitransparent, then adding 25.9g of HMDI, stirring for 10min at room temperature, adding 0.08g of organic zinc and 0.02g of potassium iodide, heating to 65-68 ℃, reacting at constant temperature for 3.5h, sampling to test that the content of isocyanate is 5.0-5.3%, cooling, and sealing to obtain prepolymer I;
the preparation method of the prepolymer II comprises the following steps: and adding 59.4g of pentaerythritol triacrylate, 11.5g of hydroxypropyl acrylate, 56.6g of HDI trimer and 0.32g of p-hydroxyanisole into another reactor, controlling the temperature to be 62-65 ℃, reacting at constant temperature for 3.5 hours, sampling to test that the content of isocyanate is 3.1-3.3%, cooling and sealing well to obtain prepolymer II.
The preparation method of the photocuring resin with antibacterial and antifouling functions comprises the following steps: adding the prepolymer I, the prepolymer II and the hydroxyl-terminated polydimethylsiloxane into a reaction container, uniformly stirring at 20-30 ℃, adding a first catalyst, raising the temperature to 82-85 ℃, reacting at a constant temperature for 4.5 hours, and measuring the content of isocyanate to be below 0.1 wt% to obtain the photocuring resin with the antibacterial and antifouling functions.
Example 3
A photocuring resin with antibacterial and antifouling functions is prepared from the following raw materials: 45.4g of prepolymer I, 47.8g of prepolymer II, 90.8g of hydroxyl-terminated polydimethylsiloxane (number average molecular weight 1500), 0.2g of a first catalyst (0.16 g of organic bismuth and 0.04g of organic tin);
the preparation method of the prepolymer I comprises the following steps: adding 14.3g of choline chloride, 20.0g of TMPTA and 19.0g of NPGDA into a reactor, uniformly stirring until the mixture is semitransparent, then adding 22.4g of IPDI, stirring for 10min at room temperature, adding 0.04g of organic bismuth and 0.02g of potassium iodide catalyst, heating to 68-70 ℃, reacting for 3.0h at constant temperature, sampling to test that the content of isocyanate is 5.5-5.7%, cooling and sealing to obtain prepolymer I;
the preparation method of the prepolymer II comprises the following steps: and adding 53.5g of pentaerythritol triacrylate, 26.1g of HMDI and 0.22g of p-hydroxyanisole into another reactor, controlling the temperature to be 58-60 ℃, reacting for 3.0 hours at constant temperature, sampling to test the content of isocyanate to be 5.2-5.4%, cooling, and sealing to obtain the prepolymer II.
The preparation method of the photocuring resin with antibacterial and antifouling functions comprises the following steps: adding the prepolymer I, the prepolymer II and the hydroxyl-terminated polydimethylsiloxane into a reaction container, uniformly stirring at 20-30 ℃, adding a first catalyst, raising the temperature to 82-85 ℃, reacting at a constant temperature for 4.5 hours, and measuring the content of isocyanate to be below 0.1 wt% to obtain the photocuring resin with the antibacterial and antifouling functions.
Example 4
A photocuring resin with antibacterial and antifouling functions is prepared from the following raw materials: 54.4g of prepolymer I, 55.8g of prepolymer II, 173.8g of hydroxyl-terminated polydimethylsiloxane (number average molecular weight 2000), 0.28g of a first catalyst (0.22 g of organic zinc and 0.06g of organic tin);
the preparation method of the prepolymer I comprises the following steps: adding 15.4g of choline chloride, 17.0g of HDDA and 17.0g of TPGDA into a reactor, uniformly stirring until the mixture is semitransparent, then adding 18.9g of TDI, stirring for 10min at room temperature, adding 0.08g of organic zinc, heating to 62-65 ℃, reacting for 3.0h at constant temperature, sampling to test that the content of isocyanate is 6.5-6.7%, cooling and sealing to obtain a prepolymer I;
the preparation method of the prepolymer II comprises the following steps: and adding 45.6g of dipentaerythritol pentaacrylate, 4.9g of hydroxyethyl methacrylate, 18.2g of HDI, 0.11g of p-hydroxyanisole and 0.07g of BHT into another reactor, controlling the temperature to 65-68 ℃, reacting for 4.0h at constant temperature, sampling to test the content of isocyanate to be 6.4-6.6%, and cooling and sealing well to obtain a prepolymer II.
The preparation method of the photocuring resin with antibacterial and antifouling functions comprises the following steps: adding the prepolymer I, the prepolymer II and the hydroxyl-terminated polydimethylsiloxane into a reaction container, uniformly stirring at 20-30 ℃, adding a first catalyst, raising the temperature to 85-88 ℃, reacting at a constant temperature for 4.5 hours, and measuring the content of isocyanate to be below 0.1 wt% to obtain the photocuring resin with the antibacterial and antifouling functions.
Example 5
A photocuring resin with antibacterial and antifouling functions is prepared from the following raw materials: 49.5g of prepolymer I, 92.1g of prepolymer II, 136.3g of hydroxyl-terminated polydimethylsiloxane (number average molecular weight 2000), 0.33g of first catalyst (0.22 g of organic zinc and 0.11g of organic bismuth);
the preparation method of the prepolymer I comprises the following steps: adding 12.9g of choline chloride, 20.0g of HDDA and 13.0g of TMPTA into a reactor, uniformly stirring until the mixture is semitransparent, then adding 20.2g of IPDI, stirring for 10min at room temperature, adding 0.09g of organic zinc, heating to 62-65 ℃, reacting for 3.0h at constant temperature, sampling to test that the content of isocyanate is 5.7-5.9%, cooling and sealing to obtain prepolymer I;
the preparation method of the prepolymer II comprises the following steps: and adding 63.6g of pentaerythritol triacrylate, 7.1g of hydroxyethyl acrylate, 52.1g of HDI biuret polyisocyanate, 0.12g of p-hydroxyanisole and 0.06g of BHT into another reactor, controlling the temperature to 65-66 ℃, reacting for 4.0 hours at constant temperature, sampling to test that the content of isocyanate is between 3.0 and 3.2 percent, and cooling and sealing to obtain a prepolymer II.
The preparation method of the photocuring resin with antibacterial and antifouling functions comprises the following steps: adding the prepolymer I, the prepolymer II and the hydroxyl-terminated polydimethylsiloxane into a reaction container, uniformly stirring at 20-30 ℃, adding a first catalyst, raising the temperature to 85-88 ℃, reacting at a constant temperature for 4.5 hours, and measuring the content of isocyanate to be below 0.1 wt% to obtain the photocuring resin with the antibacterial and antifouling functions.
Performance testing
Sample preparation: samples of the photo-curable resins having antibacterial and antifouling functions prepared in examples 1 to 5 were coated on a PC substrate to have a film thickness of 200 μm and a curing energy of 600mj/cm2Finally, the cured paint film was cut into 5cm by 5cm size panels for testing.
And (3) testing conditions are as follows:
and (3) antibacterial property: according to the national standard GB/21866-;
and (3) antibacterial durability: according to the national standard GB/21866-; according to the requirement, the antibacterial durability of more than 95.0 percent is rated as the first grade of antibacterial durability;
oil resistance marking pen: scratching the paint film by using a mark oil pen, wiping for 2-5 times by using scouring pad after 30s, and observing residual marks on the surface of the paint film;
the results of the tests on the samples of the photo-curable resins having antibacterial and antifouling functions prepared in the above examples 1 to 5 are shown in the following table:
Figure BDA0002480404690000101
the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.

Claims (10)

1. The light-cured resin with the antibacterial and antifouling functions is characterized by comprising the following raw materials: prepolymer I, prepolymer II, hydroxyl-terminated polydimethylsiloxane and first catalyst;
the preparation raw materials of the prepolymer I comprise choline chloride, diisocyanate, a second catalyst and a diluent;
the preparation raw materials of the prepolymer II comprise a hydroxy propionate monomer, polyisocyanate 1 and a polymerization inhibitor.
2. The photocurable resin of claim 1, wherein the raw materials for the preparation thereof comprise, in parts by weight: 40-80 parts of prepolymer I, 40-100 parts of prepolymer II, 80-180 parts of hydroxyl-terminated polydimethylsiloxane and 0.1-0.4 part of first catalyst;
the preparation raw materials of the prepolymer I comprise choline chloride, diisocyanate, a second catalyst and a diluent; the preparation raw materials of the prepolymer II comprise a hydroxy propionate monomer, polyisocyanate 1 and a polymerization inhibitor.
3. The light-cured resin as claimed in claim 1, wherein the prepolymer I is prepared from 12.9-15.4 parts by weight of choline chloride, 18.9-25.9 parts by weight of diisocyanate, 0.06-0.1 part by weight of second catalyst, and 33-41 parts by weight of diluent.
4. The photocurable resin of claim 3, wherein the prepolymer I is prepared by a method comprising the steps of: adding choline chloride and a diluent into a reactor, and uniformly stirring; then adding diisocyanate, and stirring for 5-15min at 20-30 ℃; adding a second catalyst, raising the temperature to 70-90 ℃, and reacting for 3-5h at constant temperature to obtain a prepolymer I.
5. The photocurable resin of claim 3 or 4 wherein the diluent is an acrylate reactive diluent.
6. The photocurable resin of claim 1 or 2, wherein the prepolymer II is prepared from 50.5-70.9 parts of hydroxy propionate monomer, 18.2-56.6 parts of polyisocyanate 1, and 0.18-0.32 part of polymerization inhibitor.
7. The photocurable resin of claim 6 wherein the hydroxy acrylate monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, pentaerythritol triacrylate, hydroxypropyl methacrylate, 2-hydroxy n-butyl acrylate, dipentaerythritol pentaacrylate.
8. The photocurable resin of claim 6, wherein the prepolymer II is prepared by a method comprising the steps of: adding a hydroxyl acrylate monomer, polyisocyanate 1 and a polymerization inhibitor into a reactor, controlling the reaction temperature at 50-70 ℃, and reacting at a constant temperature for 2.5-4h to obtain a prepolymer II.
9. The photocurable resin of claim 1 wherein said hydroxyl terminated polydimethylsiloxane is of the formula:
Figure FDA0002480404680000021
wherein n is 5-40.
10. A method for producing the photocurable resin according to any one of claims 1-9, comprising the steps of: adding the prepolymer I, the prepolymer II and the hydroxyl-terminated polydimethylsiloxane into a reaction container, uniformly stirring at 20-30 ℃, adding a first catalyst, raising the temperature to 80-90 ℃, reacting at a constant temperature for 3.5-5.5h, and measuring the content of isocyanate to be below 0.1 wt% to obtain the photocuring resin with the antibacterial and antifouling functions.
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