CN112574184B - Epoxide-substituted pyrazoline derivative, photocuring composition and preparation method - Google Patents

Epoxide-substituted pyrazoline derivative, photocuring composition and preparation method Download PDF

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CN112574184B
CN112574184B CN202011567423.3A CN202011567423A CN112574184B CN 112574184 B CN112574184 B CN 112574184B CN 202011567423 A CN202011567423 A CN 202011567423A CN 112574184 B CN112574184 B CN 112574184B
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substituted pyrazoline
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金明
陈世雄
万德成
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Abstract

The present application relates to epoxide-substituted pyrazoline derivatives represented by the following formulae (I) and (II), photocurable compositions, and methods for preparing epoxide-substituted pyrazoline derivatives represented by the formulae (I) and (II). The epoxide-substituted pyrazoline derivatives shown in the formula (I) and the formula (II) have good absorption at the wavelength of more than 350nm, and can be used as a sensitizer for photocuring polymerization; the synthesis steps of the molecules are simple, and the method is suitable for industrial production and application; meanwhile, the molecule can form chemical bond bonding with the photocured product, and the mobility of the molecule is reduced.

Description

Epoxide substituted pyrazoline derivative, light-cured composition and preparation method
Technical Field
The invention belongs to the field of new material organic chemistry, and particularly relates to preparation of an epoxide substituted pyrazoline derivative, which is used as a sensitizer in a photocuring system.
Background
Ultraviolet-visible light (UV-Vis) curing is a curing mode using ultraviolet light or visible light to cure a coating, has the advantages of rapid curing, energy conservation, environmental protection, no VOC (volatile organic solvent) generation, wide applicability and the like, and is widely applied to the fields of printing ink, electronic packaging, rapid photo-curing forming, photoresist, adhesives and the like. Photocuring can be classified into radical curing and cationic curing depending on the radical generated by the photoinitiator.
Compared with free radical curing, the cation curing system (non-acrylate) has the advantages of difficult influence of oxygen inhibition, small curing shrinkage rate and the like, and widens the research and development range of the light curing material. Under the action of ultraviolet-visible light, when the light energy is greater than the bond-breaking energy of the photoinitiator, the cationic photoinitiator generates protonic acid or Lewis acid to form a positive ion active center to initiate polymerization. This process requires that the absorption spectrum of the photoinitiator match the wavelength range of the light source.
The traditional cationic initiator mainly comprises bisaryliodonium salt and triarylsulfonium salt, and the main absorption light domain of the traditional cationic initiator is 200-330nm. This absorption domain is matched to the wavelength of a conventional mercury lamp light source. The mercury lamp has great harm to the environment, the energy is too high, and the side reactions in the curing process are more, so that the novel low-energy LED light source gradually becomes a substitute. However, the wavelength of the new LED light source is in the near uv-visible region, i.e. above 360nm, which does not match the main absorption range of conventional cationic initiators. This results in that conventional photoinitiators do not have good photoinitiating capability under LED light sources.
Photosensitizers are a class of substances that can absorb photon energy and transfer it to reactive components, and are used primarily in the field of solar cells. The addition of the LED sensitive dye in the photocuring component can effectively improve the polymerization rate of the formula under an LED light source. The photosensitizer has generally small molecular weight and is not easy to generate chemical reaction, so that a large amount of small molecules in the formula can be remained although the formula is ensured not to have unnecessary side reaction in the illumination process, and the small molecules are easy to migrate after the product is cured, so that the product performance is reduced.
Therefore, how to obtain a photosensitizer with a larger wavelength absorption peak, good electron transfer or energy transfer capability and low migration capability in a photocuring product by a simple synthesis method is a problem to be solved.
Disclosure of Invention
As a result of intensive studies to overcome the disadvantages of the prior art, the inventors have found that the lowest unoccupied orbital (LUMO) energy of pyrazoline molecules is generally higher (about-2.20 eV relative to vacuum) than that of commercially available bisaryliodonium salts and triarylsulfonium salts. Therefore, the pyrazoline molecule has good sensitization effect on the onium salt initiator; meanwhile, pyrazoline has intramolecular charge transfer, so that the pyrazoline has good absorption property in a light domain of more than 350nm, and the absorption range of the pyrazoline is greatly overlapped with that of a commercial LED light source. Therefore, when a cationically polymerizable functional group is introduced into a pyrazoline molecule, requirements of red shift of an absorption peak, strong electron transfer capability, and low mobility can be simultaneously satisfied. Meanwhile, the preparation method of the epoxide substituted pyrazoline derivative shown in the formula (I) and the formula (II) is simple and convenient, high in yield, low in cost and suitable for industrial production and application.
[ epoxide-substituted pyrazoline derivative ]
The epoxide-substituted pyrazoline derivative is shown in the following formula (I) and formula (II),
Figure GDA0003856076640000021
R 1 is selected from C 1-12 Unsubstituted or substituted by 1 to 5R 4 Substituted phenyl, unsubstituted or substituted by 1 to 9R 4 Substituted condensed ring aryl, unsubstituted or substituted by 1 to 4R 4 Substituted aromatic heterocyclic radical, or unsubstituted or substituted by 1-8R 4 Substituted benzoaromatic heterocyclic groups;
R 2 is selected from C 1-6 Alkyl radical, C 3-6 Cycloalkyl, unsubstituted or substituted by 1-5R 4 Substituted phenyl, unsubstituted or substituted by 1 to 9R 4 Substituted condensed ring aryl, unsubstituted or substituted by 1-4R 4 Substituted aromatic heterocyclic radical, unsubstituted or substituted by 1-8R 4 Substituted benzoaromatic heterocyclic groups;
R 3 selected from H, C unsubstituted or substituted by 1-3O, S, N atoms 1-6 Alkyl, unsubstituted or substituted by 1 to 3O, S, N atoms 3-6 Unsubstituted or substituted by 1 to 5R 4 Substituted benzyl, unsubstituted or substituted by 1-5R 4 Substituted phenyl;
R 4 selected from unsubstituted or substituted by 1-5R a Substituted C 1-6 Alkyl, -F, -Cl, -Br, -I, -CN, -CF 2 CF 3 、-CF 3 、-NO 2 、-NR b R b 、-OR b 、-SR b 、-C(＝O)R b 、-CO 2 R b 、-OC(＝O)R b 、-NR b C(＝O)R b 、-S(＝O)R b 、-S(＝O) 2 R b Unsubstituted or substituted by 1-5R c Substituted carbocyclic ring, unsubstituted or substituted by 1 to 5R d A substituted heterocycle;
R a each independently selected from C 1-6 Alkyl group, (CH) 2 ) r C 3-6 Cycloalkyl or- (CH) 2 ) r A phenyl group;
R b each independently selected from H, unsubstituted or substituted by 1-5R e Substituted C 1-6 Alkyl, unsubstituted or substituted by 1-5R e Substituted- (CH) 2 ) r Ph；
R c Each independently selected from unsubstituted or substituted by 1-5R e Substituted C 1-6 Alkyl, unsubstituted or substituted by 1-5R e Substituted (CH) 2 ) r Ph；
R d Each independently selected from unsubstituted or substituted by 1-5R e Substituted C 1-6 Alkyl, unsubstituted or substituted by 1-5R e Substituted (CH) 2 ) r Ph；
R e Each independently selected from-F, -Cl, -Br, -I, -OH and-NO 2 、-CN，-CF 3 、-CF 2 CF 3 、C 1-4 Alkyl radical, C 1-4 Alkoxy radical, C 3-7 Cycloalkyl, phenyl, benzyl, phenethyl, naphthyl, heterocyclic aryl, or, keto;
each r is independently 0, 1, 2, 3 or 4;
w, z are each independently selected from 0 or 1.
The foregoing term "C 1-12 The "alkyl group" of (1) is an alkyl group having 1 to 12 carbon atoms, and may be a linear or branched alkyl group, and is not particularly limited. As "C 1-12 Examples of the "alkyl group" include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
The foregoing term "C 1-6 The "alkyl group" of (1) is an alkyl group having 1 to 6 carbon atoms, and may be a linear or branched alkyl group, and is not particularly limited. Do not likeIs "C 1-6 Examples of the "alkyl group" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl and hexyl groups.
The aforementioned term "condensed ring aryl group" means a polycyclic aryl group in which two or more benzene rings are constituted by sharing a ring edge, and examples of the condensed ring aryl group include, for example, naphthyl, anthryl, phenanthryl, pyrenyl, and the like;
the term "aromatic heterocyclic group" refers to a heterocyclic group having aromatic characteristics, and examples of the aromatic heterocyclic group include furyl group, imidazolyl group, pyridyl group and the like.
The term "benzoaromatic heterocyclic group" as used herein means an aromatic heterocyclic group in which a benzene ring is fused with a heterocyclic ring, and examples of the "benzoaromatic heterocyclic group" include quinolyl, indolyl, purinyl and the like.
The foregoing term "C 3-6 The "cycloalkyl group" means a cycloalkyl group having 3 to 6 carbon atoms as "C 3-6 Examples of cycloalkyl "are, for example, cyclopropyl, methylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclobutyl, dimethylcyclobutyl, cyclohexyl and the like.
The foregoing term "C 1-4 The "alkyl group" means an alkyl group having 1 to 4 carbon atoms as "C 1-4 Examples of the "alkyl group" include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
The foregoing "Ph" represents a phenyl group.
The epoxide-substituted pyrazoline derivative of the formula (I) according to the invention, preferably R 1 、R 2 Each independently an aromatic heterocyclic group selected from the following (A) and (B):
(A) A 6-membered aromatic heterocyclic group containing 1 to 3 heteroatoms selected from the group consisting of O, N and S on the heterocyclic ring;
(B) A 5-membered aromatic heterocyclic group containing a hetero atom of any one of the following groups in the heterocyclic ring,
1) 1O, 1N, or, 1S;
2) 1S and 1N, 1O and 1N, or, 2N; or
3) 1O and 2N, or, 1S and 2N.
In addition, by introducing hybridization into the molecular structure, a new electronic structure can be further formed by the pyrazoline group and the lone pair of electrons of the heteroatom, and the absorption of the molecule is further influenced.
In the epoxide-substituted pyrazoline derivative of the formula (I) according to the invention, R is preferably 1 、R 2 Each independently selected from the group consisting of the following structural formulae:
Figure GDA0003856076640000051
wherein R is 4 The definitions of (a) are the same as those described above.
In the epoxide-substituted pyrazoline derivative represented by the formula (I) of the present invention, it is preferably selected from the group consisting of compounds represented by the following structural formulae,
Figure GDA0003856076640000061
[ Photocurable composition ]
The photocurable composition of the present invention contains the aforementioned epoxide-substituted pyrazoline derivative of the present invention and a polymerizable component containing a photoinitiator, a monomer having an epoxy group, or an ethylenic bond or a polymer.
In the photocurable composition of the present invention, the epoxide-substituted pyrazoline derivative represented by the formula (I) or (II) is preferably contained in an amount of 0.5 to 10 parts by weight relative to 100 parts by weight of the total amount of the polymerizable components. More preferably, the content of the epoxide-substituted pyrazoline derivative represented by the formula (I) or the formula (II) is 1 to 10 parts by weight.
Examples of the photoinitiator include (2, 4, 6-trimethylbenzoyl chloride) diphenylphosphine oxide (TPO) and its derivatives, 1-hydroxycyclohexylphenylketone (184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone (907), thioxanthone (ITX) and its derivatives, diaryliodonium salt (Iod), triarylsulfonium salt (6976), and the like.
Examples of the monomer having an epoxy group include monofunctional glycidyl ethers, polyfunctional aliphatic glycidyl ethers, polyfunctional aromatic glycidyl ethers, glycidyl esters, and aliphatic epoxy compounds.
Examples of the monofunctional glycidyl ether include allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, and 2-methyloctyl glycidyl ether.
Examples of the polyfunctional aliphatic glycidyl ether include 1, 6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
Examples of the polyfunctional aromatic glycidyl ethers include bisphenol a glycidyl ether, bisphenol F glycidyl ether, brominated bisphenol a glycidyl ether, biphenol glycidyl ether, tetramethylbiphenol glycidyl ether, and resorcinol glycidyl ether.
Examples of the glycidyl esters include glycidyl acrylate, glycidyl methacrylate, diglycidyl phthalate, and diglycidyl hexahydrophthalate.
Examples of the aliphatic epoxy compound include 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, 3, 4-epoxycyclohexylethyl-3, 4-epoxycyclohexylformate, ethylenecyclohexenyldioxide, propylenylcyclohexenyldioxide, 3, 4-epoxy-4-methylcyclohexyl-2-propenyloxy, and the like.
Examples of the monomer having an ethylenic bond include (meth) acrylates, acrolein, olefins, conjugated dienes, styrene, maleic anhydride, fumaric anhydride, vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth) acrylic acid, and (meth) acrylic acid derivatives such as (meth) acrylamide, vinyl halides, vinylidene halides, and the like.
In the photocurable composition of the present invention, the polymerizable component may be in the form of a polymer such as an oligomer or a prepolymer, or a copolymer formed from at least one of a monomer, an oligomer, and a prepolymer. In addition, it may be in the form of an aqueous dispersion.
As the aforementioned epoxy group-containing polymer, for example, an epoxy group-containing polymer or resin such as bisphenol a epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, novolak type epoxy resin, biphenyl type epoxy resin, hydrogenated biphenyl type epoxy resin, aliphatic type epoxy resin, and the like can be mentioned.
Examples of such an ethylenic bond-containing polymer include (meth) acrylic copolymers having a (meth) acryloyl functional group, urethane (meth) acrylates, polyester (meth) acrylates, unsaturated polyesters, polyether (meth) acrylates, silicone (meth) acrylates, epoxy resin (meth) acrylates, and the like which are water-soluble or water-dispersible.
[ Process for producing epoxide-substituted pyrazoline derivative ]
The preparation method of the epoxide-substituted pyrazoline derivative comprises the following steps (c):
Figure GDA0003856076640000091
in the aforementioned step (c), the compound represented by the formula (I) -b or the formula (II) -b and R 3 Reacting the substituted halogenated epoxide in the presence of tetrabutylammonium bromide and a base to obtain the compound shown in the formula (I) or the formula (II) respectivelyEpoxide substituted pyrazoline derivative, the reaction temperature is 0-80 ℃;
the R is 1 、R 2 、R 3 Y, w and z are as defined in the epoxide-substituted pyrazoline derivative of the formula (I).
As an example of the aforementioned step (c), for example, a method of reacting a compound represented by the formula (I) -b with R 4 The substituted halogenated epoxypropane reacts in sodium hydroxide, tetrabutylammonium bromide and toluene, and after the solvent is removed, the epoxide substituted pyrazoline derivative shown in the formula (I) is prepared by recrystallization, namely the target product.
As the foregoing step (c), optionally, the base may be selected from sodium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydride and the like; the solvent can be selected from toluene, carbon tetrachloride, tetrahydrofuran, acetonitrile, N, N' -dimethylformamide and the like.
When z =1, the method for producing the epoxide-substituted pyrazoline derivative according to the present invention further includes the following step (c'):
Figure GDA0003856076640000092
in the step (c'), the compound represented by the formula (I) -b or the formula (II) -b and R 3 The substituted halogenated epoxide reacts under the catalysis of p-toluenesulfonic acid to respectively obtain epoxide substituted pyrazoline derivatives shown in formula (I) or formula (II), and the reaction temperature is room temperature to 60 ℃.
As an example of the aforementioned step (c'), there may be mentioned, for example, a step of reacting a compound represented by the formula (II) -b with R 4 The substituted halogenated oxetane compound reacts in p-toluenesulfonic acid, and after the solvent is removed, the epoxide substituted pyrazoline derivative shown in the formula (I) is prepared by recrystallization, namely the target product.
As an embodiment of the method for producing the epoxide-substituted pyrazoline derivative, the method for producing the compounds represented by the formulae (I) to (b) and (II) to (b) includes the following steps when z =0(a 1 ) Step (b) 1 )：
Figure GDA0003856076640000101
Said step (a) 1 ) In, R 1 Substituted ethyl ketone and 4-hydroxy benzaldehyde or 5-hydroxy-2-heterocyclic aryl formaldehyde react in absolute ethyl alcohol by taking alkali as a catalyst at the temperature of room temperature to 60 ℃, and then are acidified by acid to respectively obtain the product (I) -a 1 Or (II) -a 1 (ii) a The aforementioned step (a) 1 ) The reaction time of (3) may be 0.5 to 6 hours, preferably 1 to 4 hours;
said step (b) 1 ) In the step (a), the step (a) 1 ) The (I) -a obtained in (1) 1 Or (II) -a 1 The compound is reacted with R in acetic acid 2 Carrying out reflux reaction on substituted hydrazine to respectively obtain compounds shown in formulas (I) -b and (II) -b; the aforementioned step (b) 1 ) The reaction time of (3) may be 1 to 10 hours, preferably 2 to 6 hours;
the aforementioned step (a) 1 ) The base in (4) is not particularly limited, but sodium hydroxide, potassium hydroxide or potassium carbonate is preferred.
The aforementioned step (a) 1 ) The acid in (4) is not particularly limited, but is preferably hydrochloric acid, sulfuric acid or acetic acid.
As an embodiment of the method for producing the epoxide-substituted pyrazoline derivative, there is provided a method for producing the compound represented by the formula (I) -b or the formula (II) -b, wherein when z =1, the method comprises the step of (a) 2 ) Step (b) 2 )：
Figure GDA0003856076640000111
Said step (a) 2 ) In, R 1 Substituted ethyl ketone and 4-hydroxymethyl benzaldehyde or 5-hydroxymethyl-2-heterocyclic aryl formaldehyde react in absolute ethyl alcohol by taking alkali as a catalyst to respectively obtain a product (I) -a 2 Or (II) -a 2 The reaction temperature is between room temperature and 60 ℃; the aforementioned step (a) 2 ) Is/are as followsThe reaction time may be 1 to 10 hours, preferably 2 to 6 hours;
said step (b) 2 ) In the step (a), the step (a) 2 ) The (I) -a obtained in (1) 2 Or (II) -a 2 The compound shown and R 2 Reacting substituted hydrazine in absolute ethyl alcohol by taking alkali as a catalyst to respectively obtain compounds shown as formulas (I) -b and (II) -b, wherein the reaction temperature is 80 ℃; the aforementioned step (b) 2 ) The reaction time of (3) may be 1 to 8 hours, preferably 1 to 5 hours;
the aforementioned step (a) 2 ) The base in (1) is not particularly limited, but is preferably sodium hydroxide, potassium hydroxide or potassium carbonate.
The aforementioned step (b) 2 ) The base in (1) is not particularly limited, but is preferably sodium hydroxide, potassium hydroxide or potassium carbonate.
The beneficial effects and the application are as follows:
the epoxide-substituted pyrazoline derivatives shown in the formula (I) and the formula (II) have good absorption at the wavelength of more than 350 nm. The epoxide-substituted pyrazoline derivative shown in the formula (I) and the formula (II) has good application prospect as a polymerizable photosensitizer, can be used as the photosensitizer to be applied to a photocuring composition, and can also be polymerized in a photocuring system as a polymerizable monomer to reduce the mobility of the polymerizable monomer.
The photocurable composition of the present invention contains the epoxide-substituted pyrazoline derivatives represented by the formulae (I) and (II) of the present invention, and thus has good absorption at a wavelength of 350nm or more.
The epoxide-substituted pyrazoline derivatives shown in the formula (I) and the formula (II) have the advantages of simple and convenient synthesis steps and low cost of raw materials, and are suitable for industrial production and application.
Detailed Description
Examples
In order to more clearly illustrate the disclosure, the disclosure is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the present disclosure.
The first embodiment is as follows: synthesis of target molecule (I) -1 according to the following scheme
Figure GDA0003856076640000121
(a) Sodium hydroxide and absolute ethyl alcohol are used at normal temperature for 1 hour;
(b) Sodium hydroxide, anhydrous ethanol, 80 deg.C, 2 hr
(c) Potassium hydroxide, tetrabutylammonium bromide, toluene, 110 ℃ and 4 hours;
1. synthesis of 3- (4-hydroxymethylphenyl) -1-phenyl-2-en-1-one
Acetophenone (12.00g, 0.10 mol), 4-hydroxymethylbenzaldehyde (13.62g, 0.10 mol) and absolute ethanol (30 mL) as a solvent were put in a 100mL three-necked flask equipped with a magnetic rotor, and stirred at room temperature. Then, an aqueous solution of sodium hydroxide (12.00g, 0.30mol, 12mL) was prepared and added dropwise to the reaction system through a constant pressure dropping funnel. The reaction process is monitored by a silica gel chromatography plate, after the reaction is finished, the reaction is filtered, and the filtrate is filtered after being concentrated. And washing the solid obtained by filtering twice with water, washing twice with absolute ethyl alcohol, drying, and recrystallizing with absolute ethyl alcohol to obtain yellow crystals with the yield of 89.6%. HRMS for C 16 H 12 O 3 :238.1031 (calculated value), 238.1023 (actual value).
2. Synthesis of 1, 3-diphenyl-5- (4-hydroxymethylphenyl) pyrazoline
Sodium hydroxide (5.60g, 0.14mol) and absolute ethyl alcohol (100 mL) as a solvent are added into a 250mL three-neck flask containing a magnetic rotor, and the mixture is refluxed and stirred at 80 ℃ to be dissolved; phenylhydrazine (7.57g, 0.08mol) was then added and after 15 minutes 3- (4-hydroxymethylphenyl) -1-phenyl-2-en-1-one (16.68g, 0.07mol) was added and the reaction was incubated and the progress of the reaction was monitored by means of a silica gel chromatography plate. After the reaction is finished, the reaction product is cooled to room temperature and filtered, and the obtained solid is washed twice by 95% ethanol and then recrystallized by an absolute ethanol/ethyl acetate (10/1, v/v) mixed solvent to obtain a yellow crystal product with the yield of 84.2%. HRMS for C 22 H 20 N 2 O:328.1604 (calculated value), 328.1620 (actual value).
3. Synthesis of target molecule (I)
1, 3-diphenyl-5- (4-hydroxymethylphenyl) pyrazoline (12.42g, 0.05mol), potassium hydroxide (4.49g, 0.08mol), tetrabutylammonium bromide (1.0 g) and toluene (150 mL) are added into a 250mL three-neck flask containing a magnetic rotor, the temperature is raised to reflux the toluene, and the temperature is kept for 1h; subsequently, epichlorohydrin (5.55g, 0.06mol) is added, the heat preservation reaction is continued, and the reaction process is monitored by a silica gel chromatography plate. After the reaction was completed, toluene and excess epichlorohydrin were removed by distillation under reduced pressure, followed by dissolution in dichloromethane (100 mL), washing twice with saturated brine (2 × 200 mL), washing once with deionized water (150 mL), collection of the organic phase, drying with anhydrous sodium sulfate, followed by removal of all organic solvents by suspension evaporation under reduced pressure, and purification of the obtained product by a silica gel column chromatography (petroleum ether/ethyl acetate =4/1, v/v) gave the target molecule (I) -1 in a yield of 82.1%. HRMS for C 25 H 24 N 2 O 2 :384.1834 (calculated value), 384.1842 (actual value).
The second embodiment: synthesis of target molecules (I) -2 to (I) -8
The preparation method of the pyrazoline photosensitizer is the same as that of the embodiment I, and arylethanone and R are changed 4 And the implementation can be realized. Specific yields and mass spectral characterization results are as follows.
Figure GDA0003856076640000141
Example three: synthesis of target molecules (I) -9 to (I) -14
The preparation method of the pyrazoline photosensitizer is the same as that of the first embodiment, and substituted phenylhydrazine and R are changed 4 And the implementation can be realized. Specific yields and mass spectral characterization results are as follows.
Figure GDA0003856076640000142
Figure GDA0003856076640000151
Example four: synthesis of target molecule (I) -15 according to the following scheme
Figure GDA0003856076640000152
(a) Sodium hydroxide and absolute ethyl alcohol are used at normal temperature for 2 hours;
(b) Sodium hydroxide, anhydrous ethanol, 80 deg.C, 2 hr
(c) P-methoxybenzenesulfonic acid, acetone, 40 ℃ and 10 hours;
1. synthesis of 1- (4-trifluoromethylphenyl) -3- (4-hydroxymethylphenyl) -2-en-1-one
The 4-trifluoromethyl acetophenone and 4-hydroxymethyl benzaldehyde were reacted in sodium hydroxide and anhydrous ethanol in 88.6% yield. HRMS for C 17 H 13 F 3 O 2 :306.0911 (calculated value), 306.0923 (actual value).
2. Synthesis of 1- (4-methylphenyl) -3- (4-trifluoromethylphenyl) -5- (4-hydroxymethylphenyl) -pyrazoline
The 1- (4-trifluoromethylphenyl) -3- (4-hydroxymethylphenyl) -2-en-1-one and 4-methoxyphenylhydrazine are reacted in sodium hydroxide and absolute ethyl alcohol, and the yield is 88.6%. HRMS for C 24 H 21 F 3 N 2 O 2 :426.1604 (calculated value), 426.1620 (actual value).
3. Synthesis of target molecule (I) -15
In a 250mL three-necked flask, 1- (4-methylphenyl) -3- (4-trifluoromethylphenyl) -5- (4-bromomethylphenyl) -pyrazoline (12.23g, 25.0 mmol), glycidol (16.50g, 0.25mol) and p-methoxybenzenesulfonic acid (0.42g, 2.5 mmol) and acetone (80 mL) as a solvent were charged, followed by stirring at room temperature. The progress of the reaction was checked by means of a silica gel chromatographic plate. After the reaction, the mixture was extracted with 200mL of a 20% aqueous solution of sodium hydroxide and 400mL of dichloromethane. The aqueous phase was washed 3 times with dichloromethane, the organic phases were combined, the organic phase was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the product was recrystallized from ethanol to obtain a yield of 82.6%. HRMS for C 26 H 23 F 3 N 2 O 3 :468.1741 (calculation ofValue), 468.1733 (actual value).
Example five: target molecules (I) -16 to (I) -22 were synthesized.
The preparation method of the pyrazoline derivative is basically the same as that of the fourth embodiment, and can be realized by changing methyl-substituted aryl formaldehyde and hydroxyl-containing epoxide. Specific yields and mass spectral characterization results are as follows.
Figure GDA0003856076640000161
Figure GDA0003856076640000171
Example six: synthesis of target molecule (I) -23 according to the following scheme
(a) Sodium hydroxide and absolute ethyl alcohol are used at normal temperature for 1 hour; hydrochloric acid, pH =7; (ii) a
(b) Acetic acid, 135 ℃,2h;
(c) Potassium hydroxide, acetone, 60 ℃,6h.
Figure GDA0003856076640000172
1. Synthesis of 3- (4-ethoxyphenyl) -1- (4-hydroxyphenyl) -2-en-1-one
4-ethoxyacetophenone (16.42g, 0.10 mol), 4-hydroxybenzaldehyde (12.21g, 0.10 mol) and absolute ethanol (25 mL) as a solvent were charged in a 100mL three-necked flask containing a magnetic rotor, and stirred at room temperature. Then, an aqueous solution of sodium hydroxide (12.00g, 0.30mol, 12mL) was prepared and added dropwise to the reaction system through a constant pressure dropping funnel. After the addition was completed, the reaction was carried out for 2 hours, and the reaction process was monitored by a silica gel chromatography plate. After the reaction, brine was added to adjust the pH of the system to 7, and the mixture was filtered, and the filtrate was concentrated and then filtered. And washing the solid obtained by filtering twice with water, washing twice with absolute ethyl alcohol, drying, and recrystallizing with absolute ethyl alcohol to obtain yellow crystals with the yield of 89.1%. HRMS for C 17 H 16 O 3 :268.1141 (calculation ofValue), 268.1138 (actual value).
2. Synthesis of 1-phenyl-3- (4-ethoxyphenyl) -5- (4-hydroxyphenyl) -pyrazoline
A250 mL three-necked flask containing a magnetic rotor was charged with acetic acid as a solvent (40 mL), followed by 3- (4-ethoxyphenyl) -1- (4-hydroxyphenyl) -2-en-1-one (14.09g, 0.06mmol), warmed to dissolve the solids, then added phenylhydrazine (7.57g, 0.08mol), warmed to 135 deg.C, allowed to reflux the acetic acid, and the reaction was allowed to incubate, with the progress of the reaction being monitored by silica gel chromatography. After the reaction is finished, the reaction product is cooled to room temperature and filtered, and the obtained solid is washed twice by 95% ethanol and then recrystallized by an absolute ethanol/ethyl acetate (10/1, v/v) mixed solvent to obtain a yellow crystal product with the yield of 79.4%. HRMS for C 23 H 22 N 2 O 2 :358.1701 (calculated value), 358.1720 (actual value).
3. Synthesis of target molecule (I) -23
The method is the same as the first example and the yield is 92.6 percent by using the reaction of 1-phenyl-3- (4-ethoxyphenyl) -5- (4-hydroxyphenyl) -pyrazoline and epichlorohydrin in sodium hydroxide and acetone. HRMS for C 26 H 26 N 2 O 3 :414.1941 (calculated value), 414.1933 (actual value).
Example seven: synthesis of target molecules (I) -24 to (I) -30
The preparation method of the pyrazoline derivative is basically the same as that of the sixth embodiment, and can be realized by changing substituted arylethanone and halogen-containing epoxide. Specific yields and mass spectral characterization results are as follows.
Figure GDA0003856076640000181
Figure GDA0003856076640000191
Example eight: (I) -1 LED photocuring experiments and sensitizer migration Property testing
Sample systems containing epoxide-substituted pyrazoline photosensitizers were prepared according to the following formulation (in weight percent)
Dual-functional epoxy monomer (EPOX): 97 percent
Photoinitiator (Iod): 1.5 percent
Photosensitizer ((I) -1): 1.5 percent
The above mixture of formulation examples was applied to cardboard to form a coating of about 25-30 microns at a unit power of 1000mW/cm, manufactured by Guangzhou and Guangsheng technologies, inc 2 The 365 nm LED light source (3 cm wide and 80 cm long LED surface light source) is an excitation light source and is placed on the variable speed conveyor belt. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The results show that the compounds containing this example all cure efficiently at a rate of greater than 25 m/min.
And (3) carrying out micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the migrated photosensitizer accounts for 0.2% of the mass of the original photosensitizer in the coating.
Example nine: (I) LED photocuring experiments and sensitizer migration Property testing of-8
Sample systems containing epoxide-substituted pyrazoline photosensitizers were prepared according to the following formulation (in weight percent)
Monofunctional epoxy monomer (CHO): 68.5 percent of
Difunctional epoxy monomer (EPOX): 30.0 percent
Photoinitiator (Iod): 0.5 percent
Photosensitizer ((I) -8): 1.0 percent
The above formulation example mixture was applied to cardboard to form a coating of about 30-35 microns at a unit power of 1000mW/cm, produced by Guangzhou and Guangsheng technology Ltd 2 The LED light source (an LED surface light source with the width of 3 cm and the length of 80 cm) with the emission wavelength of 385 nanometers is used as an excitation light source and is placed on a variable-speed conveyor belt. The criterion for completing photopolymerization curing is that repeated pressing and scraping of the fingernail does not generate print.
The results show that the compounds containing this example all cured efficiently at a rate of greater than 30 m/min.
And (3) carrying out micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the migrated photosensitizer accounts for 0.2% of the mass of the original photosensitizer in the coating.
Example ten: (I) LED photocuring experiments and paint Property testing of-16
The epoxy-containing sample system was prepared according to the following formulation (in weight percent)
Dual-functional epoxy monomer (EPOX): 97.0 percent
Photoinitiator (6976): 1.0 percent
Photosensitizer ((I) -16): 2.0 percent
The above mixture of formulation examples was applied to cardboard to form a coating of about 25-30 microns at a unit power of 1000mW/cm, manufactured by Guangzhou and Guangsheng technologies, inc 2 The LED light source (3 cm wide and 80 cm long LED surface light source) with the emission wavelength of 395 nm is an excitation light source and is placed on a variable-speed conveyor belt. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The results show that the compounds containing this example all cure efficiently at a rate of greater than 35 m/min.
The coating obtained by photocuring was subjected to hardness test by a hand-operated pencil hardness tester, and the hardness was measured to be 4H.
And (3) carrying out micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the migrated photosensitizer accounts for 0.2% of the mass of the original photosensitizer in the coating.
Example eleven: (I) LED photocuring experiments and paint Property testing of-25
Epoxy group-containing sample systems were prepared according to the following formulation (in weight percent)
Monofunctional epoxy monomer (CHO): 18.5 percent
Bisphenol a epoxy resin: 35.0 percent
Difunctional epoxy monomer (EPOX): 45.0 percent
Photoinitiator (6976): 0.5 percent
Photosensitizers ((I) -25): 1.0%
The above formulation example mixture was applied to cardboard to form a coating of about 30-35 microns at a unit power of 1500mW/cm, produced by Guangzhou and Guangsheng technologies, inc 2 The LED light source (3 cm wide and 80 cm long LED surface light source) with the emission wavelength of 395 nm is an excitation light source and is placed on a variable-speed conveyor belt. The criterion for completing photopolymerization curing is that repeated pressing and scraping of the fingernail does not generate print.
The results show that the compounds containing this example all cure efficiently at a rate of greater than 20 m/min.
The coating obtained by photocuring was subjected to hardness test by a hand-operated pencil hardness tester, and the hardness was found to be 4H.
And (3) carrying out a micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the photosensitizer which is migrated out accounts for 0.2% of the mass of the original photosensitizer in the coating.
Example twelve: (I) LED photocuring experiments and paint Property testing of-30
Sample systems containing acrylate and epoxy groups were prepared according to the following formulation (in weight percent):
trifunctional acrylate monomer (TMPTA): 20.0 percent
Urethane acrylate resin: 25.0 percent
Bisphenol a epoxy resin: 29.0 percent
Difunctional epoxy monomer (EPOX): 20.0 percent
Photosensitizer ((I) -31): 3.0 percent
Photoinitiator (907): 1.0 percent
Photoinitiator (Iod): 2.0 percent
The above mixture of formulation examples was applied to cardboard to form a coating of about 25-30 microns at a unit power of 2000mW/cm, produced by Guangzhou and Guangsheng technologies, inc 2 The LED light source (3 cm wide and 80 cm long) with an emission wavelength of 405 nm is an excitation light source and is placed on a variable-speed conveyor belt. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.
The results show that the compounds containing this example all cure efficiently at a rate of greater than 25 m/min.
The coating obtained by photocuring was subjected to a hardness test by a hand-operated pencil hardness tester, and the hardness was found to be 5H.
And (3) carrying out a micromolecule migration test on the coating obtained by photocuring in an organic solvent soaking mode, and measuring that the mass of the photosensitizer which is migrated out accounts for 0.3% of the mass of the original photosensitizer in the coating.
It should be understood that the above-described embodiments of the present disclosure are merely examples for clearly illustrating the disclosure and are not intended to limit the embodiments of the disclosure, and that various other modifications and changes may be made on the basis of the above-described embodiments by those skilled in the art.

Claims (6)

1. An epoxide-substituted pyrazoline derivative characterized in that: the structural formula is (I) -1
Figure FDA0003844522700000011
2. An epoxide-substituted pyrazoline derivative characterized by: the structural formula is (I) -8
Figure FDA0003844522700000012
3. An epoxide-substituted pyrazoline derivative characterized by: the structural formula is (I) -16
Figure FDA0003844522700000013
4. An epoxide-substituted pyrazoline derivative characterized in that: the structural formula is (I) -25
Figure FDA0003844522700000014
5. An epoxide-substituted pyrazoline derivative characterized in that: the structural formula is (I) -30
Figure FDA0003844522700000021
6. Use of an epoxide-substituted pyrazoline derivative according to any of claims 1-5 as sensitizer in a photocuring system.
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