Copolymers derived from substituted benzopinacols and methods for using them as polymerization initiators

Abstract

The present invention relates to a copolymer comprising, in copolymerized form, (A) an allyloxycarboxyl-substituted benzopinacol monomer of formula (I) and (B) at least one ethylenically unsaturated monomer, and to the use of the copolymer as a radical polymerization initiator. The present invention also relates to the allyloxycarboxyl-substituted benzopinacol monomer of formula (I). [Formula 1] TIFF2023540742000018.tif4784

Description

[Technical Field]

[0001] The present invention relates to copolymers derived from substituted benzopinacol compounds, methods for using the copolymers as radical polymerization initiators, and substituted benzopinacol compounds. [Background technology]

[0002] Benzopinacol (i.e., 1,1,2,2-tetraphenyl-1,2-ethanediol) was well known as a radical polymerization initiator. However, its use in some applications was limited, particularly in applications requiring low volatile organic compounds (VOCs), due to its very low solubility in common organic solvents.

[0003] For example, modifications of benzopinacol by reaction with chlorosilane or polyorganosilane / siloxane, reaction with isocyanate, or reaction with metal complexes accompanied by alcohols have been reported, for instance, in US8,487,054. It is said that modification with chlorosilane or polyorganosilane / siloxane may improve reactivity and solubility. However, the solubility of these modified benzopinacols in organic solvents has not been reported. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] US8,487,054 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] While benzopinacol has the advantages of being a radical polymerization initiator, it is desirable to provide a radical polymerization initiator that also has improved solubility in organic solvents. [Means for solving the problem]

[0006] In one aspect, the present invention, hereinafter, (A) An allyloxycarbonyl

Chemical formula

[0007] In another aspect, the present invention provides a method of using the copolymer described herein as a radical polymerization initiator.

[0008] Ni In a further aspect, the present invention provides an allyloxycarbonyl substituted benzopinacol of formula (I).

Advantages of the Invention

[0009] The present inventors have found that a copolymer containing (A) an allyloxycarbonyl Ni substituted benzopinacol monomer of formula (I) and (B) at least one ethylenically unsaturated monomer in a copolymerized form is particularly useful as a radical polymerization initiator and has a much higher solubility compared to conventional low molecular weight benzopinacol initiators, making it easier to handle during application.

Brief Description of the Drawings

[0010] [Figure 1] Figure 1 shows a 1H NMR spectrum.

Embodiments for Carrying Out the Invention

[0011] The present invention will be described in detail below. It should be understood that the present invention can be embodied in many different ways and should not be construed as being limited to the embodiments described herein. Unless otherwise specifically noted, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0012] In the context of this application, unless the context clearly dictates otherwise, the singular forms "a", "an", and "the" include plural referents.

[0013] In the context of this application, terms such as "comprising", "including", etc. are used synonymously with "containing", "having", etc. and are construed in a non-limiting and open-ended manner. That is, for example, additional components or elements may be present. Expressions such as "consisting of" or "consisting essentially of", or cognates, may be subsumed within "comprising" or cognates.

[0014] In the context of this application, when referring to a copolymer comprising (A) an allyloxycarbonyl-substituted benzopinacol monomer of formula (I) and (B) at least one ethylenically unsaturated monomer, the terms "copolymer" and "copolymerization initiator" can also be used. Ni In the context of this application, when referring to (A) an allyloxycarbonyl-substituted benzopinacol monomer of formula (I), the term "comonomer (A)" can also be used.

[0015] In the context of this application, when referring to (A) an allyloxycarbonyl-substituted benzopinacol monomer of formula (I), the term "comonomer (A)" can also be used. Ni In the context of this application, when referring to (A) an allyloxycarbonyl-substituted benzopinacol monomer of formula (I), the term "comonomer (A)" can also be used.

[0016] In the context of this application, when referring to (B) at least one ethylenically unsaturated monomer, the term "comonomer (B)" can also be used.

[0017] In the context of this application, the term "(meth)acrylate" represents acrylate and / or methacrylate.

[0018] The copolymerization initiator according to the present invention is (A) Formula (I) [ka] allyloxycarb Ni substituted benzopinacol monomer, and (B) at least one ethylenically unsaturated monomer, It contains in a copolymerized form.

[0019] The copolymer initiator according to the present invention is understood to be a copolymer containing a structural unit derived from comonomer (A) and a structural unit derived from comonomer (B) by addition copolymerization.

[0020] In some embodiments, the copolymerization initiator according to the present invention comprises comonomer (A) and comonomer (B) in a random copolymerized form.

[0021] There are no particular restrictions on the ethylenically unsaturated monomer used as comonomer (B). Any compound containing at least one olefin double bond suitable for polymerization with comonomer (A) may be used as comonomer (B). For example, ethylenically unsaturated monomers include α,β-unsaturated carboxylic acids and their esters, ethylenically unsaturated nitriles, and C1-C 20 -Vinyl esters of carboxylic acids, vinyl aromatics having up to 20 carbon atoms, vinyl halides, C1-C 20 -Vinyl ether of alcohol, C2-C having one or two olefin double bonds 20 - Unsaturated olefins, or any combination thereof, may be selected.

[0022] In some embodiments, comonomer (B) comprises at least one α,β-unsaturated carboxylic acid ester. Preferably, at least one α,β-unsaturated carboxylic acid ester comprises C1-C6 of a C3-C6 α,β-unsaturated carboxylic acid. 20 -alkyl esters, C3-C6-α,β-unsaturated carboxylic acids C3-C6 12-Selected from cycloalkyl esters and any combination thereof. More preferably, at least one α,β-unsaturated carboxylic acid ester is C1-C 20 -alkyl (meth)acrylate, C3-C 120 -cycloalkyl (meth)acrylate and any combination thereof.

[0023] Thus, the copolymerization initiator according to the invention in some further embodiments is (A) the allyloxycarbonyl-substituted benzopinacol monomer of formula (I)

Chemical formula

[0024] C1-C 20Examples of alkyl (meth)acrylates include, but are not limited to, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, e.g., 2-ethylhexyl acrylate, octyl methacrylate, e.g., 2-ethylhexyl methacrylate, nonyl acrylate This includes, for example, 3,3,5-trimethylhexyl acrylate, nonyl methacrylate, for example, 3,3,5-trimethylhexyl methacrylate, dodecyl acrylate, for example, lauryl acrylate, dodecyl methacrylate, for example, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, pentadecyl acrylate, pentadecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, or any combination thereof.

[0025] C3~C 12 -Examples of cycloalkyl(meth)acrylates include, but are not limited to, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, methylcyclohexyl acrylate, methylcyclohexyl methacrylate, t-butylcyclohexyl acrylate, t-butylcyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, or any combination thereof.

[0026] In some embodiments, the copolymer initiator according to the present invention is (A) Formula (I) [ka] allyloxycarb Ni substituted benzopinacol monomer and (B) n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, e.g., 2-ethylhexyl acrylate, octyl methacrylate, e.g., 2-ethylhexyl methacrylate, nonyl acrylate, e.g., 3,3,5-trimethylhexyl acrylate, nonyl methacrylate, e.g., 3,3,5-trimethylhexyl methacrylate A ethylenically unsaturated monomer selected from rilates, dodecyl acrylates (e.g., lauryl acrylate), dodecyl methacrylates (e.g., lauryl methacrylate), tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, pentadecyl acrylate, pentadecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, and any combination thereof. Includes.

[0027] In some further embodiments, the copolymer initiator according to the present invention is (A) Formula (I) [ka] allyloxycarb Ni substituted benzopinacol monomer and (B) n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, and at least one ethylenically unsaturated monomer selected from any combination thereof. Includes.

[0028] In a specific embodiment, the copolymerization initiator according to the present invention is (A) Formula (I) [ka] allyloxycarb Ni substituted benzopinacol monomer and (B) at least one of n-butyl acrylate and n-butyl methacrylate, at least one of 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, and at least one of lauryl acrylate and lauryl methacrylate Includes.

[0029] In any of the embodiments described herein, the copolymer initiator according to the present invention contains total structural units from comonomer (A) and total structural units from comonomer (B) in a mass ratio of 1:30 to 1:10, preferably 1:25 to 1:15, and particularly 1:20 to 1:16.

[0030] The copolymer initiator according to the present invention may have a number-average molecular weight (Mn) in the range of 5,000 to 500,000 g / mol, preferably 10,000 to 200,000 g / mol, more preferably 20,000 to 100,000 g / mol, and most preferably 30,000 to 70,000 g / mol, as measured by gel permeation chromatography (GPC) in THF with polystyrene as the standard substance.

[0031] The copolymer initiator according to the present invention was measured by gel permeation chromatography (GPC) in THF with polystyrene as the standard substance, and its mass-average molecular weight (M w The amount may be in the range of 20,000 to 1,000,000 g / mol, preferably 40,000 to 800,000 g / mol, more preferably 80,000 to 500,000 g / mol, and most preferably 100,000 to 300,000 g / mol.

[0032] There are no particular limitations on the method for preparing the copolymer initiator according to the present invention, and it may be carried out, for example, by free radical polymerization, particularly by thermal free radical polymerization of comonomer (A) and comonomer (B). Any conventional process conditions for free radical polymerization, such as solvent, polymerization temperature and polymerization initiator, can be used for the purposes of the present invention.

[0033] This invention relates to a novel compound, formula (I) [ka] allyloxycarb Ni substituted benzopinacol We also offer it.

[0034] The compound of formula (I) can be prepared by a pinacol coupling reaction of allyl 4-benzoylbenzoate. The pinacol coupling reaction is well known in the art and may be carried out through various processes. For example, the pinacol coupling reaction may be carried out in an aqueous solution of ammonium chloride, and optionally with an inert organic solvent, such as THF, in the presence of a metal reducing agent, such as Zn, Mg, and Ni powder.

[0035] The present invention further provides a method for using the above-mentioned copolymer as a radical polymerization initiator.

[0036] Copolymerization initiators can be used in a variety of systems, comprising one or more ethylenically unsaturated monomers, such as (meth)acrylates and styrene-functional monomers, or polymers containing ethylenically unsaturated functional groups, such as unsaturated polyesters. It will be understood that copolymerization initiators can be used in any system, including conventional pinacol initiators such as benzopinacol.

[0037] Copolymer initiators are particularly useful in coating materials, such as automotive coating materials, that include monomers and / or oligomer reactive diluents having at least one olefin double bond.

[0038] Embodiment Various embodiments are listed below. It will be understood that the embodiments listed below may be combined in any aspect and with other embodiments, depending on the scope of the present invention.

[0039] Embodiment 1 (A) Formula (I) [ka] allyloxycarb Ni substituted benzopinacol monomer, and (B) at least one ethylenically unsaturated monomer, A copolymer containing in a copolymerized form.

[0040] Embodiment 2 (A) Allyloxycarb of formula (I) Ni A copolymer according to Embodiment 1, comprising (B) a substituted benzopinacol monomer and (B) at least one ethylenically unsaturated monomer in a randomly copolymerized form.

[0041] Embodiment 3 (B) At least one ethylenically unsaturated monomer is an α,β-unsaturated carboxylic acid and its ester, an ethylenically unsaturated nitrile, C1-C 20 -Vinyl esters of carboxylic acids, vinyl aromatics having up to 20 carbon atoms, vinyl halides, C1-C 20 -Vinyl ether of alcohol, C2-C having one or two olefin double bonds 20 - Copolymers according to Embodiment 1 or 2, selected from unsaturated olefins or any combination thereof.

[0042] Embodiment 4 (B) At least one ethylenically unsaturated monomer is at least one α,β-unsaturated carboxylic acid ester, for example, C3-C6-α,β-unsaturated carboxylic acid C1-C 20 -alkyl esters, C3-C6-α,β-unsaturated carboxylic acids C3-C6 12-Cycloalkyl esters or any combination thereof, especially C1-C 20 -Alkyl (meth)acrylate, C3~C 12 A copolymer according to any one of Embodiments 1 to 3, comprising a cycloalkyl (meth)acrylate or any combination thereof.

[0043] Embodiment 5 (B) At least one ethylenically unsaturated monomer is C1-C 20 -Alkyl (meth)acrylate, C3~C 12 - Selected from cycloalkyl (meth)acrylates and any combination thereof, preferably C1-C 20 -Alkyl (meth)acrylate, more preferably C4~C 18 -Alkyl (meth)acrylates, especially C4-C 12 A copolymer according to any one of Embodiments 1 to 4, selected from alkyl (meth)acrylates.

[0044] Embodiment 6 (B) At least one ethylenically unsaturated monomer is n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, e.g., 2-ethylhexyl acrylate, octyl methacrylate, e.g., 2-ethylhexyl methacrylate, nonyl acrylate, e.g., 3,3,5-trimethylhexyl acrylate, nonyl methacrylate, e.g., 3,3,5-trimethyl Copolymers according to any one of Embodiments 1 to 5, selected from hexyl methacrylate, dodecyl acrylate, e.g., lauryl acrylate, dodecyl methacrylate, e.g., lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, pentadecyl acrylate, pentadecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, and any combination thereof.

[0045] Embodiment 7 (B) A copolymer according to any one of Embodiments 1 to 6, wherein at least one ethylenically unsaturated monomer is selected from n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, and any combination thereof.

[0046] Embodiment 8 (A) Formula (I) [ka] allyloxycarb Ni substituted benzopinacol monomer and (B) at least one of n-butyl acrylate and n-butyl methacrylate, at least one of 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, and at least one of lauryl acrylate and lauryl methacrylate A copolymer comprising any one of Embodiments 1 to 7.

[0047] Embodiment 9 A copolymer according to any one of Embodiments 1 to 8, wherein the total structural units from comonomer (A) and the total structural units from comonomer (B) are contained in a mass ratio of 1:30 to 1:10, preferably 1:25 to 1:15, and particularly 1:20 to 1:16.

[0048] Embodiment 10 A copolymer according to any one of Embodiments 1 to 9, wherein the number-average molecular weight (Mn) is in the range of 5,000 to 500,000 g / mol, preferably 10,000 to 200,000 g / mol, more preferably 20,000 to 100,000 g / mol, and most preferably 30,000 to 80,000 g / mol.

[0049] Embodiment 11 Mass average molecular weight (M w A copolymer according to any one of Embodiments 1 to 10, wherein the amount of ) is in the range of 20,000 to 1,000,000 g / mol, preferably 40,000 to 800,000 g / mol, more preferably 80,000 to 500,000 g / mol, and most preferably 100,000 to 300,000 g / mol.

[0050] Embodiment 12 A copolymer according to any one of Embodiments 1 to 11, which can be obtained or obtained by free radical polymerization, particularly thermal free radical polymerization.

[0051] Embodiment 13 A method for using a copolymer according to any one of Embodiments 1 to 12 as a radical polymerization initiator.

[0052] Embodiment 14 A method of use according to Embodiment 13 in a coating material comprising a monomer and / or oligomer reactive diluent having at least one olefin double bond, such as an automotive coating material.

[0053] Embodiment 15 Equation (I) [ka] allyloxycarb Ni Benzopinacol substituted with ru. [Examples]

[0054] The present invention will be further described by examples not intended to limit the scope of the invention.

[0055] Example 1: Allyloxycarb of formula (I) Ni Synthesis of rusubstituted benzopinacol 1.1 Synthesis of allyl-4-benzoylbenzoate

[0056] [ka] In a 100 mL round-bottom flask, 49 mL of N,N-dimethylformamide (DMF), 4.87 g of 4-benzoylbenzoic acid (0.0215 mol), 4.3 g of potassium carbonate (0.0323 mol), and 3.9 g of allyl bromide (0.0323 mol) were added and reacted at 65°C for 5 hours with stirring. After purification by column chromatography using a mobile phase of 1.5% methyl tert-butyl ether in chloroform, allyl 4-benzoylbenzoate was obtained in yield of 5.3 g.

[0057] 1.2 Coupling of allyl 4-benzoylbenzoate

[0058] [ka] In a 1 L round-bottom flask, 262 mL of tetrahydrofuran, 26.2 g of allyl 4-benzoylbenzoate (0.0983 mol), 19.28 g of Zn powder (0.295 mol), and 184 mL of 30% aqueous ammonium hydrochloride were added and the mixture was heated under reflux with stirring for 6 hours. After purification by column chromatography using a mobile phase of 1.5% methyl tert-butyl ether in chloroform, the compound of formula (I) was obtained in a yield of 3.28 g.

[0059] 1 H NMR (500MHz, DMSO-d6, TMS): δH=4.75-4.77(t, 2H), 5.24-5.27(dd, 1H), 5.36-5.40(dd, 1H), 6.00 (m, 1H), 6.37(s, 1H), 7.10-7.12(t, 3H), 7.27-7.31(m, 2H), 7.51-7.55(t, 2H), 7.71-7.73(m, 2H). 1 The 1H NMR spectrum is shown in Figure 1.

[0060] Example 2: Synthesis of copolymer initiator 10 g of 160 / 180 solvent naphtha was added to a 100 mL three-necked flask equipped with a nitrogen inlet, and heated to 80 °C. A solution of 0.5 g of the compound of formula (I), 3 g of 2-ethylhexyl acrylate, 3 g of n-butyl acrylate, and 3 g of lauryl acrylate dissolved in 25 g of chloroform was added to the flask over 3.25 hours with stirring. Meanwhile, a solution of 0.2 g of tert-butylperoxy-2-ethylhexanoate dissolved in 2 g of 160 / 180 solvent naphtha was added to the flask over 3.5 hours. After all additions were complete, the reaction system was kept at the same temperature with stirring for 1 hour, and then cooled to complete the polymerization. The entire process was carried out under nitrogen purging. A clear, viscous polymer solution was obtained. The conversion rate of the compound of formula (I), as measured by liquid chromatography, was 92%.

[0061] When measured by GPC in polystyrene standard THF, the obtained polymer had a number-average molecular weight (Mn) of 55,200 g / mol, a mass-average molecular weight (Mw) of 218,000 g / mol, and a PDI of 3.95.

[0062] Example 3: Test of polymerization performance 3.1 Preparation of polymerization system using copolymer initiator The transparent, viscous polymer solution obtained in Example 2 was subjected to vacuum to remove part of the solvent, and a polymer solution with a solid content of 50% was obtained by measurement according to GB24409-2020. The obtained polymer solution was used as a copolymer initiator system. Benzopinacol structural units accounted for 2.5% by mass of the total mass of the copolymer initiator system. The solvent of the copolymer initiator system was found to consist of 12.2% by mass of chloroform and 87.8% by mass of solvent naphtha, as measured by gas chromatography.

[0063] A monomer solution was prepared by mixing 90 g of trimethylolpropane triacrylate (TMPTA) and 2 g of butyl glycol with stirring. 4 g of copolymer initiator was added to the monomer solution and stirred at room temperature for 1 hour. The resulting mixture was a clear, transparent solution and was used as the polymerization system.

[0064] 3.2 Preparation of polymerization systems using benzopinacol A monomer solution was prepared by mixing 90 g of TMPTA, 2 g of butyl glycol, 0.24 g of chloroform, and 1.76 g of solvent naphtha 160 / 180 with stirring. 1 g of benzopinacol powder was added to the monomer solution and stirred at room temperature for 1 hour. The resulting mixture was a clear liquid with suspended fine particles and was used as a polymerization system.

[0065] 3.3 Preparation of polymerization systems using benzopinacol A monomer solution was prepared by mixing 90 g of TMPTA and 10 g of butyl glycol with stirring. 1 g of benzopinacol fine powder was added to the monomer solution and stirred at room temperature for 1 hour. The resulting mixture was a clear liquid with suspended fine particles and was used as a polymerization system.

[0066] 3.4 Preparation of polymerization systems using the compound of formula (I) A monomer solution was prepared by mixing 90 g of TMPTA and 10 g of butyl glycol with stirring. 1 g of the compound of formula (I) was added to the monomer solution and stirred at room temperature for 1 hour. The resulting mixture was a clear liquid with suspended fine particles and was used as a polymerization system.

[0067] The polymerization system was measured using a dynamic thermomechanical analyzer (HAAKE iQ air rheometer) to characterize the initiator's initiation performance. Measurements were performed in OSC mode at a heating rate of 4.67°C / min. The on-set temperature was determined from the measured curves as an indicator of initiation performance. The test results are summarized in Table 1.

[0068] [Table 1] a) Initiator: Copolymer of the present invention; Solvent: 2 g butyl glycol, 0.24 g chloroform, and 1.76 g solvent naphtha b) Initiator: benzopinacol; Solvent: 2g butyl glycol, 0.24g chloroform, and 1.76g solvent naphtha c) Initiator: Benzopinacol; Solvent: Butyl glycol 10g d) Initiator: Substituted benzopinacol of formula (I); Solvent: 10 g butyl glycol

[0069] The polymerization system of Example 3.1 using the copolymerization initiator of the present invention exhibits a much lower starting temperature than the polymerization system of Example 3.2 using benzopinacol, even with the same solvent composition. The starting temperature of the polymerization system using benzopinacol decreased with a much higher solvent volume, as shown in the comparison of the polymerization systems of Example 3.2 and Example 3.3. Low solubility of benzopinacol leads to poor starting efficiency, which is considered to be the reason for the high starting temperature of the polymerization system in Example 3.2.

[0070] Benzopinacol provides suitable initiation performance in polymerization systems containing a sufficient amount of solvent; however, excessive amounts of solvent can lead to undesirable VOCs, potentially requiring a long dissolution process and additional processing steps, such as filtration. Ni In the case of substituted benzopinacol, the solubility of benzopinacol is not improved, and as can be seen from the polymer system test results in Example 3.4, the initiation performance is inferior to that of benzopinacol. In contrast, the copolymer initiator of the present invention achieves the desired initiation performance, and at the same time requires only a small amount of organic solvent, simplifying the process.

[0071] Although the present invention has been described with reference to specific embodiments, it will be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those skilled in the art that various modifications and changes can be made to the methods and apparatus of the present invention without departing from the spirit and scope of the invention. Thus, the present invention is intended to include modifications and variations that fall within the scope of the appended claims and their equivalents.

Claims

1. (A) Formula (I) 【Chemistry 1】 allyloxycarbonyl-substituted benzopinacol monomer, and (B) at least one ethylenically unsaturated monomer, A copolymer containing in a copolymerized form.

2. The copolymer according to claim 1, comprising (A) the allyloxycarbonyl-substituted benzopinacol monomer of formula (I) and (B) the at least one ethylenically unsaturated monomer in a randomly copolymerized form.

3. (B) The at least one ethylenically unsaturated monomer is an α,β-unsaturated carboxylic acid and its ester, an ethylenically unsaturated nitrile, C １ ~C ２０ -Vinyl esters of carboxylic acids, vinyl aromatics having up to 20 carbon atoms, vinyl halides, C １ ~C ２０ - A vinyl ether of an alcohol, having one or two olefin double bonds. ２ ~C ２０ - The copolymer according to claim 1 or 2, selected from unsaturated olefins or any combination thereof.

4. (B) The copolymer according to any one of claims 1 to 3, wherein the at least one ethylenically unsaturated monomer comprises at least one α,β-unsaturated carboxylic acid ester.

5. (B) the at least one ethylenically unsaturated monomer is C １ to C ２０ -alkyl (meth)acrylate, C ３ to C １２ -cycloalkyl (meth)acrylate and any combination thereof, the copolymer according to any one of claims 1 to 4.

6. (B) The copolymer according to any one of claims 1 to 5, wherein the at least one ethylenically unsaturated monomer is selected from n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, pentadecyl acrylate, pentadecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, and any combination thereof.

7. (B) The copolymer according to any one of claims 1 to 6, wherein the at least one ethylenically unsaturated monomer is selected from n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, and any combination thereof.

8. (A) Formula (I) 【Chemistry 2】 allyloxycarbonyl-substituted benzopinacol monomer and (B) at least one of n-butyl acrylate and n-butyl methacrylate, at least one of 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, and at least one of lauryl acrylate and lauryl methacrylate A copolymer according to any one of claims 1 to 7, comprising:

9. The copolymer according to any one of claims 1 to 8, wherein the total structural units from comonomer (A) and the total structural units from comonomer (B) are contained in a mass ratio of 1:30 to 1:

10.

10. The copolymer according to any one of claims 1 to 9, wherein the number-average molecular weight (Mn) is in the range of 5,000 to 500,000 g / mol.

11. The copolymer according to any one of claims 1 to 10, wherein the mass-average molecular weight (Mw) is in the range of 20,000 to 1,000,000 g / mol.

12. A copolymer according to any one of claims 1 to 11, obtained by free radical polymerization.

13. A method for using the copolymer according to any one of claims 1 to 12 as a radical polymerization initiator.

14. The method of use according to claim 13 for a coating material comprising a monomer and / or oligomer reactive diluent having at least one olefin double bond.

15. Equation (I) 【Transformation 3】 Allyloxycarbonyl-substituted benzopinacol.

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