Compounds containing a perfluorinated group, a photoinitiator group, and an amide linking group

Abstract

Compounds are described that include a perfluorinated group attached to at least one terminal photoinitiator group by an organic linking group that includes at least one amide moiety. The compounds typically include the reaction product (e.g., Michael addition) of i) a compound that includes an acrylic group and a photoinitiator group with ii) an amino-functional perfluorinated compound. Also described are compositions and methods that include at least one free-radically polymerizable (e.g., fluorinated) monomer, oligomer, or combination thereof with the described fluorinated photoinitiator compound.

Description

Summary of the Invention

[0001] Although a variety of photoinitiator compounds have been reported, the industry would find advantage in photoinitiator compounds that are compatible with fluorinated free-radically polymerizable materials.

[0002] In one embodiment, compounds are described that include a perfluorinated group attached to at least one terminal photoinitiator group by an organic linking group that includes at least one amide moiety.

[0003] In an exemplary embodiment, the compound comprises: i) a compound comprising an acrylic group and a photoinitiator group; ii) includes reaction products (e.g., Michael addition) with amino-functional perfluorinated compounds.

[0004] Also described are compositions comprising at least one free-radically polymerizable monomer, oligomer, or combination thereof and a fluorinated photoinitiator compound described herein. In some preferred embodiments, at least one free-radically polymerizable monomer and / or oligomer is fluorinated.

[0005] Also described are methods of making a cured composition, comprising providing a composition comprising at least one free-radically polymerizable monomer, oligomer, or combination thereof described herein and a fluorinated photoinitiator compound, and (e.g., UV) radiation-curing the composition. In some embodiments, the method further comprises coating the polymerizable composition on a substrate prior to radiation-curing. In some embodiments, upon radiation-curing, the polymerizable composition forms a film or film layer. [Brief explanation of the drawings]

[0006] [Figure 1]1 is a graph of absorbance (A) as a function of wavelength for an exemplary fluorinated photoinitiator compound containing a perfluorinated group, a photoinitiator group, and an amide linker group, where the solid line represents a 0.1 wt % concentration in acetonitrile and the dashed line represents a 0.01 wt % concentration in acetonitrile. [Figure 2] 1 is a graph of absorbance (A) as a function of wavelength for an exemplary fluorinated photoinitiator compound containing a perfluorinated group, a photoinitiator group, and an amide linker group, where the solid line represents a 0.1 wt % concentration in acetonitrile and the dashed line represents a 0.01 wt % concentration in acetonitrile. [Figure 3] 1 is a graph of absorbance (A) as a function of wavelength for an exemplary fluorinated photoinitiator compound containing a perfluorinated group, a photoinitiator group, and an amide linker group, where the solid line represents a 0.1 wt % concentration in acetonitrile and the dashed line represents a 0.01 wt % concentration in acetonitrile. DETAILED DESCRIPTION OF THE INVENTION

[0007] Described herein are compounds comprising a perfluorinated group, which is attached to at least one terminal photoinitiator group by an organic linking group comprising at least one amide moiety.

[0008] In an exemplary embodiment, the compound has the following formula (Formula 1): [ka] [In the formula, R f is a monovalent perfluorooxyalkyl group or a divalent perfluorooxyalkylene group, R 1 is an alkylene group, optionally containing one or more catenary oxygen atoms; R 2 is H or an alkyl group of 1 to 4 carbon atoms, X is -O-, -S-, or -NR 3 -(In the formula, R 3is H or an alkyl group of 1 to 4 carbon atoms; L is a covalent bond or a divalent organic linking group; PI is a photoinitiator group; R f is a monovalent perfluorooxyalkyl group, n is 1, or R f is a divalent perfluorooxyalkylene group, then n is 2.

[0009] As used herein, the term "catenary" refers to the substitution of a carbon atom of a carbon chain with a substituent (e.g., O or N). Thus, a pendant substituent (e.g., -OH) attached to a carbon atom is not a catenary oxygen atom.

[0010] In some embodiments, a monovalent perfluorooxyalkyl group comprises 1 to 6 (e.g., straight or branched) perfluorinated carbon atoms and a single oxygen atom moiety, such as CFCFCFO-. In some embodiments, the number of perfluorinated carbon atoms is at least 2 or 3. In some embodiments, the number of perfluorinated carbon atoms is 5 or 4 or less.

[0011] In an exemplary embodiment, the monovalent perfluorooxyalkyl group has the general structure -[C m F 2m O] s -wherein, for each s, m is independently in the range of 1 to 6. In some embodiments, m is at least 2 or 3. In some embodiments, m is 5 or less than or equal to 4. In some embodiments, s is at least 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, s is 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 or less.

[0012] In one embodiment, Rf is "HFPO-". n is 1 and Rf is a monovalent perfluorooxyalkyl group, HFPO- is the terminal group CF3CF2CF2O-[CF(CF3)CF2O] s -CF(CF3)-, where s is an integer from 2 to 25, as previously described. HFPO- generally exists as a dispersion or mixture of molecules having various values ​​for s. Thus, s can be expressed as an average value. Such average values ​​are typically not integers.

[0013] In some embodiments, a divalent perfluorooxyalkylene group comprises two to six (e.g., straight or branched) perfluorinated carbon atoms and a single oxygen atom moiety, such as, for example, -CF2-CF2-O-, -CF(CF3)-CF2-O-, -CF2-CF(CF3)-O-, -CF2-CF2-CF2-O-, -CF(CF3)-O-, and -CF2-CF2-CF2-CF2-O. In some embodiments, the number of perfluorinated carbon atoms is at least two or three. In some embodiments, the number of perfluorinated carbon atoms is five or four or less.

[0014] In an exemplary embodiment, the divalent perfluorooxyalkyl group has the general structure -[C m F 2m O] s -wherein, for each s, m independently ranges from 1 to 6. In some embodiments, m is at least 2 or 3. In some embodiments, m is 5 or less than or equal to 4. In some embodiments, s is at least 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, s is 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 or less.

[0015] n is 2 and R f When is a divalent perfluorooxyalkyl group, -HFPO- is [ka] where p ranges from 2 to 6, and s and t are independently integers from 2 to 25. In some embodiments, p is 3 or 4. In some embodiments, the sum of s and t is at least 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, the sum of s and t is no greater than 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10. The divalent -HFPO- also generally exists as a dispersion or mixture of molecules having various values ​​for s and t. Thus, the sum of s and t can be expressed as an average value. Such an average value is typically not an integer.

[0016] Rf is preferably a monovalent perfluorooxyalkyl group or a divalent perfluorooxyalkylene group, although Rf may alternatively be a perfluorinated alkyl or perfluorinated alkylene group known in the art. Perfluorinated alkyl or perfluorinated alkylene groups typically contain 2 to 6 perfluorinated carbon atoms. In some embodiments, the number of perfluorinated carbon atoms is at least 2 or 3. In some embodiments, the number of perfluorinated carbon atoms is 5 or 4 or less.

[0017] Some representative compounds according to Formula 1 include: [ka] [ka] [ka]

[0018] The fluorinated photoinitiator compounds described herein can be prepared by any suitable method. In a typical embodiment, such compounds comprise the reaction product (e.g., Michael addition) of i) an amino-functional perfluorinated compound with ii) a compound comprising an acrylic group and a photoinitiator group. As used herein, "acrylic" refers to an acrylate, thioacrylate, or acrylamide.

[0019] The fluorochemical compounds described herein can be prepared in a two-step process. The first step is the reaction of a perfluorinated methyl ester compound with a polyamine to produce the corresponding perfluorinated amine. The second step is the Michael addition of the perfluorinated amine to the acrylic group of a compound containing an acrylic group and a photoinitiator group.

[0020] For each step, the reactants are combined in a suitable solvent. When a homogeneous mixture or solution is obtained, a catalyst is optionally added and the reaction mixture is heated at a temperature for a time sufficient for the reaction to occur. The progression of the Michael addition reaction is 1 This can be determined by monitoring the olefin concentration using H Fourier Transform Nuclear Magnetic Resonance (FT-NMR).

[0021] In some embodiments, fluorinated solvents are utilized. A variety of partially or fully fluorinated solvents are known, including perfluorocarbons (PFCs), hydrochlorofluorocarbons (HCFCs), perfluoropolyethers (PFPEs), and hydrofluorocarbons (HFCs), as well as fluorinated ketones and fluorinated alkylamines. Such solvents are commercially available, for example, from 3M Company (St. Paul, MN) under the trade name NOVEC.

[0022] In other embodiments, the solvent is non-fluorinated, as in the case of ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl ketone, and N-methyl pyrrolidone (NMP); ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and methyl tetrahydrofurfuryl ether; esters such as methyl acetate, ethyl acetate, and butyl acetate; and cyclic esters such as delta-valerolactone and gamma-valerolactone.

[0023] Perfluorooxyalkyl and perfluorooxyalkylene compounds can be obtained by oligomerization of hexafluoropropylene oxide, which results in terminal fluorinated carbonyl groups. The fluorinated carbonyl groups can be converted into esters by reactions known to those skilled in the art. The preparation of perfluorinated methyl ester compounds is described, for example, in U.S. Patent Nos. 3,250,808 and 9,718,896.

[0024] Amino-functional perfluorinated compounds can be prepared by reaction of the terminal ester groups of a perfluorinated compound with a polyamine.

[0025] Useful polyamines contain at least two amine groups, which are typically primary, secondary, or a combination thereof.

[0026] In some embodiments, the polyamine (e.g., diamine) comprises a terminal primary amine group (i.e., NH) and a terminal secondary amine group. Examples of such polyamines include HNCHCHCHN(CH)H, HNCHCHCHN(CHCH)H, HNCHCHCHCHCHCHN(CH)H, and [ka] Examples include:

[0027] Primary amines exhibit higher reactivity with the ester groups of perfluorinated ester compounds than secondary amines. On the other hand, secondary amine groups of polyamines (e.g., diamines) react with the acrylic groups of compounds containing photoinitiator groups.

[0028] Various compounds containing an acrylic group and a photoinitiator group have been described in the literature. In some embodiments, the photoinitiator contains a phenone group (i.e., an aromatic ketone containing a phenyl group directly bonded to a carbonyl group). Representative phenone groups include, for example, benzophenone and acetophenone.

[0029] Some representative compounds containing an acrylic group and a (e.g., phenone) photoinitiator group are described as follows: [Table 1-1] [Table 1-2]

[0030] Various (e.g., divalent) organic linking groups (e.g., L in Formula 1) are represented by these compounds as set forth in the table above. The (e.g., divalent) organic linking group can be a covalent bond or can include moieties such as ester, urethane, alkoxy, and alkylene, optionally containing one or more catenary oxygen or sulfur atoms, and combinations thereof. Optionally substituted alkylene groups are typically C1-C6 12 Alkylene and any integer interval within this range such as C2 to C6.

[0031] Some specific organic linking groups (e.g., L in Formula 1) include, for example, -R 4 X-, -R 4 XC(O)-, -R 4 NHC(O)X- or -R 4 NHC(O)XR 4 X—wherein X is the same as defined for Formula 1 and R 4is a divalent alkylene, optionally containing one or more catenary oxygens. Optionally substituted alkylene groups are typically C1-C 12 Alkylene and any integer interval within this range such as C2 to C6.

[0032] As evidenced by Formula 1, there is also an organic linking moiety between Rf and X, which is attached to linking group L. Such moieties include an amide moiety, one or more amine moieties, an alkylene moiety, and a carbonyl moiety.

[0033] The organic linking group has a sufficiently low molecular weight so that the fluorinated photoinitiator compound is within the molecular weight ranges described below. In some embodiments, the molecular weight of the organic linking group is no greater than 300, 250, 200, 150, 100, or 75 g / mole.

[0034] Compounds containing acrylic and photoinitiator groups can be synthesized by the reaction of a hydroxy-functional photoinitiator with a hydroxy-reactive acrylic compound, such as an isocyanato (C1-C4) alkyl acrylate. One representative hydroxy-functional photoinitiator is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl-propiophenone, commercially available as IRGACURE 2959, Mw=224 g / mol.

[0035] Because the perfluorinated methyl ester reactants contain a mixture of perfluorooxyalkylene groups of various chain lengths, the resulting (e.g., Michael addition) fluorinated photoinitiator compounds also contain a mixture of perfluorooxyalkylene groups of various chain lengths.

[0036] (e.g., Michael addition) photoinitiator compounds (e.g., according to Formula 1) typically have (e.g., number average) molecular weights of 5000, 4500, 4000, 3500, 3000, or 2500 g / mol or less. In some embodiments, the (e.g., number average) molecular weight is 2200, 2100, 2000, 1900, or 1800 g / mol or less. In some embodiments, the (e.g., number average) molecular weight is at least 500, 1000, or 1500 g / mol. During compound synthesis, the molecular weight can be calculated by the equivalent weights of reactants (i.e., the amino-functional perfluorinated compound and the compound comprising an acrylic group and a photoinitiator group), as further described in the Examples below. Alternatively, the molecular weight of (e.g., Michael addition) photoinitiator compounds (e.g., according to Formula 1) can be determined by nuclear magnetic resonance (NMR), liquid chromatography optionally followed by NMR, and / or mass spectrometry.

[0037] In some embodiments, the (e.g., Michael addition) photoinitiator compound (e.g., according to Formula 1) has an average weight percent fluorine of at least 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, or 55 weight percent. The weight percent fluorine can be calculated from the reactants during synthesis of the compound. Alternatively, the weight percent fluorine can be calculated using combustion ion chromatography (CIC) as described in WO 2017 / 172390. In other embodiments, the (e.g., Michael addition) photoinitiator compound (e.g., according to Formula 1) has an average weight percent fluorine ranging from at least 30, 35, or 40 weight percent up to 45 weight percent fluorine.

[0038] Photoinitiators with sufficiently high fluorine content are miscible with highly fluorinated free radically polymerizable monomers, oligomers, and mixtures thereof. Low-fluorinated compounds can simultaneously function as photoinitiators and low surface energy additives for low-fluorinated and non-fluorinated free radically polymerizable materials.

[0039] The (eg, Michael addition) photoinitiator compounds described herein (eg, according to Formula 1) are suitable for use as photoinitiators in (eg, photo)polymerizable compositions.

[0040] Photoinitiators are often characterized by their maximum absorption wavelength, or in other words, their absorption peak. For example, Irgacure 2959 is reported to have the following absorbance characteristics: [Table 2]

[0041] The absorbance of the photoinitiator solution can be determined using a spectrophotometer (according to the test method described in the Examples). The solvent of the photoinitiator solution is suitable for dissolving the photoinitiator. In a typical embodiment, acetonitrile is a suitable solvent. The concentration of the photoinitiator dissolved in the solution to determine the absorbance is high enough so that the measured absorbance is greater than the baseline "noise." In a typical embodiment, a concentration of 0.01% by weight or 0.1% by weight is useful for determining the absorbance characteristics of the photoinitiator. Those skilled in the art will understand that there is a linear relationship between absorbance and concentration. Therefore, the absorbance at other concentrations can be calculated.

[0042] 1-3, exemplary fluorinated photoinitiator compounds typically have absorbances of greater than 0.01, 0.05, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, or 0.70 at a 0.01 wt % concentration in acetonitrile solution at wavelengths in the 250-300 nm wavelength range and a 1 cm path length. Exemplary fluorinated photoinitiator compounds have peak wavelengths within the same range (e.g., about 275 nm).

[0043] Those skilled in the art will appreciate that other photoinitiator groups have different absorption characteristics. The absorption maximum wavelengths are reported for various photoinitiators in Industrial Photoinitiators, A Technical Guide, W. Arthur Green, CRC Press, Taylor and Francis Group, 2010.

[0044] In another embodiment, described is a (e.g., photo)polymerizable composition comprising at least one free-radically polymerizable (e.g., acrylic) monomer, oligomer, polymer, or combination thereof, and a fluorinated photoinitiator compound described herein.

[0045] Such photoinitiators are particularly advantageous for use in polymerizable compositions comprising fluorinated free-radically polymerizable monomers, oligomers, or combinations thereof. In some embodiments, the fluorinated free-radically polymerizable monomers, oligomers, or combinations thereof have a fluorine content of at least 25, 30, 35, 40, 45, 50, 55, 60, or 65% by weight, and typically less than 75% by weight.

[0046] In typical embodiments, the (e.g., photo)polymerizable composition comprises one or more fluorinated photoinitiator compounds in an amount of at least 0.5, 1, 1.5, 2, 2.5, 3, or 3.5 wt. % solids. The amount of fluorinated photoinitiator compound is typically no more than 15, 10, or 5 wt. % solids. The fluorinated photoinitiator can be a single compound described herein, a combination of compounds described herein, or at least one fluorinated photoinitiator described herein in combination with various fluorinated photoinitiators as described in the literature.

[0047] In one embodiment, the fluorinated photoinitiator compounds described herein are utilized during the (e.g., photo)polymerization of fluorinated oligomers containing perfluorinated (e.g., perfluorooxyalkyl or perfluorooxyalkylene) groups. Suitable fluorinated acrylate monomers and oligomers include mono- and di-(meth)acrylates having molecular weights of about 200 to 3000 g / mol, including mono- and diacrylates of perfluoropolyether oligomers, as described in U.S. Patent No. 8,658,248.

[0048] In one embodiment, the (e.g., photo)polymerizable composition includes an HFPO oligomer diacrylate as shown below, where n is selected to have a molecular weight (Mn) of at least 1000, 1500, or 2000 g / mol. [ka]

[0049] Such HFPO oligomer diacrylates can be fully cured with the fluorinated photoinitiators described herein, as described in more detail in the Examples.

[0050] Also described are methods of making a cured composition, including providing a (e.g., photo)polymerizable composition that includes a fluorinated photoinitiator described herein and radiation-curing the (e.g., photo)polymerizable composition. In some embodiments, the method further includes coating the (e.g., photo)polymerizable composition on a substrate prior to radiation-curing. In some embodiments, upon radiation-curing, the polymerizable composition forms a film or film layer.

[0051] In an exemplary embodiment, radiation curing involves exposing the (eg, coated) composition to ultraviolet (UV) and visible light wavelengths.

[0052] UV light sources can be of various types. Low intensity sources such as black lights typically produce 0.1 or 0.5 mW / cm 2 (milliwatts per square centimeter) to 10mW / cm 2 Intensities in the range of 10, 15, or 20 mW / cm are obtained (as measured by a United States National Institute of Standards and Technology approved dosimeter, e.g., UVIMAP UM 365 LS (Electronic Instrumentation & Technology, Inc., Sterling, VA)). High-intensity sources generally have intensities of 10, 15, or 20 mW / cm. 2 Up to 450mW / cm 2 Intensities ranging from up to 500, 600, 700, 800, 900, or 1000 mW / cm are obtained in some embodiments. 2 Intensities up to 1000 nm can be achieved. UV light can be provided by a variety of sources, including light-emitting diodes (LEDs), fluorescent black lights, arc lamps such as xenon-arc lamps and medium- and low-pressure mercury lamps (including germicidal lamps), microwave-powered lamps, lasers, and the like, or combinations thereof. The composition can also be polymerized with higher-intensity light sources available from Fusion UV Systems Inc. Lamps emitting ultraviolet or blue light are typically preferred. UV exposure times for polymerization and curing can vary depending on the intensity of the light source used. For example, full cure with a low-intensity light source can be achieved with exposure times ranging from about 30 to 300 seconds, while full cure with a high-intensity light source can be achieved with shorter exposure times ranging from about 1 to 20 seconds.

[0053] When the (eg, photo)polymerizable composition includes cured fluorinated free-radically polymerizable monomers, oligomers, and combinations thereof, the cured composition may have a low refractive index.

[0054] The low refractive index layer can be deposited by a process in which fluorinated acrylate monomers and / or oligomers, optionally with an adhesion promoter and / or photoinitiator, are vapor-deposited and cured by exposure to ultraviolet (UV), electron beam (e-beam), ionizing (gamma), or plasma radiation. The adhesion promoter (also called a coupling agent) can be fluorinated or non-fluorinated. Fluorinated coupling agents are described in the literature and in concurrently filed U.S. Provisional Patent Applications Attorney Docket Nos. 83052US002 and 83094US002, which are incorporated herein by reference. The process and articles are described in 81487WO003, PCT / IB2019 / 059605, 81499WO003 (PCT / US2019 / 060252), and concurrently filed U.S. Provisional Patent Applications Attorney Docket Nos. 83096US002 and 83097US002, which are incorporated herein by reference. [Table 3]

[0055] Preparation 1. Intermediates [ka] 50 g (651.485 number average equivalents, 0.076748 equivalents) of CH(O)C-HFPO-C(O)CH was prepared by a method similar to Preparation No. 26, U.S. Pat. No. 7,718,264, column 30, lines 41-53, and 6.77 g (0.076748 equivalents) of 3-(methyl)-1,3-propanediamine was added to a 250 mL flask equipped with a stir bar and stirred at room temperature under nitrogen for 1.5 hours, at which time an aliquot was taken for Fourier transform infrared (FTIR) analysis, which showed peaks at approximately 1800 and 1780 cm. -1 (Small, Large) The doublet of ester disappears, and the peak is about 1718 cm -1 The material was concentrated on a rotary evaporator at 1.5 Torr for 30 minutes to give 53.84 g of a viscous oil.

[0056] Preparation 2. Example 1 [ka] from Preparation 1 in 5 g of ethyl acetate [ka] 12.54 g (0.0177 equivalents, 707.63 number average EW) and 5.00 g (0.0169 equivalents, 296.31 EW) of AEBP were mixed with an additional 5 g of ethyl acetate in a 250 mL flask equipped with a stir bar under dry air, and after 17 hours, an aliquot was removed. 1 Analysis by H Fourier transform nuclear magnetic resonance (FT-NMR) showed that approximately 8-9% of the olefins remained. [ka] , 1.00 g (0.000678 equivalents) and 5 g of additional ethyl acetate were added and after overnight reaction, 1 Analysis by H FT-NMR showed no olefins remaining. The material was concentrated on a rotary evaporator at aspirator pressure and then at 3 Torr for 30 min to give 18.53 g of a low melting gel.

[0057] Taking into account the addition of HFPO-[C(O)NH-CHCHCH-NH(CH)] required to react with two equivalents of AEBP, the stoichiometric equivalent weight of HFPO-[C(O)NH-CHCHCH-NH(CH)] was determined to be 802.40 (1604.80 MW). Thus, the total molecular weight of the compound of Example 1 was 2197.44 g / mol, and Example 1 had 43.3 wt% fluorine.

[0058] Preparation 3. Example 2 [ka] AEBP (296.31 MW, 0.05062 mol) and 66.24 g of HFPO-C(O)NH-CHCHCH-NH(CH) (number average MW of 1246.15, 0.0532 mol) were dissolved in 90.2 g of ethyl acetate and 81.0 g of Novec 7200 in a 500 mL flask equipped with a magnetic stir bar under dry air with heating and stirring at room temperature overnight. An aliquot was added. 1 A sample was removed for H FT-NMR, and analysis showed approximately 20-24 mole percent olefin remaining, so an additional 20 mole percent (13.25 g) of HFPO-C(O)NH-CHCHCH-NH(CH) was added. After 3 days at room temperature, 1 H FT-NMR and analysis showed no olefin remaining. To the reaction was added 0.169 g of 4-hydroxyTEMPO (1790 ppm), and the reaction was concentrated at 35° C. to remove most of the Novec 7200, then heated to 85° C. at 1.3 Torr (vacuum was increased slowly to avoid foaming) to give 92.9 g of material that was cooled to a soft gel.

[0059] Taking into account the addition of HFPO-[C(O)NH-CHCHCH-NH(CH)] required to react with one equivalent of AEBP, the stoichiometric equivalent of HFPO-[C(O)NH-CHCHCH-NH(CH)] was determined to be 1570.20 g / mol. Thus, the total molecular weight of the compound of Example 2 was 1866.51 g / mol, and Example 2 had 54.3 wt% fluorine.

[0060] Preparation 4. Intermediates [ka] 50.00 g (0.223 mol, 224.26 MW) of Irgacure 2959 was charged to a 250 mL flask equipped with a stir bar, followed by 250.00 g of MEK under dry air. The Irgacure 2959 did not completely dissolve, so 0.0322 g (400 ppm based on total solids) of BHT and 0.008 g (100 ppm based on total solids) of 4-hydroxyTEMPO were added. Next, 30.52 g (0.216 mol, 141.12 MW) of IEA was added via a pressure-equalizing dropping funnel, reaching a maximum temperature of 34°C in approximately 40 minutes. The addition was complete in 1.75 hours, at which point an aliquot analyzed at 2265 cm. -1 The resulting solution showed a small -NCO peak at 45°C. After stirring overnight, FTIR showed no -NCO peak. The material was concentrated under aspirator pressure at 45°C for approximately 1.5 hours, then at 4 Torr and 50°C for approximately 30 minutes to give 81.74 g of material that solidified to a white solid.

[0061] Preparation 5. Example 3 [ka] The product of Preparation 4, 5.00 g (0.0137 mol, 365.38 MW), and 17.91 g (0.0144 mol, 1246.15 number average MW) of HFPO-C(O)NH-CHCHCH-NH(CH) were added to a 100 mL flask equipped with a stir bar under dry air, along with 25 g of Novec 7200 and 10 g of ethyl acetate. The reaction, which was initially cloudy, became clear after 2 hours of mixing at room temperature. After 3 days of mixing at room temperature, 1 Analysis of an aliquot by H FT-NMR showed that approximately 5 mole percent olefin remained, and 0.95 g (0.00072 mole) of HFPO-C(O)NH-CHCHCH-NH(CH) was added. After stirring overnight, the aliquot 1 H FT-NMR and analysis showed no olefin remained. The reaction was concentrated on a rotary evaporator at aspirator pressure for approximately 30 minutes and at 69°C at 3 Torr for approximately 30 minutes to give 23.25 g of material that solidified to a white solid.

[0062] Taking into account the addition of HFPO-[C(O)NH-CHCHCH-NH(CH)] required to react with one equivalent of AEBP, the stoichiometric equivalent of HFPO-[C(O)NH-CHCHCH-NH(CH)] was determined to be 1377.88 g / mol. Thus, the total molecular weight of the compound of Example 2 was 1743.26 g / mol, and Example 2 had 50.5% fluorine by weight.

[0063] UV-VIS measurements of photoinitiators Solutions of fluorinated photoinitiators were prepared at 0.1 wt % and 0.01 wt % in acetonitrile. The solutions were loaded into spectrophotometer cuvettes. The UV-VIS spectra of the photoinitiator solutions were measured using a Lambda 365 UV-Vis spectrometer (PerkinElmer, Waltham, MA) with a 10 mm path length. The UV-VIS absorbance as a function of wavelength for the compounds of Examples 1-3 are shown in Figures 1-3.

[0064] Curing Effectiveness Evaluation of the curing efficacy of the materials was performed by spin-coating (Weinview SC100, 3000 RPM, 10 seconds) various concentrations of mixtures of HFPO oligomer diacrylate and fluorinated photoinitiator materials onto unprimed PET substrates. The HFPO oligomer diacrylate and fluorinated PI mixtures were diluted in solvent (Novec 7200 or 1,1,1-trifluorotoluene, 1:4) to achieve a "dry" thickness of approximately 1-2 micrometers. Immediately after spin-coating, the samples were transferred to a conveyor belt and exposed to a UVC germicidal lamp (12) in a water-cooled, nitrogen-purged enclosure. The UVC lamp was allowed to warm and stabilize for 30 minutes before dosimetry characterization and spin-coating. UV dosimetry was completed using an EIT Power Puck II (EIT, Leesburg, VA). The measured peak irradiance was 10 mW / cm. 2 and a line speed of 7 feet per minute (2.13 m / min) was selected to give 54 mJ / cm 2If the deposited film was not fully cured as determined by the criteria listed in Table 2 below, the film was exposed to UVC light again until the film was fully cured, or the film was not fully cured after six consecutive passes.

[0065] The curing effectiveness or level of cure of the cured films was qualitatively evaluated according to the following criteria: [Table 4] [Table 5]

[0066] Although Example 1 had poor miscibility with HFPO oligomer diacrylate, it is suspected that Example 1 is compatible with free-radically polymerizable monomers and oligomers having lower fluorine content. Furthermore, Example 1 can simultaneously function as a photoinitiator and low surface energy additive for low-fluorinated or non-fluorinated free-radically polymerizable materials. The present invention includes the following aspects. (1) A compound comprising a perfluorinated group, the perfluorinated group being attached to at least one terminal photoinitiator group by an organic linking group comprising at least one amide moiety. (2) The compound according to item 1, wherein the perfluorinated group is a perfluorooxyalkyl group or a perfluorooxyalkylene group. Equation (3) [ka] [In the formula, R f is a monovalent perfluorooxyalkyl group or a divalent perfluorooxyalkylene group, R 1 is an alkylene group, optionally containing one or more catenary oxygen atoms; R 2 is H or an alkyl group of 1 to 4 carbon atoms, X is -O-, -S-, or -NR 3 -(In the formula, R 3 is H or an alkyl group of 1 to 4 carbon atoms; L is a covalent bond or a divalent organic linking group; PI is a photoinitiator group; R f is a monovalent perfluorooxyalkyl group, n is 1, or R f is a divalent perfluorooxyalkylene group, then n is 2. (4) The compound according to item 3, wherein the divalent organic linking group comprises a moiety selected from ester, urethane, alkoxy, and alkylene optionally containing one or more catenary oxygen or sulfur atoms, and combinations thereof. (5) The compound according to any one of items 1 to 4, wherein the photoinitiator group comprises a phenone group. (6) The compound according to item 5, wherein the photoinitiator group is selected from benzophenone and acetophenone. (7) The compound according to any one of items 1 to 6, having a number average molecular weight of 5000, 4500, 4000, 3500, 3000, 2500, or 2000 g / mol or less. (8) The compound according to any one of items 1 to 7, having an average weight percent fluorine of at least 30, 35, 40% by weight. (9)i) a compound comprising an acrylic group and a photoinitiator group; ii) Compounds comprising reaction products with amino-functional perfluoropolyether compounds. (10) The compound according to item 9, further characterized by any one of items 2 to 8. (11) A method for making a compound containing a perfluorinated group and a terminal photoinitiator group, comprising the Michael addition of i) a compound containing an acrylic group and a photoinitiator group, and ii) an amino-functional perfluoropolyether compound. (12) A polymerizable composition comprising at least one free-radically polymerizable monomer, oligomer, or combination thereof, and the fluorinated photoinitiator compound according to any one of items 1 to 11. (13) The composition according to item 12, wherein the free-radically polymerizable monomer, oligomer, or combination thereof is fluorinated. (14) The composition according to item 13, wherein the free-radically polymerizable monomer, oligomer, or combination thereof has a fluorine content of at least 25, 30, or 35% by weight. (15) The polymerizable composition according to any one of items 12 to 14, comprising an oligomer having a perfluorooxyalkylene group. (16) Preparing the polymerizable composition according to any one of items 12 to 15; and radiation-curing said photopolymerizable composition. 17. The method of claim 16, wherein the radiation curing comprises exposing the composition to ultraviolet wavelengths. (18) The method according to item 16 or 17, further comprising coating the polymerizable composition on a substrate prior to radiation curing. (19) The method according to any one of items 16 to 18, wherein the polymerizable composition forms a film or film layer upon radiation curing.

Claims

1. formula 【Chemistry 1】 [In the formula, R ｆ is a monovalent perfluorooxyalkyl group or a divalent perfluorooxyalkylene group, R １ is an alkylene group, optionally containing one or more catenary oxygen atoms; R ２ is H or an alkyl group of 1 to 4 carbon atoms, X is —O—, —S—, or —NR ３ - (wherein, R ３ is H or an alkyl group of 1 to 4 carbon atoms; L is a covalent bond or a divalent organic linking group; PI is a photoinitiator group; R ｆ is a monovalent perfluorooxyalkyl group, n is 1, or R ｆ is a divalent perfluorooxyalkylene group, then n is 2. A compound having the formula:

2. 2. The compound of claim 1, wherein the divalent organic linking group comprises a moiety selected from ester, urethane, alkoxy, and alkylene optionally containing one or more catenary oxygen or sulfur atoms, and combinations thereof.

3. The compound of claim 1 , wherein the photoinitiator group comprises a phenone group.

4. The compound of claim 3 , wherein the photoinitiator group is selected from benzophenone and acetophenone.

5. 10. The compound of claim 1 having a number average molecular weight of 5000 g / mol or less.

6. 10. The compound of claim 1 having an average weight percent fluorine of at least 30% by weight.

7. A method for preparing a compound according to any one of claims 1 to 6, comprising the Michael addition of i) a compound comprising an acrylic group and a photoinitiator group, and ii) an amino-functional perfluoropolyether compound.

8. A polymerizable composition comprising at least one free-radically polymerizable monomer, oligomer, or combination thereof, and the fluorinated photoinitiator compound of any one of claims 1 to 6.

9. 9. The polymerizable composition of claim 8, wherein the free-radically polymerizable monomer, oligomer, or combination thereof is fluorinated.

10. 10. The polymerizable composition of claim 9, wherein the free-radically polymerizable monomer, oligomer, or combination thereof has a fluorine content of at least 25% by weight.

11. The polymerizable composition of claim 8 comprising an oligomer having a perfluorooxyalkylene group.

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