阅读说明：本技术 一种耐烟头烫耐污阻燃光固化树脂及光固化涂料 (Smoke head scalding resistant stain resistant flame retardant photocureable resin and photocureable coating ) 是由 谢国仁 郭常州 于 2020-12-11 设计创作，主要内容包括：本发明提供了一种耐烟头烫耐污阻燃光固化树脂,按照以下步骤制备得到：A)将羟基丙烯酸酯和四溴苯酐在催化剂的作用下进行反应,得到端羧基丙烯酸酯化合物；B)将所述端羧基丙烯酸酯化合物与酚醛环氧树脂进行反应,得到带环氧基团的化合物；C)将所述带环氧基团的化合物与四溴苯酐、端羟基有机硅氟多元醇进行反应,得到耐烟头烫耐污阻燃光固化树脂。本发明通过化学接枝反应制备得到光固化树脂,制备得到的光固化树脂同时具备耐高温性能和耐污性能,使得耐烟头烫性能更加突出。本发明还提供了一种光固化涂料。(The invention provides a cigarette end scalding resistant stain resistant flame retardant photocurable resin which is prepared according to the following steps: A) reacting hydroxyl acrylic ester with tetrabromophthalic anhydride under the action of a catalyst to obtain a carboxyl-terminated acrylic ester compound; B) reacting the carboxyl-terminated acrylate compound with novolac epoxy resin to obtain a compound with an epoxy group; C) and reacting the compound with the epoxy group with tetrabromophthalic anhydride and hydroxyl-terminated organic silicon fluorine polyol to obtain the cigarette end burning resistant stain resistant flame retardant photocuring resin. The light-cured resin is prepared through chemical grafting reaction, and the prepared light-cured resin has high temperature resistance and stain resistance, so that the cigarette end scalding resistance is more outstanding. The invention also provides a photocureable coating.)

1. The cigarette end scalding resistant stain resistant flame retardant photocurable resin is prepared according to the following steps:

A) reacting hydroxyl acrylic ester with tetrabromophthalic anhydride under the action of a catalyst to obtain a carboxyl-terminated acrylic ester compound;

B) reacting the carboxyl-terminated acrylate compound with novolac epoxy resin to obtain a compound with an epoxy group;

C) and reacting the compound with the epoxy group with tetrabromophthalic anhydride and hydroxyl-terminated organic silicon fluorine polyol to obtain the cigarette end burning resistant stain resistant flame retardant photocuring resin.

2. The resin as claimed in claim 1, wherein the hydroxy acrylate comprises one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, ditrimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

3. The cigarette end scalding and stain resistant flame retardant photocurable resin as claimed in claim 1, wherein the molar ratio of the hydroxyl acrylate to the tetrabromophthalic anhydride is 1 (0.5-2).

4. The cigarette end scalding and stain resistant flame retardant photocurable resin according to claim 1, wherein the catalyst is one or more of triphenyl phosphine, triethylamine and benzyl trimethyl ammonium chloride;

the mass ratio of the total mass of the hydroxyl acrylic ester and the tetrabromophthalic anhydride to the mass of the catalyst is 100: (0.1-5).

5. The cured resin of claim 1, wherein the reaction temperature in step A) is 100-125 ℃;

the reaction time in the step A) is 2-3 hours.

6. The cigarette end scalding and stain resistant flame retardant photocurable resin as claimed in claim 1, wherein the amount of the novolac epoxy resin, tetrabromophthalic anhydride and hydroxyl terminated acrylate is in the molar ratio of (1-3): (2-5): (2-6).

7. The cured resin of claim 1, wherein the reaction temperature in step B) is 80-120 ℃;

the reaction time in the step B) is 3-4 hours.

8. The resin of claim 1, wherein the hydroxyl terminated silicone-fluorine polyol is selected from perfluoropolyethers and/or hydroxyl silicone oil polyols;

the mol ratio of the compound with epoxy groups, tetrabromophthalic anhydride and the hydroxyl-terminated organic silicon fluorine polyol is (0.5-5): (0.5-2): 1.

9. the cured resin of claim 1, wherein the reaction temperature in step C) is 80-120 ℃;

the reaction time in the step C) is 3-4 hours.

10. A photo-curable coating comprising a photoinitiator and the flame-retardant photo-curable resin of any one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to a cigarette end burning resistant stain resistant flame retardant photocureable resin and a photocureable coating.

Background

The photo-curing coating is also called photosensitive coating, which is ultraviolet light as coating curing energy and is also called ultraviolet light curing coating. The energy of ultraviolet light is used to initiate polymerization and cross-linking reaction between low-molecular prepolymer or oligomer in the paint and monomer molecule as active diluent to obtain hardened paint film, which is chemically dried by forming chemical bond. The photocureable coating can be quickly cured to form a film on flammable substrates such as paper, plastics, leather, wood and the like without heating.

The main components of the photocureable coating mainly comprise acrylate resin, vinyl resin, epoxy resin and the like, and the acrylate resin has light color, excellent weather resistance, difficult yellowing, heat resistance, corrosion resistance and good optical performance, so the photocureable coating is widely used for film-forming materials of photocureable paint coatings.

The research of acrylate photocureable coating in China starts from the 60 s and 80 s of the 20 th century and starts the industrial process, and the acrylate photocureable coating has made remarkable achievement in solvent type and water-based systems so far and covers various fields of daily life. The performance of the current acrylate photocureable coating at home and abroad is gradually improved along with the diversification of vinyl monomers and auxiliaries and the further improvement of a synthesis process; meanwhile, with the steady development of domestic economy, the demand of acrylate coatings is also greatly increased. Along with the wider application range of the acrylate photocureable coating, the performance requirements of the acrylate coating are also more and more comprehensive.

For example, in the coating applied to the fields of indoor metal building materials, kitchen furniture or electric appliances, etc., people hope to provide good matte effect and excellent stain resistance, and in order to overcome the defects that the flame point of the acrylate resin is not high, the char yield is low in the combustion process, and the flame retardant property of the acrylate resin coating is poor, the acrylate resin is hoped to have certain flame retardant property. However, the existing acrylate light-cured resin on the market basically has only single functional characteristics, such as only flame retardant performance or only stain resistant performance.

Disclosure of Invention

The invention aims to provide a cigarette end burning resistant stain resistant flame retardant photocurable resin and a photocurable coating.

The invention provides a cigarette end scalding resistant stain resistant flame retardant photocurable resin which is prepared according to the following steps:

A) reacting hydroxyl acrylic ester with tetrabromophthalic anhydride under the action of a catalyst to obtain a carboxyl-terminated acrylic ester compound;

B) reacting the carboxyl-terminated acrylate compound with novolac epoxy resin to obtain a compound with an epoxy group;

C) and reacting the compound with the epoxy group with tetrabromophthalic anhydride and hydroxyl-terminated organic silicon fluorine polyol to obtain the cigarette end burning resistant stain resistant flame retardant photocuring resin.

Preferably, the hydroxyl acrylate comprises one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, ditrimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

Preferably, the molar ratio of the hydroxyl acrylic ester to the tetrabromophthalic anhydride is 1 (0.5-2).

Preferably, the catalyst is one or more of triphenylphosphine, triethylamine and benzyltrimethylammonium chloride;

the mass ratio of the total mass of the hydroxyl acrylic ester and the tetrabromophthalic anhydride to the mass of the catalyst is 100: (0.1-5).

Preferably, the reaction temperature in the step A) is 100-125 ℃;

the reaction time in the step A) is 2-3 hours.

Preferably, the dosage relationship of the novolac epoxy resin, tetrabromophthalic anhydride and hydroxyl-terminated acrylate is that the molar ratio is (1-3): (2-5): (2-6).

Preferably, the reaction temperature in the step B) is 80-120 ℃;

the reaction time in the step B) is 3-4 hours.

Preferably, the hydroxyl-terminated silicone-fluorine polyol is selected from perfluoropolyether and/or hydroxyl silicone oil polyol;

the mol ratio of the compound with epoxy groups, tetrabromophthalic anhydride and the hydroxyl-terminated organic silicon fluorine polyol is (0.5-5): (0.5-2): 1.

preferably, the reaction temperature in the step C) is 80-120 ℃;

the reaction time in the step C) is 3-4 hours.

The invention provides a photocureable coating which comprises the above-mentioned cigarette end scalding resistant and stain resistant flame-retardant photocureable resin.

The invention provides a cigarette end scalding resistant stain resistant flame retardant photocurable resin which is prepared according to the following steps: A) reacting hydroxyl acrylic ester with tetrabromophthalic anhydride under the action of a catalyst to obtain a carboxyl-terminated acrylic ester compound; B) reacting the carboxyl-terminated acrylate compound with novolac epoxy resin to obtain a compound with an epoxy group; C) and reacting the compound with the epoxy group with tetrabromophthalic anhydride and hydroxyl-terminated organic silicon fluorine polyol to obtain the cigarette end burning resistant stain resistant flame retardant photocuring resin. The light-cured resin is prepared through chemical grafting reaction, and the prepared light-cured resin has high temperature resistance and stain resistance, so that the cigarette end scalding resistance is more outstanding. Experimental results show that the hardness of a paint film formed by the resin is 2H, the adhesive force is 5B, the flexibility is excellent, the stain resistance is unchanged for 500 times, the flame retardant effect is excellent, and no mark is left after the cigarette end is scalded.

Detailed Description

The invention provides a cigarette end scalding resistant stain resistant flame retardant photocurable resin which is prepared according to the following steps:

A) reacting hydroxyl acrylic ester with tetrabromophthalic anhydride under the action of a catalyst to obtain a carboxyl-terminated compound containing an acrylic group;

B) reacting the carboxyl-terminated acrylic group-containing compound with novolac epoxy resin to obtain a compound with an epoxy group;

C) and reacting the compound with the epoxy group with tetrabromophthalic anhydride and hydroxyl-terminated organic silicon fluorine polyol to obtain the cigarette end burning resistant stain resistant flame retardant photocuring resin.

First, a carboxyl-terminated acrylic group-containing compound is synthesized.

In the invention, the hydroxyl acrylate (terminal hydroxyl acrylate) is preferably one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, ditrimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate; the molar ratio of the hydroxyl acrylic ester to the tetrabromophthalic anhydride is preferably 1 (0.5-2), and more preferably 1: (1-1.5), and most preferably 1: 1.

In the invention, the catalyst is preferably selected from one or more of triphenylphosphine, triethylamine and benzyltrimethylammonium chloride, and is more preferably benzyltrimethylammonium chloride; the mass ratio of the total mass of the hydroxyl acrylic ester and the tetrabromophthalic anhydride to the mass of the catalyst is 100: (0.1 to 5), preferably 100: (0.5 to 4), more preferably 100: (1-3), most preferably 100: (1-2).

In the invention, the reaction temperature for synthesizing the carboxyl-terminated acrylic group-containing compound is preferably 100-125 ℃, more preferably 105-120 ℃, and most preferably 110-115 ℃; the reaction time for synthesizing the carboxyl-terminated acrylic group-containing compound is preferably 2-3 hours.

Then, an epoxy group-containing compound was synthesized.

And reacting the carboxyl-terminated acrylic group-containing compound with novolac epoxy resin to obtain the epoxy group-containing compound.

In the invention, the dosage relationship of the novolac epoxy resin, tetrabromophthalic anhydride and hydroxyl-terminated acrylate is that the molar ratio is (1-3): (2-5): (2-6), more preferably 2: 4: 4.

the reaction temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 95-100 ℃; the reaction time is preferably 3 to 4 hours.

And finally, preparing the cigarette end scalding resistant stain resistant flame retardant light-cured resin.

And reacting the compound with the epoxy group with tetrabromophthalic anhydride and hydroxyl-terminated organic silicon fluorine polyol to obtain the cigarette end burning resistant stain resistant flame retardant photocuring resin.

In the present invention, the hydroxyl-terminated silicone-fluorine polyol is selected from perfluoropolyether and/or hydroxyl silicone oil polyol; specifically, the perfluoropolyether is preferably a product of model LF-600X available from Asahi glass company, Japan, or a product of model GK570 available from Dajin Japan; the hydroxyl polysiloxane is preferably a TEGO5000 model commercial product available from Digao, Inc., or a SISIBM4000 model commercial product available from Sisco, Inc.

In the invention, the mol ratio of the compound with epoxy groups, tetrabromophthalic anhydride and hydroxyl-terminated organic silicon fluorine polyol is (0.5-5): (0.5-2): 1, more preferably (1 to 4): (1-1.5): 1, most preferably 2:1: 1.

In the invention, the reaction temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 95-100 ℃; the reaction time is preferably 4 hours.

The invention also provides a preparation method of the cigarette end burning resistant stain resistant flame-retardant photocureable resin, which is consistent with the preparation method of the cigarette end burning resistant stain resistant flame-retardant photocureable resin and is not repeated herein.

Based on the above, the invention also provides a photocureable coating, which comprises the above-mentioned cigarette end burning resistant and stain resistant flame-retardant photocureable resin, a photoinitiator and optionally a functional auxiliary agent or monomer.

Specifically, in the embodiment of the present invention, the photocurable coating may be formed according to the following components in percentage by mass:

cigarette end scalding resistant stain resistant flame retardant photocurable resin: 65-75%, TMPTA monomer: 20-25%, leveling agent: 0.2-0.6% of a photoinitiator and 3-4% of a photoinitiator.

In the invention, the photoinitiator and the leveling agent are functional auxiliaries commonly used by those skilled in the art, for example, the photoinitiator can be selected from 1173, and the leveling agent can be selected from BYK 333. The person skilled in the art can also select other photoinitiators or leveling agents, or even more functional auxiliaries, according to the actual needs to meet the actual production requirements.

The invention provides a cigarette end scalding resistant stain resistant flame retardant photocurable resin which is prepared according to the following steps: A) reacting hydroxyl acrylic ester with tetrabromophthalic anhydride under the action of a catalyst to obtain a carboxyl-terminated compound containing an acrylic group; B) reacting the carboxyl-terminated acrylic group-containing compound with novolac epoxy resin to obtain a compound with an epoxy group; C) and reacting the compound with the epoxy group with tetrabromophthalic anhydride and hydroxyl-terminated organic silicon fluorine polyol to obtain the cigarette end burning resistant stain resistant flame retardant photocuring resin. The invention introduces a phenolic epoxy structure and an organic silicon fluorine structure into the main chain, and has high temperature resistance effect. The introduction of organosilicon fluorine group has stain resistance, self-cleaning effect and high temperature resistance. The introduction of bromine-containing groups has flame retardant effect. Meanwhile, the coating has high temperature resistance and stain resistance, so that the cigarette end scalding resistance is outstanding.

For further illustration of the present invention, the following detailed description will be made of the smoke-resistant, smudge-resistant, flame-retardant photocurable resin and photocurable coating provided by the present invention with reference to the following examples, which should not be construed as limiting the scope of the present invention.

Example 1

541g pentaerythritol triacrylate and 464g tetrabromophthalic anhydride react for 3 hours under the action of 10g triphenyl phosphorus at 115 ℃ to obtain a carboxyl-terminated acrylate compound;

adding a carboxyl-terminated acrylic acid group-containing compound into 125g of novolac epoxy resin at 100 ℃, reacting for 4 hours, and testing the acid value of a reactant to be less than or equal to 5mgKOH/g to obtain a compound with an epoxy group;

the compound reacts with 232g of tetrabromophthalic anhydride and 1000g of hydroxyl-terminated organic silicon polyol TEGO5000, and after the reaction is finished, the acid value of a test reactant is less than or equal to 5mgKOH/g, and the reaction is terminated.

Example 2

In comparison with example 1, the pentaerythritol triacrylate was changed to hydroxyethyl methacrylate in the first step to 130g, and the other conditions were kept unchanged.

Example 3

In comparison with example 1, the tetrabromophthalic anhydride was changed to tetrachlorophthalic anhydride 285g in the first step, and the other conditions were kept unchanged.

Example 4

Compared with example 1, the organosilicon polyol TEGO5000 in the third step is changed into the organofluorine polyol LF-600X, and other conditions are kept unchanged.

The ultraviolet curing cigarette end burning and stain resistant resin prepared in the examples 1-4 and the commercial (changxing) UV stain resistant resin (comparative example 1) are prepared into a paint film by mixing the following components:

resin: 65-75%; monomer (b): 20-25%, leveling agent: 0.2-0.6% of a photoinitiator and 3-4% of a photoinitiator.

The monomer is TMPTA, the photoinitiator is 1173, and the flatting agent is BYK 333.

The properties of the paint films were tested and the results are shown in Table 1. Wherein the coating film hardness is measured according to GB/T6739-2006; adhesion was determined according to GB/T9286-1998; and (3) flexibility measurement: preparing a paint film on the tinplate, and bending the tinplate to a certain angle to see the cracking degree; boiling property: boiling in 100 deg.C water for 30min, and observing the change of paint film; oil resistance pen wiping: the smudge resistance of the coating was measured by the number of scratch erasability measurements by oil pen wiping in the same area of the coating. Cigarette end scalding resistance test: the Chinese cigarette is ignited to burn on the paint film, the whole cigarette is wiped clean with paper after being burnt out, and the damage degree of the paint film surface is observed.

TABLE 1 paint film property testing in the examples of the invention

As can be seen from table 1, the photocurable resin prepared by the method of the present invention has multiple functions of high temperature resistance, stain resistance, flame retardancy, etc. Meanwhile, the paint has good hardness, flexibility, adhesive force, boiling resistance and other properties. The resin on the market has single performance and single pollution resistance, and cannot meet the integration of multiple functions.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.