Self-initiated ultraviolet curing oligomer and preparation method thereof
Technical Field
The invention belongs to the field of preparation of UV (ultraviolet curing) oligomers, and particularly relates to a preparation method of an ultraviolet curing oligomer capable of self-initiating.
Background
The ultraviolet curing coating is one of the most environment-friendly coating varieties at present, and has the advantages of energy conservation, high efficiency, environmental protection and the like, so the ultraviolet curing coating is an environment-friendly coating variety which is developed in China in the last 20 years. With the rapid development of scientific technology and modern industry, Ultraviolet (UV) curing materials are highlighted in the material field today. The photoinitiator is used as a key component of the UV curing material and is widely applied to the fields of UV curing coatings, printing ink, adhesives, microelectronics, printing plates and the like.
Since the concept of the photoinitiator was first proposed in the environment-friendly and energy-saving UV-curable coating developed by Bayer corporation in germany in 1968, the photoinitiator was successively applied to the development of various UV-curable products in countries around the world. In recent years, with the increasing perfection of energy-saving and environment-friendly laws and regulations, new requirements are put forward on UV curing products, namely, the 5E (high efficiency, wide adaptability, economy, energy conservation and environment friendliness) principle is taken as a standard, so that higher requirements are put forward on photoinitiators. The traditional photoinitiator is a micromolecular photoinitiator which has the defects of easy volatilization, easy migration, low initiation efficiency, high viscosity, easy yellowing, odor and the like, so that the development requirement of rapidness and environmental protection in the industrial production process is difficult to meet. Therefore, the development of novel photoinitiators is urgently needed, and macromolecular photoinitiators are effective in solving the above problems. This is due to the fact that macrophotoinitiators contain multiple photoactive groups in the main chain (or side chains) which can generate free radicals (or ions) under the conditions of light; the free radical (or ion) further initiates the monofunctional group (or polyfunctional group) monomer to polymerize, so that the monomer has excellent properties of high activity, low volatility, low toxicity, environmental protection, miscibility, low mobility and the like. Therefore, new macromolecular photoinitiators are gradually receiving a great deal of attention. However, macrophotoinitiators have some disadvantages, such as low initiation efficiency, high cost, etc., which make macroinitiators very slow to develop in recent years, so it is an urgent task to develop UV-curable oligomers that are self-initiating without the need for initiators.
Thus, the defects of easy volatilization, easy migration, low initiation efficiency, pungent smell and the like of the common initiator are avoided. Is a self-initiated ultraviolet light curable oligomer.
Disclosure of Invention
The ultraviolet curing agent aims to solve the problems of easy volatilization, easy migration, low initiation efficiency, pungent smell and the like of the common initiator used for ultraviolet curing by curtain coating. A method for preparing a self-initiated ultraviolet light curing oligomer is invented.
The technical scheme of the invention is as follows: a uv-curable self-initiating oligomer consisting of: mass ratio of 2-hydroxy-2-methyl-1-phenyl-1-propanone: acrylic (methacrylic) hydroxy ester monomer: diisocyanate: antioxidant: polymerization inhibitor: catalyst 1:1-1.05:1: 0.01: 0.005: 0.001; the self-initiation ultraviolet curing oligomer can be self-cured under the irradiation of 200-400nm ultraviolet light, and after curing, the detection system has high hardness and the curing degree RAU of more than 90 percent.
The purity of the 2-hydroxy-2-methyl-1-phenyl-1-acetone is more than 99 percent.
The acrylic acid (methacrylic acid) hydroxy ester monomer comprises one or a mixture of more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate.
The diisocyanate comprises toluene diisocyanate; diphenylmethane diisocyanate; 1, 6-hexamethylene diisocyanate; isophorone diisocyanate.
The catalyst comprises dibutyltin dilaurate, stannous octoate, bismuth neodecanoate, zinc neodecanoate, methanesulfonic acid, p-toluenesulfonic acid, 1, 2-dimethylimidazole, 1, 4-diazabicyclo and triphenylphosphine.
The preparation method of the ultraviolet light curable self-initiation oligomer comprises the steps of uniformly mixing diisocyanate, an antioxidant, a polymerization inhibitor and a catalyst, dripping 2-hydroxy-2-methyl-1-phenyl-1-acetone at the temperature of less than 45 ℃, reacting for 3 hours at the temperature of 60-65 ℃ after dripping, dripping acrylic acid (methacrylic acid) hydroxy ester, and reacting at the temperature of 70-75 ℃ until the isocyanate value is less than 0.1 percent to reach the synthesis end point.
Has the advantages that:
the invention introduces special functional groups into the acrylate polyurethane system, which can be self-initiated to become a macromolecular initiator and can also be cross-linked and polymerized. The ultraviolet light cured oligomer prepared by the invention can be self-cured under the irradiation of ultraviolet light with 200-400nm without adding an initiator. The curing agent has the advantages of non-volatility, no migration, high initiation efficiency, no pungent smell after curing, high glass transition temperature of a cured film-forming material, high hardness, high curing degree (RAU) and the like. Is an effective method and way for replacing the traditional initiator.
Drawings
FIG. 1 is an infrared spectrum of R1 synthesized in example 1.
FIG. 2 is an infrared spectrum of R2 synthesized in example 2.
Detailed Description
The preparation used in the invention is not limited to manufacturers as long as the preparation is qualified industrial products, and is a conventional product sold in the market.
Throughout the application, the following terms have the indicated meanings:
the present invention will be further described with reference to the following examples.
A uv-curable self-initiating oligomer, the synthetic oligomer being synthesized from: 2-hydroxy-2-methyl-1-phenyl-1-acetone, acrylic acid (methacrylic acid) hydroxy ester monomer, diisocyanate, antioxidant, polymerization inhibitor and catalyst, wherein the molar ratio of the acrylic acid hydroxy ester monomer to the acrylic acid (methacrylic acid) hydroxy ester monomer is as follows: 1:1-1.05:1:0.01: 0.0051:0.001.
The synthesis process comprises the steps of adding diisocyanate, an auxiliary agent and a catalyst into a flask, dropwise adding 2-hydroxy-2-methyl-1-phenyl-1-acetone at the temperature of less than 45 ℃, reacting for 3 hours at the temperature of 60-65 ℃ after dropwise adding, dropwise adding acrylic acid (methacrylic acid) hydroxy ester, reacting for 4 hours at the temperature of 70-75 ℃, and detecting that the isocyanate (-NCO) value is less than 0.1 percent to obtain a synthetic product of ultraviolet curing self-initiation.
The synthetic composition must have 2-hydroxy-2-methyl-1-phenyl-1-propanone, which is a key component for generating free radicals, and must have a purity of more than 99%.
The hydroxyl acrylate monomer refers to one or a mixture of more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and the like, but is not limited to the above-mentioned other hydroxyl (methacrylic) acrylates.
The diisocyanate refers to a compound containing two isocyanate (-NCO) functional groups, mainly refers to but is not limited to Toluene Diisocyanate (TDI); diphenylmethane diisocyanate (MDI); 1, 6-Hexamethylene Diisocyanate (HDI); isophorone diisocyanate (IPDI for short). TDI and IPDI are preferred.
The catalyst is selected from: organotins including, but not limited to, dibutyltin dilaurate, stannous octoate; metal carboxylates, including but not limited to: bismuth neodecanoate, zinc neodecanoate, and the like; organic acids including, but not limited to, methanesulfonic acid, p-toluenesulfonic acid; amino or organic base: including but not limited to 1, 2-dimethylimidazole, 1, 4-diazabicyclo; triphenylphosphine.
The synthesis process of the finger is as follows: adding diisocyanate, an auxiliary agent and a catalyst into a flask, dropwise adding 2-hydroxy-2-methyl-1-phenyl-1-acetone at the temperature of less than 45 ℃, after the dropwise adding, controlling the temperature to be 60-65 ℃ for reaction for 3 hours, dropwise adding acrylic acid (methacrylic acid) hydroxy ester, reacting for 4 hours at the temperature of 70-75 ℃, and detecting that the isocyanate (-NCO) value is less than 0.1 percent to reach the synthesis end point.
The self-initiation ultraviolet light curing oligomer refers to the oligomer which can be self-cured under the irradiation of 200-400nm ultraviolet light without adding any initiator, and the cured detection system has high hardness and the curing degree (RAU) of more than 90 percent.
The antioxidant is as follows: selected from the common but not limited to: 2, 6-di-tert-butyl-4-methylphenol (264), bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythrityl tetrakis [ beta- (3, 5-tert-butyl-4-hydroxyphenyl) propionate, etc. 2, 6-di-tert-butyl-4-methylphenol (264) is generally preferred.
The polymerization inhibitor refers to a phenolic polymerization inhibitor, including but not limited to: 2,4, 6-Trinitrophenol (TNP), 1, 4-Benzoquinone (BQ), p-Hydroxyanisole (HEMQ) and Hydroquinone (HQ), 2, 6-di-tert-butylhydroquinone (MTBHQ), preferably p-Hydroxyanisole (HEMQ).
Example 1 Synthesis of self-initiated UV-curable oligomer R1
TABLE 1 synthetic formulation Table
Adding 1,2, 3, 4 components into a flask, adding A11 dropwise at a temperature below 45 deg.C, and controlling temperature at 60-65 deg.C
After reacting for 3 hours, adding HEA dropwise, and detecting that the isocyanate (-NCO) value is less than 0.1 percent after reacting for 4 hours at 70-75 ℃ to obtain a synthetic product R1 self-initiated by ultraviolet curing. The IR spectrum of the resulting composition is shown in FIG. 1.
Example 2 Synthesis of self-initiated UV-curable oligomer R2
TABLE 2 synthetic formulation Table
Adding 1,2, 3 and 4 components into a flask, dropwise adding A11 at the temperature of less than 45 ℃, controlling the temperature to react for 3 hours at 60-65 ℃ after dropwise adding, dropwise adding HPA, reacting for 4 hours at 70-75 ℃, and detecting that the isocyanate (-NCO) value is less than 0.1% to obtain the ultraviolet curing self-initiated synthetic product R2. The IR spectrum of the synthesized compound is shown in FIG. 2.
Example 3 Synthesis of self-initiated UV-curable oligomer R3
TABLE 3 synthetic formulation Table
Adding 1,2, 3 and 4 components into a flask, dropwise adding A11 at the temperature of less than 45 ℃, controlling the temperature to react for 3 hours at 60-65 ℃ after dropwise adding, dropwise adding HEA, reacting for 4 hours at 70-75 ℃, and detecting that the isocyanate (-NCO) value is less than 0.1% to obtain the ultraviolet curing self-initiated synthetic product R3.
Example 4 Synthesis of self-initiated UV-curable oligomer R4
TABLE 4 synthetic formulation Table
Adding 1,2, 3 and 4 components into a flask, dropwise adding A11 at the temperature of less than 45 ℃, controlling the temperature to react for 3 hours at 60-65 ℃ after dropwise adding, dropwise adding HPA, reacting for 4 hours at 70-75 ℃, and detecting that the isocyanate (-NCO) value is less than 0.1% to obtain the ultraviolet curing self-initiated synthetic product R4.
Example 5 Synthesis of self-initiated UV-curable oligomer R5
TABLE 5 synthetic formulation Table
Adding 1,2, 3 and 4 components into a flask, dropwise adding A11 at the temperature of less than 45 ℃, controlling the temperature to be 60-65 ℃ after the dropwise adding is finished, reacting for 3 hours, dropwise adding HEMA, reacting for 4 hours at the temperature of 70-75 ℃, and detecting that the isocyanate (-NCO) value is less than 0.1% to obtain a synthetic product R5 of ultraviolet curing self-initiation.
Example 6 Synthesis of self-initiated UV-curable oligomer R6
TABLE 6 synthetic formulation Table
Adding 1,2, 3 and 4 components into a flask, dropwise adding A11 at the temperature of less than 45 ℃, reacting at the temperature of 60-65 ℃ for 3 hours after dropwise adding, dropwise adding HEA and HPA, reacting at the temperature of 70-75 ℃ for 4 hours, and detecting that the isocyanate (-NCO) value is less than 0.1% to obtain the ultraviolet curing self-initiated synthetic product R6.
Example 7 preparation of UV curable coating
The coatings were formulated according to the following formulation in Table 7.
The above components were mixed to prepare a coating material, and the coating material was formed into a film on glass with a 100 μm coater at 450mj/cm2Curing under mercury lamp, measuring the curing degree RAU by infrared spectrum, measuring the hardness by pencil hardness meter, and measuring the related indexes as shown in the following table
Item
|
Group 1
|
2 groups of
|
Group 3
|
4 groups of
|
5 groups of
|
Curing degree of 450mj/cm2 |
91
|
92
|
92
|
91
|
75
|
Hardness H
|
3
|
3
|
4
|
3
|
2 |
From the above test data it can be seen that: as can be seen from comparison of groups 1,2, 3, 4 and 5, wherein group 5 is a conventional UV-curable formulation, the synthesized self-curable oligomers R1, R3, R5 and R6 can be UV-cured without adding an initiator, and the curing degree and hardness are higher than those of the conventional oligomers, indicating that the polymers are excellent,
therefore, the specific self-initiating UV curable oligomers of the present invention are preferred.