CN109879988A - A kind of radical photopolymerization dark curing initiation system and preparation method thereof - Google Patents
A kind of radical photopolymerization dark curing initiation system and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of photocurings to cause system, in particular to a kind of radical photopolymerization dark curing initiation system and preparation method thereof belongs to free radical polymerization preparation technical field.It includes following component by weight percentage: the first component: photosensitizer, 0.01-1% that the dark curing, which causes system,；Second component: aided initiating, 0.5-1%, the aided initiating are the water-soluble polypeptide with antioxidant activity comprising tyrosine residue.Radical photopolymerization dark curing of the invention causes system compared with the dark curing light initiation system reported before, have the advantage that component be simply only two Component Systems, without transition metal element good biocompatibility can be used for the fields such as health care, raw material is easy to get, the good long-term storage of stability is not easy that oxygenolysis, the low irradiation time of required irradiation light intensity are short, initiation polymerisation conversion height, polymerization exotherm is few, polymerization system temperature is low, polymerization process does not generate the harmful substances such as strong basicity and strong oxidizing property.
Description
Technical field
The present invention relates to a kind of photopolymerization curing initiation system, in particular to a kind of radical photopolymerization dark curing primosome
System and preparation method thereof, belongs to radical photopolymerization preparation technical field.
Background technique
Currently, photocuring technology is used widely in the skin layers such as coating, adhesive, varnish solidification field, because
Light can penetrate wherein, therefore keep photopolymerization curing process quick and abundant, and the range of the general cured thickness is often at several microns
To between 50 microns.But in the light-cured resin that thick film solidifies or be added to filler (especially pigment), because solidifying component
The effects of to the absorption of light, scattering, reflection, causes light intensity to decay with light path serious, influences curing depth and curing efficiency, seriously
When even cannot solidify.This photocuring system is that photocuring technology is different from classical heat cure and oxidation to the shielding action of light
The critical defect of reduction curing.
How to overcome this defect is photocuring technology facing challenges.Compared to traditional heat curing techniques, photocuring skill
Art has following advantage: 1. ambient temperature curable；2. Diamond Search discharges；3. the controllability with polymerization time and polymerization space；4. light is solid
It is simple, cheap etc. to change equipment.Therefore, if above-mentioned technology disadvantage can be overcome, there is more wide application prospect.
People start with from each factor for influencing photopolymerization efficiency, to overcoming the problems, such as that optical attenuation done many trials.Wherein wrap
It includes: improving light intensity, introduce additive, adjustment polymerization component, be, using infrared photosensitizer, use using the light float of photosensitizer
One-component or multicomponent photoinitiator etc., though there is certain improvement, be very difficult to avoid completely and have application limitation.
It is then to design a kind of dark curing that can continue to cause polymerization after light source that leaves to draw that another kind, which overcomes the thinking of optical attenuation,
Agent is sent out, i.e., after illumination, polymerization does not stop immediately, and continuation carries out after being detached from light source.This dark curing behavior can be
Largely overcome the problems, such as thick film solidify or the resin solidification comprising filler in illumination it is insufficient.The synthesis such as He Minghui
Light produces alkaline free radical polymerization photoinitiator, it and peroxide form light initiation system, the former releases strong when light irradiates
Basic amine, highly basic amine are then spread in polymerization system, react in diffusion with peroxide, classical oxidation occurs also
Original polymerization.It in the system, only needs locally to irradiate through light, polymerization is just spread from illumination center to surrounding, is continued at the place of being protected from light
Occur.Distance even up to 7cm, the discovery of this dark curing light initiation system for polymerizeing sprawling realize light polymerization technique
Application in the resin system polymerization comprising filler carbon black.Cause in photopolymerization in addition, this primosome ties up to, with alkali
Generating generation rapid polymerization makes system local temperature rise sharply, and up to 167-210 DEG C, which can be such that peroxide therein decomposes
Living radical is generated, autoacceleration dark curing effect is further generated.The high temperature that the polymerization generates can also cause the polymerization of sulphur-alkene and
Anionic polymerisation makes its application field further expansion.But this dark curing system has following defect: being 1. only capable of utilizing nocuousness
Low penetration ultraviolet source；2. there are storage stabilities for the peroxide for including in system；3. in the initiation system
Generated base alkaline agent is only capable of being dissolved in organic solvent, will generate VOC emission；4. a large amount of heat is released in polymerization, usually make system local temperature can
Up to 150 DEG C or more, there are heat dissipation problems.The above dark curing behavior relies primarily on the effect of Photobase generator, generated
Alkali is that highly basic easily causes unwanted side reaction.
Aguirre-Soto etc. reports another kind of dark curing light initiation system, includes three kinds of components: methylene blue, two different
Propyl amine and diphenyl iodnium, after light irradiates, methylene blue absorbs luminous energy and transits to excitation state the system, and light occurs with amine
Chemical reaction generates methylene blue leuco compound, and the latter is spread in resin occurs redox reaction with salt, generates reactive species
Cause free radical polymerization, makes light shield part dark curing, resin solidification depth can be made to reach 1.2cm.It is particularly noteworthy that
This dark curing process, because generated initiation intermediate diffusion velocity is slow, therefore polymerization speed is slow, the heat of polymerization generated therebetween
It is few, so, which can't cause autoacceleration dark curing behavior because of heat production.Moreover, the dark curing that this system causes
Required light intensity is only in 3-30mW/cm2Range.But there are two defects for this system: 1. dark curing rate is slow, and curing time even can
Up to 30min；2. to be needed in practical applications convenient for the diffusion of system photochemical reaction intermediate frequently with low viscosity monomer
It is blended with crosslinking agent.
Garra etc. reports the dark curing reaction mediated with the peroxylradicals that free radical oxygen inhibition generates, the system
It is made of monovalent copper, salt compounded of iodine and stannous 2-ethylhexoate with either high redox catalytic activity.In radiation area, excitation state
Monovalent copper and salt compounded of iodine react, and generate first initiation reactive species, cause conventional free radical polymerization.Because it is low to irradiate light intensity
(LED light 405nm light source only 4mW/cm2), free radical formation speed is slow, the macromolecular chain segment of growth easily be dissolved in low viscosity tree
Oxygen in rouge reacts, and generates peroxy radical ROO, continues thereafter with generation and causes inert ROOH, this is generated in situ
Inertia intermediate then diffuse to light shield area and monovalent copper redox reaction occur, generate the reactive species for causing polymerization
RO, monovalent copper are then oxidized to diformazan copper, are then lived again by Bivalent Tin reduction, participate in next circulation.Caused by the system
Dark polymerizing curable range up to 2.9cm.Main problem existing for this system is: the system is excessively high containing transition metal active
(under sunlight 90s can completion of cure) system is unstable, and application conditions are harsh；Cu-contained catalyst is not commercialized also at present.
A kind of rich promising dark curing, which causes system, then can be used to cause controllable radical photopolymerization, Boyer project
Group designs a kind of light initiation system recently, can cause controllable free radical polymerization dark curing, which is contaminated by photosensitizer xanthene
Material and vitamin C composition.Explanation to its dark polymerizing curable mechanism is: under light irradiation, the photosensitizer of excitation state is by molten in system
The molecule oxygen quenching of solution generates singlet oxygen, which generates H under the action of reducing agent vitamin C2O2.Work as light source
After removing, H2O2It generates reactive species initiation with the ascorbic acid effect in system again to polymerize, H2O2It is potentially to cause in system
Reactive intermediate.By mechanism of polymerization it is found that light irradiation step of the photopolymerization dark reaction in early period need to carry out under air conditions,
The oxygen inhibition effect of previous free radical polymerization is become into the necessary condition that polymerization occurs.But the system is during causing polymerization
The reactive intermediate H of generation2O2For strong oxidizing property, easily makes to be embedded in cell therein and other reactive intermediates are impaired, answer it
It is limited with range.
The dark polymerizing curable of another kind of classics is then the polymerization caused by cation.Known by discussed above, free radical polymerization
Dark curing needs to design special light initiation system to realize, and itself is a well-known dark curings for cationic polymerization
Process.This is because causing the reactive species H of polymerization+Service life, long diffusion was slow, so it needs a relatively high temperature promotion poly-
It closes.
The some research achievements obtained in dark polymerizing curable field in recent years are described above, it can be found that free radical polymerization
The key of dark curing is to design special light initiation system.Its mentality of designing is based primarily upon two o'clock: 1. dark curing process needs
Light-initiated to generate a kind of reactive intermediate, which starts subsequent redox reaction, generates new reactive species and draws
Shade polymerizing curable；2. light irradiation, which generates reactive species, quickly causes free radical polymerization, localized heat release temperature is increased, and makes heat therein
Polymerization initiator, which decomposes, generates second of living radical, causes dark polymerizing curable, which is also referred to as Frontal polymerization.It is based on
The free radical polymerization dark curing light initiation system of both thinkings design, during causing polymerization or part generation is big
The heat or generation strong oxidizing property and strong basicity intermediate, these effects of amount can cause active component to be damaged, limit it
Application range.The present invention designs a kind of free radical polymerization dark curing light initiation system, and the advantage of the system is: the system water
Dissolubility is good, and can cause the dark polymerizing curable of hydrogel, component is simply only two Component Systems, without transition metal element biofacies
Capacitive can be used for well the fields such as health care, raw material is easy to get, the good long-term storage of stability is not easy oxygenolysis, required irradiation light intensity
Low irradiation time is short, the high, polymerization exotherm that causes polymerisation conversion makes that polymerization system temperature is low, polymerization process does not generate highly basic less
The harmful substances such as property and strong oxidizing property.In addition, this radical photopolymerization dark curing invented causes system, key therein
Component aided initiating causes the performance of dark polymerizing curable never by it is found that and understanding.
Summary of the invention
The present invention provides a kind of radical photopolymerization dark curing and causes system, primosome system favorable solubility in water,
Biocompatibility is excellent, and initiation polymerization exotherm is few, required light intensity < 30mW/cm2, light application time is short, effective gram of the initiation system
The low problem of light utilization efficiency in polymerizable resin system has been taken, can be used for preparing Multipurpose water gel.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of radical photopolymerization dark curing initiation system, the dark curing cause system and are made for Photopolymer System to be added
Dark curing reaction solution.It is in terms of 100% by dark curing reaction solution total weight, it includes below with weight percent which, which causes system,
Than the component of meter:
First component: photosensitizer, 0.01-1%；
Second component: aided initiating, 0.5-1%, the aided initiating are that having comprising tyrosine residue is anti-oxidant
Active water solubility polypeptide.
After light initiation system of the invention is subjected to 400-700nm visible light exposure 2-5 minutes, it is detached from the sustainable generation of light source
Free radical activity kind causes dark polymerizing curable, and final light polymerisation conversion is up to 80% or more.
Radical photopolymerization dark curing of the invention causes system compared with the dark curing light initiation system reported before,
To have the advantage that component simply be only two Component Systems, can be used for medical treatment without transition metal element good biocompatibility and defends
The fields such as raw, raw material are easy to get, the good long-term storage of stability is not easy that oxygenolysis, the low irradiation time of required irradiation light intensity be short, initiation
It is harmful that polymerisation conversion is high, polymerization exotherm is few, polymerization system temperature is low, polymerization process does not generate strong basicity and strong oxidizing property etc.
Substance.In addition, this radical photopolymerization dark curing invented causes system, key component aided initiating therein causes
The performance of dark polymerizing curable is never by it is found that and understanding.
Preferably, the photosensitizer is camphorquinone, riboflavin, Eosin Y, Erythrosin B, rose-bengal or as photosensitive
One of the dyestuff that agent uses, wherein the effect of camphorquinone is best, with the water-soluble polypeptide composition containing tyrosine residue
Dark polymerization initiation system can make photopolymerization conversion ratio reach 90% or more.
Preferably, the photosensitizer component are as follows: tetraiodofluorescein disodium, camphorquinone, riboflavin.Preferably, institute
The aided initiating group stated is divided into the water-soluble polypeptide containing tyrosine residue.
Preferably, the water-soluble polypeptide is selected from: TT (dityrosine), TTT (three polytyrosines), TTTT (four
Polytyrosine), TTTTT (five polytyrosines), TGGG (tyrosine-Gly-Gly-Gly), GTGG (glycine-junket
Propylhomoserin-Gly-Gly), GGTG (Gly-Gly-tyrosine-glycine), GGGT (the sweet ammonia of Gly-Gly-
Acid-tyrosine) one or more of or water-soluble fibroin peptide, sericin peptide taken.
Preferably, the system includes following component by weight percentage: photosensitizer 0.05-0.08%, helping initiation
Agent 0.25-0.5%.
A method of system is caused using the radical photopolymerization dark curing and causes radical photopolymerization, this method
It is that the radical photopolymerization dark curing is caused system to be added in Photopolymer System so that dark curing reaction solution, dark curing is made
The additional amount of initiation system is the 0.5-2% of Photopolymer System gross mass, and dark curing reaction solution is placed in nitrogen charging in closed container
Deoxygenation is subsequently placed at < 30mW/cm2Light intensity under irradiate 2-5 ± 1 minute, finally stand 2 hours or more in dark place, obtain target
Polymer.
Preferably, the Photopolymer System includes: polymerized monomer containing unsaturated double-bond, vinyl group is introduced day
The biocompatibility functional polymer so prepared in macromolecule, the functional list of unsaturation for preparing vinyl group introducing oligomer
Body and functional materials.
Preferably, the polymerized monomer containing unsaturated double-bond is selected from: acrylamide, acrylic acid, two propylene of methylene
Amide, n-isopropyl acrylamide, N, N- acrylamide, N- vinylpyrrolidone, methacrylic acid glycol ester；It will
Vinyl group is introduced into the biocompatible hydrogel macromolecule prepared in natural polymer and is selected from: glucose modified acrylate
Presoma, chitin modified acrylate presoma, sodium alginate-modified acrylate presoma；Vinyl group is introduced
The functional presoma of the unsaturation of oligomer preparation is selected from: poly(N-isopropylacrylamide), is gathered polyethyleneglycol diacrylate
Ethylene glycol fumarate, functional materials are selected from: polylactic acid, chitosan, polyethylene glycol, cellulose, carbon nanotube, graphene,
Nanoparticle.The above component can arbitrarily be selected according to different using purpose, can also carry out conventional selection according to art technology.
Radical photopolymerization dark curing of the present invention causes the preparation method of system, and key component aided initiating is to include junket
The water-soluble polypeptide with antioxidant activity of histidine residue causes the performance of radical photopolymerization dark curing never by people
Recognized.It is needed in the water solubility polypeptide comprising tyrosine residue.
Radical photopolymerization dark curing of the invention causes system and the photopolymerization dark curing of foregoing description causes system phase
Than having the advantages that simple only two components systems of system composition, can be used for without transition metal element good biocompatibility
The fields such as health care, raw material are easy to get, the good long-term storage of stability is not easy oxygenolysis, the low irradiation time of required irradiation light intensity
It is short, cause that polymerisation conversion is high, polymerization exotherm is few, polymerization system temperature is low, polymerization process does not generate strong basicity and Strong oxdiative
The harmful substances such as property.
Radical photopolymerization dark curing of the invention causes system to the various water-soluble monomers containing unsaturated double-bond
Light-initiated solidification, it is widely applicable, therefore use purpose for different, can the water-soluble monomer of flexible choice different performance gathered
It closes or is copolymerized.
Aided initiating in radical photopolymerization dark curing initiation system of the invention because of its good biocompatibility and
Water solubility, additional amount can be adjusted arbitrarily.
Radical photopolymerization dark curing of the invention causes system because aided initiating has antioxidant activity, can effectively remove
Free radical and active oxygen in system.So with the light-initiated cured hydrogel of this system be especially suitable for medical wound
Dressing.
The beneficial effects of the present invention are: radical photopolymerization dark curing of the invention causes system, polymerisation conversion can be made
Reach 80% or more, and required irradiation time is short, irradiation light intensity is low, substantially increases the utilization rate of luminous energy, can effectively overcome
Thick film solidifies or in having system existing for filler, caused by absorbing, reflect and scatter because of component the problem of light shield.This
Outside, radical photopolymerization dark curing of the invention, which causes system, has many characteristics, such as good water-soluble, biocompatibility.
Detailed description of the invention
Fig. 1 is the dark polymerisation conversion histogram of embodiment 1-3.
Specific embodiment
Below by specific embodiment, technical solution of the present invention is described further.It should be understood that reality of the invention
It applies and is not limited by the following examples, the accommodation in any form and/or change made to the present invention fall within this hair
Bright protection scope.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field
Rule method.
Embodiment 1
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: camphorquinone (CQ) 0.5%,
Second component: dityrosine (TT) 0.5%,
Dark curing is prepared according to above-mentioned proportion and causes system, is in terms of 100%, by dark curing by dark curing reaction solution weight
Initiation system is added in the aqueous solution containing 30% acrylamide and is sufficiently mixed, and obtains transparent clear dark curing reaction solution.That is, dark
Curing reaction liquid composition are as follows: camphorquinone 0.5%, dityrosine 0.5%, the aqueous solution 99% containing 30% acrylamide.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 2 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and add
Enter methanol and precipitating is precipitated, precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
Embodiment 2
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: riboflavin (RF) 0.5%,
Second component: dityrosine (TT) 0.5%,
Dark curing is prepared according to above-mentioned proportion and causes system, is in terms of 100% by dark curing reaction solution weight.By dark curing
Initiation system is added in the aqueous solution containing 30% acrylamide and is sufficiently mixed, and obtains transparent clear dark curing reaction solution.That is, dark
Curing reaction liquid composition are as follows: riboflavin 0.5%, dityrosine 0.5%, the aqueous solution 99% containing 30% acrylamide.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 5 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and be added
Precipitating is precipitated in methanol, and precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
Embodiment 3
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: tetraiodofluorescein disodium (EB) 0.01%,
Second component: dityrosine (TT) 0.5%,
Dark curing is prepared according to above-mentioned proportion and causes system, is in terms of 100% by dark curing reaction solution weight.By dark curing
Initiation system is added in the aqueous solution containing 30% acrylamide and is sufficiently mixed, and obtains transparent clear dark curing reaction solution.That is, dark
Curing reaction liquid composition are as follows: tetraiodofluorescein disodium 0.01%, dityrosine 0.5%, the aqueous solution containing 30% acrylamide
99%.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 5 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and be added
Precipitating is precipitated in methanol, and precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
Embodiment 4
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: tetraiodofluorescein disodium (EB) 0.01%,
Second component: dityrosine (TT) 0.5% is in terms of 100% by dark curing reaction solution weight.
Dark curing is caused into system addition Photopolymer System, dark curing reaction solution is made, the Photopolymer System is by 30% propylene
Aqueous solution, sodium acrylate and the acrylic acid composition of amide, obtain transparent clear dark curing reaction solution after mixing.Dark curing reaction
Liquid composition are as follows: the aqueous solution of 30% acrylamide of tetraiodofluorescein disodium 0.0002g, dityrosine 0.01g, 1mL, 0.3g
Sodium acrylate and 0.5g acrylic acid.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 5 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and add
Enter methanol and precipitating is precipitated, precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
Embodiment 5
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: camphorquinone (CQ) 0.5%,
Second component: three polytyrosines (TTT) 0.5%,
Dark curing is prepared according to above-mentioned proportion and causes system, is in terms of 100% by dark curing reaction solution weight.By dark curing
Initiation system is added in the aqueous solution containing 30% acrylamide and is sufficiently mixed, and obtains transparent clear dark curing reaction solution.That is, dark
Curing reaction liquid composition are as follows: camphorquinone 0.5%, three polytyrosines 0.5%, the aqueous solution 99% containing 30% acrylamide.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 2 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and be added
Precipitating is precipitated in methanol, and precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
Embodiment 6
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: camphorquinone (CQ) 0.5%,
Second component: four polytyrosines (TTTT) 0.5%,
Dark curing is prepared according to above-mentioned proportion and causes system, is in terms of 100% by dark curing reaction solution weight.By dark curing
Initiation system is added in the aqueous solution containing 30% acrylamide and is sufficiently mixed, and obtains transparent clear dark curing reaction solution.That is, dark
Curing reaction liquid composition are as follows: camphorquinone 0.5%, four polytyrosines 0.5%, the aqueous solution 99% containing 30% acrylamide.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 2 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and be added
Precipitating is precipitated in methanol, and precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
Embodiment 7
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: camphorquinone (CQ) 0.5%,
Second component: TGGG 0.5%,
Dark curing is prepared according to above-mentioned proportion and causes system, is in terms of 100% by dark curing reaction solution weight.By dark curing
Initiation system is added in the aqueous solution containing 30% acrylamide and is sufficiently mixed, and obtains transparent clear dark curing reaction solution.That is, dark
Curing reaction liquid composition are as follows: camphorquinone 0.5%, TGGG 0.5%, the aqueous solution 99% containing 30% acrylamide.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 2 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and be added
Precipitating is precipitated in methanol, and precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
Embodiment 8
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: camphorquinone (CQ) 0.5%,
Second component: GTGG 0.5%,
Dark curing is prepared according to above-mentioned proportion and causes system, is in terms of 100% by dark curing reaction solution weight.By dark curing
Initiation system is added in the aqueous solution containing 30% acrylamide and is sufficiently mixed, and obtains transparent clear dark curing reaction solution.That is, dark
Curing reaction liquid composition are as follows: camphorquinone 0.5%, GTGG 0.5%, the aqueous solution 99% containing 30% acrylamide.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 2 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and be added
Precipitating is precipitated in methanol, and precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
Embodiment 9
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: camphorquinone (CQ) 0.5%,
Second component: GGTG 0.5%,
Dark curing is prepared according to above-mentioned proportion and causes system, is in terms of 100% by dark curing reaction solution weight.By dark curing
Initiation system is added in the aqueous solution containing 30% acrylamide and is sufficiently mixed, and obtains transparent clear dark curing reaction solution.That is, dark
Curing reaction liquid composition are as follows: camphorquinone 0.5%, GGTG 0.5%, the aqueous solution 99% containing 30% acrylamide.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 2 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and be added
Precipitating is precipitated in methanol, and precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
Embodiment 10
A kind of radical photopolymerization dark curing initiation system, each component are as follows:
First component: camphorquinone (CQ) 0.5%,
Second component: GGGT 0.5%,
Dark curing is prepared according to above-mentioned proportion and causes system, is in terms of 100% by dark curing reaction solution weight.By dark curing
Initiation system is added in the aqueous solution containing 30% acrylamide and is sufficiently mixed, and obtains transparent clear dark curing reaction solution.That is, dark
Curing reaction liquid composition are as follows: camphorquinone 0.5%, GGGT 0.5%, the aqueous solution 99% containing 30% acrylamide.
Photopolymerization reaction: prepared dark curing reaction solution is placed in the transparent glass test tube of sealing, and nitrogen charging deoxygenation 10 divides
Clock is placed under 150W Metal halogen lamp and irradiates 2 minutes, light intensity about 20mW/cm2.It is subsequently placed at dark place and stands 2 hours, open plug and be added
Precipitating is precipitated in methanol, and precipitating is collected by centrifugation, weighs after dry, calculates polymerisation conversion, evaluates light-initiated efficiency.
The photopolymerization dark curing conversion ratio of above-described embodiment 4-10 is as shown in table 1.
The dark polymerisation conversion of 1 embodiment 4-10 of table
A is not stood after representing light irradiation, the conversion ratio for directly methanol being added to measure；B represents quiet through 2 hours dark places after light irradiates
Postpone the conversion ratio measured；C indicates polymerization system are as follows: aqueous solution, 0.3g sodium acrylate and the 0.5g third of 1mL30% acrylamide
Olefin(e) acid.
As shown in Table 1, after the embodiment 4-10 polymerisation conversion that non-dark place is stood after light irradiates is far below standing 2 hours
Polymerisation conversion, illustrate that the initiation system has and significantly cause the feature of dark polymerizing curable.Wherein embodiment 5,9 and 10
In, polymerisation conversion nearly reaches 100%, shows that initiation system CQ/TTT, CQ/GGTG and CQ/GGGT cause dark polymerizing curable
Performance is very excellent, and few initiation systems can reach so far.In addition, packet can be caused by causing system EB/TT in embodiment 4
Copolymerization containing the water-soluble polymerics monomer such as acrylamide, sodium acrylate and acrylic acid shows that dark polymerizing curable of the invention causes
System has wider application range.
The photopolymerization conversion ratio of above-described embodiment 1-3 as shown in FIG. 1, FIG. 1 is dityrosine (TT) respectively with three kinds not
Three kinds of same photosensitizer composition cause the conversion ratio for the dark polymerizing curable that systems cause.It can see camphorquinone (CQ) and dimerization
The initiation system performance of tyrosine composition is the most excellent, and the dark polymerisation conversion caused nearly reaches 100%, has for one kind
The dark polymerizing curable of potential using value causes system.
Finally it should be noted that the above enumerated are only specific embodiments of the present invention.It is clear that the invention is not restricted to
Above embodiments can also have many variations.Those skilled in the art can directly lead from present disclosure
Out or all deformations for associating, it is considered as protection scope of the present invention.
Claims (7)
1. a kind of radical photopolymerization dark curing causes system, which causes system and is made secretly for Photopolymer System to be added
Curing reaction liquid, it is characterised in that: by dark curing reaction solution total weight be 100% in terms of, the dark curing cause system include below with
The component of weight percent meter:
First component: photosensitizer, 0.01-1 %；
Second component: aided initiating, 0.5-1%, the aided initiating are comprising tyrosine residue with antioxidant activity
Water-soluble polypeptide.
2. radical photopolymerization dark curing according to claim 1 causes system, it is characterised in that: the photosensitizer is
One of camphorquinone, riboflavin, Eosin Y, Erythrosin B, rose-bengal or the dyestuff used as photosensitizer.
3. radical photopolymerization dark curing according to claim 1 causes system, it is characterised in that: the water solubility is more
Peptide is selected from: tri- polytyrosine of TT (dityrosine), TTT(), tetra- polytyrosine of TTTT(), five polytyrosine of TTTTT() and, TGGG
(tyrosine-Gly-Gly-Gly), GTGG(Gly-Tyr-Gly-Gly), GGTG(glycine-
One or more of Gly-Tyr-glycine), GGGT(Gly-Gly-Gly-tyrosine), either
Water-soluble fibroin peptide, sericin peptide taken.
4. radical photopolymerization dark curing according to claim 1 causes system, it is characterised in that the system includes following
Component by weight percentage: photosensitizer 0.05-0.08%, aided initiating 0.25-0.5%.
5. a kind of cause the side that system causes radical photopolymerization using radical photopolymerization dark curing described in claim 1
Method, it is characterised in that: this method is that the radical photopolymerization dark curing is caused to system to be added in Photopolymer System with system
At dark curing reaction solution, the additional amount that dark curing causes system is the 0.5-2% of Photopolymer System gross mass, and dark curing is anti-
It answers liquid to be placed in nitrogen charging deoxygenation in closed container, is subsequently placed at < 30 mW/cm2Light intensity under irradiate 2-5 ± 1 minute, finally in dark
Place's standing 2 hours or more, obtain subject polymer.
6. according to the method described in claim 5, it is characterized by: the Photopolymer System includes: containing unsaturated double-bond
Vinyl group is introduced into the biocompatibility functional polymer prepared in natural polymer, introduces vinyl group by polymerized monomer
The unsaturated functional monomer and functional materials of oligomer preparation.
7. according to the method described in claim 6, it is characterized by: the polymerized monomer containing unsaturated double-bond is selected from: propylene
Amide, acrylic acid, methylene diacrylamine, n-isopropyl acrylamide, N, N- acrylamide, N- vinyl pyrrolidine
Ketone, methacrylic acid glycol ester；Vinyl group is introduced into the biocompatible hydrogel macromolecule prepared in natural polymer
It is selected from: glucose modified acrylate presoma, chitin modified acrylate presoma, sodium alginate-modified propylene
Acid esters presoma；The functional presoma of unsaturation that vinyl group introduces oligomer preparation is selected from: poly- (N- isopropyl acrylamide
Amine), polyethyleneglycol diacrylate, polyethylene glycol fumarate, functional materials are selected from: polylactic acid, chitosan, poly- second two
Alcohol, cellulose, carbon nanotube, graphene, nanoparticle.
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| CN113181157A (en) * | 2021-05-24 | 2021-07-30 | 万华化学集团股份有限公司 | Preparation method of vitamin A acetate micro-capsule |
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