CN115611943B - Organic phosphorus initiator and preparation method thereof, and photocurable composition - Google Patents
Organic phosphorus initiator and preparation method thereof, and photocurable composition Download PDFInfo
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- 239000003999 initiator Substances 0.000 title claims abstract 14
- 238000002360 preparation method Methods 0.000 title claims abstract 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims 2
- 239000011574 phosphorus Substances 0.000 title claims 2
- 229910052698 phosphorus Inorganic materials 0.000 title claims 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 3
- 239000001257 hydrogen Substances 0.000 claims abstract 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052801 chlorine Inorganic materials 0.000 claims abstract 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 6
- 238000006243 chemical reaction Methods 0.000 claims 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 3
- 239000003513 alkali Substances 0.000 claims 3
- 239000011230 binding agent Substances 0.000 claims 3
- 238000006460 hydrolysis reaction Methods 0.000 claims 3
- 238000000034 method Methods 0.000 claims 3
- 230000035484 reaction time Effects 0.000 claims 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 2
- 239000007858 starting material Substances 0.000 claims 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6551—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a four-membered ring
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明提供了一种有机磷类引发剂及其制备方法、光固化组合物。有机磷类引发剂，其具有通式I所示结构。其中，R1表示C1‑C4的直链或支链烷基；Ra、Rb相互独立地表示氢、C1‑C20的直链或支链烷基；p、q相互独立地表示1‑5的整数；X表示氯原子或溴原子。上述有机磷类引发剂应用于光固化组合物中时，具有比传统有机磷引发剂更好的溶解性，且具有良好的反应活性，不仅能够应用在自由基引发体系中，在混杂型体系中也具有较好的引发效果，能够固化彻底。同时，引发剂分子量较大，且结构中含有可聚合基团，因此不易挥发或迁移，原子利用率高。 The present invention provides an organophosphorus initiator and a preparation method thereof, and a photocurable composition. The organophosphorus initiator has a structure shown in the general formula I. Wherein, R1 represents a C1 - C4 straight chain or branched alkyl group; Ra and Rb independently represent hydrogen, a C1 - C20 straight chain or branched alkyl group; p and q independently represent an integer of 1-5; and X represents a chlorine atom or a bromine atom. When the above-mentioned organophosphorus initiator is applied to a photocurable composition, it has better solubility than a traditional organophosphorus initiator and has good reactivity. It can not only be applied in a free radical initiation system, but also has a good initiation effect in a mixed system and can be cured thoroughly. At the same time, the initiator has a large molecular weight and contains a polymerizable group in the structure, so it is not easy to volatilize or migrate, and the atomic utilization rate is high.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to an organic phosphorus initiator, a preparation method thereof and a photo-curing composition.
Background
With the development of photosensitive resin compositions, higher requirements are put on photoinitiators, and the acyl phosphine photoinitiators are widely applied due to extremely high initiating polymerization activity, high photosensitivity and wide photosensitivity range, and the existing common photoinitiators are:
However, the problem of the procreation toxicity of the photo-initiator TPO may be banned or limited in many applications, and many of its homologous initiators may face this problem, as well as the curing rate, color and solubility problems of the same products.
In recent years, CN109897063A, CN107916026A, CN106554430A reports organic phosphorus initiators with different structures respectively, but the reaction is relatively complex, and the three wastes in the reaction process are always targets to be solved. In addition, these initiators have no initiating effect in hybrid systems, and it is hypothesized that ultraviolet absorption and other structures in the system produce competing absorption. Therefore, the organic phosphorescent initiator with simple reaction, less three wastes, good product activity and excellent solubility is a target pursued in industry.
Disclosure of Invention
The invention mainly aims to provide an organic phosphorus initiator, a preparation method thereof and a photocuring composition, so as to solve the problems of low atomic utilization rate, insufficient product activity and insufficient solubility in the application process of the organic phosphorus initiator in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided an organic phosphorus-based initiator having a structure represented by general formula I:
Wherein R 1 represents a linear or branched alkyl group of C 1-C4, R a、Rb represents hydrogen or a linear or branched alkyl group of C 1-C20 independently of each other, p and q represent an integer of 1 to 5 independently of each other, and X represents a chlorine atom or a bromine atom.
Further, R 1 is methyl or ethyl, preferably ethyl.
Further, R a and R b independently of each other represent hydrogen, a linear or branched alkyl group of C 1-C5.
Further, R a and R b independently of each other represent hydrogen or methyl.
Further, the organophosphorus initiator is one or more of the following compounds:
According to another aspect of the present invention, there is also provided a method for preparing the above-mentioned organophosphorus initiator, comprising the steps of:
Step S1, carrying out hydrolysis reaction on a raw material a under an alkaline condition to obtain an intermediate b;
Step S2, reacting the intermediate b with the raw material c under the action of an acid binding agent to obtain an intermediate d;
step S3, reacting the intermediate d with a raw material e to obtain an organic phosphorus initiator;
wherein R 1、Ra、Rb, p, q, X have the same definition as before.
In the step S1, the alkaline condition is provided by alkali, the alkali is selected from one or more of sodium hydroxide, potassium carbonate, potassium hydroxide and sodium carbonate, the reaction temperature of the hydrolysis reaction is preferably less than or equal to 10 ℃, the reaction time is preferably 2-6 hours, the step S1 preferably comprises the steps of mixing a raw material a and an aqueous solution of the alkali to form a first pre-reaction system, then carrying out the hydrolysis reaction to obtain an intermediate b, the concentration of the aqueous solution of the alkali is 10-20wt%, and the weight ratio of the raw material a to the aqueous solution of the alkali is 1:3-8.
Further, the acid-binding agent is selected from one or more of sodium carbonate, sodium hydroxide, potassium carbonate, sodium methoxide, pyridine and triethylamine, preferably, the reaction temperature in the step S2 is less than or equal to 10 ℃, the reaction time is 1-4 h, preferably, the molar ratio of the raw material b to the raw material C is 1 (1-1.4), the dosage of the acid-binding agent is 2-4 times of the weight of the raw material b, preferably, the reaction in the step S2 is carried out in a first organic solvent, and the first organic solvent is selected from one or more of dichloromethane, dichloroethane, toluene and benzene.
Further, the reaction temperature in the step S3 is 60-150 ℃, the reaction time is 2-4h, the molar ratio of the intermediate d to the raw material e is 1 (1-2), and the reaction in the step S3 is preferably carried out in a second organic solvent, wherein the second organic solvent is one or more selected from dichloromethane, benzene, toluene, xylene and N, N-dimethylformamide.
According to a further aspect of the present invention there is also provided a photocurable composition comprising a photoinitiator which is one or more of the above-mentioned organophosphorus initiators, preferably the photocurable composition is a free radical system or a hybrid system of a free radical system and a cationic system.
The invention provides an organic phosphorus initiator with a general formula I structure, which has better solubility than the traditional organic phosphorus initiator and good reactivity when applied to a photo-curing composition, can be applied to a free radical initiation system, has better initiation effect in a hybrid system, and can be cured thoroughly. Meanwhile, the initiator has larger molecular weight and contains polymerizable groups in the structure, so the initiator is not easy to volatilize or migrate, and the atom utilization rate is high. Besides, the raw material utilization rate in the preparation process of the organophosphorus initiator is high, even no byproducts are generated, a diluent is not needed in the preparation process, and the preparation process is economic and environment-friendly.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As described in the background section, the organic phosphorus initiator in the prior art has the problems of more three wastes in the synthesis process, low atomic utilization rate, insufficient product activity, insufficient solubility and the like in the application process.
In order to solve the problems, the invention provides an organic phosphorus initiator, which has a structure shown in a general formula I:
Wherein R 1 represents a linear or branched alkyl group of C 1-C4, R a、Rb represents hydrogen or a linear or branched alkyl group of C 1-C20 independently of each other, p and q represent an integer of 1 to 5 independently of each other, and X represents a chlorine atom or a bromine atom.
The invention provides an organic phosphorus initiator with a general formula I structure, which has better solubility than the traditional organic phosphorus initiator and good reactivity when applied to a photo-curing composition, can be applied to a free radical initiation system, has better initiation effect in a hybrid system, and can be cured thoroughly. Meanwhile, the initiator has larger molecular weight and contains polymerizable groups in the structure, so the initiator is not easy to volatilize or migrate, and the atom utilization rate is high. Besides, the raw material utilization rate in the preparation process of the organophosphorus initiator is high, even no byproducts are generated, a diluent is not needed in the preparation process, and the preparation process is economic and environment-friendly.
When R a、Rb is a hydrogen atom, the corresponding benzene ring of the general formula I has no substituent, and p and q are 5. When R a、Rb is a linear or branched alkyl group of C 1-C20, p and q represent the number of substituents. Such asP is 5 and q is 1.
In order to further balance the properties of the initiator in all respects to give it a combination of better activity, solubility and good atom utilization, in a preferred embodiment R 1 is methyl or ethyl, preferably ethyl.
While improving the overall performance, in view of raw materials and cost issues, in a preferred embodiment, R a and R b independently represent hydrogen, C 1-C5 straight or branched alkyl, and preferably R a and R b independently represent hydrogen or methyl.
Illustratively, the above-mentioned organophosphorus initiator is one or more of the following compounds:
According to another aspect of the present invention, there is also provided a method for preparing the above-mentioned organophosphorus initiator, comprising the steps of:
Step S1, carrying out hydrolysis reaction on a raw material a under an alkaline condition to obtain an intermediate b;
Step S2, reacting the intermediate b with the raw material c under the action of an acid binding agent to obtain an intermediate d;
step S3, reacting the intermediate d with a raw material e to obtain an organic phosphorus initiator;
Wherein R 1、Ra、Rb, p, q, X have the same definition as previously described.
The preparation method has simple procedures, high raw material utilization rate in the preparation process, no byproducts, no diluent, and economic and environment-friendly preparation process. The prepared organophosphorus initiator has good reactivity and solubility in a photocuring composition, is thoroughly cured, is not easy to migrate, and has good comprehensive performance. The initiator can be applied to a free radical system and has photosensitive effect on a hybrid system.
The raw material a, the raw material c and the raw material e adopted in the preparation method are all known compounds in the prior art, or can be prepared by adopting a preparation method known in the prior art.
In order to further improve the hydrolysis reaction efficiency, in a preferred embodiment, in the step S1, the alkaline condition is provided by alkali, and the alkali is selected from one or more of sodium hydroxide, potassium carbonate, potassium hydroxide and sodium carbonate, and more preferably, the reaction temperature of the hydrolysis reaction is less than or equal to 10 ℃ and the reaction time is 2-6 hours.
Preferably, the step S1 comprises the steps of mixing a raw material a and an aqueous alkali solution to form a first pre-reaction system, and then carrying out hydrolysis reaction to obtain an intermediate b, wherein the concentration of the aqueous alkali solution is 10-20wt%, and the weight ratio of the raw material a to the aqueous alkali solution is 1:3-8. The dosage relation of the raw materials is controlled within the range, the pH environment of the hydrolysis reaction system is more suitable, and the transitional waste of auxiliary raw materials can be avoided on the basis of improving the reaction efficiency.
The reaction of the intermediate b and the raw material c can be promoted to proceed forward in the presence of an acid-binding agent, and in order to improve the purification effect of the intermediate d on the basis of further improving the reaction efficiency while considering the cost of the raw material and further improving the production environment-friendliness, in a preferred embodiment, the acid-binding agent is selected from one or more of sodium carbonate, sodium hydroxide, potassium carbonate, sodium methoxide, pyridine, triethylamine. Meanwhile, in order to further improve the reaction stability and safety, preferably, the reaction temperature in the step S2 is less than or equal to 10 ℃ and the reaction time is 1-4 h. In the actual reaction process, the reaction temperature may be slightly different depending on the kind of raw materials, which is capable of being adjusted by those skilled in the art through the actual reaction.
Preferably, the mol ratio of the raw material b to the raw material c is 1 (1-1.4), and the dosage of the acid binding agent is 2-4 times of the weight of the raw material b. The dosage relation of each reaction raw material is controlled within the range, the reaction is more efficient, and meanwhile, excessive waste of the raw materials is avoided.
In order to further increase the stability of the reaction, in a preferred embodiment, the reaction in step S2 is preferably carried out in a first organic solvent. The type of solvent used in the present invention is not particularly limited as long as it can dissolve the reaction raw materials and has no adverse effect on the reaction, and for example, the first organic solvent may be selected from one or more of dichloromethane, dichloroethane, benzene, toluene. The specific reaction concentration may be adjusted.
In a preferred embodiment, the reaction temperature in step S3 is 60 to 150 ℃ and the reaction time is 2 to 4 hours. Under this temperature condition, the reaction of intermediate e and starting material c is more efficient. Preferably, the molar ratio of the intermediate d to the raw material e is 1 (1-2). The weight ratio of the two is controlled within the range, so that the reaction efficiency can be improved, and meanwhile, the waste of raw materials can be avoided.
Preferably, the reaction in step S3 is carried out in a second organic solvent. The type of solvent used in the present invention is not particularly limited as long as it can dissolve the reaction raw materials and has no adverse effect on the reaction, and for example, the second organic solvent may be selected from one or more of methylene chloride, benzene, toluene, xylene, N-dimethylformamide.
In the steps, the utilization rate of the reaction raw materials is higher, byproducts are basically avoided, purification and solvent recovery can be performed through a method commonly used in the field of organic synthesis after the reaction, and the recovered solvent can be recycled, so that three wastes are basically not generated, and the method is environment-friendly. Preferably, in the step S1, after the hydrolysis reaction, the reaction solution is extracted with ethyl acetate to obtain an organic phase, the organic phase is concentrated under reduced pressure to obtain an intermediate b, in the step S2, after the reaction is finished, the organic phase is filtered and concentrated in sequence to obtain an intermediate d, and in the step S3, after the reaction is finished, the organic phosphorus initiator is obtained by filtering and recrystallizing in sequence.
According to a further aspect of the present invention there is also provided a photocurable composition comprising a photoinitiator which is one or more of the above-mentioned organophosphorus initiators, preferably the photocurable composition is a free radical system or a hybrid system of a free radical system and a cationic system.
The photocurable composition is used for coating a substrate such as plastic, metal, glass, ceramic, wood, wall, or optical fiber, a protective film material such as a hard coat agent, an antifouling film, an antireflection film, or an impact buffer film, a photocurable adhesive, an adhesive, a photodecomposition type coating material, a coating film, a molded article, an optical recording medium such as a hologram material, an optical molding resin such as an ink (resin) for 3D printing, a resist for electronic circuit and semiconductor manufacturing, a resist for electronic material such as a color filter, a black matrix, or a dry film in a display, an interlayer insulating film, a light extraction film, a brightening film, a sealing material, a printing ink such as screen printing, offset printing, or gravure printing, an optical member such as a photo-curable ink for ink-jet printing, a lens array, a light guide plate, a light diffusion plate, or a diffraction element, a photo-spacer, a rib wall, or a nanoimprint material.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Preparation example
(1) Preparation of intermediate b
Adding 50g of 15% sodium hydroxide aqueous solution into a 100ml four-port bottle, stirring and cooling the system to 5-10 ℃, slowly dropwise adding 15.8g of raw material a for about 30min, keeping the temperature at 5-10 ℃ and stirring for 2h after the dropwise adding is finished, stopping stirring when the content of the raw material a is less than 1%, adjusting the pH of the system by concentrated hydrochloric acid to be 7-8, extracting reaction liquid (50 ml of 3) by using ethyl acetate, merging organic layers, washing the organic layers by using saturated sodium chloride once, separating the liquid, concentrating the organic phases under reduced pressure to obtain b, and obtaining the product b 16.2g.
Product b was further confirmed by nuclear magnetism ：1H NMR(500MHz,Chloroform-d)δ5.80(s,2H),5.42-5.38(t,1H),5.22(brs,1H),4.94(brs,1H),4.25(s,4H),3.98-3.73(m,2H),1.71-1.65(m,2H),0.88-0.82(t,3H).
(2) Preparation of intermediate 1d
250ML of dichloromethane, 30.0g of triethylamine and 17.6g of compound b are added into a 500mL four-port bottle, stirring is carried out, the temperature is reduced to below 0 ℃, 18.7g of raw material 1C is slowly added dropwise, the dropwise addition is completed for about 30min, the temperature is slowly raised to room temperature after the dropwise addition is completed, stirring is continued for 2h, TLC (thin layer chromatography) is carried out to track the reaction, after the reaction is completed, the reaction solution (50 mL of 3) is washed by water, the solution is separated, the organic phase is concentrated, and crude product 1d is obtained, 25g of methanol is added into the crude product 1d, and the mixture is beaten at room temperature to obtain 1d of solid 26.4g.
Product 1d was further confirmed by nuclear magnetism ：1H NMR(500MHz,Chloroform-d)δ7.42-7.15(m,5H),5.80(s,2H),5.42-5.38(m,1H),4.24(s,4H),3.98-3.73(m,2H),1.71-1.66(q,2H),0.83-0.87(t,3H).
(3) Preparation of product 1 f:
14.1g of intermediate 1d and 50mL of toluene are added into a 100mL four-port bottle, the temperature is raised to 100 ℃, 7.5g of raw material 1e is dripped for about 30min, the temperature is kept at 100 ℃ after the dripping is finished, stirring is continued for 2h, HPLC tracking reaction is carried out, when the raw material 1d is less than 1%, stirring is stopped, the reaction solution starts to be cooled to 0 ℃, the compound 1f is obtained by filtering, and the light yellow solid product 1f is obtained by recrystallizing methanol, namely, 17.6g.
Product 1f was further confirmed by nuclear magnetism ：1H NMR(500MHz,Chloroform-d)δ7.85-7.61(m,5H),7.31-7.24(m,5H),5.80(s,2H),5.29-5.27(m,1H),4.57-4.51(m,2H),4.25(s,4H),1.73-1.68(q,2H),0.87-0.82(t,3H).
As can be seen from the synthesis of the above products, the synthesis is relatively simple, no by-products are generated, and the atomic utilization rate is high.
(4) Examples 2 to 9 preparation
By way of example, products 2-9 were synthesized having the following structures (see Table 1 for details).
TABLE 1
Evaluation of Performance
The application properties of the initiator of the present invention were evaluated by formulating an exemplary photocurable composition (i.e., photosensitive resin composition, parts by mass). Wherein the components of the application composition in the radical system photocurable composition are shown in Table 2 and the components of the application composition in the hybrid system photocurable composition are shown in Table 3. The irradiation conditions of the compositions in the table are classified into mercury lamp irradiation, 385nm ultraviolet irradiation and 405nm ultraviolet irradiation, and the details are shown in the table.
TABLE 2 free-radical systems
TABLE 3 hybrid system
6110 3, 4-Epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate, taiteral Corp
E201 bisphenol A epoxy acrylate, jiangsu Kaifeng phosphorus Ruiyang chemical Co., ltd
TMPO 3-hydroxymethyl-3-ethyloxetane, a powerful electronic New Material Co.Ltd
TMPTA (TMPTA) trimethylolpropane triacrylate, jiangsu Kaifeng phosphorus Ruiyang chemical Co., ltd
BYK307 leveling agent, BYK Germany
PAG30101 4, 4-dimethylphenyl iodonium hexafluorophosphate, available from Hemsl New Material Co., ltd
Titanium white, shandong Yufeng chemical Co., ltd
PSS306:9, 10-diethoxy-2-ethyl anthracene, a company of Strong electronic New Material Co., ltd
184 Hydroxy cyclohexyl phenyl ketone, WU Hua Xiangke Jie Biotechnology Co., ltd
TPO 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, changsha New Yu high molecular technology Co., ltd
TPO-L2, 4, 6-trimethylbenzoyl ethyl phenylphosphonate, changsha New Yu high molecular technology Co., ltd
2. Performance evaluation method
(1) Sensitivity evaluation
The photocurable composition was stirred and mixed under a yellow lamp, and the mixture was roll-coated on a PET template to form a coating film having a film thickness of about 50 μm, and the composition was observed for curing by exposing it to light by using a mercury lamp (100％,1m/min,1140mJ)、LED385nm(100％,3m/min,2568mJ/cm2)、LED405nm(100％,3m/min,2568mJ/cm2) according to the corresponding manner in the table, and evaluated according to the following criteria:
1. oil, unconsolidated
2. Surface oil, bottom layer solidification
3. Surface adhesion and heavier finger print after hand touch
4. Basic dry surface, slightly astringent after touching with hands, light fingerprint
5. Completely cured, smooth surface and no fingerprint after hand touch
The test results are shown in Table 4:
TABLE 4 Table 4
Experiments show that the initiator of the invention can be applied not only to free radical systems but also to hybrid systems and has long-wavelength initiator effect.
In conclusion, the initiator provided by the invention has very excellent application performance in the field of photo-curing and has a wide application prospect. In addition, the initiator of the invention is not limited to the field of photo-curing application, and all systems such as coating, printing ink, adhesive and photoresist are all protected by the initiator of the invention.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. An organic phosphorus initiator is characterized by having a structure shown in a general formula I:
Wherein R 1 represents a linear or branched alkyl group of C 1-C4;
R a and R b independently of one another represent hydrogen, C 1-C5 straight-chain or branched alkyl;
p and q independently represent an integer of 1 to 5, and X represents a chlorine atom or a bromine atom.
2. The organophosphorus initiator of claim 1, wherein R 1 is methyl or ethyl.
3. The organophosphorus initiator of claim 1, wherein R 1 is ethyl.
4. An organophosphorus initiator according to any of claims 1 to 3, characterized in that R a and R b independently of one another represent hydrogen or methyl.
5. The organophosphorus initiator according to claim 1, characterized in that it is one or more of the following compounds:
6. a process for the preparation of an organophosphorus initiator according to any of claims 1 to 5, characterized in that it comprises the following steps:
Step S1, carrying out hydrolysis reaction on a raw material a under an alkaline condition to obtain an intermediate b;
step S2, reacting the intermediate b with the raw material c under the action of an acid binding agent to obtain an intermediate d;
Step S3, reacting the intermediate d with a raw material e to obtain the organophosphorus initiator;
Wherein R 1、Ra、Rb, p, q, X have the same definition as any one of claims 1 to 5.
7. The method according to claim 6, wherein in the step S1, the alkaline condition is provided by a base selected from one or more of sodium hydroxide, potassium carbonate, potassium hydroxide, and sodium carbonate.
8. The preparation method according to claim 7, wherein the reaction temperature of the hydrolysis reaction is less than or equal to 10 ℃ and the reaction time is 2-6 h.
9. The preparation method of the catalyst according to claim 7, wherein the step S1 comprises the steps of mixing the raw material a and an aqueous alkali solution to form a first pre-reaction system, and then carrying out the hydrolysis reaction to obtain the intermediate b, wherein the concentration of the aqueous alkali solution is 10-20wt%, and the weight ratio of the raw material a to the aqueous alkali solution is 1:3-8.
10. The preparation method according to claim 6, wherein the acid binding agent is one or more selected from sodium carbonate, sodium hydroxide, potassium carbonate, sodium methoxide, pyridine and triethylamine.
11. The preparation method according to claim 10, wherein the reaction temperature in the step S2 is less than or equal to 10 ℃ and the reaction time is 1-4 h.
12. The process according to claim 10, wherein the molar ratio of the starting material b to the starting material c is 1:
(1-1.4), wherein the dosage of the acid binding agent is 1-3 times of the weight of the raw material b.
13. The preparation method according to claim 10, wherein the reaction in step S2 is performed in a first organic solvent selected from one or more of dichloromethane, dichloroethane, toluene, benzene.
14. The preparation method according to claim 6, wherein the reaction temperature in the step S3 is 60-150 ℃ and the reaction time is 2-4 hours.
15. The preparation method according to claim 14, wherein the molar ratio of the intermediate d to the raw material e is 1 (1-2).
16. The preparation method according to claim 14, wherein the reaction in step S3 is performed in a second organic solvent selected from one or more of dichloromethane, benzene, toluene, xylene, N-dimethylformamide.
17. A photocurable composition comprising a photoinitiator, characterized in that said photoinitiator is one or more of the organophosphorus initiators of any of claims 1 to 5.
18. The photocurable composition according to claim 17, characterized in that it is a radical system or a hybrid system of a radical system and a cationic system.
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| CN101065388A (en) * | 2004-11-23 | 2007-10-31 | 西巴特殊化学品控股有限公司 | Process for preparing acylphosphanes and derivatives thereof |
| CN103073658A (en) * | 2011-10-26 | 2013-05-01 | 深圳市有为化学技术有限公司 | Photoinitiator mixture of novel aromatic hydroxyl ketone and acylphosphine oxide, and composite system of photoinitiator mixture and photoabsorber |
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| US2856369A (en) * | 1953-05-08 | 1958-10-14 | Shell Dev | Epoxy-substituted esters of phosphoruscontaining acid and their polymers |
| CN109517432A (en) * | 2018-11-13 | 2019-03-26 | 长沙新宇高分子科技有限公司 | A kind of composition of the acylphosphine oxide containing liquid and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101065388A (en) * | 2004-11-23 | 2007-10-31 | 西巴特殊化学品控股有限公司 | Process for preparing acylphosphanes and derivatives thereof |
| CN103073658A (en) * | 2011-10-26 | 2013-05-01 | 深圳市有为化学技术有限公司 | Photoinitiator mixture of novel aromatic hydroxyl ketone and acylphosphine oxide, and composite system of photoinitiator mixture and photoabsorber |
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