CN111072796B - Pyrrolone photoinitiation system and application - Google Patents

Pyrrolone photoinitiation system and application Download PDF

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CN111072796B
CN111072796B CN201911401654.4A CN201911401654A CN111072796B CN 111072796 B CN111072796 B CN 111072796B CN 201911401654 A CN201911401654 A CN 201911401654A CN 111072796 B CN111072796 B CN 111072796B
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photosensitizer
pyrrolone
methyl
pyrrole
photoinitiating system
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CN111072796A (en
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聂俊
汤立群
朱晓群
李三保
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Anqing Beihuada Science And Technology Park Co ltd
Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract

The invention discloses a pyrrolyl ketone photoinitiation system, relating to the technical field of photoinitiation systems. The invention also provides application of the photoinitiation system in coating, printing ink, adhesive, photoresist and 3D printing. The invention has the beneficial effects that: the photosensitizer, pyrrolidone, sensitizes onium cation photoinitiators by absorbing light of long wavelength and generates radicals and cations. Because the pyrrolyl ketone has a wide absorption spectrum, the system can be matched with LED light sources or mercury lamps with different wave bands to initiate free radical and cationic photopolymerization.

Description

Pyrrolone photoinitiation system and application
Technical Field
The invention relates to the technical field of photoinitiation systems, in particular to a pyrrolyl ketone photoinitiation system and application thereof.
Background
Photopolymerization technology is a green technology widely used in coatings, inks, adhesives, microelectronics, dental restorations and biomaterials. In the photocuring process, the monomer or resin can be directly excited by light to cause polymerization, or the photosensitizer and the photoinitiator can be excited by light to cause polymerization. Wherein the photosensitizer or photoinitiator determines whether the oligomer and the diluent can be rapidly converted from liquid state to solid state under the irradiation of light. The photosensitizer and the photoinitiator have the following basic characteristics: the initiator has certain light absorption capacity in an ultraviolet region (250-400nm) or a visible light region (400-800nm), and generates active fragments capable of initiating polymerization after directly or indirectly absorbing light energy. In photopolymerization, the initiation mechanism is different, and the photopolymerization can be divided into radical photopolymerization and cationic photopolymerization, wherein the radical photopolymerization is the most widely applied, the corresponding radical photoinitiator has many varieties and is well developed, and the main problems of the radical photopolymerization are oxygen inhibition and volume shrinkage.
In contrast to free radical photopolymerization, cationic photopolymerization is generally a ring-opening polymerization of epoxy groups or a cationic polymerization of electron-rich carbon-carbon double bonds (e.g., vinyl ethers) catalyzed by protonic acids generated by cationic photoinitiators under light irradiation. The cationic photoinitiator mainly comprises onium salts, metal organics and organosilanes. Wherein, iodonium salt, sulfonium salt and iron arene are most representative. Cationic photopolymerization has no oxygen inhibition problem and has the advantage of small curing shrinkage, but generally has the disadvantages of low curing speed, large use amount of cationic photoinitiator and high price and high manufacturing cost. Moreover, the maximum absorption wavelength of most cationic photoinitiators is below 330nm, and the utilization rate of the cationic photoinitiators for common light sources is low. Therefore, only mercury lamps can be used as a light source to initiate polymerization, but the mercury pollution problem caused by mercury lamps is getting worse and the application thereof is limited. LED light sources can replace mercury lamps and have evolved rapidly. LED light sources have many advantageous features such as: the LED light source does not generate ozone, has long service life, simple and safe operation, low heat production, narrow spectral line width, low energy consumption and the like, but the LED light source is limited by packaging technology and materials, and the LED light source with the wavelength higher than 365nm can be stably used.
The traditional cationic photoinitiator cannot realize cationic photopolymerization excited by a long-wavelength LED light source. The effective solution is to use a photosensitizer to sensitize the cationic photoinitiator, and after the photosensitizer can absorb the long-wavelength light radiation energy, the sensitizing cationic photoinitiator generates radical cations so that cationic photopolymerization can be polymerized under the irradiation of the long-wavelength LED. The use of ITX is a high-efficiency long-wavelength photosensitizer, but the use is greatly limited due to the problems of toxicity and the like. Some dyes can also be used as photosensitizers, but the sensitizing effect is not ideal, and the problems of slow curing speed, low curing degree and the like exist.
Therefore, a photosensitizer capable of absorbing long-wavelength radiation energy and excellent in photosensitization performance is an urgent need for the development of cationic photopolymerization technology. The formula of the photosensitizer-cationic photoinitiator system has very important value for cationic long-wavelength photopolymerization. In addition, through the mixing of monomers or resins, the performance of the material can be changed, and the material can be better applied to the fields of photopolymerization, such as coatings, printing ink, adhesives, photoresist, 3D printing and the like. In the polymerization of a hybrid system, a photoinitiator is often required to initiate both cationic monomer polymerization and radical monomer polymerization, and a radical initiator and a cationic initiator are usually required to be compounded, but efficient photoinitiator systems at long wavelengths are rare. The formula of the photosensitizer-cationic photoinitiator system has very important value for long-wavelength photopolymerization of the hybrid system.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a photoinitiating system capable of initiating at long wavelengths.
The invention solves the technical problems through the following technical means:
a pyrrolyl ketone photoinitiation system comprises a photosensitizer and a photoinitiator, wherein the photosensitizer is pyrrolyl ketone, and the photoinitiator is onium salts.
Preferably, the structural formula of the pyrrolyl ketone is as follows:
Figure GDA0002970808290000031
Figure GDA0002970808290000041
wherein R is1-30The substituent group is-CnHn+1Or H or halogen substituents-F, -Cl, -Br, -I; or a substituent containing O: -CHO, -COOH, -OH, -CH2OCH3(ii) a Or N-containing substituents-NH2、 -NO2-CN, or a substituent containing S: -HS, -SO3H or an aromatic hydrocarbon, alkene or alkyne whole chain or branched chain.
R in the above structural formula 525To one of the carbon atoms of the intermediate carbocyclic chain; r in the general structural formula 630Attached to one of the carbon atoms of the intermediate carbocyclic chain.
The structural general formula is that a similar conjugated system is combined by a pyrrole group, a double bond and a carbonyl group to cause light absorption in the range of 300-600 nm.
Preferably, said R is5、R9、R15、R20Also having the following groups:
Figure GDA0002970808290000042
Figure GDA0002970808290000051
preferably, the reaction formula of the pyrrolyl ketone is as follows:
Figure GDA0002970808290000052
Figure GDA0002970808290000061
preferably, the preparation method of the pyrrolyl ketone comprises the following steps: adding alpha-H-free aldehyde and alpha-H-containing ketone substances into an organic reagent, using weak base as a catalyst, heating and reacting in a nitrogen atmosphere in a dark place, standing for 10min in an ice water bath to separate out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with an organic solvent to obtain the product.
Has the advantages that: compared with the conventional preparation method of the claisen-Schmidt reaction, the preparation method provided by the invention has the advantages that after the crude product is produced by primary crystallization in the modes of heating and cooling in an ice water bath, the product is generated more quickly, the product purity is higher than that of primary recrystallization by the fractional-step two-time crystallization method, the product yield is improved, and the secondary crystallization mode is improved from 50% to 60% compared with the primary crystallization yield.
Preferably, the onium salts include iodonium salts or sulfonium salts.
Has the advantages that: the system photosensitizer has good photosensitization effect on onium salt, and enables the cationic photopolymerization to have high conversion rate and high curing speed. The usage amount of the cationic photoinitiator is small, and the cost is reduced.
Preferably, the reaction is heated for 1h at 50-60 ℃ in a nitrogen atmosphere in the absence of light.
Preferably, the weak base is 1mol/L NaOH aqueous solution or sodium alkoxide aqueous solution.
Preferably, the mass ratio of the photosensitizer to the photoinitiator is 0.5-5: 1-10.
Preferably, the mass ratio of the photosensitizer to the photoinitiator is 1: 3.
Preferably, the applicable wavelength range of the photoinitiation system is 200-600 nm.
Preferably, the light source comprises an LED light source or a mercury light source.
The second technical problem to be solved by the present invention is to provide the application of the above-mentioned pyrrolone photoinitiation system.
The invention solves the technical problems through the following technical means:
an application of the pyrrolidone photoinitiation system in paint, printing ink, adhesive, photoresist and 3D printing.
The invention has the advantages that:
(1) the photosensitizer, pyrrolidone, sensitizes onium cation photoinitiators by absorbing light of long wavelength and generates radicals and cations. Because the pyrrolyl ketone has a wider absorption spectrum, the system can be matched with LED light sources or mercury lamps with different wave bands to initiate free radical and cationic photopolymerization;
(2) the photoinitiation system in the invention has good solubility in most cationic polymerization monomers such as epoxy, vinyl ether and the like and free radical polymerization monomers such as acrylate and styrene; the system still has very good curing effect on cationic photopolymerization under the condition of low-light-intensity irradiation;
(3) the photoinitiation system is applied to a system mixed by cations or cations and free radicals, has a quick curing effect, and has an anti-oxygen polymerization inhibition effect on the polymerization of a free matrix system;
(4) the photosensitizer structure is a ketone with pyrrole substituent groups, and a conjugated system formed by the pyrrole groups, double bonds and carbonyl groups has the characteristic of long-wavelength light absorption.
Drawings
FIG. 1 is a graph showing an ultraviolet absorption spectrum of 1, 3-bis (1-methyl-1H-pyrrol-2-yl) prop-2-en-1-one as a photosensitizer in example 1 of the present invention;
FIG. 2 is a graph showing EPOX (epoxy resin) photopolymerization conversion rate curves of a cationic photoinitiator system combining a photosensitizer 1, 3-bis (1-methyl-1H-pyrrol-2-yl) prop-2-en-1-one and an iodonium salt under the irradiation of a 365, 405 and 465nm light source;
FIG. 3 is a graph showing the conversion of photopolymerization of a mixed system (epoxy resin EPOX 80 wt%, acrylic resin TPGDA 20 wt%) initiated by a cationic photoinitiator system of a photosensitizer 1, 3-bis (1-methyl-1H-pyrrol-2-yl) prop-2-en-1-one in combination with an iodonium salt under irradiation of a light source of 405 nm;
FIG. 4 is a chart showing an ultraviolet absorption spectrum of 1, 5-bis (1-methyl-1H-pyrrol-2-yl) penta-1, 4-dienone as a photosensitizer in example 9 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
The method for measuring the ultraviolet absorption range of the photosensitizer comprises the following steps: the ultraviolet absorption range of the photosensitizer was measured using an ultraviolet spectrophotometer (instrument model Hitachi U-3010, manufacturer: Hitachi Co., Japan).
The sample was formulated as acetonitrile solution (3X 10)-5mol/L) using an ultraviolet-visible spectrophotometer (scan speed of 120 nm. multidot.min)-1) And testing the ultraviolet absorption curve of the sample at room temperature to obtain the ultraviolet absorption range of each photosensitizer.
The method for measuring the conversion rate of the characteristic peak comprises the following steps: and (3) recording the change condition of the characteristic absorption peak in the system in real time by using a real-time infrared spectrometer (instrument model: Nicolet 5700 FTIR; manufacturer: Thermo company in America).
The testing process comprises the following steps: coating a sample prepared from a photoinitiator and a monomer according to a ratio on a KBr salt sheet, covering another KBr salt sheet to isolate oxygen, and testing an epoxy peak (910 cm) in a polymerization reaction by real-time infrared under the irradiation of an LED lamp source-1) Or peak of carbon-carbon double bond (1640 cm)-1) And (4) transformation condition. The scanning rate and the acquisition rate of the instrument are respectively 4scan s-1,4cm-1. The conversion rate of the characteristic peak in the reaction system can be calculated by using the change value of the peak area according to the following formula:
DC％＝(1-At/A0)*100％
wherein DC% represents the double bond conversion, AtAnd A0The peak areas of characteristic absorption peaks before and after the polymerization reaction are shown, respectively.
The following examples all used LED lamps as the light source and diphenyliodonium hexafluoroantimonate as the iodonium salt.
Example 1
Preparation method of photosensitizer 1, 3-bis (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-ketone
The structural formula is as follows:
Figure GDA0002970808290000091
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and N-methyl-2-acetyl pyrrole in a molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1h in a nitrogen atmosphere in a dark place, standing for 10min in an ice water bath, separating out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with ethanol to obtain the product.
As shown in FIG. 1, the absorption range of the photosensitizer prepared in this example is 300-450 nm.
Example 2
Preparing a photoinitiation system of 1 wt% of photosensitizer 1, 3-bis (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into cationic monomer epoxy resin EPOX by taking the weight of cationic monomer as 100%, and polymerizing under the illumination of 405nm and 465nm respectively (the light intensity is 100 mW/cm)2)。
And (3) measuring results: as shown in FIG. 2, the conversion of epoxy bonds was 65% by light irradiation for 600 s. The light irradiation is 600s at 465nm, the epoxy bond conversion rate is 47%, and the curing effect is good.
Example 3
Preparing a photoinitiation system of 2 weight percent of photosensitizer 1, 3-bis (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-one and 4 weight percent of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into monomers (epoxy resin EPOX 80 weight percent and oxetane TMPO 20 weight percent) according to the weight of the monomers as 100 percent, and polymerizing under 365nm illumination (the light intensity is 100 mW/cm)2)。
And (3) measuring results: as shown in FIG. 2, the conversion of epoxy bonds was 61% by light irradiation for 600 s.
Example 4
Preparing a photoinitiation system of 1 wt% of photosensitizer 1, 3-bis (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-one and 3 wt% of diphenyliodonium hexafluoroantimonate, adding the photoinitiation system into mixed monomers (epoxy resin EPOX 80 wt% and acrylic resin TPGDA 20 wt%) according to the weight of the monomers being 100%, and polymerizing under the illumination of 405nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the light irradiation is 600s, the conversion rate of epoxy bonds is 60 percent, the conversion rate of double bonds is 85 percent, and the curing effect of the mixed system is good.
Example 5
Preparing a photoinitiation system of 1 wt% of photosensitizer 1, 3-bis (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into mixed monomers (epoxy resin EPOX 80 wt%, oxetane MOX-10420 wt%) according to the weight of the monomers as 100%, and polymerizing under the illumination of 405nm (the light intensity is 5 mW/cm)2)。
And (3) measuring results: as shown in FIG. 3, the light irradiation is 600s, the epoxy bond conversion rate is 60%, the epoxy bond conversion rate is 67%, and the curing effect is good at low light intensity.
Example 6
Preparation method of photosensitizer 1- (furan-2-yl) -3- (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-one
The structural formula is as follows:
Figure GDA0002970808290000111
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole-carbaldehyde and 2-acetylfuran in a molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 1: 1), heating and reacting for 1h in a nitrogen atmosphere in a dark place, standing for 10min by using an ice water bath to separate out a light yellow crude product, washing the crude product by using deionized water, drying in vacuum, and recrystallizing by using ethanol to obtain the photosensitizer of which the absorption range is 300-450 nm.
1 wt% of photosensitizer 1- (furan-2-yl) -3- (1-methyl) is preparedA photoinitiation system of (E) -1H-pyrrole-2-yl) prop-2-ene-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, wherein the photoinitiation system is added into monomer epoxy resin EPOX according to the weight of the monomer of 100%, and polymerization is carried out under the illumination of 385nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: and (5) irradiating for 600s, wherein the epoxy bond conversion rate is 55%. The curing effect is good.
Example 7
Preparation method of 3- (1-methyl-1H-pyrrole-2-yl) -1- (thiophene-2-yl) prop-2-ene-1-ketone
The structural formula is as follows:
Figure GDA0002970808290000121
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and N-methyl-2-acetyl thiophene with the molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1 hour in a nitrogen atmosphere in a dark place, standing for 10 minutes in an ice water bath, separating out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, recrystallizing with ethanol to obtain a product
The absorption range of the photosensitizer prepared in this example is 300-450 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer 3- (1-methyl-1H-pyrrole-2-yl) -1- (thiophene-2-yl) prop-2-ene-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOX by taking the weight of the monomer as 100%, and polymerizing under the illumination of 395nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, and the epoxy bond conversion rate is 50%. The curing effect is good.
Example 8
Process for preparing 1, 5-bis (1-methyl-1H-pyrrol-2-yl) penta-1, 4-dienone
The structural formula is as follows:
Figure GDA0002970808290000131
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and acetone with the molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1h in a dark place in a nitrogen atmosphere, standing for 10min in an ice water bath to separate out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with ethanol to obtain a product
As shown in FIG. 4, the absorption range of the photosensitizer prepared in this example is 300-500 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer 1, 5-bis (1-methyl-1H-pyrrole-2-yl) penta-1, 4-dienone and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOx according to the weight of the monomer being 100%, and polymerizing under the illumination of 405nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the light irradiation is 600s, and the epoxy bond conversion rate is 61%. The curing effect is good.
Example 9
Process for preparing 2, 6-bis ((1-methyl-1H-pyrrol-2-yl) methylene) cyclohex-1-one
The structural formula is as follows:
Figure GDA0002970808290000132
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and cyclohexanone in a molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1 hour in a dark place in a nitrogen atmosphere, standing for 10 minutes in an ice water bath to separate out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with ethanol to obtain a product
The absorption range of the photosensitizer prepared in this example is 300-500 nm.
1 wt% ofA photoinitiation system of photosensitizer 2, 6-bis ((1-methyl-1H-pyrrole-2-yl) methylene) cyclohex-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, wherein the photoinitiation system is added into monomer epoxy resin EPOx according to the weight of the monomer of 100%, and the polymerization is carried out under the illumination of 405nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the light irradiation is 600s, and the epoxy bond conversion rate is 56 percent. The curing effect is good.
Example 10
Preparation method of 4, 4-dimethyl-2, 6-bis ((1-methyl-1H-pyrrole-2-yl) methylene) cyclohex-1-one
The structural formula is as follows:
Figure GDA0002970808290000141
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and 4, 4-dimethylcyclohexanone in a molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1h in a nitrogen atmosphere in a dark place, standing for 10min in an ice water bath to precipitate a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with ethanol to obtain a product
The absorption range of the photosensitizer prepared in this example is 300-500 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer 4, 4-dimethyl-2, 6-bis ((1-methyl-1H-pyrrole-2-yl) methylene) cyclohex-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOx according to the weight of the monomer of 100%, and polymerizing under the illumination of 395nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the light irradiation is 600s, and the epoxy bond conversion rate is 53 percent. The curing effect is good.
Example 11
(E) Preparation method of (E) -1- (anthracene-9-yl) -3- (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-ketone
The structural formula is as follows:
Figure GDA0002970808290000151
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and 9-acetyl anthracene with a molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1 hour in a dark place in a nitrogen atmosphere, standing for 10 minutes in an ice water bath, precipitating a light yellow crude product, washing the crude product with deionized water, performing vacuum drying, and recrystallizing with ethanol to obtain the product.
The absorption range of the photosensitizer prepared in the embodiment is 300-550 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer (E) -1- (anthracene-9-yl) -3- (1-methyl-1H-pyrrole-2-yl) propyl-2-ene-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOx according to the weight of the monomer being 100%, and polymerizing under the illumination of 465nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, and the epoxy bond conversion rate is 50%. The curing effect is good.
Example 12
(E) Preparation method of (E) -3- (1-methyl-1H-pyrrole-2-yl) -1- (naphthalene-1-yl) prop-2-ene-1-ketone
The structural formula is as follows:
Figure GDA0002970808290000161
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole-carbaldehyde and 2-acetyl naphthalene in a molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1h in a dark place in a nitrogen atmosphere, standing for 10min in an ice water bath, separating out a light yellow crude product, washing the crude product with deionized water, performing vacuum drying, and recrystallizing with ethanol to obtain the product.
The absorption range of the photosensitizer prepared in this example is 300-500 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer (E) -3- (1-methyl-1H-pyrrole-2-yl) -1- (naphthalene-1-yl) prop-2-ene-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOX by taking the weight of the monomer as 100%, and polymerizing under 465nm illumination (the light intensity is 100 mW/cm)2)。
And (3) measuring results: and (5) irradiating for 600s, wherein the epoxy bond conversion rate is 55%. The curing effect is good.
Example 13
(E) Preparation method of (E) -3- (1-methyl-1H-pyrrole-2-yl) -1-phenylpropan-2-en-1-one
The structural formula is as follows:
Figure GDA0002970808290000171
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and acetyl benzene with the molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1h in a dark place in a nitrogen atmosphere, standing for 10min in an ice water bath to separate out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with ethanol to obtain the product.
The absorption range of the photosensitizer prepared in this example is 300-450 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer (E) -3- (1-methyl-1H-pyrrole-2-yl) -1-phenylpropan-2-ene-1-ketone and 3 wt% of diphenyliodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOx according to the weight of the monomer being 100%, and polymerizing under the illumination of 465nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, and the epoxy bond conversion rate is 60 percent. The curing effect is good.
Example 14
Preparation method of ((E) -3- (1-methyl-1H-pyrrole-2-yl) -1- (pyran-4-yl) prop-2-ene-1-ketone
The structural formula is as follows:
Figure GDA0002970808290000172
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and 1-acetylpyrene with the molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1h in a nitrogen atmosphere in a dark place, standing for 10min in an ice water bath, precipitating a light yellow crude product, washing the crude product with deionized water, performing vacuum drying, and recrystallizing with ethanol to obtain the product. The absorption range of the photosensitizer prepared in the embodiment is 300-550 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer ((E) -3- (1-methyl-1H-pyrrole-2-yl) -1- (pyran-4-yl) propyl-2-ene-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOx according to the weight of the monomer being 100%, and polymerizing under the illumination of 465nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the light irradiation is 600s, and the epoxy bond conversion rate is 58%. The curing effect is good.
Example 15
(E) Preparation method of (E) -1-cyclohexyl-3- (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-ketone
The structural formula is as follows:
Figure GDA0002970808290000181
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and acetyl cyclohexanone in a molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L of NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1h in a dark place in a nitrogen atmosphere, standing for 10min in an ice water bath to separate out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with ethanol to obtain the product.
The absorption range of the photosensitizer prepared in this example is 300-450 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer (E) -1-cyclohexyl-3- (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOX by taking the weight of the monomer as 100%, and polymerizing under the illumination of 405nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the light irradiation is 600s, and the epoxy bond conversion rate is 61%. The curing effect is good.
Example 16
(E) Preparation method of (E) -1- (cyclohex-2-en-1-yl) -3- (1-methyl-1H-pyrrole-2-yl) prop-2-en-1-one
The structural formula is as follows:
Figure GDA0002970808290000191
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and 3-acetyl cyclohexyl-2-ketene with the molar ratio of 1:1 into an aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1h in a nitrogen atmosphere in a dark place, standing for 10min in an ice water bath, separating out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with ethanol to obtain the product.
The absorption range of the photosensitizer prepared in this example is 300-450 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer (E) -1- (cyclohex-2-en-1-yl) -3- (1-methyl-1H-pyrrole-2-yl) prop-2-en-1-one and 3 wt% of diphenyl iodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOX by taking the weight of the monomer as 100%, and polymerizing under the illumination of 405nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the light irradiation is 600s, and the epoxy bond conversion rate is 58%. The curing effect is good.
Example 17
(E) Process for the preparation of (5- (3- (1-methyl-1H-pyrrol-2-yl) acryloyl) cyclopent-1, 3-dien-1-yl) iron (1, 3-dien-1-yl) cyclopent-1, 3-dien-1-yl) iron
The structural formula is as follows:
Figure GDA0002970808290000201
the preparation method comprises the following steps:
adding N-methyl-2-pyrrole formaldehyde and acetyl ferrocene with the molar ratio of 1:1 into aqueous solution containing ethanol and 0.1mol/L NaOH (the volume ratio of the ethanol to the aqueous solution of the NaOH is 2: 1), heating and reacting for 1 hour in a dark place in nitrogen atmosphere, standing for 10 minutes in an ice water bath to separate out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with ethanol to obtain the product.
The absorption range of the photosensitizer prepared in this example is 300-450 nm.
Preparing a photoinitiation system of 1 wt% of photosensitizer (E) -cyclopentyl-1, 3-diene-1-yl (5- (3- (1-methyl-1H-pyrrole-2-yl) acryloyl) cyclopentyl-1, 3-diene-1-yl) iron and 3 wt% of diphenyliodonium hexafluoroantimonate, adding the photoinitiation system into monomer epoxy resin EPOX according to the weight of the monomer of 100%, and polymerizing under the illumination of 395nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the light irradiation is 600s, and the epoxy bond conversion rate is 56 percent. The curing effect is good.
Comparative example 1
Preparing 3 wt% of diphenyliodonium hexafluoroantimonate system, adding diphenyliodonium hexafluoroantimonate into epoxy resin EPOX according to the weight of a monomer being 100%, and polymerizing under the illumination of 360nm, 385nm and 405nm respectively (the light intensity is 100 mW/cm)2) The illumination is 600s, the epoxy conversion rate is 19 percent, 15 percent and 8 percent respectively, and the epoxy resin is not cured.
Comparative example 2
Preparing 1 wt% of photosensitizer 1, 3-bis (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-ketone system, adding the photosensitizer 1, 3-bis (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-ketone into epoxy resin EPOX based on 100% of the weight of the epoxy resin EPOX, and polymerizing under the illumination of 360nm, 385nm and 405nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, the epoxy conversion rate is 10 percent, 7 percent and 5 percent respectively, and the epoxy resin is not cured.
Comparative example 3
Preparing 1 wt% of photosensitizer 1- (furan-2-yl) -3- (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-ketone, adding the photosensitizer 1- (furan-2-yl) -3- (1-methyl-1H-pyrrole-2-yl) prop-2-ene-1-ketone into epoxy resin EPOX according to the weight of 100% of the epoxy resin EPOX, and polymerizing under the illumination of 360nm, 385nm and 405nm respectively (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, the epoxy conversion rate is respectively 8%, 5% and 2%, and the epoxy resin is not cured.
Comparative example 4
Preparing 1 wt% of photosensitizer 3- (1-methyl-1H-pyrrole-2-yl) -1- (thiophene-2-yl) prop-2-ene-1-ketone, adding the photosensitizer 3- (1-methyl-1H-pyrrole-2-yl) -1- (thiophene-2-yl) prop-2-ene-1-ketone into epoxy resin EPOX based on 100% of the weight of the epoxy resin EPOX, and polymerizing under the illumination of 360nm, 385nm and 405nm (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, the epoxy conversion rate is respectively 9%, 5% and 6%, and the epoxy resin is not cured.
Comparative example 5
Preparing 1 wt% of photosensitizer 1, 5-bis (1-methyl-1H-pyrrole-2-yl) penta-1, 4-dienone, adding the photosensitizer 1, 5-bis (1-methyl-1H-pyrrole-2-yl) penta-1, 4-dienone into epoxy resin EPOX based on 100% of the weight of the epoxy resin EPOX, and polymerizing under the illumination of 360nm, 385nm and 405nm respectively (the light intensity is 100 mW/cm)2) And 600s of illumination.
And (3) measuring results: the epoxy conversion rates were 4%, 6%, 2%, respectively, and the epoxy resin was uncured.
Comparative example 6
Preparing 1 wt% of photosensitizer 2, 6-bis ((1-methyl-1H-pyrrole-2-yl) methylene) cyclohex-1-one, adding the photosensitizer 2, 6-bis ((1-methyl-1H-pyrrole-2-yl) methylene) cyclohex-1-one into epoxy resin EPOX based on 100% of the weight of the epoxy resin EPOX, and polymerizing under the illumination of 360nm, 385nm and 405nm respectively (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, the epoxy conversion rate is 10 percent, 7 percent and 3 percent respectively, and the epoxy resin is not cured.
Comparative example 7
Preparing 1 wt% of photosensitizer 4, 4-dimethyl-2, 6-bis ((1-methyl-1H-pyrrole-2-yl) methylene) cyclohex-1-one, adding the photosensitizer 4, 4-dimethyl-2, 6-bis ((1-methyl-1H-pyrrole-2-yl) methylene) cyclohex-1-one into epoxy resin EPOX based on 100% of the weight of the epoxy resin EPOX, and polymerizing under the illumination of 360nm, 385nm and 405nm respectively (the light intensity is 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, the epoxy conversion rate is 6%, 4% and 5%, respectively, and the epoxy resin is not cured.
Comparative example 8
1 wt% of photosensitizer was prepared using a commercial photoinitiator thioxanthone ITX and 3 wt% of diphenyliodonium hexafluoroantimonate, the thioxanthone and diphenyliodonium hexafluoroantimonate were added to an epoxy resin EPOX at 100% by weight of the epoxy resin EPOX, and polymerization was carried out under 465nm illumination (light intensity 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, and the epoxy bond conversion rate is 15 percent. The epoxy resin is uncured.
Comparative example 9
Preparation of 1% wt photosensitizer Using commercial photoinitiator thioxanthone ITX and 3% wt diphenyliodonium hexafluoroantimonate, thioxanthone and diphenyliodonium hexafluoroantimonate were added to epoxy resin EPOX at 100% by weight of epoxy resin EPOX, and polymerized under illumination of 405nm (light intensity 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, and the epoxy bond conversion rate is 50%. The epoxy resin has better curing effect and is similar to a pyrrolyl ketone-onium salt system.
Comparative example 10
Formulation of 1% wt photosensitizer Using a commercial photoinitiator Camphorquinone CQ and 3% wt diphenyliodonium hexafluoroantimonate, Camphorquinone CQ and diphenyliodonium hexafluoroantimonate were added to epoxy resin EPOX at 100% by weight of epoxy resin EPOX, and polymerized under illumination of 405nm (light intensity 100 mW/cm)2)。
And (3) measuring results: the illumination is 600s, and the epoxy bond conversion rate is 30 percent. The degree of cure is low and the part is not completely cured.
From the results of the measurements of the comparative example, it was found that under long wavelength irradiation, EPOX curing could not be achieved by a single photosensitizer or a single cationic photoinitiator diphenyliodonium hexafluoroantimonate, and that EPOX curing could be achieved effectively only when the photosensitizer and diphenyliodonium hexafluoroantimonate constituted a cationic photoinitiator system. Compared with common commercial thioxanthone ITX serving as a photosensitizer and camphorquinone CQ, the ITX can cure the epoxy resin under a light source of 405nm, the effect is similar to that of a pyrrolyl ketone-onium salt system, and the ITX cannot react as the photosensitizer under 465 nm. CQ photosensitization was poor at 405 nm. In contrast, the pyrrolyl ketone-onium salt cationic photoinitiator system has obvious application advantages.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. A pyrrolyl ketone photoinitiating system characterized in that: the photosensitizer is pyrrolyl ketone, and the photoinitiator is onium salt;
the structural general formula of the pyrrolyl ketone is shown as follows:
Figure FDA0002970808280000011
Figure FDA0002970808280000021
wherein R is1-30The substituent group is-CnHn+1Or H or halogen substituents-F, -Cl, -Br, -I; or a substituent containing O: -CHO, -COOH, -OH, -CH2OCH3(ii) a Or N-containing substituents-NH2、-NO2-CN, or a substituent containing S: -HS, -SO3H or an aromatic hydrocarbon, alkene or alkyne whole chain or branched chain.
2. The pyrrolone photoinitiating system of claim 1, wherein: the R is5、R9、R15、R20Also having the following groups:
Figure FDA0002970808280000022
3. the pyrrolone photoinitiating system of claim 1, wherein: the reaction formula of the pyrrolyl ketone is as follows:
Figure FDA0002970808280000023
Figure FDA0002970808280000031
4. the pyrrolone photoinitiating system of claim 1, wherein: the preparation method of the pyrrolyl ketone comprises the following steps: adding alpha-H-free aldehyde and alpha-H-containing ketone substances into an organic reagent, using weak base as a catalyst, heating and reacting in a nitrogen atmosphere in a dark place, standing for 10min in an ice water bath to separate out a light yellow crude product, washing the crude product with deionized water, drying in vacuum, and recrystallizing with an organic solvent to obtain the product.
5. The pyrrolone photoinitiating system of claim 1, wherein: the onium salts include iodonium salts or sulfonium salts.
6. The pyrrolone photoinitiating system of claim 4, wherein: the reaction is heated for 1h at 50-60 ℃ in a nitrogen atmosphere in the dark.
7. The pyrrolone photoinitiating system of claim 4, wherein: the weak base is 1mol/L NaOH aqueous solution or sodium alkoxide aqueous solution.
8. The pyrrolone photoinitiating system of claim 1, wherein: the mass ratio of the photosensitizer to the photoinitiator is 0.5-5: 1-10.
9. Use of a pyrrolone photoinitiating system as defined in any one of claims 1 to 8 in coatings, inks, adhesives, photoresists, 3D printing.
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