WO2023216432A1

WO2023216432A1 - Thioxanthone derivative, method for preparing same, and use thereof

Info

Publication number: WO2023216432A1
Application number: PCT/CN2022/109095
Authority: WO
Inventors: 王辰龙; 赵文超; 王永林; 吕东旭; 张珏
Original assignee: 艾坚蒙(安庆)科技发展有限公司; 北京英力科技发展有限公司
Priority date: 2022-05-10
Filing date: 2022-07-29
Publication date: 2023-11-16
Also published as: CN114805296A

Abstract

The present application relates to a thioxanthone derivative, a method for preparing same, and use thereof. The thioxanthone derivative has a structure represented by formula (1). The thioxanthone derivative provided by the present application contains more double bonds, and can participate in polymerization reactions. It does not contain non-curing components, which is beneficial to reducing the mobility rate of photoinitiators. The thioxanthone derivative can be used in the fields of food package printing, medicine package printing, furniture painting, book printing, advertisement printing, and the like.

Description

A kind of thioxanthone derivative, preparation method and use thereof

Cross-references to related applications

This application requires the priority of the Chinese patent application submitted to the China Patent Office on May 10, 2022, with the application number 202210505858.8 and the invention name "A Thiaxanthone Derivative, Preparation Method and Use", and its entire contents Incorporated herein by reference.

Technical field

The present application relates to the field of photosensitive polymer materials, and relates to a thioxanthone derivative, its preparation method and its use.

Background technique

Light-curing technology is becoming more and more widely used, especially because of its inherent advantages of low VOC release. It is mainly used in fast-curing coatings, printing inks and adhesives. Photoinitiators play an important role in UV curing systems. They can absorb energy of specific wavelengths to generate active species to initiate the polymerization of the entire system. However, adding small molecule photoinitiators to the system will cause a series of disadvantages such as yellowing, odor, and toxicity in the system.

In order to overcome these shortcomings, macromolecule photoinitiators have attracted widespread attention because they can overcome the inherent defects of small molecule photoinitiator systems. The macromolecules themselves have low toxicity. After curing, the fragments of the photoinitiator remain small. The transformation of the photoinitiator fragments into macromolecules can greatly reduce its mobility, which can greatly reduce its toxicity, yellowing and unpleasant odor. . However, although the current macromolecule photoinitiator IGM Resin Company's Omnipol TX can further reduce the migration problem of small molecules, its migration amount is still high. Although in the existing technology, acrylic esters will be bonded to thioxanthone in order to obtain The amount of migration is lower, but the reduction is limited. Therefore, it is necessary to develop a new photoinitiator or co-photoinitiator to further reduce the amount of migration.

Contents of the invention

Therefore, the technical problem to be solved by this application is to overcome the defect of high migration amount of photoinitiator or photoinitiator in the prior art, thereby providing a thioxanthone derivative, preparation method and use thereof.

In order to solve the above problems, this application adopts the following solution:

A thioxanthone derivative having a structure shown in formula (1):

in

G is the dehydroxylated group of n-valent alcohol, n=n ₁ +n ₂ , n is an integer from 3 to 6, n ₂ is an integer from 2 to 5; preferably n is an integer from 4 to 6, n ₂ is Integer from 3 to 5;

A is

R ₃ is optionally substituted C1-C8 alkylene;

B ₁ and B ₂ are each independently a single bond,

In the formula, R ₁ and R ₂ are each independently H, -CH ₃ , and m is an integer ranging from 0 to 5;

R is H or -CH ₃ .

What needs explanation is: in this application, the group after removal of hydroxyl group of n-hydric alcohol refers to the groups other than hydroxyl group in n-hydric alcohol.

Examples of n-valent alcohols include but are not limited to: pentaerythritol, di(trimethylolpropane) ether or di(pentaerythritol) ether, etc. n-valent alcohols also include ethyl oxidation derivatives of n-valent alcohols or propyl oxidation derivatives thereof .

The term "substituted" means that any one or more hydrogen atoms on a specified atom are replaced by a substituent, as long as the substituted compound is stable. The term "optionally substituted" means that it may or may not be substituted. Unless otherwise specified, the type and number of substituents may be arbitrary based on what is achievable.

In this application, the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group.

In this application, n=n ₁ +n ₂ , n is an integer from 4 to 6, such as 4, 5 or 6, n ₂ is an integer from 3 to 5, such as 3, 4 or 5, n ₁ is nn ₂ , That is, n ₁ is 1, 2 or 3.

In this application, R ₃ is optionally substituted C1-C8 alkylene, preferably unsubstituted C1-C8 alkylene. Examples of C1-C8 alkylene include but are not limited to the terms used herein. "Alkylene" means a straight or branched chain consisting solely of carbon and hydrogen. Examples of "alkylene" include methylene, ethylene, propylene, butylene, pentylene and 3-methylpentylene. Preferably, _R3 is methylene.

In an optional embodiment of the present application, G is selected from at least one of the following structures,

Optionally, G can also be selected from the following structures:

The average of the sum of P ₁ , P ₂ , P ₃ and P ₄ is 5;

Optionally, G is selected from glycerol, diglycerol, triglycerol, triethanolamine, trimethylolpropane, dimethylolpropane, pentaerythritol, dipentatriol, residues of sugar alcohols and mixtures thereof; preferably, the The sugar alcohols are sorbitol, mannitol and xylitol.

In an alternative embodiment of the present application, the A group is at the 2- or 4-substituted position of the benzene ring.

In an optional embodiment of the present application, R is H, n ₁ is 1, and n ₂ is an integer from 3 to 5.

In an optional embodiment of the present application, the thioxanthone derivative is selected from any one of the following compounds:

The above compounds are easier to synthesize, and the product physical properties (such as fluidity and solubility) are more conducive to use in compositions.

This application also provides a method for preparing the thioxanthone derivative as described above, which includes the following steps:

(a) reacting an n-valent alcohol with G as the core group and an acrylic compound;

(b) reacting the reaction product of step (a) with the compound represented by formula (2) to obtain a thioxanthone derivative;

in:

R ₄ is -OR ₃ -COOH, and R ₃ is optionally substituted C1-C8 alkylene. R ₃ has the same definition as in formula (1), preferably, R ₃ is methylene.

In an optional embodiment of the present application, step (a) and step (b) are performed independently in the presence of an acidic catalyst, a polymerization inhibitor and a solvent.

In an optional embodiment of the present application, the acidic catalyst is selected from at least one of p-toluenesulfonic acid, benzenesulfonic acid or a strongly acidic cation exchange resin, and the added amount of the acidic catalyst is the mass of an acrylic compound. 1% to 20%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or 20%. Optionally, the acrylic compound may be acrylic acid or methacrylic acid.

In an optional embodiment of the present application, in order to prevent acrylic acid and its esters from free radical polymerization during the reaction process, a certain amount of polymerization inhibitor needs to be added to the reaction solution, and the polymerization inhibitor is selected from parabens. At least one of diphenol, 4-methoxyphenol, tetrachlorobenzoquinone, 1,4-naphthoquinone or polymerization inhibitor 701, the amount of polymerization inhibitor added is 0.1% to 15% of the mass of the acrylic compound, For example, 1%, 2%, 3%, 4%, 5%, or 15%.

In an optional embodiment of the present application, in step (a), the reaction liquid of the n-alcohol in which G is the core group and the acrylic compound is subjected to extraction and separation, in order to remove unreacted n-alcohol and Its monoester and/or polyester. For example, the n-valent alcohol can be pentaethoxylated (EO5) pentaerythritol, with the structure

The average of the sum of P ₁ , P ₂ , P ₃ and P ₄ is 5

In an optional embodiment of the present application, in step (a), water is used for extraction and separation, and the amount of water used is 0.1 to 0.5 times the weight of the n-valent alcohol with G as the core group, for example, 0.1 times, 0.2x, 0.3x, 0.4x or 0.5x. When the amount of water is below 0.1 times, the removal effect of intermediates with a low degree of esterification is not good. When the amount of water is 0.5 times, the intermediates with a low degree of esterification can be completely removed. If the water amount is increased further, it will lead to a waste of water. In the usual incomplete esterification process of polyols, it is difficult to accurately control the content of each component of the product, and components with a specific degree of esterification cannot be extracted from it. The inventor of the present application found in experiments that different solvents have different solubility characteristics of products and intermediates, and the extraction method can be used to extract and separate them. In this application, it is preferred to use the highly polar solvent water to separate components containing more hydroxyl groups, and to use less polar solvents such as alkane solvents to separate components that do not contain thioxanthone groups, and finally the purified The target product of this application is a thioxanthone derivative.

When performing step (b), it is preferable to add a catalyst. This is mainly because the polymerization inhibitor and catalyst will also separate with water during water extraction. In order to ensure the reaction of (b), add acrylic compound mass 1 ~20% of the catalyst, and the polymerization inhibitor is also 0.1% to 15% of the mass of the acrylic compound. In an optional embodiment of the present application, in step (b), the reaction liquid with the compound represented by formula (2) is subjected to extraction and separation, with the purpose of removing components that do not contain thioxanthone groups.

In an optional embodiment of the present application, in step (b), an alkane solvent is used for extraction and separation. The alkane solvent is selected from n-hexane, heptane, petroleum ether, cyclohexane or methylcyclohexane. of at least one. Alkane solvents have good compatibility with fully esterified polyols, but have poor solubility for components containing thioxanthone. Therefore, components that do not contain thioxanthone groups can be well separated. .

In an optional embodiment of the present application, in step (b), the extraction separation meets at least one of the process conditions (1)-(2):

(1) The extraction temperature is 25-70°C, preferably, the extraction temperature is 25-65°C; and

(2) The amount of alkane solvent used is 0.1 to 5 times the weight of the product. Preferably, the amount of alkane solvent used is 0.5 to 2 times the weight of the product.

The weight of the product here can be obtained by calculating the sum of the masses of the polyol, acrylic compound and thioxanthone contained in the product according to the structural formula of the product.

In the optional solution of this application, this application uses n-valent alcohol to first synthesize the intermediate polyol acrylate with at least 1 hydroxyl group with (meth)acrylic acid, and then removes the polyhydroxy compounds with insufficient esterification degree through extraction, and then Perform an esterification reaction with a carboxyl-containing thioxantrone compound, and use an alkane solvent to extract the components without thioxantrone groups to obtain the purified target product thioxanthone derivative, which contains more bis It contains bonding groups and does not contain non-curing components, which is more conducive to reducing the mobility of the photoinitiator.

In an optional implementation of this application, the method includes:

Add n-valent alcohols with G as the core group, acrylic compounds, acidic catalysts, polymerization inhibitors and solvents into the reaction vessel, and continue to introduce air. It is advisable to maintain the air flow rate without affecting the reflux condensation. The reflux dehydration reaction will give the first Primary esterification reaction liquid;

The first esterification reaction liquid is extracted with water to remove unreacted n-valent alcohol or its ethoxylated or propoxylated derivatives and its monoesterified products and/or double esterified products. The added amount of water is G is 0.1 to 0.5 times the weight of the n-alcohol of the core group;

Add the compound represented by formula (2) to the extracted solution, add an acid catalyst, introduce air, and continue the reflux dehydration reaction to completely esterify the hydroxyl group; and

Add an alkane solvent to the obtained product for extraction, so that the components that do not contain thioxanthone groups are dissolved in the alkane solvent, and then separate the phases. The lower organic phase is concentrated to obtain the product. The extraction temperature is 25-65°C. The amount of alkane solvent used is 0.5 to 2 times the expected amount of product.

In an optional implementation of this application, the method includes:

Add n-valent alcohols with G as the core group, acrylic compounds, acidic catalysts, polymerization inhibitors and solvents into the reaction vessel, continue to introduce air, and reflux dehydration reaction to obtain the first esterification reaction liquid;

Add the compound represented by formula (2) to the extracted solution, add an acid catalyst, introduce air, continue the reflux dehydration reaction, so that the hydroxyl group is completely esterified, and wash the reaction solution with an alkaline aqueous solution to separate the acidic compound. Remove the solvent under reduced pressure; and

Add an alkane solvent to the product obtained by removing the solvent under reduced pressure for extraction, so that the components that do not contain thioxanthone groups are dissolved in the alkane solvent, and then the phases are separated. The lower organic phase is concentrated to obtain the product. The extraction temperature is 25-65°C, the amount of alkane solvent is 0.5 to 2 times the weight of the product.

The present application also provides a photocurable composition, comprising: (a) at least one thioxanthone derivative as described above and (b) at least one free radical polymerizable ethylenically unsaturated compound.

The photocurable composition including the aforementioned thioxanthone derivative has low mobility.

In an optional embodiment of the present application, the added amount of component (a) is 0.1 to 25% of the total weight of the photocurable composition, and a more preferred addition amount is 0.1 to 25% of the total weight of the photocurable composition. 10%.

In an optional embodiment of the present application, the added amount of component (b) is 90 to 99.9% of the total weight of the photocurable composition.

Ethylenically unsaturated compounds denote ethylenically unsaturated monomers, oligomers, prepolymers and mixtures thereof, which are capable of free radical polymerization.

In an optional embodiment of the present application, the component (b) is selected from epoxy acrylate resin, modified epoxy acrylate resin, polyurethane acrylate resin, polyester acrylate resin, polyether acrylate resin Resin, acrylated polyacrylate, epoxy methacrylate resin, polyurethane methacrylate resin, polyester methacrylate resin, polyether methacrylate resin, acrylated polymethacrylate, vinyl At least one of a propyl ether compound, an acrylate monomer, or a methacrylate monomer. The acrylate monomer or methacrylate monomer is independently monofunctional, difunctional or polyfunctional. Optionally, the acrylate monomer may be (3) propoxylated glyceryl triacrylate.

Additives can be used in the photocurable composition, and the additives are selected from triethylamine, triethanolamine, N-methyldiethanolamine, N,N-diethylethanolamine, amine additives Photomer 4250, N,N- Ethyl dimethylbenzoate, 2-ethylhexyl N,N-dimethylbenzoate, dimethylaminoethyl benzoate, 4-(dimethylamino)-benzoic acid-(2-ethyl) At least one of hexyl ester, 4-dimethylaminobenzoic acid ethyl ester, polyethylene glycol di-(p-dimethylaminobenzoic acid) ester or active amine.

The photocurable composition may also contain other additives to meet performance requirements, such as pigments, fillers, leveling additives, defoaming additives, polymerization inhibitors, solvents, etc.

According to another aspect of the present application, there is provided a use of the photocurable composition as described above in food packaging printing, pharmaceutical packaging printing, furniture coating, book printing or advertising printing.

According to yet another aspect of the present application, a photocurable product is provided, which is formed by photocuring a photocurable composition, wherein the photocurable composition is the photocurable composition as described above, preferably The photocurable product is selected from any one of coatings, adhesives, and printing inks.

According to yet another aspect of the present application, a curing method of a photocurable composition is provided, including:

The photocurable composition as described above is coated on the substrate; and, the photocurable composition is cured by using a light source with an emission band in the UV-visible light region.

Substrates include but are not limited to: wood, paper, plastic, coating or metal, etc. Coating methods include but are not limited to: offset printing, gravure printing, flexographic printing, inkjet printing or 3D printing, etc.

The coating amount of the photocurable composition is such that after photopolymerization, a coating with a thickness of 5 to 100 μm is obtained.

Beneficial effects:

The thioxanthone derivative provided by the present application has a structure shown in formula (1), and is directly bonded to the benzene ring of thioxanthone.

structure, while combining G group and acrylate structure and other groups, and controlling n=n ₁ + n ₂ , n is an integer from 3 to 6, n2 is an integer from 2 to 5, so that the structure of the thiaxantone derivative With higher double bond content and higher acrylate functionality, the thioxanthone derivatives can more fully participate in the polymerization during curing, allowing the photoinitiator to be more effectively fixed in the cross-linked network of the polymer. This significantly reduces the mobility of the initiator. At the same time, the thioxanthone derivatives provided by this application all contain acrylate groups, can participate in free radical polymerization, are fixed in the cross-linked network of the polymer, and do not contain non-curing components. At the same time, the thioxanthone derivative provided by this application has good compatibility with acrylate and has high migration stability. It does not need to add a solvent to dissolve the photoinitiator, and it can maintain a low migration amount even if a pigment is added. In terms of post-cured hardness, using the low-migration photoinitiator provided by this application will not significantly affect the post-cured hardness.

Detailed ways

Example 1

This embodiment provides a compound represented by formula (3), and its preparation method includes the following steps:

Put 10g of pentaerythritol, 15g of acrylic acid, 1.2g of p-toluenesulfonic acid, 0.21g of hydroquinone, and 50g of toluene into a 250ml three-necked bottle. Pour air into the bottle, heat to 110°C and reflux, and perform a reflux dehydration reaction for 6 hours. The reaction solution After the temperature drops to room temperature, add 1g of water, stir for 30 minutes, let stand for liquid separation, and separate pentaerythritol diacrylate and pentaerythritol monoacrylate (aqueous phase). The separated organic phase contains pentaerythritol triacrylate, and then add it to the organic phase. Add 0.8g p-toluenesulfonic acid, 0.21g hydroquinone, and 22.29g 2-carboxymethoxythioxanthone, heat to reflux, reflux and dehydrate for 4 hours, and then cool to room temperature. Then add 2g sodium carbonate and 30g water, wash with water for 30 minutes, and let stand for liquid separation. The upper organic phase is washed twice with 30g of water for 30 minutes each time. After standing for liquid separation, the organic phase is rotary evaporated at 60°C to remove the organic phase. of toluene, then add 30g of cyclohexane, keep the temperature at 50°C, stir for 30 minutes and then separate the liquids. The upper cyclohexane solution contains pentaerythritol tetraacrylate. The lower yellow oil is rotary evaporated under reduced pressure at 60°C to obtain 15.3g of a yellow transparent substance. Liquid, 1H-NMR data δ: (CDCl3, ppm) 4.1-4.3 (integrated area 7.98, hydrogen atom of pentaerythritol methylene), 4.7-4.9 (integrated area 2.13, 2-carboxymethoxythioxanthone methylene) hydrogen atom), 5.8-6.3 (integrated area 8.98, hydrogen atom of acryloyl group), 7.2-8.5 (integrated area 7.15, aromatic hydrogen atom), the product was determined to be a compound of formula (3).

Example 2

This embodiment provides a compound represented by formula (4), and its preparation method includes the following steps:

Put 20g of ethoxylated (EO5) pentaerythritol, 10g of acrylic acid, 0.9g of p-toluenesulfonic acid, 0.2g of 4-methoxyphenol, and 100g of toluene into a 250ml three-necked bottle. Pour air into the bottle and heat to 110°C. Reflux and reflux dehydration reaction for 6 hours. After the reaction solution reaches room temperature, add 10g of water, stir for 30 minutes, let stand for liquid separation, then add 0.6g of p-toluenesulfonic acid and 0.2g of 4-methoxyphenol to the separated organic phase. 12.41g 2-carboxymethoxythioxanthone, heated to reflux, reflux dehydration reaction for 4 hours, and then cooled to room temperature. Then add 2g sodium carbonate and 30g water, wash with water for 30 minutes, and let stand for liquid separation. The upper organic phase is washed twice with 30g of water, 30 minutes each time. After standing for liquid separation, the organic phase is evaporated at 60°C to remove the organic phase. Toluene in the solution, then add 25g n-hexane, keep the temperature at 60°C, stir for 30 minutes and then separate the liquids. The upper n-hexane solution contains ethoxylated pentaerythritol tetraacrylate, and the lower yellow oil is evaporated under reduced pressure at 60°C to obtain 25.6g yellow transparent liquid, 1H-NMR data δ: (CDCl3, ppm) 3.4-3.7 (integrated area 21.21, ethoxy hydrogen atom), 4.2-4.3 (integrated area 8.00, pentaerythritol methylene hydrogen atom), 4.7 -4.8 (integrated area 2.08, hydrogen atom of 2-carboxymethoxythioxanthone methylene group), 5.8-6.4 (integrated area 8.98, hydrogen atom of acryloyl group), 7.2-8.5 (integrated area 7.12, aromatic hydrogen atom ), the product was determined to be a compound of formula (4).

Example 3

This embodiment provides a compound represented by formula (5), and its preparation method includes the following steps:

Put 5g of dicondensate (1,1,1-trimethylolpropane), 4g of acrylic acid, 0.3g of p-toluenesulfonic acid, 0.25g of polymerization inhibitor 701, and 100g of toluene into a 250ml three-neck bottle, and introduce air into the bottle , heated to 110°C and refluxed, refluxed and dehydrated for 6 hours. After the reaction solution dropped to room temperature, 1g of water was added, stirred for 30 minutes, left to stand for liquid separation, and pentaerythritol diacrylate and pentaerythritol monoacrylate (aqueous phase) were separated. The separated organic The phase contains pentaerythritol triacrylate, then add 0.3g p-toluenesulfonic acid, 0.25g inhibitor 701, 6.29g 2-carboxymethoxythioxanthone to the organic phase, heat to reflux, reflux dehydration reaction for 4 hours, reduce to room temperature. Then add 2g sodium carbonate and 30g water, wash with water for 30 minutes, and let stand for liquid separation. The upper organic phase is washed twice with 30g of water, 30 minutes each time. After standing for liquid separation, the organic phase is evaporated at 60°C to remove the organic phase. A yellow viscous substance was obtained from the toluene in the solution, then 25g petroleum ether was added, stirred at room temperature for 30 minutes and then separated. The petroleum ether phase contained dicondensate (1,1,1-trimethylolpropane) tetraacrylate, and the lower layer was yellow. The oil was desolvated by rotary evaporation at 60°C to obtain 10.2g of yellow transparent liquid, 1H-NMR data δ: (CDCl3, ppm) 0.8-0.9 (integrated area 6.00, dicondensation (1,1,1-trimethylolpropane ), 1.3-1.5 (integrated area 4.05, hydrogen atom of methylene group on dicondensation (1,1,1-trimethylolpropane)), 3.5-3.6 (integrated area 3.99, dicondensate) Dicondensation (1,1,1-trimethylolpropane) hydrogen atoms of methylene groups at both ends of the oxygen ether), 3.8-4.1 (integrated area 8.35, dicondensation (1,1,1-trimethylolpropane) -OCH2- hydrogen atom connected to the ester), 4.7-4.9 (integrated area 2.1, hydrogen atom of 2-carboxymethoxythioxanthone methylene group, 5.8-6.4 (integrated area 9.05, acryloyl hydrogen atom), 7.2-8.5 (integrated area 7.1, aromatic hydrogen), the product is determined to be a compound of formula (5).

Example 4

This embodiment provides a compound represented by formula (6), and its preparation method includes the following steps:

Put 20g of dipentaerythritol ether, 22.67g of acrylic acid, 2.0g of benzenesulfonic acid, 0.057g of hydroquinone, and 100g of toluene in a 250ml three-necked bottle. Pour air into the bottle, heat to 120°C and reflux, and perform reflux dehydration reaction for 6 hours. After the reaction solution cools to room temperature, add 10g of water, stir for 30 minutes, let stand for liquid separation, and separate out the water-soluble polyols. Then add 2.0g of benzenesulfonic acid, 0.057g of hydroquinone, and 28.15g of hydroquinone to the separated organic phase. 2-Carboxymethoxythioxanthone, heated to reflux, reflux dehydration reaction for 4 hours, then cooled to room temperature. Add 2g sodium carbonate and 40g water, wash with water for 30 minutes, and let stand for liquid separation. The upper organic phase is washed twice with 40g of water, 30 minutes each time. After standing for liquid separation, the organic phase is rotary evaporated at 60°C to remove the organic phase. of toluene, then add 40g of methylcyclohexane, keep it at 50°C, stir for 30 minutes and then separate the liquids. The upper methylcyclohexane phase contains dipentaerythritol hexaacrylate. The lower yellow oil is evaporated under reduced pressure at 60°C. Dissolve to obtain 53.86g of yellow transparent liquid, 1H-NMR data δ: (CDCl3, ppm) 3.5-3.6 (integrated area 4.12, hydrogen atom of methylene group connected to dipentaerythritol and oxygen ether), 4.2-4.4 (integrated area 12.02, hydrogen atom of -OCH2- connected to dipentaerythritol and ester), 4.7-4.9 (integrated area 2.00, hydrogen atom of methylene group of 2-carboxymethoxythioxanthone), 5.8-6.4 (integrated area 15.56, propylene Acyl hydrogen atom), 7.2-8.5 (integrated area 6.89, aromatic hydrogen), and the product was determined to be a compound of formula (6).

The components involved in the following examples are as follows:

G3POTA is (3) propoxylated glyceryl triacrylate, produced by Taiwan Guojing Chemical Co., Ltd.;

Photomer 3316 is a low viscosity modified epoxy acrylate resin produced by IGM RESINS;

Photomer 4250 is an acrylated amine sensitizer, manufactured by IGM RESINS;

Ciba CROMOPHTAL BLUE A3R is a blue pigment produced by Ciba;

ITX is 2-isopropylthiaxantrone, and the manufacturer is IGM RESINS.

Example 5

This embodiment provides a photocurable composition, and its preparation method includes the following steps: weigh the following raw materials: G3POTA 2.3g, Photomer 3316 2.3g, Photomer 4250 0.3g and formula (4) compound 0.2g; then put it at 60 ℃, stir and dissolve, then lower to room temperature, and prepare a photocurable composition.

Example 6

This embodiment provides a photocurable composition, and its preparation method includes the following steps: weigh the following raw materials: G3POTA 2.3g, Photomer 3316 2.3g, Photomer 4250 0.3g and formula (6) compound 0.2g; however, put it at 60 ℃, stir and dissolve, then lower to room temperature, and prepare a photocurable composition.

Example 7

This embodiment provides a photocurable composition, and its preparation method includes the following steps: weigh the following raw materials: G3POTA 2.3g, Photomer 3316 2.3g, Photomer 4250 0.3g, Ciba CROMOPHTAL BLUE A3R pigment 0.5g and the compound of formula (4) 0.2g; then stir and dissolve it at 60°C and then lower it to room temperature to prepare a photocurable composition.

Example 8

This embodiment provides a photocurable composition, and its preparation method includes the following steps: weigh the following raw materials: G3POTA 2.3g, Photomer 3316 2.3g, Photomer 4250 0.3g, Ciba CROMOPHTAL BLUE A3R pigment 0.5g and the compound of formula (6) 0.2g; then stir and dissolve it at 60°C and then lower it to room temperature to prepare a photocurable composition.

Comparative example 1

This comparative example provides a comparative compound represented by formula (8), and its preparation method includes the following steps:

Put 8.3g of ethoxylated (EO7) trimethylolpropane, 3.5g of acrylic acid, 0.04g of p-toluenesulfonic acid, 0.004g of hydroquinone, and 30g of toluene into a 100ml three-neck bottle, and introduce air into the bottle. Heat to 120°C and reflux, reflux and dehydrate for 6 hours. After the reaction solution reaches room temperature, add 2g of water, stir for 30 minutes, let stand for liquid separation, then add 0.04g of p-toluenesulfonic acid, 0.004g of hydroquinone, 1.75 to the organic phase. g 2-carboxymethoxythioxanthone, heated to reflux, reflux dehydration reaction for 4 hours, and then cooled to room temperature. Add 0.5g sodium carbonate and 20g water, wash with water for 30 minutes, and let stand for liquid separation. The upper organic phase is washed twice with 20g of water, 30 minutes each time. After standing for liquid separation, the organic phase is evaporated at 60°C to remove the organic phase. of toluene in the solution, then add 20g n-hexane, stir for 30 minutes at room temperature and then separate the liquids. The n-hexane phase contains ethoxylated (EO7) trimethylolpropane triacrylate. The lower yellow oil is evaporated under reduced pressure at 60°C. After desolvation, 3.65g of yellow transparent liquid was obtained, 1H-NMR data δ: (CDCl3, ppm) 0.8-0.9 (integrated area 3.00, hydrogen atom of trimethylolpropane terminal methyl group), 1.5-1.7 (integrated area 2.01 , hydrogen atom of methylene group in trimethylolpropane), 3.8-4.3 (integrated area 34.10, -OCH2- and -OCH2CH2- hydrogen atoms on trimethylolpropane), 4.7-4.9 (integrated area 2.08, 2-carboxylic group The hydrogen atom of the methylene group of methoxythioxanthone), 5.8-6.4 (integrated area 6.07, hydrogen atom of acryloyl group), 7.2-8.5 (integrated area 7.02, aromatic hydrogen), is a compound of formula (8).

Comparative example 2

This comparative example provides a photocurable composition, and its preparation method includes the following steps: weigh the following raw materials: G3POTA 2.3g, Photomer 3316 2.3g, Photomer 4250 0.3g and formula (8) compound 0.2g; then put it at 60 ℃, stir and dissolve, then lower to room temperature, and prepare a photocurable composition.

Comparative example 3

This comparative example provides a photocurable composition, and its preparation method includes the following steps: weigh the following raw materials: G3POTA 2.3g, Photomer 3316 2.3g, Photomer 4250 0.3g and ITX 0.2g; then stir and dissolve them at 60°C Cool to room temperature and prepare a photocurable composition.

Comparative example 4

This comparative example provides a photocurable composition, and its preparation method includes the following steps: weigh the following raw materials: G3POTA 2.3g, Photomer 3316 2.3g, Photomer 4250 0.3g, Ciba CROMOPHTAL BLUE A3R pigment 0.5g and the compound of formula (8) 0.2g; then stir and dissolve it at 60°C and then lower it to room temperature to prepare a photocurable composition.

Comparative example 5

This comparative example provides a photocurable composition, and its preparation method includes the following steps: weigh the following raw materials: G3POTA 2.3g, Photomer 3316 2.3g, Photomer 4250 0.3g, Ciba CROMOPHTAL BLUE A3R pigment 0.5g and ITX 0.2g; then Stir and dissolve it at 60°C and then lower it to room temperature to prepare a photocurable composition.

Pendulum Hardness and Mobility Testing

Pendulum hardness test:

The photocurable compositions obtained in Examples 5-8 and Comparative Examples 2-5 were coated on a glass plate using a 25 μm wire rod, and cured once under a 395 nm LED light source at a speed of 10 m/min, and the cured coating film was tested. Pendulum hardness.

Initiator mobility test:

1) Weigh the weight of the substrate glass plate to be used, and then apply the photocurable composition obtained in Examples 5-8 and Comparative Examples 2-5 on the glass plate using a 25 μm wire rod, and use a 395nm LED light source Cure once at a belt speed of 10m/min to form a coating film on the glass plate, and then weigh the weight of the substrate after coating; then subtract the weight of the substrate before coating from the weight of the substrate after coating to obtain the coating Film weight;

2) Calculate the mass percentage of the photoinitiator (compound represented by formula (4), compound represented by formula (6), compound represented by formula (8), ITX) in the respective photocurable compositions, and then use the coating film weight Multiply by the mass percentage of the photoinitiator in the respective photocurable composition to obtain the photoinitiator content A1 in the coating film;

3) Soak the coated substrate in ethanol with a volume concentration of 95%, and keep it in a 40°C oven for 72 hours. The leaching solution is quantitatively analyzed by HPLC for the photoinitiator content A2, and the photoinitiator mobility W=A2/A1 is calculated. ×100%. The test data are shown in Table 1 and Table 2 below.

Table 1

	实施例5Example 5	实施例6Example 6	对比例2Comparative example 2	对比例3Comparative example 3
摆式硬度Pendulum hardness	0.6850.685	0.7020.702	0.6800.680	0.7200.720
迁移率mobility	0.52％0.52%	0.25％0.25%	5.23％5.23%	69.75％69.75%

Table 2

	实施例7Example 7	实施例8Example 8	对比例4Comparative example 4	对比例5Comparative example 5
摆式硬度Pendulum hardness	0.6200.620	0.6550.655	0.6500.650	0.6620.662
迁移率mobility	0.95％0.95%	0.30％0.30%	8.25％8.25%	72.30％72.30%

It can be seen from the test data that the mobility of the compounds of formula (4) and formula (6) provided in this application is significantly lower than the comparative example of the compound of formula (8) containing only two acrylate double bonds. Since the low-migration photoinitiator provided in this application contains more double bonds, its mobility is significantly reduced compared to the comparative compound having two double bonds per molecule. Therefore, the low-migration photoinitiator provided in this application is more suitable for fields such as food and drug packaging that have strict requirements on initiator mobility.

Obviously, the above-mentioned embodiments are only examples for clear explanation and are not intended to limit the implementation. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. An exhaustive list of all implementations is neither necessary nor possible. The obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

A thioxanthone derivative, characterized in that it has a structure shown in formula (1):

in

G is the dehydroxylated group of n-valent alcohol, n=n 1 +n 2 , n is an integer from 3 to 6, and n 2 is an integer from 2 to 5;

A is
R 3 is optionally substituted C1-C8 alkylene;

B 1 and B 2 are each independently a single bond,
In the formula, R 1 and R 2 are each independently H, -CH 3 , and m is an integer ranging from 0 to 5;

R is H or -CH 3 .
The thioxanthone derivative according to claim 1, wherein R3 is methylene.
The thioxanthone derivative according to claim 1 or 2, wherein G is selected from at least one of the following structures:

Optionally, G is selected from glycerol, diglycerol, triglycerol, triethanolamine, trimethylolpropane, dimethylolpropane, pentaerythritol, dipentatriol, residues of sugar alcohols and mixtures thereof; preferably, The sugar alcohols are sorbitol, mannitol and xylitol.
The thioxanthone derivative according to any one of claims 1 to 3, wherein R is H, n 1 is 1, and n 2 is an integer from 3 to 5.
The thioxanthone derivative according to any one of claims 1 to 4, characterized in that the thioxanthone derivative is selected from any one of the following compounds:
A method for preparing the thioxanthone derivative according to any one of claims 1 to 5, characterized in that it includes the following steps:

(a) reacting an n-valent alcohol with G as the core group and an acrylic compound;

(b) reacting the reaction product of step (a) with the compound represented by formula (2) to obtain a thioxanthone derivative;

in:

R 4 is -OR 3 -COOH, and R 3 is optionally substituted C1-C8 alkylene.
The method of claim 6, wherein step (a) and step (b) are carried out independently in the presence of an acidic catalyst, a polymerization inhibitor and a solvent.
The method according to claim 6 or 7, wherein the acidic catalyst is selected from at least one of p-toluenesulfonic acid, benzenesulfonic acid or a strongly acidic cation exchange resin, and the added amount of the acidic catalyst is acrylic acid. 1% to 20% of the mass of similar compounds.
The method according to any one of claims 6 to 8, characterized in that the polymerization inhibitor is selected from hydroquinone, 4-methoxyphenol, tetrachlorobenzoquinone, 1,4-naphthoquinone or polymerization inhibitor. At least one of the polymerization agents 701 is used, and the addition amount of the polymerization inhibitor is 0.1% to 15% of the mass of the acrylic compound.
The method according to any one of claims 6 to 9, characterized in that in step (a), the reaction solution obtained by reacting an n-valent alcohol in which G is a core group and an acrylic compound is subjected to extraction and separation.
The method of claim 10, wherein in step (a), water is used for extraction and separation, and the amount of water used is 0.1 to 0.5 times the weight of the n-alcohol with G as the core group.
The method according to any one of claims 6 to 11, characterized in that in step (b), the reaction liquid with the compound represented by formula (2) is extracted and separated.
The method of claim 12, wherein in step (b), an alkane solvent is used for extraction and separation, and the alkane solvent is selected from n-hexane, heptane, petroleum ether, cyclohexane or methylcyclohexane. at least one of them.
A photocurable composition, comprising: (a) at least one thioxanthone derivative as described in any one of claims 1 to 5 and (b) at least one free radical polymerizable ethylenic formula Saturated compounds.
The photocurable composition according to claim 14, wherein the added amount of component (a) is 0.1 to 25% of the total weight of the photocurable composition.
The photocurable composition according to claim 14 or 15, wherein the added amount of component (b) is 90 to 99.9% of the total weight of the photocurable composition.
The photocurable composition according to any one of claims 14 to 16, wherein the component (b) is selected from the group consisting of epoxy acrylate resin, modified epoxy acrylate resin, polyurethane acrylate resin, polyurethane acrylate resin, and polyurethane acrylate resin. Ester acrylate resin, polyether acrylate resin, acrylated polyacrylate, epoxy methacrylate resin, polyurethane methacrylate resin, polyester methacrylate resin, polyether methacrylate resin, acrylic At least one of esterified polymethacrylate, allyl ether compound, acrylate monomer or methacrylate monomer.
The photocurable composition according to any one of claims 14 to 17, characterized in that the photocurable composition further includes an auxiliary agent, and the auxiliary agent is selected from the group consisting of triethylamine, triethanolamine, and N-methyl Diethanolamine, N,N-diethylethanolamine, amine additive Photomer 4250, N,N-ethyl dimethylbenzoate, N,N-dimethylbenzoic acid-2-ethylhexyl ester, benzoic acid Dimethylaminoethyl ester, 4-(dimethylamino)-benzoic acid-(2-ethyl)hexyl ester, 4-dimethylaminoethyl benzoate, polyethylene glycol di-(p-dimethylamino) At least one of benzoate) ester or active amine.
The use of the photocurable composition according to any one of claims 14 to 18 in food packaging printing, pharmaceutical packaging printing, furniture coating, book printing or advertising printing.
A photocurable product, which is formed by photocuring a photocurable composition, wherein the photocurable composition is the photocurable composition according to any one of claims 14 to 18.
A method for curing a photocurable composition, which is characterized by including:

Coating the photocurable composition according to any one of claims 14 to 18 on a substrate; and curing the photocurable composition by using a light source with an emission band in the UV-visible light region.
The method of claim 21, wherein the substrate is selected from wood, paper, plastic, coating or metal.
The method of claim 21 or 22, wherein the coating method is selected from offset printing, gravure printing, flexographic printing, inkjet printing or 3D printing.