CN114316781B

CN114316781B - Curable composition, cured coating, coating product and preparation method

Info

Publication number: CN114316781B
Application number: CN202011057200.2A
Authority: CN
Inventors: 张志鹏
Original assignee: Shanghai Feikai Material Technology Co ltd
Current assignee: Shanghai Feikai Material Technology Co ltd
Priority date: 2020-09-30
Filing date: 2020-09-30
Publication date: 2022-06-28
Anticipated expiration: 2040-09-30
Also published as: CN114316781A

Abstract

The invention discloses a curable composition, a cured coating, a coating product and a preparation method, and belongs to the field of coatings. The curable composition comprises the following components in percentage by mass: 30-80% of acrylate oligomer, 5-50% of alkylphenol polyoxyethylene (methyl) acrylate, 1-10% of photoinitiator and 0.1-10% of auxiliary agent; wherein the residual mass percentage of the alkylphenol polyoxyethylene ether in the alkylphenol polyoxyethylene ether (methyl) acrylate is less than 2 percent. The alkylphenol polyoxyethylene ether (methyl) acrylate with the dosage has better dilution effect, and when the alkylphenol polyoxyethylene ether (methyl) acrylate is cooperated with the epoxy acrylate oligomer and the polyurethane (methyl) acrylate oligomer, the curing speed of the curable composition can obtain better balance capability, and the curable composition is easier to construct, stronger in adhesive force, better in chemical resistance and lower in cost.

Description

Curable composition, cured coating, coated product and preparation method

Technical Field

The invention relates to the field of coatings, and in particular relates to a curable composition, a cured coating, a coating product and a preparation method.

Background

The curable composition is a green environment-friendly coating, takes ultraviolet light with certain wavelength as energy for curing a coating film, has the characteristics of low energy consumption, small air pollution, high curing speed and the like, and generally comprises the following components: oligomers, photoinitiators, reactive diluents, and other adjuvants.

Reactive diluents commonly used in curable compositions of the related art include, but are not limited to: styrene, alkylphenol ethoxylate (meth) acrylate, vinyl acetate, N-vinylpyrrolidone, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like. Wherein, the alkylphenol polyoxyethylene (methyl) acrylate is used as a diluent and has at least the following advantages: better balance ability to the curing speed of the coating, easy construction, strong adhesive force, strong diluting ability, good chemical resistance and low cost.

In the process of implementing the invention, the inventor finds that at least the following problems exist in the prior art:

the residual quantity of alkylphenol polyoxyethylene ether in the currently used alkylphenol polyoxyethylene ether (methyl) acrylate is high, on one hand, the alkylphenol polyoxyethylene ether is a non-UV (Ultraviolet) component and can migrate to the surface of a coating layer in the curing process to cause environmental pollution; on the other hand, even if the diluent is used in an extremely low amount in the UV coating, the residue of alkylphenol ethoxylate far exceeds the limit amount of european legislation, so that the amount of alkylphenol ethoxylate (meth) acrylate used in the curable composition is greatly limited, and it is difficult to satisfy both the range of use and the export requirement of the diluent in the UV coating; on the other hand, when the system contains more non-UV components, micro breakpoints can be formed on the surface of the cured film to influence the strength of the coating, and the breakpoints are often formed at the breakpoints, so that the breaking elongation of the coating is reduced, and the flexibility of the coating is poor. In addition, in order to meet the export requirement of the existing UV coating, alkylphenol ethoxylate (methyl) acrylate is usually replaced by other acrylate diluents, which can cause the production cost of the coating to be too high or the performance to be reduced, and reduce the competitiveness of the coating product.

Disclosure of Invention

In view of the above, the present invention provides a curable composition, a cured coating, a coated product and a preparation method, which can solve the above technical problems.

Specifically, the method comprises the following technical scheme:

in one aspect, embodiments of the present invention provide a curable composition, which includes the following components in percentage by mass: 30-80% of acrylate oligomer, 5-50% of alkylphenol polyoxyethylene (methyl) acrylate, 1-10% of photoinitiator and 0.1-10% of auxiliary agent;

wherein the residual mass percentage of the alkylphenol polyoxyethylene ether in the alkylphenol polyoxyethylene ether (methyl) acrylate is less than 2%.

In some possible implementations, the acrylate oligomer includes: epoxy acrylate oligomers and urethane (meth) acrylate oligomers;

wherein the mass percent of the epoxy acrylate oligomer in the curable composition is 10-50%;

the mass percentage of the urethane (meth) acrylate oligomer in the curable composition is 10% to 60%.

In some possible implementations, the weight average molecular weight of the epoxy acrylate oligomer is 2000-8000;

The weight average molecular weight of the urethane (meth) acrylate oligomer is 2000-8000.

In some possible implementations, the alkylphenol ethoxylate (meth) acrylate is prepared by:

providing an alkylphenol ethoxylate (meth) acrylate feedstock, wherein the alkylphenol ethoxylate (meth) acrylate feedstock comprises: alkylphenol polyoxyethylene (meth) acrylates and alkylphenol ethoxylates;

mixing the alkylphenol polyoxyethylene ether (methyl) acrylate raw material and monoisocyanate with double bonds, and carrying out addition reaction on the alkylphenol polyoxyethylene ether and the monoisocyanate with double bonds in the presence of a first polymerization inhibitor and a first catalyst to obtain an oligomer, thereby finishing the treatment of the alkylphenol polyoxyethylene ether (methyl) acrylate raw material.

Mixing the alkylphenol polyoxyethylene (methyl) acrylate raw material and acid anhydride, and carrying out esterification reaction on the alkylphenol polyoxyethylene and the acid anhydride in the presence of a second polymerization inhibitor and a second catalyst to obtain an esterification reaction product;

and separating the esterification reaction product from the alkylphenol polyoxyethylene ether (methyl) acrylate through post-treatment to finish the treatment of the raw material of the alkylphenol polyoxyethylene ether (methyl) acrylate.

In some possible implementations, the ratio of the molar amount of the anhydride to the molar amount of the alkylphenol ethoxylate is greater than 1.

In some possible implementations, the separating the esterification reaction product from the alkylphenol ethoxylate (meth) acrylate by post-treatment includes: diluting the reaction solution by using a diluent;

neutralizing the diluted reaction liquid by using alkali liquor;

washing the neutralized reaction solution by using a washing solution to remove the esterification reaction product;

and adding a third polymerization inhibitor into the washed product, carrying out reduced pressure distillation at a set temperature, and separating to obtain the alkylphenol polyoxyethylene (methyl) acrylate.

In some possible implementations, the curable composition further includes: a colorant.

In another aspect, embodiments of the present invention provide a method of preparing any one of the curable compositions described above, the method comprising:

uniformly mixing a diluent and an auxiliary agent according to the mass percent of each component in the curable composition to form a first intermediate system;

uniformly mixing the acrylate oligomer and the first intermediate system to form a second intermediate system;

and uniformly mixing a photoinitiator and an optional colorant with the second intermediate system to obtain the curable composition.

In yet another aspect, embodiments of the present invention provide a cured coating obtained by curing any one of the curable compositions described above.

In yet another aspect, embodiments of the present invention also provide a coated product, including: the product comprises a product substrate and a cured coating positioned on the surface of the product substrate, wherein the cured coating is as described above.

In some possible implementations, the coated product includes: optical fiber, commodity, or vehicle product.

In another aspect, an embodiment of the present invention provides a preparation method of the above-mentioned coated product, where the preparation method of the coated product includes: providing a product substrate;

Forming a cured coating on the surface of the product substrate by a curing process using any one of the curable compositions referred to above.

In some possible implementations, the curing process includes: UV curing, electron beam curing, laser curing, or LED curing.

The technical scheme provided by the embodiment of the invention at least has the following beneficial effects:

1. according to the curable composition provided by the embodiment of the invention, the alkylphenol polyoxyethylene ether (methyl) acrylate with the residual quantity of the alkylphenol polyoxyethylene ether being less than 2% is used, so that the alkylphenol polyoxyethylene ether (methyl) acrylate has a larger dosage range (5% -50%) in the curable composition, and thus, the alkylphenol polyoxyethylene ether (methyl) acrylate has a better dilution effect, when the alkylphenol polyoxyethylene ether (methyl) acrylate synergistically acts with the epoxy acrylate oligomer and the polyurethane (methyl) acrylate oligomer, the curing speed of the curable composition can obtain better balance capability, and the curable composition is easier to construct, stronger in adhesive force, better in chemical resistance, lower in cost and high in market competitiveness.

2. According to the curable composition provided by the embodiment of the invention, the alkylphenol polyoxyethylene ether (methyl) acrylate with the residual quantity of the alkylphenol polyoxyethylene ether being less than 2% is used, so that the non-UV components in the coating are greatly reduced, and the phenomenon that excessive non-UV components migrate to the surface of the coating to pollute the environment in the curing process can be avoided; furthermore, the certification of ROCH regulations of European Union can be met, and the product competitiveness is improved; furthermore, the mechanical property of the coating can be improved, the curing speed of the coating is increased, and the prepared coating has better flexibility.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a high performance liquid chromatogram of the product provided in example 1;

FIG. 2 is a high performance liquid chromatogram of the product provided in example 2;

FIG. 3 is a high performance liquid chromatogram of the product provided in example 3;

FIG. 4 is a high performance liquid chromatogram of the product provided in example 4.

Detailed Description

In order to make the technical solutions and advantages of the present invention clearer, the following will describe embodiments of the present invention in further detail with reference to the accompanying drawings.

The photo-curing technology refers to a photo-processing technology for rapidly polymerizing a liquid photo-curing coating into a solid coating by irradiating ultraviolet light with a certain wavelength, and is called as a 'green technology' because of excellent environmental protection. The curable composition generally comprises: oligomers, photoinitiators, reactive diluents and other auxiliaries.

A typical example of a reactive diluent is alkylphenol polyoxyethylene (meth) acrylates, such as nonylphenol polyoxyethylene (meth) acrylates. Wherein, the alkylphenol polyoxyethylene ether (methyl) acrylate is obtained by esterifying alkylphenol polyoxyethylene ether and (methyl) acrylic acid, is commonly used for adjusting the viscosity of a coating system and improving the construction performance, and is used as a diluent monomer in the coating. Currently, alkylphenol ethoxylates (meth) acrylate products on the market usually have alkylphenol ethoxylates remaining therein, and the residual amount of the alkylphenol ethoxylates is 2% to 5%. The residual alkylphenol polyoxyethylene ether in the alkylphenol polyoxyethylene ether (methyl) acrylate cannot participate in the photocuring process, can migrate to the surface of the cured coating, and can be quickly decomposed into alkylphenol when discharged into the environment. Alkylphenol is a recognized environmental hormone that mimics estrogen, has an effect on sexual development of an organism, interferes with the endocrine function of an organism, and is toxic to reproductive systems. Meanwhile, alkylphenol can be accumulated in organisms continuously through food chains, and researches show that the alkylphenol is extremely harmful even if the discharged concentration is low. In recent years, alkylphenol ethoxylates have been listed as a class of restriction in european legislation.

In order to avoid exceeding the limits of alkylphenol ethoxylates (the european union regulation limits of 0.1%), the usage of alkylphenol ethoxylates (meth) acrylates in coatings is greatly limited, i.e. the usage is generally lower than the desired usage, which ultimately affects the coating quality; furthermore, the problem that alkylphenol polyoxyethylene ether migrating to the surface of the cured coating exceeds the standard, so that environmental pollution is caused and the coating is difficult to export is avoided; still further, in order to improve the mechanical properties and curing speed of the coating.

The embodiment of the invention provides a curable composition, which comprises the following components in percentage by mass:

30-80% of acrylate oligomer, 5-50% of alkylphenol polyoxyethylene (methyl) acrylate, 1-10% of photoinitiator and 0.1-10% of auxiliary agent.

Wherein the residual mass percentage of the alkylphenol polyoxyethylene ether in the alkylphenol polyoxyethylene ether (methyl) acrylate is less than 2 percent.

1. According to the curable composition provided by the embodiment of the invention, the alkylphenol polyoxyethylene ether (methyl) acrylate with the residual quantity of the alkylphenol polyoxyethylene ether being less than 2% is used, so that the alkylphenol polyoxyethylene ether (methyl) acrylate has a larger dosage range (5% -50%) in the curable composition, and thus, the alkylphenol polyoxyethylene ether (methyl) acrylate with the dosage has a better dilution effect, when the alkylphenol polyoxyethylene ether (methyl) acrylate is synergistically acted with the epoxy acrylate oligomer and the polyurethane (methyl) acrylate oligomer, the curing speed of the curable composition can obtain better balance capability, and the curable composition is easier to construct, stronger in adhesive force, better in chemical resistance, lower in cost and high in market competitiveness.

2. According to the curable composition provided by the embodiment of the invention, the alkylphenol polyoxyethylene ether (methyl) acrylate with the residual quantity of the alkylphenol polyoxyethylene ether being less than 2% is used, so that the non-UV component in the coating is greatly reduced, and the phenomenon that the excessive non-UV component migrates to the surface of the coating to pollute the environment in the curing process can be avoided; furthermore, the certification of European Union ROCH regulations can be met, and the product competitiveness is improved; furthermore, the mechanical property of the coating can be improved, the curing speed of the coating is improved, and the prepared coating has better flexibility.

Therefore, in the embodiment of the invention, the residual mass percentage of the alkylphenol ethoxylate in the alkylphenol ethoxylate (meth) acrylate is less than 2%, so that the side effect caused by the excessive alkylphenol ethoxylate is avoided (the residual amount of the alkylphenol ethoxylate in the curable composition is less than 0.1%, and the product can be conveniently exported through ROCH regulation certification of European Union), and meanwhile, the beneficial effect caused by the alkylphenol ethoxylate (meth) acrylate is further optimized, on the premise of obtaining the high-performance curable composition, the cost of the curable composition is reduced, and the market competitiveness of the coating product is improved.

In the embodiment of the invention, the alkylphenol polyoxyethylene ether (methyl) acrylate with the residual mass percent of alkylphenol polyoxyethylene ether less than 2% can be prepared by the following method:

(1) in one possible implementation, the alkylphenol ethoxylate (meth) acrylate is prepared by the following method:

providing an alkylphenol ethoxylate (meth) acrylate raw material, wherein the alkylphenol ethoxylate (meth) acrylate raw material comprises: alkylphenol ethoxylates (meth) acrylates and alkylphenol ethoxylates.

Mixing an alkylphenol polyoxyethylene ether (methyl) acrylate raw material and monoisocyanate with double bonds, carrying out addition reaction on the alkylphenol polyoxyethylene ether and the monoisocyanate with double bonds in the presence of a first polymerization inhibitor and a first catalyst to obtain an oligomer, and separating to obtain the alkylphenol polyoxyethylene ether (methyl) acrylate to finish the treatment of the alkylphenol polyoxyethylene ether (methyl) acrylate raw material.

The oligomer is prepared by taking alkylphenol ethoxylates and monoisocyanate with double bonds as reaction raw materials and performing addition reaction in the presence of a first polymerization inhibitor and a first catalyst, and the chemical structural formula of the oligomer is as follows:

Wherein R is₁An alkyl group having 5 to 12 carbon atoms such as nonyl, isopentyl, octyl, heptyl, decyl, etc.;

R₂is H or an alkyl group, such as methyl.

n is any integer from 1 to 20.

According to the preparation method of the alkylphenol polyoxyethylene ether (methyl) acrylate provided by the embodiment of the invention, the raw material of the alkylphenol polyoxyethylene ether (methyl) acrylate is mixed with the monoisocyanate with double bonds, and under the condition that a polymerization inhibitor and a catalyst exist, the monoisocyanate with double bonds can be subjected to addition reaction with the alkylphenol polyoxyethylene ether in the raw material of the alkylphenol polyoxyethylene ether (methyl) acrylate, so that the low polymer of the monoisocyanate and the alkylphenol polyoxyethylene ether is obtained. Because the monoisocyanate has carbon-carbon double bonds, the oligomer also has the unsaturated carbon-carbon double bonds, can directly participate in curing and film forming, and is beneficial to improving the wear resistance and adhesive force of the coating. Therefore, the method effectively solves the problem of environmental safety caused by the residual alkylphenol polyoxyethylene ether in the alkylphenol polyoxyethylene ether (methyl) acrylate, and the alkylphenol polyoxyethylene ether acrylate is not lost. The generated oligomer can participate in the curing reaction along with alkylphenol polyoxyethylene (methyl) acrylate, so that an additional post-treatment process is not needed, the treatment process is simplified, the treatment cost is reduced, and a coating generated by the oligomer participating in the curing reaction can obtain better comprehensive performance.

The mass concentration of the alkylphenol ethoxylates in the alkylphenol ethoxylate (meth) acrylate raw material is 2% -5%, under the circumstance, the content of the generated oligomer in the coating composition is relatively small, and when the low-content oligomer participates in the curing reaction of the coating system, not only is the curing performance of the coating not adversely affected, but also the buffer performance, the adhesive force and the wear resistance of the cured coating can be optimized.

After the treatment process of the alkylphenol polyoxyethylene (methyl) acrylate is finished, the finally obtained reaction product comprises the following components: alkylphenol polyoxyethylene (methyl) acrylate with very low content of alkylphenol polyoxyethylene (at least lower than 2%), oligomer, a first polymerization inhibitor and a first catalyst. The basic performance of the coating system is not influenced because the contents of the first polymerization inhibitor and the first catalyst are very small. Further, a small amount of a polymerization inhibitor is generally added to the coating system before use to deactivate radicals and prevent polymerization during transportation, etc., and thus the presence of the first polymerization inhibitor is actually desirable.

In the embodiment of the invention, the alkylphenol ethoxylates and the monoisocyanate with double bonds are in equimolar amount, so that the monoisocyanate with double bonds can be ensured not to be left after addition reaction, excessive monoisocyanate (the monoisocyanate is difficult to remove) is avoided, and the adverse effect on the performance of subsequent products (paint and cured coating) is further prevented.

In some possible implementation manners, the alkylphenol ethoxylate (meth) acrylate raw material, the double-bond monoisocyanate, the first polymerization inhibitor and the first catalyst are put into a reaction kettle, and stirring is started to uniformly stir the components. And (3) heating the interior of the reaction kettle to a set temperature, carrying out heat preservation reaction, and measuring the residual quantity of alkylphenol ethoxylates in real time by using High Performance Liquid Chromatography (HPLC) in the reaction process so as to determine the reaction end point. For example, when the residual quantity of alkylphenol ethoxylates is less than 0.6%, the alkylphenol ethoxylates does not substantially adversely affect the curing system.

In the embodiment of the invention, the reaction temperature of the addition reaction is 30-100 ℃, the long reaction time and the low production efficiency can be caused by the low temperature, and the double bonds in the acrylic ester are easy to polymerize at the high temperature to generate side reaction. For example, the temperature of the addition reaction can be from 50 ℃ to 90 ℃ or from 50 ℃ to 80 ℃, further examples of which include, but are not limited to: 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, etc. In this temperature range, not only the reaction rate of the addition reaction is high (which is beneficial to reducing the reaction time), but also the polymerization of double bonds in the acrylate and the generation of side reactions can be avoided.

The reaction time of the addition reaction is determined according to the time of reaching the end point of the reaction, and when the mass concentration of the alkylphenol ethoxylate in the alkylphenol ethoxylate (meth) acrylate raw material is 2% to 5%, the addition reaction can be completed within 2 to 5 hours, for example, within 3 hours.

After the addition reaction is finished, filtering the reaction system to prevent the reaction system from being mixed with undesired dust or particles, discharging and packaging to obtain a ready-to-use product. The above-mentioned filtration treatment may be performed by using a filter bag of 5 μm, or by using a filter, for example.

In the examples of the present invention, the monoisocyanate having a double bond includes: isocyanate ethyl acrylate and/or methacrylate isocyanate.

The alkylphenol polyoxyethylene is at least one selected from isoamyl phenol polyoxyethylene, octyl phenol polyoxyethylene, nonyl phenol polyoxyethylene, heptyl phenol polyoxyethylene and decyl phenol polyoxyethylene. (correspondingly, the alkylphenol polyoxyethylene ether (meth) acrylate is selected from at least one of isopentenylphenol polyoxyethylene ether (meth) acrylate, octylphenol polyoxyethylene ether (meth) acrylate, nonylphenol polyoxyethylene ether (meth) acrylate, heptylphenol polyoxyethylene ether (meth) acrylate, and decylphenol polyoxyethylene ether (meth) acrylate).

As an example, the alkylphenol polyoxyethylene ether (meth) acrylate is nonylphenol polyoxyethylene ether (meth) acrylate; correspondingly, the alkylphenol polyoxyethylene is nonylphenol polyoxyethylene.

The first polymerization inhibitor used in the embodiment of the present invention is used to prevent the double bond polymerization of the acrylate monomer, and is exemplarily selected from at least one of p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, and hydroquinone. When the first polymerization inhibitor is used, in order to further improve the effect of inhibiting polymerization, compressed air is introduced into the reaction system to form oxygen inhibition with the first polymerization inhibitor.

The amount of the first polymerization inhibitor used in the reaction system is 200ppm to 1000ppm, and an excessively high content of the polymerization inhibitor traps radicals, terminates UV curing, and increases the product cost. For example, the polymerization inhibitor may be used in an amount of 300ppm to 800ppm or 400ppm to 700ppm in the reaction system. For example, the polymerization inhibitor is used in an amount of 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, etc. When the amount of the polymerization inhibitor is within the above range, the curing process of the coating system is not affected, the cost is lower, and the market competitiveness of the product is improved.

The first catalyst used in embodiments of the present invention is selected from at least one of dibutyltin dilaurate, monobutyltin oxide, organobismuth, organosilver, and organozinc/bismuth. For example, the first catalyst is dibutyltin dilaurate. The first catalyst of the above kind is selected, which not only promotes a higher reaction rate but also has a low cost.

The first catalyst is used in the reaction system in an amount of 200ppm to 2000ppm, so that not only can a better reaction rate be obtained, but also excessive introduction of the first catalyst is avoided. For example, the first catalyst is used in an amount of 500ppm to 1600ppm, or 700ppm to 1300ppm, in the reaction system. For example, the first catalyst is used in an amount of 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 1100ppm, 1200ppm, 1300ppm, or the like.

In summary, the above preparation method of alkylphenol ethoxylate (meth) acrylate provided in the embodiments of the present invention has at least the following advantages:

1.1, the reaction of monoisocyanate with double bond and alkylphenol polyoxyethylene ether, such as nonylphenol polyoxyethylene ether, can reduce the content of alkylphenol polyoxyethylene ether which can not participate in curing reaction in the raw material of alkylphenol polyoxyethylene ether (methyl) acrylate, so that the mass concentration of the alkylphenol polyoxyethylene ether is reduced to below 2 percent and further reduced to below 1 percent or below 0.5 percent. For example, after the above treatment, the content of alkylphenol ethoxylate may be 1.8%, 1.6%, 1.4%, 1.2%, 0.8%, 0.6%, 0.4%, 0.2%, 0.15%, 0.13%, 0.1%, 0.08%, 0.06%, 0.04%, 0.02%, 0.017%, 0.015%, etc., to achieve purification of alkylphenol ethoxylate (meth) acrylate, and the reaction thereof may only generate the above oligomer, and no other substance that cannot participate in curing is generated.

And 1.2 based on the chemical structure of the oligomer, the oligomer and the purified alkylphenol polyoxyethylene (methyl) acrylate can participate in the photocuring reaction together, so that the buffering performance, the wear resistance and the adhesive force of a cured coating are improved, and meanwhile, other post-treatment is not needed after the reaction, so that the treatment process is simplified, and the production cost is reduced.

(2) In another possible implementation, the alkylphenol ethoxylate (meth) acrylate is prepared by the following method:

providing an alkylphenol polyoxyethylene ether (methyl) acrylate raw material, wherein the alkylphenol polyoxyethylene ether (methyl) acrylate raw material comprises the following components: alkylphenol ethoxylates (meth) acrylates and alkylphenol ethoxylates.

Mixing alkylphenol polyoxyethylene ether (methyl) acrylate raw material and acid anhydride, and carrying out esterification reaction on the alkylphenol polyoxyethylene ether and the acid anhydride in the presence of a second polymerization inhibitor and a second catalyst to obtain an esterification reaction product.

And (3) separating the esterification reaction product from the alkylphenol polyoxyethylene ether (methyl) acrylate through post-treatment to finish the treatment of the alkylphenol polyoxyethylene ether (methyl) acrylate raw material.

According to the preparation method of the alkylphenol polyoxyethylene ether (methyl) acrylate provided by the embodiment of the invention, the alkylphenol polyoxyethylene ether (methyl) acrylate raw material and the acid anhydride are mixed, and the acid anhydride and the alkylphenol polyoxyethylene ether in the alkylphenol polyoxyethylene ether (methyl) acrylate raw material can perform esterification reaction in the presence of the first polymerization inhibitor and the catalyst, so that the alkylphenol polyoxyethylene ether which is not easy to separate is converted into an esterification reaction product which is easy to separate. And (3) separating the esterification reaction product from the alkylphenol polyoxyethylene ether (methyl) acrylate through post-treatment, namely obtaining the high-purity alkylphenol polyoxyethylene ether (methyl) acrylate, and finishing the treatment of the raw material of the alkylphenol polyoxyethylene ether (methyl) acrylate. The preparation method of the alkylphenol polyoxyethylene ether (methyl) acrylate provided by the embodiment of the invention effectively solves the problem of environmental safety caused by the residual alkylphenol polyoxyethylene ether in the alkylphenol polyoxyethylene ether (methyl) acrylate, and the treatment method is simple and easy to operate, has low cost, has no loss of the alkylphenol polyoxyethylene ether acrylate, and is convenient for large-scale popularization and utilization.

After the alkylphenol polyoxyethylene ether (methyl) acrylate is treated by the method, the finally obtained reaction product comprises: high-purity alkylphenol polyoxyethylene ether (methyl) acrylate with extremely low content of alkylphenol polyoxyethylene ether, a second polymerization inhibitor and a second catalyst. The content of the second polymerization inhibitor and the second catalyst is very small, so that the basic performance of the coating system is not influenced. Further, before use, a small amount of a polymerization inhibitor is generally added to the coating system to act as a radical-deactivation agent to prevent polymerization during transportation or the like, and thus the presence of the second polymerization inhibitor is actually desirable.

Generally, the alkylphenol ethoxylate (meth) acrylate product currently on the market contains 2% to 5% of alkylphenol ethoxylate, in the embodiment of the present invention, the mass concentration of alkylphenol ethoxylate in the raw alkylphenol ethoxylate (meth) acrylate is 2% to 5%, that is, the commercially available alkylphenol ethoxylate (meth) acrylate product is used as the raw alkylphenol ethoxylate (meth) acrylate, and the commercially available alkylphenol ethoxylate (meth) acrylate product is purified by the treatment method provided in the embodiment of the present invention, so that the mass concentration of alkylphenol ethoxylate that cannot participate in the curing reaction is reduced to 2% or less, further reduced to 1% or less, and further reduced to 0.5% or less or 0.05% or less. For example, after the above treatment, the content of alkylphenol ethoxylates may be 1.8%, 1.6%, 1.4%, 1.2%, 0.8%, 0.6%, 0.4%, 0.2%, 0.15%, 0.13%, 0.1%, 0.08%, 0.06%, 0.04%, 0.02%, 0.017%, 0.015%, etc. The alkylphenol ethoxylate (methyl) acrylate with high purity, for example, purity higher than 97.5%, for example, the purity of the alkylphenol ethoxylate acrylate can be 97.75%, 98%, 98.25%, 98.5%, 98.75%, 99%, etc.

In the embodiment of the present invention, when the alkylphenol ethoxylate (meth) acrylate raw material is treated, the ratio of the molar amount of the acid anhydride to the molar amount of the alkylphenol ethoxylate is greater than 1, for example, the molar amount of the acid anhydride is 1.5 times to 20 times or 3 times to 6 times of the molar amount of the alkylphenol ethoxylate, for example, the molar amount of the acid anhydride is 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, 20 times of the molar amount of the alkylphenol ethoxylate, and the like.

Anhydrides used in the examples of the present invention include: at least one of acetic anhydride, succinic anhydride, propionic anhydride, acrylic anhydride, and maleic anhydride. The anhydrides of the above types including mono-anhydride and di-anhydride can effectively reduce the residue of alkylphenol ethoxylates.

Wherein, one end of an esterification reaction product generated by the reaction of the diacid anhydride and the alkylphenol polyoxyethylene has an ester group, and the other end has a carboxyl group, and the esterification reaction product can be completely removed by a simple post-treatment process. The esterification reaction product generated by the reaction of the monoacid anhydride and the alkylphenol polyoxyethylene ether comprises: a first product with ester groups and a second product with carboxyl groups.

In some possible implementation modes, the acid anhydride used in the embodiment of the invention is maleic anhydride or succinic anhydride, so that the treatment cost can be further reduced, and the post-treatment process can be further simplified.

The alkylphenol polyoxyethylene is at least one selected from isoamyl phenol polyoxyethylene, octyl phenol polyoxyethylene, nonyl phenol polyoxyethylene, heptyl phenol polyoxyethylene and decyl phenol polyoxyethylene. (correspondingly, the alkylphenol polyoxyethylene ether (meth) acrylate is selected from at least one of isopentylphenol polyoxyethylene ether (meth) acrylate, octylphenol polyoxyethylene ether (meth) acrylate, nonylphenol polyoxyethylene ether (meth) acrylate, heptylphenol polyoxyethylene ether (meth) acrylate, and decylphenol polyoxyethylene ether (meth) acrylate). As an example, the alkylphenol polyoxyethylene ether (meth) acrylate is nonylphenol polyoxyethylene ether (meth) acrylate; correspondingly, the alkylphenol polyoxyethylene is nonylphenol polyoxyethylene.

The second polymerization inhibitor used in the embodiment of the present invention is used to prevent the double bond polymerization of the acrylate monomer, and is illustratively selected from at least one of p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, and hydroquinone.

When the second polymerization inhibitor is adopted, in order to further improve the polymerization inhibition effect, compressed air is introduced into the reaction system to form oxygen inhibition with the second polymerization inhibitor, so that the polymerization inhibition effect is improved.

The second polymerization inhibitor is used in an amount of 200ppm to 1000ppm, for example, 300ppm to 800ppm or 400ppm to 700ppm in the reaction system. For example, the second polymerization inhibitor is used in an amount of 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, or the like. When the amount of the second polymerization inhibitor is within the above range, it does not affect the curing process of the coating system, and it is less expensive.

The second catalyst used in the embodiment of the invention is at least one selected from triphenylphosphine, triethylamine, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetramethylammonium bromide and tetramethylammonium chloride, and the second catalyst of the above kind is selected, so that not only can a higher reaction rate be obtained, but also the cost is low.

The second catalyst is used in the reaction system in an amount of 200ppm to 2000ppm, for example 500ppm to 1600ppm, or 700ppm to 1300 ppm. For example, the second catalyst is used in an amount of 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 1100ppm, 1200ppm, 1300ppm, or the like.

In the embodiment of the present invention, the temperature of the esterification reaction is 30 ℃ to 100 ℃, particularly 50 ℃ to 90 ℃ or 60 ℃ to 80 ℃ in consideration of the reaction rate, the reaction time and the polymerization problem of the acrylate, and further, for example, the reaction temperature of the above addition reaction includes, but is not limited to: 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, etc. In this temperature range, not only the reaction rate of the esterification reaction is high (which is beneficial to reducing the reaction time), but also the double bond polymerization in the acrylate and the side reaction can be avoided.

The reaction time of the esterification reaction is determined according to the arrival time of the reaction end point, and when the mass concentration of the alkylphenol polyoxyethylene in the alkylphenol polyoxyethylene (meth) acrylate raw material is 2-5%, the esterification reaction can be finished in 2-5 hours, for example, 3 hours.

In some possible implementations, the post-treatment process includes the steps of: the reaction liquid is diluted by the diluent, so that the density of an organic phase in the reaction liquid is reduced, the organic phase and an inorganic phase are easier to separate, and the flowing and the separation of the two phases are facilitated.

Illustratively, the diluent is toluene, which not only facilitates optimization of the above-described effects, but also has low cost and ease of removal.

The addition mass of the diluent is 30-80 percent, for example 40-60 percent, of the total mass of the reaction liquid and the diluent, and when the addition amount of the diluent is the above, the organic phase and the inorganic phase are easier to be layered, the removal process of the diluent is more facilitated to be simplified, and the operation efficiency is improved.

In some possible implementation modes, the reaction solution is transferred to a water-washing neutralization kettle, a certain amount of diluent is added into the reaction solution, stirring is started to mix the mixture evenly, and then the reaction solution is allowed to stand. Wherein, the stirring time is ensured to be uniform, and the standing time is ensured to be enough to separate the mixture, wherein, the upper layer is an organic phase, and the lower layer is a water phase.

After the reaction solution is diluted with a diluent and separated into layers, the diluted reaction solution is neutralized with an alkali solution to neutralize excess acid anhydride and the esterification reaction product, so that the salt formed is precipitated in the lower layer solution and is easily removed.

In some possible implementations, before the neutralization treatment, the acid value of the reaction system is first determined by acid-base titration, and the alkali input amount is calculated according to the acid value. Then, cooling to 40 ℃ or below, adding alkali liquor into the water washing neutralization kettle, stirring for a set time, for example, 5-15 minutes, stopping stirring, standing for layering, and then discharging the lower water layer.

Wherein the acid value AV means: in the present invention, the amount of alkali solution added is shown by taking the alkali solution as a 10% sodium hydroxide solution by mass concentration, and the amount of sodium hydroxide added is (AV × total mass of reaction system × 1.1 × 40)/(56.1 × 1000 × 10%), wherein 56.1 is the molecular mass of KOH and 1.1 is an excess coefficient.

In view of the exothermic nature of the neutralization reaction, in order to prevent hydrolysis of the acrylic ester, the reaction solution including the esterification reaction product and alkylphenol polyoxyethylene (meth) acrylic ester is cooled to 40 ℃ or less, for example, 5 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ or the like, before the post-treatment.

After the neutralization treatment, the neutralized reaction solution is washed with a washing solution to remove the esterification reaction product.

In some possible implementation modes, the washing solution is deionized water, a set amount of deionized water is added into the water washing neutralization kettle, the mixture is stirred for a set time, for example, 10 minutes to 20 minutes and then is kept stand for layering, and after layering is finished, the lower layer of wastewater is drained. The washing process is repeated 2 to 4 times in order to improve the washing effect.

The amount of the washing liquid is 10-50% of the total mass of the reaction system, for example 20-30%, so as to obtain better washing effect.

By distillation under reduced pressure, alkylphenol ethoxylate (meth) acrylate can be thoroughly and efficiently separated from by-products remaining after washing with water, such as toluene. Wherein the final toluene content must be less than 500ppm, and the lower the toluene residue, the better, for example, the final toluene content can be 450ppm, 400ppm, 350ppm, 300ppm, 250ppm, 200ppm, 150ppm, 100ppm, 50ppm, etc.

The third polymerization inhibitor is at least one of p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol and hydroquinone.

When the third polymerization inhibitor is adopted, in order to further improve the polymerization inhibition effect, compressed air is introduced into the reaction system to form oxygen inhibition with the third polymerization inhibitor, so that the polymerization inhibition effect is improved.

The third polymerization inhibitor is used in an amount of 200ppm to 1000ppm, for example 300ppm to 800ppm or 400ppm to 700ppm, in the product system after washing. For example, the third polymerization inhibitor is used in an amount of 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, or the like. When the amount of the third polymerization inhibitor is within the above range, it does not affect the curing process of the coating system, and it is less expensive.

In some possible implementation modes, the washed product is transferred to a desolventizing reaction kettle, a third polymerization inhibitor is added into the desolventizing reaction kettle, compressed air is introduced into the desolventizing reaction kettle, stirring is started, the temperature is controlled to be lower than 80 ℃, and reduced pressure distillation is carried out.

In some possible implementations, embodiments of the present invention provide that the curable composition further includes: the colorant, illustratively, is present in the curable composition in an amount of 0.01% to 5% by weight.

By using the colorant in percentage by mass, the color developing function can be realized on the premise of not influencing the basic performance of the coating, for example, the colors of blue, orange, green, brown, gray, white, red, black, yellow, purple, powder, cyan and the like can be displayed, and the identification degree of the prepared coating is improved.

The following description is made of the kinds and effects of the respective components involved in the curable composition provided in the examples of the present invention, respectively:

(1) for acrylate oligomers

In some possible implementations, the acrylate-based oligomer includes an epoxy acrylate oligomer and a urethane (meth) acrylate oligomer; wherein the mass percent of the epoxy acrylate oligomer in the curable composition is 10-50%; the urethane (meth) acrylate oligomer is present in the curable composition in an amount of 10 to 60% by mass.

The epoxy acrylate oligomer enables the curable composition to have at least the following advantages: good chemical corrosion resistance, high adhesive force, high hardness of the cured film and higher curing speed. The polyurethane (methyl) acrylate oligomer can form hydrogen bonds among high polymer molecular chains due to the inclusion of urethane bonds, so that a film formed by the polyurethane (methyl) acrylate oligomer has excellent mechanical wear resistance and flexibility, higher elongation at break, excellent chemical resistance and high-temperature and low-temperature resistance.

The embodiment of the invention selects the epoxy acrylate oligomer and the polyurethane (methyl) acrylate oligomer as the resin matrix of the curable composition, the resin matrix has high content of unsaturated bonds such as double bonds (can be rapidly crosslinked and cured in a short time after being irradiated by light rays), can accelerate curing by synergistic cooperation with other components, and has high curing degree and small influence of a coloring agent. In addition, the resin matrix and other components have synergistic effect, so that the prepared coating has better curing speed and flexibility. The above advantages make the curable composition provided by the embodiments of the present invention particularly suitable for use as an inner coating of an optical fiber.

Further, embodiments of the present invention provide curable compositions wherein the weight average molecular weight of the epoxy acrylate oligomer is 2000-8000, such as 2000-4000. The weight average molecular weight of the urethane (meth) acrylate oligomer is 2000-8000, such as 2000-4000.

By making the weight average molecular weights of the epoxy acrylate oligomer and the urethane (meth) acrylate oligomer both 2000-8000, it can be further ensured that the hardness and flexibility of the coating formed by the coating are significantly improved compared to the prior art.

For example, the epoxy acrylate oligomer is at least one selected from the group consisting of bisphenol a epoxy acrylate, novolac epoxy acrylate, and urethane-modified epoxy acrylate.

The urethane (meth) acrylate oligomer is at least one selected from the group consisting of an aromatic urethane acrylate, an aliphatic urethane (meth) acrylate, and a urethane-modified acrylate.

(2) For alkylphenol polyoxyethylene ether (methyl) acrylate

The alkylphenol polyoxyethylene (methyl) acrylate is a diluent, has a polymerizable functional group, can directly participate in a monomer for curing and film forming, and is used for adjusting the viscosity of a system.

By making the mass percent of the alkylphenol polyoxyethylene (methyl) acrylate be 5-50%, the curable composition can be ensured to have good coating and curing effects, and the viscosity of the curable composition is kept at 2000-10000cps, such as 5000-8500cps, and further 6500-8000 cps.

As an example, the alkylphenol polyoxyethylene ether (meth) acrylate is nonylphenol polyoxyethylene ether (meth) acrylate.

(3) For photoinitiators

The photoinitiator is a substance which can absorb ultraviolet light and generate a reactive intermediate with the capability of initiating polymerization through chemical change. Acrylate systems are mostly polymerized using free radicals, and thus a variety of free radical photoinitiators may be used in the curable compositions provided by embodiments of the present invention.

In some possible implementations, the photoinitiator includes: a first type of photoinitiator and/or a second type of photoinitiator;

wherein the first photoinitiator is at least one of alpha-hydroxyalkyl phenone derivatives, alpha-amino ketones derivatives and acyl phosphine oxides, and the first photoinitiator is a cracking photoinitiator; the second kind of photoinitiator is selected from benzophenone and/or benzophenone derivatives, and the second kind of photoinitiator is a polyhydrogen photoinitiator. Under the action of light, the two types of photoinitiators can release active free radicals to promote polymerization.

The embodiment of the invention enables the first photoinitiator and the second photoinitiator to be compounded for use, and has better curing effect.

For example, when the first type of photoinitiator is a mixture of an α -hydroxyalkylphenone derivative and an α -aminoketone derivative, the mass ratio of the α -hydroxyalkylphenone derivative to the α -aminoketone derivative includes, but is not limited to: 1:1, 1:2, 1:3, 2:1, 2:3, etc.

When the first type of photoinitiator is a mixture of an alpha-hydroxyalkylphenone derivative, an alpha-aminoketone derivative, and an acylphosphine oxide, the mass ratio of the alpha-hydroxyalkylphenone derivative, the alpha-aminoketone derivative, and the acylphosphine oxide includes, but is not limited to: 1:1:1, 1:2:1, 1:3:1, 2:1:1, 2:3:1, 1:1:2, 1:2:2, 1:3:2, 2:1:2, 2:3:2, etc.

Exemplary α -hydroxyalkylphenone derivatives are 1-hydroxycyclohexylbenzophenone (abbreviated as photoinitiator 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (abbreviated as photoinitiator 1173), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone (abbreviated as photoinitiator 907), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (photoinitiator 2959 for short), 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ] (photoinitiator 127 for short), and the like.

Exemplary α -aminoketone derivatives are 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (abbreviated as photoinitiator 369), 2- (4-methylbenzyl-2- (dimethylamino) -1- [4- (4-morpholino) phenyl ] -1-butanone, 2-benzyl-2- (dimethylamino) -1- [3, 4-dimethoxyphenyl ] -1-butanone, and the like.

Illustratively, acylphosphine oxides are bis (2,4, 6-trimethylbenzoyl) phosphine oxide (abbreviated as photoinitiator 819), bis (2,4, 6-trimethylbenzoyl) - (2, 4-dipentyloxyphenyl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide (abbreviated as photoinitiator TPO), 2,4, 6-trimethylbenzoyl ethoxyphenylphosphine oxide (abbreviated as photoinitiator TEPO), and the like.

Illustratively, the benzophenone derivative is 2,4, 6-trimethylbenzophenone and/or 4-methylbenzophenone, 2-methoxycarbonylbenzophenone, 4 '-bis (chloromethyl) -benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 4' -bis (dimethylamino) -benzophenone, 4 '-bis (diethylamino) benzophenone, 3' -dimethyl-4-methoxybenzophenone, 4- (4-methylphenylsulfanyl) benzophenone, 2,4, 6-trimethyl-4 '-phenylbenzophenone, 3-methyl-4' -phenylbenzophenone, or the like.

Considering that the coloring agent can absorb ultraviolet light and influence the light absorption of the photoinitiator, and the coloring agent in the coating can possibly scatter the ultraviolet light, so that the ultraviolet light is difficult to reach the bottom of the coating. The embodiment of the invention effectively solves the technical problems by using the photoinitiator of the kind, is particularly suitable for colored and film-layer-thickness curing systems, and has better coating curing performance.

(4) For coloring agent

Illustratively, the colorant is selected from at least one of titanium dioxide, carbon black, phthalocyanine blue, phthalocyanine green, benzidine yellow, permanent red, and permanent violet. I.e., the colorant is selected from any one, two, three, four, five, six, or seven of the above ingredients.

For example, when the colorant is a mixture of titanium dioxide and carbon black, the mass ratio of the two includes, but is not limited to: 1:1, 1:2, 1:3, 2:1, 2:3, etc.

Colorants of the above-mentioned kind, when used in combination with other components in the curable composition, can impart good color to the curable composition without affecting the photocuring reaction.

(5) For the adjuvant

In the embodiment of the present application, the auxiliary agent may be at least one selected from a defoaming agent, a leveling agent, a wetting agent, a dispersing agent, and a polymerization inhibitor.

The auxiliary agents in the mass ratio are matched with other components of the curable composition to give the curable composition corresponding properties. For example, the defoaming agent is matched with other components to eliminate air bubbles in the curable composition, so that the curable composition can form a smooth coating on the surface of an optical fiber, and the mechanical property of the coating is improved. The leveling agent cooperates with other components to provide fluidity to the curable composition, to assist in leveling the coating, and to level the coating without generating bumps or pits. The wetting agent and the dispersing agent act in cooperation with other components to improve the suspension stability of the curable composition and make the components of the curable composition uniform. The polymerization inhibitor is matched with other components to prevent the curable composition from self-polymerization and thermal polymerization, and improve the stability of the curable composition.

Illustratively, the defoamer is selected from at least one of TEGO FOAMEX1488, TEGO FOAMEX800, TEGO FOAMEX815N, TEGO FOAMEX860, and TEGO FOAMEX 4000. The antifoaming agents have the advantages of good intersolubility with other components, good antifoaming effect, low price and easy acquisition.

Illustratively, the leveling agent is selected from at least one of TEGO WET240, TEGO WET250, TEGO WET270, TEGO WET500, TEGO WET 510. The flatting agents and other components have good intersolubility, so that the surface of the coating is smooth, and the flatting agent is low in price and easy to obtain.

Illustratively, both the wetting agent and the dispersing agent may be at least one selected from the group consisting of electrically neutral polyamide and polyester mixtures, low molecular weight unsaturated carboxylic acid polymers, alkyl ammonium salts of acidic group-containing block copolymers, pigment affinic group-containing high molecular weight block copolymer solutions, polyurethane derivatives, polyacrylates, and acryloxy-modified organosiloxanes. The wetting agents and the dispersing agents have good intersolubility with other components, good wetting and dispersing effects, low price and easy acquisition.

Illustratively, the polymerization inhibitor is selected from at least one of hydroquinone, tert-butylhydroquinone, methyl hydroquinone and diphenylamine. The polymerization inhibitor has good intersolubility with other components, can play a good role in inhibiting polymerization, avoids the self-polymerization of the curable composition, and has low price and easy acquisition.

In some possible implementations, embodiments of the present disclosure provide a curable composition including the following components in percentage by mass: 30-50% of epoxy acrylate oligomer with the weight-average molecular weight of 2000-4000, 30-50% of polyurethane (methyl) acrylate oligomer with the weight-average molecular weight of 2000-4000, 5-20% of alkylphenol polyoxyethylene (methyl) acrylate, 2-5% of photoinitiator, 0.5-3% of auxiliary agent and the balance of colorant.

The curable composition provided by the embodiments of the present invention may be used in different applications, for example, as a varnish, ink, paint or coating composition.

The curable composition provided by the embodiment of the invention can be used for preparing a coating with better mechanical properties, and particularly has lower elastic modulus and higher elongation at break. The elastic modulus is an index for measuring the difficulty of the material to generate elastic deformation, the elastic elongation is the ratio of the elongation of the coating at break to the initial length of the coating, and the elastic modulus is an index for representing the flexibility and the elastic performance of the coating. The lower the elastic modulus, the higher the elongation at break, indicating better flexibility of the coating.

In another aspect, an embodiment of the present invention further provides a coated product, where the coated product includes: the curable composition comprises a product matrix and a cured coating positioned on the surface of the product matrix, wherein the cured coating is prepared by using the curable composition provided by the embodiment of the invention.

In some possible embodiments, the cured coating may be made by UV curing, electron beam curing, laser curing, or LED curing. Illustratively, the cured coating is made by UV curing.

In some possible implementations, the coating product includes, but is not limited to: optical fibers, commodity or vehicle products, and the like.

For example, when the coating product is an optical fiber, the cured coating can be used as an inner coating and/or a buffer layer of the optical fiber, and the cured coating can dissipate and weaken the stress generated when the optical fiber is slightly bent, so that the signal attenuation of the optical fiber is effectively avoided; in particular, the curable composition provided by the embodiment of the invention can be cured more quickly, can be matched with the drawing speed of the optical fiber, can meet the increase of the optical fiber sales, and can also obviously reduce the production cost.

When the coated product is a commodity, it includes, but is not limited to: the cured coating can be used as a protective glue layer or a protective finish paint layer of the daily necessities.

When the coated product is a vehicle product, it includes, but is not limited to: such as automobiles, bicycles, electric vehicles, and like vehicle products, boats, airplanes, and the like, the cured coating may serve as a protective coating for the above vehicle products to provide a soft touch.

In yet another aspect, embodiments of the present invention also provide a method of preparing a curable composition as described in any one of the above, the method comprising:

and uniformly mixing the diluent and the auxiliary agent according to the mass percent of each component in the curable composition to form a first intermediate system.

And uniformly mixing the acrylate oligomer and the first intermediate system to form a second intermediate system.

And uniformly mixing the photoinitiator, the optional colorant and the second intermediate system to obtain the curable composition.

By the above production method, a curable composition having uniformly dispersed components can be obtained. Wherein the photoinitiator, the colorant and the second intermediate system are mixed uniformly and then filtered, for example, using a filter bag of 1um size, to remove undesired impurities therein.

The viscosity of the first intermediate is low, the auxiliary agent can be well mixed uniformly in the first intermediate, the acrylic ester oligomer and the first intermediate system are mixed uniformly after the auxiliary agent is fully mixed uniformly, and finally the initiator is added to prevent the situation that heating is involved in the preparation process and further curing occurs. And finally adding the coloring agent, wherein the dosage of the coloring agent can be adjusted according to the color phase.

The invention is further described below by means of specific examples:

the alkylphenol polyoxyethylene ether (methyl) acrylate raw material related to each specific embodiment below is a commercial product, and comprises the following components: alkylphenol polyoxyethylene ether (methyl) acrylate and alkylphenol polyoxyethylene ether with the residual mass percentage of 2.7 percent.

Example 1

The embodiment provides high-purity nonylphenol polyoxyethylene ether acrylate which is prepared by the following method:

600kg of nonylphenol polyoxyethylene ether acrylate raw material, 5.8kg of ethyl isocyanate acrylate, 0.3kg of p-hydroxyanisole and 0.6kg of dibutyltin dilaurate are added into a reaction kettle, stirring is started to uniformly stir the components, and compressed air is introduced into the reaction kettle. Heating the interior of the reaction kettle to 75 ℃ within 1 hour, carrying out heat preservation reaction, after reacting for 3 hours, determining the residual quantity of the polyoxyethylene nonyl phenyl ether by using a high performance liquid chromatography, when the residual quantity of the polyoxyethylene nonyl phenyl ether is less than 0.6%, determining that the reaction end point is reached, stopping the reaction, separating from the reaction product to obtain polyoxyethylene nonyl phenyl ether acrylate, filtering, discharging and packaging.

The residue of the nonylphenol polyoxyethylene ether in the nonylphenol polyoxyethylene ether acrylate in example 1 was tested by a high performance liquid chromatography external standard method, and the test result showed that the residual amount of the nonylphenol polyoxyethylene ether was 0.017%.

Fig. 1 is a liquid chromatogram of the reaction product provided in example 1, where the retention time is about 9.2min and the retention time is 11-25min, respectively, the peak of nonylphenol polyoxyethylene ether acrylate indicates that nonylphenol polyoxyethylene ether is effectively removed from nonylphenol polyoxyethylene ether acrylate raw material, and thus, high-purity nonylphenol polyoxyethylene ether acrylate is obtained.

Example 2

The embodiment provides high-purity octyl phenol polyoxyethylene ether acrylate, which is prepared by the following method:

600kg of octyl phenol polyoxyethylene ether acrylate raw material, 5.4kg of ethyl methacrylate isocyanate, 0.3kg of hydroquinone and 0.6kg of organic bismuth are put into a reaction kettle, stirring is started to uniformly stir the components, and compressed air is introduced into the reaction kettle. Heating the inside of the reaction kettle to 75 ℃ within 1 hour, carrying out heat preservation reaction, after reacting for 3 hours, determining the residual quantity of the octylphenol polyoxyethylene ether by using a high performance liquid chromatography, when the residual quantity of the octylphenol polyoxyethylene ether is less than 0.6%, determining that the reaction end point is reached, stopping the reaction, separating from the reaction product to obtain octylphenol polyoxyethylene ether acrylate, filtering, discharging and packaging.

The residue of the octylphenol polyoxyethylene ether in the octylphenol polyoxyethylene ether acrylate in example 2 is tested by adopting a high performance liquid chromatography external standard method, and the test result shows that the residual amount of the octylphenol polyoxyethylene ether is 0.02%.

FIG. 2 is a liquid chromatogram of the reaction product obtained in example 2, where the peak of the raw material octylphenol polyoxyethylene ether is at a retention time of about 9.2min and the peak of the product octylphenol polyoxyethylene ether acrylate is at a retention time of 11-25 min. This shows that in this example, the octylphenol polyoxyethylene ether is effectively removed from the octylphenol polyoxyethylene ether acrylate raw material, and the high-purity octylphenol polyoxyethylene ether acrylate is obtained.

Example 3

The embodiment provides high-purity nonylphenol polyoxyethylene ether methacrylate which is prepared by the following method:

600kg of nonylphenol polyoxyethylene ether methacrylate raw material, 19.86kg of maleic anhydride, 0.31kg of p-hydroxyanisole and 0.62kg of tetramethylammonium chloride are put into a reaction kettle, stirring is started to uniformly stir the components, and compressed air is introduced into the reaction kettle. Heating the interior of the reaction kettle to 75 ℃ within 1 hour, carrying out heat preservation reaction, after reacting for 3 hours, determining the residual quantity of the polyoxyethylene nonyl phenyl ether by using a high performance liquid chromatography, and when the residual quantity of the polyoxyethylene nonyl phenyl ether is less than 0.6%, determining that the reaction end point is reached, and stopping the reaction.

Cooling the reaction liquid to be less than 40 ℃, transferring the cooled reaction liquid to a washing neutralization kettle, adding 900kg of toluene and 88.56kg of sodium hydroxide solution with the mass fraction of 10% into the washing neutralization kettle, stirring for 10min, standing for 1h, and discharging lower-layer wastewater. And adding 150kg of deionized water into the washing neutralization kettle, stirring for 10min, standing for 1h, discharging lower-layer wastewater, and repeatedly washing once.

Transferring the reaction product solution after washing to a desolventizing reaction kettle, adding 0.31kg of p-hydroxyanisole, introducing compressed air, controlling the temperature to be 75 ℃, removing toluene by reduced pressure distillation until the content of the toluene is less than 500ppm, and finally filtering to obtain colorless to light yellow transparent nonylphenol polyoxyethylene ether methacrylate.

The residue of the polyoxyethylene nonyl phenyl ether in the polyoxyethylene nonyl phenyl ether methacrylate in example 3 is tested by a high performance liquid chromatography external standard method, and the test result shows that the residue of the polyoxyethylene nonyl phenyl ether is 0.017%.

Fig. 3 is a liquid chromatogram of the reaction product provided in example 3, where the retention time is about 9.2min and the retention time is about 11-25min, which shows that the nonylphenol polyoxyethylene ether is effectively removed from the nonylphenol polyoxyethylene ether acrylate raw material, and thus, high-purity nonylphenol polyoxyethylene ether methacrylate is obtained.

Example 4

600kg of nonylphenol polyoxyethylene ether acrylate raw material, 20.27kg of succinic anhydride, 0.31kg of hydroquinone and 1.24kg of triphenylphosphine are added into a reaction kettle, stirring is started to uniformly stir the components, and compressed air is introduced into the reaction kettle. Heating the interior of the reaction kettle to 70 ℃ within 1 hour, carrying out heat preservation reaction, after reacting for 3 hours, determining the residual quantity of the polyoxyethylene nonyl phenyl ether by using a high performance liquid chromatography, and when the residual quantity of the polyoxyethylene nonyl phenyl ether is less than 0.6%, determining that the reaction end point is reached, and stopping the reaction.

Cooling the reaction liquid to be less than 40 ℃, transferring the cooled reaction liquid to a washing neutralization kettle, adding 900kg of toluene and 87.62kg of sodium hydroxide solution with the mass fraction of 10% into the washing neutralization kettle, stirring for 10min, standing for 1h, and discharging lower-layer wastewater. Adding 150kg of deionized water into the water washing neutralization kettle, stirring for 10min, standing for 1h, discharging the lower-layer wastewater, and repeatedly washing once.

Transferring the reaction product solution after water washing to a desolventizing reaction kettle, adding 0.31kg of hydroquinone, introducing compressed air, controlling the temperature to be 75 ℃, removing toluene by reduced pressure distillation until the content of the toluene is less than 500ppm, and finally filtering to obtain colorless to light yellow transparent nonyl phenol polyoxyethylene ether acrylate.

The residue of the nonylphenol polyoxyethylene ether in the nonylphenol polyoxyethylene ether acrylate in example 4 was tested by a high performance liquid chromatography external standard method, and the test result showed that the residue of the nonylphenol polyoxyethylene ether was 0.019%.

Fig. 4 is a liquid chromatogram of nonylphenol polyoxyethylene ether acrylate provided in example 4, where the retention time is about 9.2min and the retention time is about 11-25min, respectively, the peak of nonylphenol polyoxyethylene ether acrylate as a raw material, which indicates that nonylphenol polyoxyethylene ether is effectively removed from nonylphenol polyoxyethylene ether acrylate raw material in this example, and high-purity nonylphenol polyoxyethylene ether acrylate is obtained.

Example 5

The embodiment provides a curable composition, which comprises the following components in percentage by mass: novolac epoxy acrylate with weight average molecular weight of 3000 20%, aliphatic polyurethane (meth) acrylate with weight average molecular weight of 6000, nonylphenol polyoxyethylene ether acrylate 30% provided in example 1, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) 3%, photoinitiator 2, 4, 6-trimethyl-4' -phenylbenzophenone 1%, TEGO (polyethylene glycol terephthalate)FOAMEX1488 defoaming agent 1%, TEGO WET240 leveling agent 2%, Solsperse ^TM0.5% of W100 dispersant, 0.5% of hydroquinone and the balance of phthalocyanine green colorant.

The curable composition is prepared by the following method:

according to the mass percent of each component in the curable composition, nonylphenol polyoxyethylene ether (methyl) acrylate, TEGO FOAMEX1488 defoaming agent, TEGO WET240 leveling agent and Solsperse^TMAdding a W100 dispersant and hydroquinone into a reactor, starting stirring, and heating to 50 ℃.

Slowly adding novolac epoxy acrylate and aliphatic polyurethane (methyl) acrylate into a reactor, uniformly stirring, adding a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), a photoinitiator 2, 4, 6-trimethyl-4' -phenyl benzophenone and a colorant phthalocyanine green, uniformly stirring, and filtering by using a 1um filter bag to obtain the curable composition product.

Example 6

The embodiment provides a curable composition, which comprises the following components in percentage by mass: 50% of bisphenol A type epoxy acrylate with the weight-average molecular weight of 4000, 25% of aliphatic aromatic urethane acrylate with the weight-average molecular weight of 6000, 15% of octylphenol polyoxyethylene ether acrylate provided in example 2, and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] photoinitiator ]-1-acetone 3%, photoinitiator 2,4, 6-trimethyl benzophenone 1%, TEGO FOAMEX815N defoamer 2%, TEGO WET250 leveling agent 1%, Solsperse^TM0.5 percent of W200 dispersant, 0.5 percent of methyl hydroquinone and the balance of permanent red colorant.

The curable composition is prepared by the following method:

according to the mass percent of each component in the curable composition, 15 percent of octyl phenol polyoxyethylene ether acrylate, 2 percent of TEGO FOAMEX815N defoaming agent, 1 percent of TEGO WET250 leveling agent and Solsperse^TMW200 dispersant 0.5% and methyl hydroquinone 0.5% were added to the reactor, stirring was started and the temperature was raised to 55 ℃.

50% of bisphenol A type epoxy acrylate and 25% of aliphatic aromatic urethane acrylate are slowly added into the reactor. Uniformly stirring, adding 3% of photoinitiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, 1% of photoinitiator 2,4, 6-trimethylbenzophenone and 2% of colorant permanent red, uniformly stirring, and filtering by using a 1um filter bag to obtain the curable composition product.

Example 7

The embodiment provides a curable composition, which comprises the following components in percentage by mass: 20% of polyurethane modified epoxy acrylate with the weight average molecular weight of 4000, 21% of aliphatic polyurethane (meth) acrylate with the weight average molecular weight of 2000, 50% of nonylphenol polyoxyethylene ether methacrylate provided in example 3, 2% of photoinitiator bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1% of photoinitiator 4-methylbenzophenone, 3% of TEGO FOAMEX4000 antifoaming agent, 0.1% of TEGO WET510 leveling agent, and Solsperse ^TM0.5 percent of WV400 dispersant, 0.4 percent of diphenylamine and the balance of colorant titanium dioxide.

The curable composition is prepared by the following method:

according to the mass percent of each component in the curable composition, 50 percent of nonylphenol polyoxyethylene ether methacrylate, 3 percent of TEGO FOAMEX4000 defoaming agent, 0.1 percent of TEGO WET510 flatting agent and 0.1 percent of Solsperse^TMWV400 dispersant 0.5% and diphenylamine 0.4% were added to the reactor, the stirring was turned on and the temperature was raised to 60 ℃.

Slowly adding 20% of polyurethane modified epoxy acrylate with the molecular weight of 4000 and 21% of aliphatic polyurethane (methyl) acrylate with the molecular weight of 2000 into a reactor, uniformly stirring, adding 2% of photoinitiator bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1% of photoinitiator 4-methylbenzophenone and 2% of colorant titanium dioxide, uniformly stirring, and filtering by using a 1um filter bag to obtain the curable composition product.

Example 8

The embodiment provides a curable composition, which comprises the following components in percentage by mass: phenol epoxy acrylate with weight average molecular weight of 2000.5% and aromatic hydrocarbon with weight average molecular weight of 400055% of aromatic polyurethane acrylate, 20% of nonylphenol polyoxyethylene ether acrylate provided in example 4, and 2-methyl-1- [4- (methylthio) phenyl ] photoinitiator ]-2- (4-morpholinyl) -1-propanone 4%, photoinitiator 4, 4' -bis (diethylamino) benzophenone 1%, TEGO FOAMEX860 antifoaming agent 2%, TEGO WET500 leveling agent 0.5%, Solsperse^TM0.5% of W200 dispersant, 0.5% of hydroquinone and the balance of phthalocyanine blue as colorant.

The curable composition is prepared by the following method:

according to the mass percent of each component in the curable composition, 20 percent of nonylphenol polyoxyethylene ether acrylate, 2 percent of TEGO FOAMEX860 defoaming agent, 0.5 percent of TEGO WET500 leveling agent and Solsperse^TMW200 dispersant 0.5% and hydroquinone 0.5% were added to the reactor, the stirring was turned on and the temperature was raised to 50 ℃.

14.5 percent of novolac epoxy acrylate with molecular weight of 2000 and 55 percent of aromatic urethane acrylate with molecular weight of 4000 are slowly added into a reactor, evenly stirred and added with 4 percent of photoinitiator 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone, 1 percent of photoinitiator 4, 4' -bis (diethylamino) benzophenone and 2 percent of colorant phthalocyanine blue. Stirring, filtering with 1um filter bag to obtain curable composition.

Example 9

The embodiment provides a curable composition, which comprises the following components in percentage by mass: 25.5% of bisphenol A epoxy acrylate with a weight average molecular weight of 3000, 37% of aliphatic polyurethane (meth) acrylate with a molecular weight of 5000, 20% of nonylphenol polyoxyethylene ether acrylate provided in example 1, 4% of photoinitiator 1-hydroxycyclohexyl benzophenone, 1.5% of photoinitiator 4, 4' -bis (chloromethyl) -benzophenone, 3% of TEGO FOAMEX1488 antifoaming agent, 1% of TEGO WET250 leveling agent, and Solsperse ^TM0.5 percent of WV400 dispersant, 0.5 percent of methyl hydroquinone and the balance of permanent violet as colorant.

The curable composition is prepared by the following method:

depending on the mass percentages of the components in the curable composition,25% of nonylphenol polyoxyethylene ether acrylate, 3% of TEGO FOAMEX1488 defoaming agent, 1% of TEGO WET250 flatting agent and 1% of Solsperse^TM0.5 percent of WV400 dispersant and 0.5 percent of methyl hydroquinone are added into a reactor, the stirring is started, and the temperature is increased to 55 ℃.

25.5% of bisphenol A type epoxy acrylate having a molecular weight of 3000 and 37% of aliphatic urethane (meth) acrylate having a molecular weight of 5000 were slowly added to the reactor. Uniformly stirring, adding 4% of photoinitiator 1-hydroxycyclohexyl benzophenone, 1.5% of photoinitiator 4, 4' -bis (chloromethyl) -benzophenone and 2% of colorant permanent violet, uniformly stirring, and filtering by using a 1um filter bag to obtain the curable composition product.

Comparative example 1

30 percent of nonylphenol polyoxyethylene ether acrylate (the residual amount of the nonylphenol polyoxyethylene ether is 5 percent), 1 percent of TEGO FOAMEX1488 defoaming agent, 2 percent of TEGO WET240 flatting agent and Solsperse^TMW100 dispersant 0.5% and hydroquinone 0.5% were added to the reactor, the stirring was turned on and the temperature was raised to 50 ℃.

20 percent of novolac epoxy acrylate with the weight-average molecular weight of 3000 and 40 percent of aliphatic polyurethane (methyl) acrylate with the weight-average molecular weight of 6000 are slowly added into a reactor, and after being uniformly stirred, 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) serving as a photoinitiator, 1 percent of 2, 4, 6-trimethyl-4' -phenyl benzophenone serving as a photoinitiator and 2 percent of phthalocyanine green serving as a colorant are added. Stirring evenly, and then filtering by using a 1um filter bag to obtain a curable composition product.

Comparative example 2

30 percent of nonylphenol polyoxyethylene ether methacrylate (the residual amount of nonylphenol polyoxyethylene ether is 3 percent), 1 percent of TEGO FOAMEX1488 antifoaming agent, 2 percent of TEGO WET240 leveling agent and Solsperse^TMW100 dispersant 0.5% and hydroquinone 0.5% were added to the reactor, the stirring was turned on and the temperature was raised to 50 ℃.

20 percent of novolac epoxy acrylate with the molecular weight of 3000 and 40 percent of aliphatic polyurethane (methyl) acrylate with the molecular weight of 6000 are slowly added into a reactor. After stirring evenly, adding 3 percent of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 1 percent of photoinitiator 2, 4, 6-trimethyl-4' -phenyl benzophenone and 2 percent of colorant phthalocyanine green. Stirring and stirring evenly, and then filtering by using a 1um filter bag to obtain a curable composition product.

Test examples

This test example evaluates the properties of the curable compositions provided in examples 4 to 9 and comparative examples 1 to 2, respectively, as follows:

(1) speed of curing

Using 0.1J/cm²The ultraviolet energy is used for carrying out ultraviolet curing on the curable compositions to form a film with the thickness of about 0.07 +/-0.01 mm, and the film is placed in a dark place for 4 hours after being cured to be tested.

The cure speed test procedure is as follows:

step 1, turning on an infrared spectrometer;

step 2, measuring a background spectrum;

step 3, taking a proper amount of the curable composition (i.e. a sample which is not cured) by a dropper, placing the curable composition on the surface of the crystal, and measuring the infrared spectrum of each curable composition.

Step 4, mixing 1400cm^-1Is integrated and then the standard absorption peak is integrated (e.g., 1700 cm)^-1Absorption peak of (b), the area integral ratio of the two absorption peaks is defined as: AU liquid.

And 5, fixing the curing film to be detected on the surface of the crystal, and then measuring the infrared spectrum of the curing film.

And 6, repeating the step 4, and determining the area integral ratio of the two absorption peaks as an AU sample.

The curing speed calculation formula is as follows:

(2) modulus and elongation

Using 0.1J/cm²The curable compositions were subjected to UV curing to form films having a length of 140mm, a width of 12mm and a height of 0.15 mm.

The modulus and elongation test procedure is as follows:

1. and opening a power switch of the universal testing machine.

2. And turning on the power supply of the computer and starting the powertest software.

3. The 50N sensors were selected, online, and the desired assay protocol was selected.

4. Adjusting the distance between the two clamps to be 50mm +/-1 mm, clamping a test sample strip which is prepared in advance on the clamps, inputting relevant data of a sample to be tested in user parameters, wherein the stretching speed of the sample is as follows: 20mm/min, then click "run".

5. Calculating by using software: elastic modulus (MPa) and elongation at break (%).

Wherein, the residual quantity of alkylphenol polyoxyethylene is measured by HPLC.

The test results are shown in table 1:

TABLE 1

As can be seen from Table 1, by controlling the residues of alkylphenol ethoxylates in alkylphenol ethoxylates (meth) acrylate, the APE residues in the coatings of the examples are all lower than 0.1%, the ROCH standard can be met, excellent elastic modulus and elongation performance are shown, and the mechanical properties and curing speed of the coatings are remarkably improved.

Therefore, the curable composition provided by the embodiment of the invention is particularly suitable for inner coatings of optical fibers, and the coating with lower elastic modulus and higher elongation at break has better flexibility, can dissipate and weaken stress generated when the optical fibers are slightly bent, and effectively avoids optical fiber signal attenuation; further, the curable composition provided by the embodiment of the invention can be cured more quickly, so that the production cost is greatly reduced, and the increase of the optical fiber sales is met.

The above description is only for the convenience of understanding the technical solutions of the present invention by those skilled in the art, and is not intended to limit the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A curable composition is characterized by comprising the following components in percentage by mass: 30-80% of acrylate oligomer, 5-50% of alkylphenol polyoxyethylene (methyl) acrylate, 1-10% of photoinitiator and 0.1-10% of auxiliary agent;

wherein the residual mass percentage of alkylphenol polyoxyethylene ether in the alkylphenol polyoxyethylene ether (methyl) acrylate is less than 2 percent;

wherein the alkylphenol polyoxyethylene ether (methyl) acrylate is prepared by one of the following methods:

mixing the alkylphenol polyoxyethylene ether (methyl) acrylate raw material and monoisocyanate with double bonds, and carrying out addition reaction on the alkylphenol polyoxyethylene ether and the monoisocyanate with double bonds in the presence of a first polymerization inhibitor and a first catalyst to obtain an oligomer, so as to finish the treatment of the alkylphenol polyoxyethylene ether (methyl) acrylate raw material;

Or,

providing alkylphenol polyoxyethylene ether (methyl) acrylate raw material, wherein the alkylphenol polyoxyethylene is

The raw materials of the vinyl ether (methyl) acrylate comprise: alkylphenol polyoxyethylene (meth) acrylates and alkylphenol ethoxylates;

mixing the alkylphenol polyoxyethylene (methyl) acrylate raw material and acid anhydride, and adding a second polymerization inhibitor

And in the presence of a second catalyst, carrying out esterification reaction on the alkylphenol polyoxyethylene and anhydride to obtain an esterification reaction product;

2. The curable composition of claim 1, wherein the acrylate oligomer comprises: epoxy acrylate oligomers and urethane (meth) acrylate oligomers;

3. The curable composition of claim 2 wherein the weight average molecular weight of the epoxy acrylate oligomer is 2000-8000;

4. The curable composition according to claim 1, wherein the ratio of the molar amount of the acid anhydride to the molar amount of the alkylphenol ethoxylate is greater than 1.

5. The curable composition of claim 1, wherein said separating the esterification reaction product from alkylphenol ethoxylate (meth) acrylate by post-treatment comprises: diluting the reaction solution by using a diluent;

neutralizing the diluted reaction liquid by using alkali liquor;

6. The curable composition according to any one of claims 1 to 5, further comprising: a colorant.

7. A process for preparing a curable composition according to any one of claims 1 to 6, characterized in that it comprises:

uniformly mixing a diluent and an auxiliary agent according to the mass percentage of each component in the curable composition to form a first intermediate system;

8. A cured coating obtained by curing the curable composition according to any one of claims 1 to 6.

9. A coated product, characterized in that it comprises: a product substrate, a cured coating on a surface of the product substrate, the cured coating as set forth in claim 8.

10. The coated product of claim 9, wherein the coated product comprises: optical fiber, commodity, or vehicle product.

11. A method of preparing a coated product, the method comprising: providing a product substrate;

forming a cured coating on the surface of the product substrate by a curing process using the curable composition of any one of claims 1 to 6.

12. The method of preparing a coated product according to claim 11, wherein the curing process comprises: UV curing, electron beam curing, laser curing, or LED curing.