CN109879988B - Free radical photopolymerization dark curing initiation system and preparation method thereof - Google Patents
Free radical photopolymerization dark curing initiation system and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a photocuring initiation system, in particular to a free radical photopolymerization dark curing initiation system and a preparation method thereof, belonging to the technical field of free radical polymerization preparation. The dark cure initiation system comprises the following components in weight percent: a first component: 0.01-1% of photosensitizer; a second component: 0.5-1% of co-initiator, wherein the co-initiator is water-soluble polypeptide with antioxidant activity and containing tyrosine residue. Compared with the previously reported dark curing photoinitiation system, the free radical photopolymerization dark curing initiation system has the following advantages: the components are simple and only two-component systems, the composite material does not contain transition metal elements, has good biocompatibility, can be used in the fields of medical treatment and health and the like, has easily obtained raw materials, good stability, short irradiation time, high polymerization conversion rate, less polymerization heat release, low polymerization system temperature and no harmful substances such as strong basicity, strong oxidizing property and the like in the polymerization process, is not easy to oxidize and decompose after being stored for a long time, and has low required irradiation light intensity and short irradiation time.
Description
Technical Field
The invention relates to a photopolymerization curing initiation system, in particular to a free radical photopolymerization dark curing initiation system and a preparation method thereof, belonging to the technical field of free radical photopolymerization preparation.
Background
Currently, the photo-curing technology is widely applied in the field of surface thin layer curing of coatings, adhesives, varnishes and the like, and the photo-polymerization curing process is rapid and sufficient because light can penetrate through the photo-curing technology, and the curing thickness is usually in the range of several micrometers to 50 micrometers. However, in the case of a thick film curing or a photo-curing resin added with a filler (particularly, a pigment), the light intensity is seriously attenuated along with the light path due to the absorption, scattering, reflection and the like of the light by the curing component, so that the curing depth and the curing efficiency are influenced, and even the curing cannot be performed in the case of serious light intensity. The light shielding effect of the light curing system is a fatal defect of the light curing technology which is different from the classical heat curing and the redox curing.
How to overcome this drawback is a challenge facing photocuring technology. Compared with the traditional thermal curing technology, the photo-curing technology has the following advantages: firstly, the material can be solidified at room temperature; zero VOC emission; the polymerization time and the polymerization space are controllable; fourthly, the light curing equipment is simple and cheap, etc. Therefore, if the technical disadvantages can be overcome, the method has wider application prospects.
Many attempts have been made to overcome the problem of light attenuation starting from various factors that affect the efficiency of photopolymerization. Which comprises the following steps: the method has the advantages of improving light intensity, introducing additives, adjusting polymerization components, utilizing the light bleaching behavior of a photosensitizer, adopting an infrared photosensitizer, adopting a single-component or multi-component photoinitiator and the like, and is difficult to completely avoid and has application limitation although certain improvement is achieved.
Another idea for overcoming light attenuation is to design a dark curing initiator which can continuously initiate polymerization after leaving the light source, namely that polymerization does not stop immediately after the light source is finished, and the polymerization is continuously carried out after leaving the light source. This dark cure behavior can overcome, to a large extent, the problem of insufficient light in thick film curing or curing of resins containing fillers. The photo-base generation type free radical polymerization photoinitiator is synthesized by He Ming et al, and forms a photo-initiation system with peroxide, wherein the photo-initiation system releases strong basic amine during photo-irradiation, the strong basic amine is diffused in a polymerization system, and reacts with the peroxide while diffusing, so that classical redox polymerization is carried out. In this system, polymerization proceeds from the center of light to the periphery, and proceeds in the dark, by only partial exposure to light. The distance of polymerization propagation can even reach 7cm, and the discovery of the dark curing photoinitiation system realizes the application of the photopolymerization technology in the polymerization of resin systems containing filler carbon black. In addition, in the initiation of photopolymerization, rapid polymerization occurs with the generation of alkali to cause the local temperature of the system to rise sharply, which can reach 167-. The high temperature generated by the polymerization can also initiate the sulfur-alkene polymerization and the anion polymerization, so that the application field of the catalyst is further expanded. However, this dark cure system has the following disadvantages: firstly, only harmful low-penetrability ultraviolet light sources can be utilized; ② the peroxide contained in the system has storage stability problem; thirdly, the alkali-producing agent in the initiation system can only be dissolved in an organic solvent, and VOC is discharged; fourthly, a large amount of heat is released by polymerization, the local temperature of the system can often reach more than 150 ℃, and the heat dissipation problem exists. The above dark curing behavior mainly depends on the action of photobase generators, and the generated alkali is strong alkali and easily causes unwanted side reactions.
Another class of dark cure photoinitiation systems is reported by Aguirre-Soto et al, which comprises three components: the system is irradiated by light, the methylene blue absorbs light energy and transits to an excited state, and generates photochemical reaction with amine to generate methylene blue leuco bodies, and the methylene blue leuco bodies are diffused in resin and generate redox reaction with onium salts to generate active species to initiate free radical polymerization, so that the light-shielded part is dark-cured, and the curing depth of the resin can reach 1.2 cm. Particularly, this dark curing process is not self-accelerating due to heat generation because the polymerization rate is slow because the diffusion rate of the generated initiation intermediate is slow and the heat of polymerization generated therebetween is small. Furthermore, the light intensity required for the dark cure initiated by this system is only 3-30mW/cm 2 And (3) a range. However, this system has two drawbacks: firstly, the dark curing speed is slow, and the curing time can even reach 30 min; secondly, in order to facilitate the diffusion of the photochemical reaction intermediate of the system, low-viscosity monomers are often adopted and need to be blended with a crosslinking agent in practical application.
Garra et al report a peroxidic free radical mediated dark cure reaction with radical oxygen inhibition, consisting of monovalent copper with high redox catalytic activity, an iodonium salt and stannous 2-ethylhexanoate. In the irradiation zone, the monovalent copper in an excited state reacts with the iodonium salt to generate a first initiating species, which initiates conventional radical polymerization. Because the irradiation light intensity is low (the LED lamp 405nm light source is only 4 mW/cm) 2 ) The free radical generating speed is slow, the growing macromolecule chain segment is easy to react with oxygen dissolved in low-viscosity resin to generate peroxy radical ROO, then the peroxy radical ROO is generated, the initiation inert ROOH is generated continuously, the in-situ generated inert intermediate is diffused to the light shielding area to generate oxidation-reduction reaction with monovalent copper to generate active species RO for initiating polymerization, the monovalent copper is oxidized into dimethyl copper, and then the dimethyl copper is reduced by divalent tinRegenerating and participating in the next cycle. The curing range of the dark polymerization initiated by the system can reach 2.9 cm. The main problems with this system are: the system containing transition metal with too high activity (the system can be completely cured in 90s under sunlight) is unstable and has harsh application conditions; copper-containing catalysts are not currently commercialized.
A promising class of dark cure initiation systems is available for initiating controlled free radical photopolymerization, and Boyer task group recently devised a photo initiation system that initiates controlled free radical photopolymerization dark cure, the system consisting of a photosensitizer xanthene dye and vitamin C. The explanation for its mechanism of dark polymerization curing is: under light irradiation, the photosensitizer in an excited state is quenched by molecular oxygen dissolved in the system to generate singlet oxygen, and the singlet oxygen generates H under the action of a reducing agent ascorbic acid C 2 O 2 . When the light source is removed, H 2 O 2 Then reacts with ascorbic acid in the system to generate active species to initiate polymerization, H 2 O 2 Is a potential initiation active intermediate in the system. As is clear from the polymerization mechanism, the photo-polymerization dark reaction is carried out under air conditions in the early stage of light irradiation, and the oxygen inhibition effect of the conventional radical polymerization is changed to the essential condition for the polymerization. However, the reactive intermediate H generated in the polymerization initiation process of the system 2 O 2 The cells and other active intermediates embedded in the cells are easy to damage due to strong oxidizing property, so that the application range of the cells and other active intermediates is limited.
Another class of classical dark polymerization curing is polymerization initiated by cations. From the above discussion, the dark curing by radical polymerization requires the design of a special photoinitiation system, and cationic polymerization is a well-known dark curing process. This is because the active species H which initiates the polymerization + The long lifetime is slow to diffuse, so it requires a relatively high temperature to promote polymerization.
With the above introduction of some research results in the field of dark polymerization curing in recent years, it can be found that the key of the dark curing by radical polymerization is the design of a special photoinitiation system. The design idea is mainly based on two points: firstly, a dark curing process needs photo-initiation to generate an active intermediate, the active intermediate starts a subsequent oxidation-reduction reaction, and new active species are generated to initiate dark polymerization curing; secondly, active species are generated by light irradiation to quickly initiate free radical polymerization, the local exothermic temperature is raised, so that a thermal polymerization initiator in the active species is decomposed to generate a second active free radical to initiate dark polymerization and solidification, and the polymerization mode is also called front-line polymerization. The free radical polymerization dark curing photoinitiation system designed based on the two concepts can generate a large amount of heat locally or generate strong oxidizing and strong alkaline intermediates in the process of initiating polymerization, and the effects can cause damage to active components and limit the application range of the system. The invention designs a free radical polymerization dark curing photoinitiation system, which has the advantages that: the system has good water solubility, can initiate hydrogel dark polymerization and solidification, has simple components which are only two-component systems, does not contain transition metal elements, has good biocompatibility, can be used in the fields of medical treatment and health and the like, has easily obtained raw materials, good stability, long-term storage and difficult oxidative decomposition, has low required irradiation light intensity and short irradiation time, high initiated polymerization conversion rate, has low polymerization exothermic quantity so that the polymerization system has low temperature, and does not generate harmful substances such as strong basicity, strong oxidizing property and the like in the polymerization process. In addition, the performance of the invented radical photopolymerization dark cure initiation system, in which the key component co-initiator, initiates the dark polymerization cure, has never been discovered and recognized.
Disclosure of Invention
The invention provides a free radical photopolymerization dark curing initiation system which has good solubility in water, excellent biocompatibility, less exothermic heat of initiated polymerization and required light intensity<30mW/cm 2 The light irradiation time is short, the initiating system effectively overcomes the problem of low utilization efficiency of light in a polymerization resin system, and the initiating system can be used for preparing multi-purpose hydrogel.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a free radical photopolymerization dark curing initiation system is used for preparing dark curing reaction liquid by adding a photopolymerization system. The dark curing initiation system comprises the following components in percentage by weight, based on the total weight of the dark curing reaction liquid as 100 percent:
a first component: 0.01 to 1 percent of photosensitizer;
a second component: 0.5-1% of co-initiator, wherein the co-initiator is water-soluble polypeptide with antioxidant activity and containing tyrosine residue.
After the photo-initiation system is irradiated by 400-700nm visible light for 2-5 minutes, the free radical active species can be continuously generated to initiate dark polymerization and solidification after being separated from a light source, and the final photo-polymerization conversion rate can reach more than 80%.
Compared with the previously reported dark curing photoinitiation system, the free radical photopolymerization dark curing initiation system has the following advantages: the components are simple and only two-component systems, the composite material does not contain transition metal elements, has good biocompatibility, can be used in the fields of medical treatment and health and the like, has easily obtained raw materials, good stability, short irradiation time, high polymerization conversion rate, less polymerization heat release, low polymerization system temperature and no harmful substances such as strong basicity, strong oxidizing property and the like in the polymerization process, is not easy to oxidize and decompose after being stored for a long time, and has low required irradiation light intensity and short irradiation time. In addition, the performance of the invented radical photopolymerization dark cure initiation system, in which the key component is an initiator aid, for initiating dark polymerization cure has never been discovered and recognized.
Preferably, the photosensitizer is one of camphorquinone, riboflavin, eosin Y, erythrosine B, Bengal red or dyes used as the photosensitizer, wherein the effect of the camphorquinone is optimal, and the dark polymerization initiation system consisting of the camphorquinone and the water-soluble polypeptide containing tyrosine residues can enable the photopolymerization conversion rate to reach more than 90%.
Preferably, the photosensitizer comprises the following components: tetraiodofluorescein disodium, camphorquinone and riboflavin. Preferably, the coinitiator component is a water-soluble polypeptide containing a tyrosine residue.
Preferably, the water-soluble polypeptide is selected from the group consisting of: TT (dimeric tyrosine), TTT (trimeric tyrosine), TTTT (tetrameric tyrosine), TTTTT (pentameric tyrosine), TGGG (tyrosine-glycine), GTGG (glycine-tyrosine-glycine), GGTG (glycine-tyrosine-glycine), GGGT (glycine-tyrosine), or water-soluble silk peptide and sericin peptide.
Preferably, the system comprises the following components in weight percent: 0.05 to 0.08 percent of photosensitizer and 0.25 to 0.5 percent of auxiliary initiator.
The method for initiating free radical photopolymerization by adopting the free radical photopolymerization dark curing initiation system comprises the steps of adding the free radical photopolymerization dark curing initiation system into a photopolymerization system to prepare dark curing reaction liquid, wherein the adding amount of the dark curing initiation system is 0.5-2% of the total mass of the photopolymerization system, placing the dark curing reaction liquid into a closed container, filling nitrogen for removing oxygen, and then placing the sealed container into a closed container<30mW/cm 2 Irradiating for 2-5 +/-1 min under the light intensity, and finally standing for more than 2 hours in a dark place to obtain the target polymer.
Preferably, the photopolymerizable system comprises: the polymer is prepared from a polymerized monomer containing unsaturated double bonds, a biocompatible functional polymer prepared by introducing ethylene groups into a natural polymer, an unsaturated functional monomer prepared by introducing ethylene groups into an oligomer and a functional substance.
Preferably, the unsaturated double bond-containing polymerized monomer is selected from: acrylamide, acrylic acid, methylenebisacrylamide, N-isopropylacrylamide, N-diethylacrylamide, N-vinylpyrrolidone, ethylene glycol methacrylate; the biocompatible hydrogel polymer prepared by introducing vinyl groups into natural polymers is selected from: a glucose-modified acrylate precursor, a chitosan-modified acrylate precursor and a sodium alginate-modified acrylate precursor; the unsaturated functional precursor prepared by introducing an ethylene group into an oligomer is selected from the group consisting of: poly (N-isopropyl acrylamide), polyethylene glycol diacrylate, polyethylene glycol fumarate, functional substances selected from: polylactic acid, chitosan, polyethylene glycol, cellulose, carbon nano tubes, graphene and nano particles. The above components can be arbitrarily selected according to different purposes of use, and can be selected conventionally according to the technique in the field.
In the preparation method of the free radical photopolymerization dark curing initiation system, the key component co-initiator is water-soluble polypeptide containing tyrosine residue and having antioxidant activity, and the performance of initiating the free radical photopolymerization dark curing is not known. The water-soluble polypeptide desirably contains a tyrosine residue.
Compared with the photo-polymerization dark curing initiation system introduced in the foregoing description, the free radical photo-polymerization dark curing initiation system of the invention has the following advantages: the system is simple in composition, only adopts a two-component system, does not contain transition metal elements, has good biocompatibility, can be used in the fields of medical treatment and health and the like, has easily obtained raw materials, good stability, short irradiation time, high polymerization conversion rate, less polymerization heat release, low polymerization system temperature and no harmful substances such as strong basicity and strong oxidizing property and the like in the polymerization process, is not easy to oxidize and decompose after being stored for a long time, and has low required irradiation light intensity and short irradiation time.
The free radical photopolymerization dark curing initiation system can carry out photoinitiation curing on various water-soluble monomers containing unsaturated double bonds, and has wide application range, so that the water-soluble monomers with different properties can be flexibly selected for polymerization or copolymerization aiming at different use purposes.
The addition amount of the co-initiator in the free radical photopolymerization dark curing initiation system can be adjusted at will due to good biocompatibility and water solubility.
The free radical photopolymerization dark curing initiation system has antioxidant activity and can effectively remove free radicals and active oxygen in the system. Hydrogels cured photoinitiated with this system are therefore particularly suitable for use as medical wound dressings.
The invention has the beneficial effects that: the free radical photopolymerization dark curing initiation system can ensure that the polymerization conversion rate reaches more than 80 percent, has short required irradiation time and low irradiation light intensity, greatly improves the utilization rate of light energy, and can effectively overcome the problem of light shielding caused by component absorption, reflection and scattering in thick film curing or systems with fillers. In addition, the free radical photopolymerization dark curing initiation system has the characteristics of good water solubility, biocompatibility and the like.
Drawings
FIG. 1 is a bar graph of dark polymerization conversion for examples 1-3.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that various modifications and/or alterations may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.5 percent of Camphorquinone (CQ),
a second component: dimeric tyrosine (TT) 0.5%,
and (3) preparing a dark curing initiation system according to the proportion, and adding the dark curing initiation system into an aqueous solution containing 30% of acrylamide and fully mixing the mixture to obtain a transparent and clear dark curing reaction solution, wherein the weight of the dark curing reaction solution is 100%. Namely, the dark curing reaction liquid had the following composition: camphorquinone 0.5%, dimeric tyrosine 0.5%, and 30% acrylamide in water solution 99%.
Photopolymerization: placing the prepared dark curing reaction solution in a sealed transparent glass test tube, filling nitrogen to remove oxygen for 10 minutes, placing the test tube under a 150W metal halide lamp for irradiation for 2 minutes, wherein the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to separate out a precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
Example 2
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.5% of Riboflavin (RF),
a second component: dimeric tyrosine (TT) 0.5%,
preparing a dark curing initiation system according to the proportion, and taking the weight of the dark curing reaction liquid as 100 percent. And adding the dark curing initiation system into an aqueous solution containing 30% of acrylamide, and fully mixing to obtain a transparent and clear dark curing reaction solution. Namely, the dark curing reaction solution had the following composition: riboflavin 0.5%, dimeric tyrosine 0.5%, and acrylamide 30% in water 99%.
Photopolymerization: the prepared dark curing reaction liquid is placed in a sealed transparent glass test tube, nitrogen is filled for deoxygenation for 10 minutes, the sealed transparent glass test tube is placed under a 150W metal halogen lamp for irradiation for 5 minutes, and the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
Example 3
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.01 percent of tetraiodofluorescein disodium (EB),
a second component: dimeric tyrosine (TT) 0.5%,
preparing a dark curing initiation system according to the proportion, and taking the weight of the dark curing reaction liquid as 100 percent. And adding the dark curing initiation system into an aqueous solution containing 30% of acrylamide, and fully mixing to obtain a transparent and clear dark curing reaction solution. Namely, the dark curing reaction liquid had the following composition: 0.01% of tetraiodofluorescein disodium, 0.5% of dimeric tyrosine and 99% of an aqueous solution containing 30% of acrylamide.
Photopolymerization: the prepared dark curing reaction solution is placed in a sealed transparent glass test tube, nitrogen is filled for deoxygenation for 10 minutes, the sealed transparent glass test tube is placed under a 150W metal halogen lamp for irradiation for 5 minutes, and the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
Example 4
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.01 percent of tetraiodofluorescein disodium (EB),
a second component: dimeric tyrosine (TT) 0.5%, based on 100% by weight of the dark curing reaction solution.
And adding a dark curing initiation system into a photopolymerization system to prepare dark curing reaction liquid, wherein the photopolymerization system consists of 30% acrylamide aqueous solution, sodium acrylate and acrylic acid, and mixing to obtain transparent and clear dark curing reaction liquid. The dark curing reaction liquid comprises the following components: 0.0002g of tetraiodofluorescein disodium, 0.01g of dimeric tyrosine, 1mL of a 30% acrylamide aqueous solution, 0.3g of sodium acrylate and 0.5g of acrylic acid.
Photopolymerization: placing the prepared dark curing reaction solution in a sealed transparent glass test tube, filling nitrogen to remove oxygen for 10 minutes, placing the test tube under a 150W metal halide lamp for irradiation for 5 minutes, wherein the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to separate out a precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
Example 5
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.5 percent of Camphorquinone (CQ),
a second component: 0.5 percent of trimeric tyrosine (TTT),
preparing a dark curing initiation system according to the proportion, and taking the weight of the dark curing reaction liquid as 100 percent. And adding the dark curing initiation system into an aqueous solution containing 30% of acrylamide, and fully mixing to obtain a transparent and clear dark curing reaction solution. Namely, the dark curing reaction solution had the following composition: camphorquinone 0.5%, trityrosine 0.5%, and 30% acrylamide in water solution 99%.
Photopolymerization: the prepared dark curing reaction solution is placed in a sealed transparent glass test tube, nitrogen is filled for deoxygenation for 10 minutes, the sealed transparent glass test tube is placed under a 150W metal halogen lamp for irradiation for 2 minutes, and the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to separate out a precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
Example 6
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.5 percent of Camphorquinone (CQ),
a second component: 0.5 percent of tetrapolytyrosine (TTTT),
preparing a dark curing initiation system according to the proportion, and taking the weight of the dark curing reaction liquid as 100 percent. And adding the dark curing initiation system into an aqueous solution containing 30% of acrylamide, and fully mixing to obtain a transparent and clear dark curing reaction solution. Namely, the dark curing reaction liquid had the following composition: camphorquinone 0.5%, tetrapolytyrosine 0.5%, and 30% acrylamide in water solution 99%.
Photopolymerization: the prepared dark curing reaction liquid is placed in a sealed transparent glass test tube, nitrogen is filled for deoxygenation for 10 minutes, the sealed transparent glass test tube is placed under a 150W metal halogen lamp for irradiation for 2 minutes, and the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
Example 7
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.5 percent of Camphorquinone (CQ),
a second component: 0.5 percent of TGGG,
preparing a dark curing initiation system according to the proportion, and taking the weight of the dark curing reaction liquid as 100 percent. And adding the dark curing initiation system into an aqueous solution containing 30% of acrylamide, and fully mixing to obtain a transparent and clear dark curing reaction solution. Namely, the dark curing reaction liquid had the following composition: camphorquinone 0.5%, TGGG 0.5%, and 30% acrylamide in water 99%.
Photopolymerization: the prepared dark curing reaction liquid is placed in a sealed transparent glass test tube, nitrogen is filled for deoxygenation for 10 minutes, the sealed transparent glass test tube is placed under a 150W metal halogen lamp for irradiation for 2 minutes, and the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
Example 8
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.5 percent of Camphorquinone (CQ),
a second component: 0.5 percent of GTGG,
preparing a dark curing initiation system according to the proportion, and taking the weight of the dark curing reaction liquid as 100 percent. And adding the dark curing initiation system into an aqueous solution containing 30% of acrylamide, and fully mixing to obtain a transparent and clear dark curing reaction solution. Namely, the dark curing reaction liquid had the following composition: camphorquinone 0.5%, GTGG 0.5%, and 30% acrylamide in water solution 99%.
Photopolymerization: the prepared dark curing reaction liquid is placed in a sealed transparent glass test tube, nitrogen is filled for deoxygenation for 10 minutes, the sealed transparent glass test tube is placed under a 150W metal halogen lamp for irradiation for 2 minutes, and the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
Example 9
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.5 percent of Camphorquinone (CQ),
a second component: 0.5 percent of GGTG,
preparing a dark curing initiation system according to the proportion, and taking the weight of the dark curing reaction liquid as 100 percent. And adding the dark curing initiation system into an aqueous solution containing 30% of acrylamide, and fully mixing to obtain a transparent and clear dark curing reaction solution. Namely, the dark curing reaction liquid had the following composition: camphorquinone 0.5%, GGTG 0.5%, and acrylamide 30% in water solution 99%.
Photopolymerization: the prepared dark curing reaction liquid is placed in a sealed transparent glass test tube, nitrogen is filled for deoxygenation for 10 minutes, the sealed transparent glass test tube is placed under a 150W metal halogen lamp for irradiation for 2 minutes, and the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
Example 10
A free radical photopolymerization dark curing initiation system comprises the following components:
a first component: 0.5 percent of Camphorquinone (CQ),
a second component: 0.5 percent of GGGT (gas-liquid GT),
preparing a dark curing initiation system according to the proportion, and taking the weight of the dark curing reaction liquid as 100 percent. And adding the dark curing initiation system into an aqueous solution containing 30% of acrylamide, and fully mixing to obtain a transparent and clear dark curing reaction solution. Namely, the dark curing reaction liquid had the following composition: camphorquinone 0.5%, GGGT 0.5%, and 30% acrylamide in water 99%.
Photopolymerization: the prepared dark curing reaction liquid is placed in a sealed transparent glass test tube, nitrogen is filled for deoxygenation for 10 minutes, the sealed transparent glass test tube is placed under a 150W metal halogen lamp for irradiation for 2 minutes, and the light intensity is about 20mW/cm 2 . And then standing for 2 hours in a dark place, opening a plug, adding methanol to precipitate, centrifugally collecting the precipitate, drying, weighing, calculating the polymerization conversion rate, and evaluating the photoinitiation efficiency.
The photopolymerizing dark curing conversion ratios of the above examples 4-10 are shown in Table 1.
TABLE 1 dark polymerization conversion for examples 4-10
a represents the conversion rate measured by directly adding methanol without standing after light irradiation; b represents the conversion rate measured after standing in the dark for 2 hours after light irradiation; c represents that the polymer system is: 1mL of 30% aqueous acrylamide solution, 0.3g of sodium acrylate, and 0.5g of acrylic acid.
As can be seen from Table 1, the polymerization conversion rate after light irradiation in examples 4-10 without standing in the dark is much lower than that after standing for 2 hours, indicating that the initiation system has a characteristic of initiating curing by dark polymerization. In examples 5, 9 and 10, the polymerization conversion rate almost reached 100%, indicating that the initiation systems CQ/TTT, CQ/GGTG and CQ/GGGT are excellent in initiating the dark polymerization curing property, and few initiation systems have been able to achieve so far. In addition, the initiation system EB/TT in the example 4 can initiate the copolymerization of water-soluble polymerization monomers including acrylamide, sodium acrylate, acrylic acid and the like, and the dark polymerization curing initiation system has a wide application range.
The photopolymerization conversion rates of the above examples 1 to 3 are shown in FIG. 1, and FIG. 1 shows the conversion rates of dark polymerization curing initiated by three initiation systems each composed of dimeric tyrosine (TT) and three different photosensitizers. The initiator system composed of Camphorquinone (CQ) and dimeric tyrosine has the most excellent performance, and the conversion rate of the initiated dark polymerization almost reaches 100 percent, so that the initiator system is a dark polymerization curing initiator system with potential application value.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by the person skilled in the art from the present disclosure are to be considered within the scope of the present invention.
Claims (5)
1. The application of the free radical photopolymerization dark curing reaction liquid in the aspect of free radical photopolymerization dark curing is characterized in that:
the free radical photopolymerization dark curing reaction liquid is prepared by adding a dark curing initiation system into a photopolymerization system, wherein the addition amount of the dark curing initiation system is 0.5-2% of the total mass of the photopolymerization system, and the total weight of the free radical photopolymerization dark curing reaction liquid is 100%,
the dark curing initiation system consists of the following components in percentage by weight:
a first component: 0.01-1% of photosensitizer;
a second component: 0.5-1% of co-initiator, wherein the co-initiator is water-soluble polypeptide with antioxidant activity and containing tyrosine residue;
the photosensitizer is one of camphorquinone, riboflavin, eosin Y, erythrosine B, Bengal red or a dye used as the photosensitizer; the water-soluble polypeptide is selected from: one or more of dimeric tyrosine, trimeric tyrosine, tetrameric tyrosine, pentameric tyrosine, tyrosine-glycine, glycine-tyrosine-glycine, glycine-tyrosine-glycine, glycine-tyrosine, or water-soluble silk peptide and sericin peptide;
the photopolymerization system is an aqueous solution containing 30% by mass of acrylamide.
2. Use according to claim 1, characterized in that the dark cure initiation system consists of the following components in weight percent: 0.5% of photosensitizer and 0.5% of auxiliary initiator.
3. Use according to claim 1, characterized in that: the application is the method for initiating the free radical photopolymerization by the free radical photopolymerization dark curing reaction solution, which comprises the steps of placing the free radical photopolymerization dark curing reaction solution in a closed container, filling nitrogen for removing oxygen, and then placing the closed container in a closed container<30 mW/cm 2 Irradiating for 2-5 minutes under the light intensity, and finally standing for more than 2 hours in a dark place to obtain the target polymer.
4. Use according to claim 3, characterized in that: the irradiation conditions were: irradiating for 2 minutes under a 150W metal halide lamp with the light intensity of 20mW/cm 2 。
5. The application of the free radical photopolymerization dark curing reaction liquid in the aspect of free radical photopolymerization dark curing is characterized in that the application is as follows:
the free radical photopolymerization dark curing reaction liquid comprises the following components: 0.0002g of tetraiodofluorescein disodium, 0.01g of dimeric tyrosine, 1mL of a 30% acrylamide aqueous solution, 0.3g of sodium acrylate and 0.5g of acrylic acid;
photopolymerization: placing the prepared dark curing reaction solution in a sealed transparent glass test tube, filling nitrogen to remove oxygen for 10 minutes, placing the test tube under a 150W metal halide lamp for irradiation for 5 minutes, wherein the light intensity is 20mW/cm 2 And then left to stand in the dark for 2 hours.
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