CN113880974A - Photocurable liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, and preparation method and application thereof - Google Patents
Photocurable liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, and preparation method and application thereof Download PDFInfo
- Publication number
- CN113880974A CN113880974A CN202111226698.5A CN202111226698A CN113880974A CN 113880974 A CN113880974 A CN 113880974A CN 202111226698 A CN202111226698 A CN 202111226698A CN 113880974 A CN113880974 A CN 113880974A
- Authority
- CN
- China
- Prior art keywords
- photoinitiator
- pyrrole
- liquid
- curing
- acrylate resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 51
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 20
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical group C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000000168 pyrrolyl group Chemical group 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052739 hydrogen Chemical group 0.000 claims abstract description 4
- 239000001257 hydrogen Chemical group 0.000 claims abstract description 4
- 150000002148 esters Chemical group 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 3
- -1 pyrrole compound Chemical class 0.000 claims abstract description 3
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 2
- 238000000016 photochemical curing Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 15
- 230000001678 irradiating effect Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 125000004386 diacrylate group Chemical group 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003847 radiation curing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- MREIFUWKYMNYTK-UHFFFAOYSA-N 1H-pyrrole Chemical group C=1C=CNC=1.C=1C=CNC=1 MREIFUWKYMNYTK-UHFFFAOYSA-N 0.000 claims 3
- 150000002009 diols Chemical class 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 30
- 238000000576 coating method Methods 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000010276 construction Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000001029 thermal curing Methods 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
- C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
-
- 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
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D135/02—Homopolymers or copolymers of esters
-
- 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
- C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
- C09D155/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
A light-cured liquid based on a pyrrolo-pyrrole structure photoinitiator and acrylate resin and a preparation method and application thereof belong to the technical field of light curing, wherein the structure of the photoinitiator is shown as follows, and the photoinitiator is tetraaryl substituted pyrrole [3,2-b]A pyrrole compound, R1 is a substituent on a phenyl group connected with a nitrogen atom of a pyrrole ring, R2 is a substituent on a phenyl group connected with a carbon atom of a pyrrole ring, an acrylate resin monomer is an ester containing a C ═ C unsaturated bond,
r1 is methyl, methoxy or hydrogen; r2 is nitro. The beneficial effects are that: 1. the photoinitiator has different sensitivities to different wavelengths; 2. ultraviolet light is adopted for curing, and the traditional thermal curing is not adopted; 3. the obtained curing liquid can realize irradiation curing through an environment-friendly LED ultraviolet light source, the problem that the curing liquid needs to be irradiated immediately after coating in ultraviolet curing construction is solved, the distribution operation of coating and irradiation can be realized, and the construction mode of obtaining the similar water-based coating through irradiation curing is favorably realized.
Description
Technical Field
The invention belongs to the technical field of photocuring, and particularly relates to preparation and application of a photocuring liquid based on a pyrrolopyrrole structure photoinitiator and an acrylate resin, which is used at room temperature without avoiding light.
Background
The photopolymerization technology is a low-cost green technology which can ensure that a photoinitiator in a photopolymerization system is excited by light under mild conditions to generate active species playing a role in initiating monomer polymerization and the system is rapidly changed from a liquid state to a solid state. Photopolymerization systems are generally composed of photoinitiators, oligomers, monomers and auxiliaries which are responsible for meeting the particular use requirements of the material. Photopolymerization technology has a wide range of applications, such as printing inks and different types of coatings. Recently, the scope has been further expanded by more advanced techniques such as dental curing or lithography-based ceramic fabrication.
Photoinitiators are important components of photocuring systems and can be classified into three categories: cracking type initiator, photosensitive type initiator and cationic photoinitiator. The ideal photoinitiator should be cheap and simple to synthesize; the photoinitiator and the photocracking product thereof are nontoxic and tasteless; the stability is good, and the long-time storage is convenient; higher initiation efficiency and the like. In different photocuring systems, a photoinitiator with proper activity is selected, so that the use amount is small, no pollution is caused, and the photoinitiator is cheap and easy to obtain.
In large-area construction, the light is inevitably contacted, and the light causes the light curing liquid to generate white gel, so that the construction process is influenced. The large-area light source has high cost and is difficult to manufacture, and in the future, if a method for constructing the large area of the light curing liquid by using the radiation curing coating needs to be solved, the light curing liquid which can be stable and not be degraded at room temperature without being shaded is needed. At present, the radiation curing coating is also a limiting factor that the wide development of water-based coatings in large-area coating such as building coatings and the like is not achieved. If the radiation curing liquid coating is stable and does not keep out of the sun, the problems that the aqueous coating pollutes a solvent and the UV light curing powder coating needs a heat-sensitive substrate and is heated and melted are solved.
Disclosure of Invention
The primary object of the present invention is to provide a photocurable liquid based on a pyrrolopyrrole structure photoinitiator and an acrylate resin, which is used at room temperature without avoiding light, wherein the structure of the pyrrolopyrrole structure photoinitiator is shown below, and the photoinitiator is a tetraaryl-substituted pyrrole [3,2-b ] pyrrole compound, wherein R1 is a substituent on a phenyl group connected with a nitrogen atom of a pyrrole ring, and R2 is a substituent on a phenyl group connected with a carbon atom of a pyrrole ring. The acrylate resin monomer is an ester containing a C ═ C unsaturated bond.
R1 represents a methyl group, a methoxy group, a hydrogen atom or the like; r2 is nitro.
The preparation method of the photocuring liquid mainly comprises two steps: the first preparation method is that the acrylate resin and the pyrrolo-pyrrole photoinitiator are mixed according to a certain proportion in a dark condition and are stirred uniformly. And (3) continuing stirring, irradiating by using an LED irradiation head with the irradiation wavelength of 470 nmm right above until the color of the mixture is not changed any more, and stopping stirring to obtain the photocuring liquid. The second preparation method is that trimethylolpropane triacrylate and pyrrole initiator can be mixed with hydrogen peroxide according to a certain proportion and stirred uniformly. And (3) continuously stirring, and irradiating by using an LED irradiation head with the irradiation wavelength of 470 nmm right above the mixture to change the light curing liquid into colorless, wherein the hydrogen peroxide accounts for 0.1-4% of the mass fraction of the resin to obtain the colorless light curing liquid.
After the photocuring solution is prepared by the first preparation method or the second preparation method, the photocuring solution does not need to be protected from light, and can be stable and does not generate gel under sunlight. It can be applied by radiation curing with 365nm light source, and is solidified into solid by liquid crosslinking before irradiation. The 365nm light source is preferably an environment-friendly LED light source, and is also suitable for ultraviolet light sources such as a high-pressure mercury lamp, a medium-pressure mercury lamp and a low-pressure mercury lamp.
Further, the acrylate resin comprises trimethylolpropane triacrylate or polyethylene glycol (glycol) diacrylate.
Further, the components are mixed according to a certain proportion, the mass fraction of the pyrrolopyrrole photoinitiator is 0.1-2%, preferably 0.2-1%, based on the mass of the acrylate resin being 1%. During mixing, the pyrrole and pyrrole photoinitiator can be firstly dissolved in a small amount of organic solvents such as dichloromethane, ethanol, acetone and the like, and then the acrylate resin is added, wherein the solvent accounts for 1-5% of the mass of the resin, and preferably 2-3%.
The pyrrolopyrrole photoinitiator has an absorption peak between 450 and 480nm, and only the system fades in the irradiation process of the irradiation head of the LED with the irradiation wavelength of 470nm, and no polymerization reaction occurs. In addition, the illumination intensity of the light source of the LED irradiation head with the irradiation wavelength of 470nm is in the range of 30-100 mW cm-2, preferably 50-80 mW cm-2.
The invention has the advantages and beneficial effects that:
(1) the photoinitiator has different sensitivities to different wavelengths, and after the 470nmLED irradiation head is used for irradiation, curing liquid does not need to be protected from light, and large-area operation such as coating is used. The limitation that a large-area light source needs to be manufactured in large-area construction in the traditional ultraviolet curing process is avoided, and the large-area light source is difficult to manufacture. And the number of the first and second electrodes,
(2) the present invention uses ultraviolet light curing rather than traditional thermal curing. By comparison, ultraviolet light is cured; the curing time is short, the efficiency is high, the polymerization rate is high, and the yield is good; energy is saved, the ultraviolet curing technology does not need to be heated for a long time, and water and electricity are saved; the method is environment-friendly, organic volatile substances are not adopted in the formula of the ultraviolet curing technology, and the discharge amount of three wastes is small.
(3) The curing liquid obtained by the invention can realize irradiation curing through an environment-friendly LED ultraviolet light source, avoids the problem that the curing liquid needs to be irradiated immediately after being coated in ultraviolet curing construction, can realize the distribution operation of coating and irradiation, and is beneficial to realizing the construction mode of obtaining the similar water-based coating by irradiation curing.
Drawings
FIG. 1 shows the nuclear magnetic hydrogen spectrum (a) and the carbon spectrum (b) of the PyBH photoinitiator of the compound of example 1.
Figure 2. absorption spectra of (a) the compound of example 1, PyBH photoinitiator, (b) the compound of comparative example 1, PyBMe and PyBOMe photoinitiator.
FIG. 3 is a graph showing the change of the gel fraction with irradiation time in the photocuring solution obtained by irradiating (a), (b), and (c) a compound PyBH/trimethylolpropane triacrylate with a 470nm LED irradiation head.
FIG. 4 shows the change curve of the gel fraction of a photocuring solution obtained after a compound PyBH/trimethylolpropane triacrylate is irradiated by a 470nmLED irradiation head under sunlight and the change curve of the gel fraction of a commercial photoinitiator TPO under sunlight.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
in a preferred embodiment of the present invention, R1 ═ H and R2 ═ NO 2. The following is the structural formula for the compound PyBH:
the synthetic route is as follows:
in a dry double-mouth bottle, stirring is started, then 1.51g of p-nitrobenzaldehyde, 0.93g of aniline and 0.19g of p-toluenesulfonic acid are added, 30ml of glacial acetic acid is added, the mixture is subjected to oil bath reaction at 90 ℃ and air condensation, 0.86g of 2, 3-butanedione is added after the reaction is carried out for 0.5h, and the reaction is continued for 3.5 h. After the reaction is finished, cooling at room temperature to separate out a precipitate, performing suction filtration and drying, recrystallizing by using dichloromethane, and performing suction filtration and drying again to obtain a pure compound.
FIG. 1 shows (a) nuclear magnetic hydrogen and (b) carbon spectra of PyBH described above.
1H NMR(400MHz,CDCl3)δ8.10(d,J＝8.0Hz,4H),7.56-7.47(m,4H),7.45-7.37(m,5H),7.37-7.29(m,5H),6.82(s,2H).
13C NMR(101MHz,DMSO)δ145.47,139.96,139.25,135.26,134.19,130.32,129.61,128.50,128.27,127.84,125.96,125.72,125.18,97.48.
Comparative example 1
The following is the structural formula for the compound PyBMe:
synthetic route for PyBMe according to the procedure of the example, 0.93g of aniline was replaced by g of p-methylaniline, and the other procedures were not changed.
Comparative example 2:
the following is the structural formula for the compound PyBOMe:
the synthetic route of PyBOMe is carried out according to the procedures of the examples, replacing 0.93g of aniline by g of p-anisidine, and carrying out other operations.
Example 2
A dichloromethane solution with the concentration of 5 multiplied by 10 < -5 > molL < -1 > PyBH is prepared, and the ultraviolet-visible absorption spectrum of the solution is measured. As shown in fig. 2(a), PyBH has a distinct absorption peak at 467.
Comparative example 3
The uv-vis absorption spectra of PyBH in example 2 were measured by replacing it with PyBMe and PyBOMe, respectively. As shown in fig. 2 (b). PyBMe and PyBOMe have distinct absorption peaks at 434 and 478, respectively.
Example 3:
weighing 1g of trimethylolpropane triacrylate into a glass bottle wrapped with tinfoil paper, weighing 2mg of photoinitiator PyBH, stirring, uniformly mixing, and pouring the liquid into a transparent glass bottle. And (3) irradiating the mixture right above by using an LED irradiation head with the irradiation wavelength of 470 nmm until the color of the mixture is not changed any more, and stopping stirring to obtain the photocuring liquid.
Example 4:
weighing 1g of polyethylene glycol (glycol) diacrylate, putting the weighed polyethylene glycol (glycol) diacrylate into a glass bottle wrapped with tin foil paper, weighing 2mg of photoinitiator PyBH, stirring, uniformly mixing, and pouring liquid into a transparent glass bottle. Irradiating the mixture right above by using an LED irradiation head with the light intensity of 77.4mWcm-2 and the irradiation wavelength of 470 nmM until the color of the mixture is not changed any more, and stopping stirring to obtain the photocuring liquid. The experimental results show that the sample of example 4 still has a noticeable color after fading compared to the sample of example 3, whereas the former fades almost to no color, i.e. different monomers fade differently, so that no fading is actually observed.
Example 5:
weighing 1g of trimethylolpropane triacrylate, putting the trimethylolpropane triacrylate into a glass bottle wrapped with tin foil paper, weighing 2mg of photoinitiator PyBH, adding 1 drop of hydrogen peroxide, stirring, uniformly mixing, and pouring the liquid into a transparent glass bottle. And (3) directly above the mixture, irradiating the mixture by using an LED irradiation head with the light intensity of 77.4mW cm < -2 > and the irradiation wavelength of 470nm until the color of the mixture is not changed any more, and stopping stirring to obtain the photocuring liquid. After the curing obtained by the radiation of the 365LED radiation head is continued, the liquid state is changed into the solid state after the curing, and the color is related to the influence of the monomer contained in the light curing liquid.
Example 6:
weighing 1g of polyethylene glycol (glycol) diacrylate, putting the weighed polyethylene glycol (glycol) diacrylate into a glass bottle wrapped with tin foil paper, weighing 2mg of photoinitiator PyBH, adding 1 drop of hydrogen peroxide, stirring, uniformly mixing, and pouring the liquid into a transparent glass bottle. And (3) irradiating the mixture right above by using an LED irradiation head with the irradiation wavelength of 470 nmm until the color of the mixture is not changed any more, and stopping stirring to obtain the photocuring liquid. After the curing obtained by the radiation of the 365LED radiation head is continued, the liquid state is changed into the solid state after the curing, and the color is related to the influence of the monomer contained in the light curing liquid.
Example 7:
the light-cured liquid obtained by irradiating PyBH and trimethylolpropane triacrylate (TMPTA) by a 470nmLED irradiation head is respectively 0.2 wt%: 1 wt%, 1.0 wt%: 1 wt% of the double bond, continuously using a 365LED irradiation head to cure, then changing the liquid state into a solid state, monitoring the change of the characteristic peak area of the double bond at 6170cm-1 by using an infrared spectrometer, and determining the conversion rate of the double bond. The results of double bond conversion are shown in FIG. 3 (a). When the mass fraction of the initiator PyBH is 1.0 wt%, the gel rate reaches more than 30%.
Comparative example 4:
double bond conversion was determined by replacing PyBH with PyBMe as in example 7. The results of double bond conversion are shown in FIG. 3 (b). When the mass fraction of the initiator PyBMe is 0.2 wt%, the gel fraction reaches more than 50%.
Comparative example 5:
the double bond conversion was determined by replacing PyBH in example 7 with PyBOMe, respectively. The results of double bond conversion are shown in FIG. 3 (c). When the mass fraction of the initiator PyBOMe is 1.0 wt%, the gel fraction reaches more than 50%.
Example 8:
a photocurable liquid obtained by irradiating PyBH and trimethylolpropane triacrylate (TMPTA) with a 470nmLED irradiation head and a liquid sample of a commercial photoinitiator TPO and trimethylolpropane triacrylate (TMPTA) were placed under the same conditions in the sunlight, and changes in the sample were observed and the gel fraction was measured, with the results shown in fig. 4. The TPO-containing liquid sample is deteriorated within a hour and a second, and the TPO-containing liquid sample is not deteriorated and gelled after being placed for a week, so that the TPO-containing liquid sample is beneficial to liquid normal-temperature construction, does not need to be similar to UV powder coating and the like, needs a thermosensitive base material and is heated and melted, and has outstanding advantages.
Claims (7)
1. A light-cured liquid based on a pyrrole-pyrrole structure photoinitiator and an acrylate resin, which is characterized in that the structure of the photoinitiator based on the pyrrole-pyrrole structure is shown as follows, the photoinitiator is a tetraaryl substituted pyrrole [3,2-b ] pyrrole compound, R1 is a substituent on a phenyl group connected with a nitrogen atom of a pyrrole ring, R2 is a substituent on the phenyl group connected with a carbon atom of the pyrrole ring, the acrylate resin monomer is an ester containing a C ═ C unsaturated bond,
r1 is methyl, methoxy or hydrogen; r2 is nitro.
2. The photocurable liquid based on a pyrrolopyrrole structure photoinitiator and an acrylate resin according to claim 1, wherein the acrylate resin is trimethylolpropane triacrylate or polyethylene glycol (diol) diacrylate.
3. The method for preparing a photocurable liquid based on a pyrrolopyrrole structure photoinitiator and an acrylate resin according to claim 1 or 2, wherein the first preparation method comprises: firstly, mixing acrylate resin and a pyrrole-pyrrole photoinitiator according to a certain proportion in a dark condition, uniformly stirring, continuously stirring, irradiating by using an LED (light-emitting diode) irradiating head with the irradiation wavelength of 470 nmm right above until the color of the mixture is not changed any more, and stopping stirring to obtain the photocuring liquid;
or the second preparation method comprises the following steps: mixing trimethylolpropane triacrylate, a pyrrolopyrrole initiator and hydrogen peroxide according to a certain proportion, uniformly stirring, continuously stirring, irradiating by using an LED (light-emitting diode) irradiating head with the irradiating wavelength of 470 nmm right above, and enabling the photocuring liquid to be colorless, wherein the hydrogen peroxide is 0.1-4% of the mass fraction of the resin to obtain the colorless photocuring liquid.
4. The method for preparing the photocuring liquid according to claim 3, wherein the photocuring liquid is stable and does not gel in sunlight without being protected from light after the first preparation method or the second preparation method, and is subjected to radiation curing application by a 365nm light source, and is cured into a solid by liquid crosslinking before irradiation.
5. The method for preparing the photo-curing liquid as claimed in claim 3, wherein the mixing according to a certain proportion is: according to the mass of the acrylate resin being 1, the mass fraction of the pyrrolopyrrole photoinitiator is in the range of 0.1-2%, when in mixing, the pyrrolopyrrole photoinitiator is firstly dissolved in a small amount of dichloromethane, ethanol or acetone organic solvent, and then the acrylate resin is added, and the solvent accounts for 1-5% of the mass of the resin.
6. The preparation method of the photocuring liquid as claimed in claim 3, wherein the pyrrolopyrrole photoinitiator has an absorption peak between 450 and 480nm, and only the system is faded and no polymerization reaction occurs in the irradiation process of the LED irradiation head with the irradiation wavelength of 470 nm; in addition, the illumination range of the light source of the LED illumination head with the illumination wavelength of 470 nmis 50-80 mW cm < -2 >.
7. Use of a photocurable fluid based on a pyrrolopyrrole structure photoinitiator and an acrylate resin according to claim 1 or 2 at room temperature without being protected from light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111226698.5A CN113880974B (en) | 2021-10-21 | 2021-10-21 | Photocurable liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111226698.5A CN113880974B (en) | 2021-10-21 | 2021-10-21 | Photocurable liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113880974A true CN113880974A (en) | 2022-01-04 |
| CN113880974B CN113880974B (en) | 2022-10-25 |
Family
ID=79004125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111226698.5A Active CN113880974B (en) | 2021-10-21 | 2021-10-21 | Photocurable liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113880974B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006086646A2 (en) * | 2005-02-10 | 2006-08-17 | The Regents Of The University Of Colorado, A Body Corporate | Stress relaxation in crosslinked polymers |
| CN101560061A (en) * | 2009-05-27 | 2009-10-21 | 上海交通大学 | Method for preparing patterned polymer brush |
| US20130289155A1 (en) * | 2010-11-12 | 2013-10-31 | Coloplast A/S | Novel polymeric photoinitiators |
| PL401473A1 (en) * | 2012-11-05 | 2014-05-12 | Instytut Chemii Organicznej Polskiej Akademii Nauk | New, highly fluorescent heterocyclic substances and their preparation |
| JP2016127083A (en) * | 2014-12-26 | 2016-07-11 | 出光興産株式会社 | Material for organic electroluminescent element, organic electroluminescent element and electronic apparatus |
| CN109180841A (en) * | 2018-09-05 | 2019-01-11 | 南通悦升新材料科技有限公司 | A kind of application of photoinitiator in the colourless photocuring 3D printing of long wavelength |
| CN109867781A (en) * | 2019-01-29 | 2019-06-11 | 江汉大学 | A kind of porous conjugated polymer material and preparation method thereof |
| CN109942475A (en) * | 2019-04-03 | 2019-06-28 | 北京化工大学 | One-component long wavelength light initiator and preparation method thereof of the one kind containing azole derivatives |
| CN110950768A (en) * | 2019-11-08 | 2020-04-03 | 武汉大学 | Photobleachable visible light initiator and preparation method and application thereof |
| WO2020185105A1 (en) * | 2019-03-14 | 2020-09-17 | Instytut Chemii Organicznej Pan | Improved method for the synthesis of pyrrolo[3,2-b]pyrroles |
| JPWO2019058859A1 (en) * | 2017-09-20 | 2020-11-05 | 富士フイルム株式会社 | Coloring composition, cured film, pattern forming method, color filter, solid-state image sensor and image display device |
| CN112028893A (en) * | 2020-09-29 | 2020-12-04 | 天津理工大学 | Photoinitiator with pyrrolopyrrole structure and preparation method and application thereof |
| WO2021144395A1 (en) * | 2020-01-15 | 2021-07-22 | Fundació Institut Català D'investigació Química (Iciq) | Carboxylic dithiocarbamic acid anhydride compounds and compositions thereof |
-
2021
- 2021-10-21 CN CN202111226698.5A patent/CN113880974B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006086646A2 (en) * | 2005-02-10 | 2006-08-17 | The Regents Of The University Of Colorado, A Body Corporate | Stress relaxation in crosslinked polymers |
| CN101560061A (en) * | 2009-05-27 | 2009-10-21 | 上海交通大学 | Method for preparing patterned polymer brush |
| US20130289155A1 (en) * | 2010-11-12 | 2013-10-31 | Coloplast A/S | Novel polymeric photoinitiators |
| PL401473A1 (en) * | 2012-11-05 | 2014-05-12 | Instytut Chemii Organicznej Polskiej Akademii Nauk | New, highly fluorescent heterocyclic substances and their preparation |
| CN104870447A (en) * | 2012-11-05 | 2015-08-26 | 波兰科学院有机化学研究所 | Strongly fluorescent heterocycles and a method for their synthesis |
| JP2016127083A (en) * | 2014-12-26 | 2016-07-11 | 出光興産株式会社 | Material for organic electroluminescent element, organic electroluminescent element and electronic apparatus |
| JPWO2019058859A1 (en) * | 2017-09-20 | 2020-11-05 | 富士フイルム株式会社 | Coloring composition, cured film, pattern forming method, color filter, solid-state image sensor and image display device |
| CN109180841A (en) * | 2018-09-05 | 2019-01-11 | 南通悦升新材料科技有限公司 | A kind of application of photoinitiator in the colourless photocuring 3D printing of long wavelength |
| CN109867781A (en) * | 2019-01-29 | 2019-06-11 | 江汉大学 | A kind of porous conjugated polymer material and preparation method thereof |
| WO2020185105A1 (en) * | 2019-03-14 | 2020-09-17 | Instytut Chemii Organicznej Pan | Improved method for the synthesis of pyrrolo[3,2-b]pyrroles |
| CN109942475A (en) * | 2019-04-03 | 2019-06-28 | 北京化工大学 | One-component long wavelength light initiator and preparation method thereof of the one kind containing azole derivatives |
| CN110950768A (en) * | 2019-11-08 | 2020-04-03 | 武汉大学 | Photobleachable visible light initiator and preparation method and application thereof |
| WO2021144395A1 (en) * | 2020-01-15 | 2021-07-22 | Fundació Institut Català D'investigació Química (Iciq) | Carboxylic dithiocarbamic acid anhydride compounds and compositions thereof |
| CN112028893A (en) * | 2020-09-29 | 2020-12-04 | 天津理工大学 | Photoinitiator with pyrrolopyrrole structure and preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| LIANG-SHENG DUAN等: ""One-Pot Synthesis of Tetraarylpyrrolo[3,2-b]pyrrole Dopant-Free Hole-Transport Materials for Inverted Perovskite Solar Cells"", 《CHINESEJOURNALOFCHEMICALPHYSICS》 * |
| YUANYUAN XU等: ""Radical Photopolymerization Using 1,4-Dihydropyrrolo[3,2-b]pyrrole Derivatives Prepared via One-Pot Synthesis"", 《ACS OMEGA》 * |
| 崔艳艳等: ""前线聚合研究及应用进展(下)"", 《高分子通报》 * |
| 简凯等: ""自由基型光引发剂的研究进展"", 《涂料技术与文摘》 * |
| 许媛媛: ""新型并吡咯化合物的合成及其光化学应用研究"", 《优秀博硕士学位论文全文数据库（硕士） 医药卫生科技辑》 * |
| 默圆等: ""深层光固化研究进展"", 《精细化工》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113880974B (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | New multifunctional benzophenone-based photoinitiators with high migration stability and their applications in 3D printing | |
| US5446073A (en) | Photopolymerization process employing a charge transfer complex without a photoinitiator | |
| WO2000071544A1 (en) | Chromene compounds | |
| CN112239624B (en) | Ophthalmic lens comprising a visible light-cured color-changing coating | |
| KR101367572B1 (en) | Polymer compounds comprising dye and curable resin composition comprising the same | |
| CN110615904B (en) | Photochromic plate and manufacturing process thereof | |
| CN103210000A (en) | Photoinitiator compositions | |
| CN112028893B (en) | Photopolymerization system prepared from photoinitiator based on pyrrolopyrrole structure and application | |
| Dumur | Recent advances on photobleachable visible light photoinitiators of polymerization | |
| CN111072796B (en) | Pyrrolone photoinitiation system and application | |
| CN114133877B (en) | Photo-curing composition glue containing large conjugated aromatic ring acrylic acid compound monomer, and use method and application thereof | |
| CN110950768B (en) | Photobleachable visible light initiator and preparation method and application thereof | |
| CN113880974B (en) | Photocurable liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, and preparation method and application thereof | |
| Meng et al. | Upconversion nanoparticle-assisted cationic and radical/cationic hybrid photopolymerization using sulfonium salts | |
| Crivello | Sensitization of cationic photopolymerizations | |
| Zhang et al. | Naphthoquinone-Based Oxime Esters for Free Radical Photopolymerization under Sunlight or a Blue Light-Emitting Diode | |
| You et al. | The three-component photoinitiating systems based on flavonol sulfonate and application in 3D printing | |
| Ma et al. | Synthesis and properties of acyldiphenylphosphine oxides photoinitiators carrying triphenylamine or pyrene group for free radical photopolymerization | |
| CN112939779B (en) | Terephthaloyl formate type photoinitiator suitable for UV-LED deep photopolymerization and preparation method thereof | |
| CN114907500A (en) | Carbon quantum dot visible light initiator system and application thereof | |
| CN113943241A (en) | Photocuring coating suitable for outdoor coating and storage and preparation method thereof | |
| CN114656418B (en) | (E) -benzo five-membered ring-styryl sulfonium salt derivative and preparation and application thereof | |
| CN110078719A (en) | A kind of cumarin-sesamol biology base photoinitiator and preparation method thereof | |
| Zuo et al. | N-Vinylcarbazole in thiol-ene click reactions: A versatile additive for sunlight-cured luminescent coatings and information encryption | |
| WO2021172341A1 (en) | Photoradically polymerizable composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |