Coating composition comprising binder polymer obtainable by copolymerizing monomer mixture comprising vinyl monomer and butenolide monomer

Abstract

The invention relates to a coating composition comprising a binder polymer which can be obtained by copolymerizing a monomer mixture comprising a vinyl monomer M1 and a butenolide monomer M2, the vinyl monomer M1 having a 13C chemical shift difference between alpha-C and beta-C of the vinyl group of at least 25 ppm, and wherein the butenolide monomer M2 is a substituted 5-hydroxy-2 (5H)-furanone of general formula (I) wherein R1 is any one of-C (O) R2,-C (O) OR2,-C (O) NR2R3,-S (O) R2,-S (O2) R2,-C (O) SR2,-C (S) SR2 and-C (S) NR2R3 wherein R2 is an alkyl or aryl group, and wherein R3 is hydrogen, alkyl or aryl group, or wherein R2 and R3 together with the nitrogen atom through which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl group. The invention further relates to a substrate coated with a coating deposited from the coating composition, a binder polymer and a novel butenolide monomer M2. # imgabs0 #

Description

Field of the Invention

[0001] The present invention relates to a coating composition comprising a binder polymer obtainable by copolymerizing a monomer mixture comprising a vinyl monomer and a butenolide monomer, to a substrate coated with a coating deposited from the coating composition, to a binder polymer obtainable by copolymerizing a monomer mixture comprising a vinyl monomer, and to novel butenolide monomers. Background of the Invention

[0003] Polyacrylates or other addition polymers are widely used as film-forming polymers in paints and coatings. Film-forming polymers are also referred to as binder polymers since such polymers serve to bind together any particulate materials such as color pigments and extender pigments.

[0004] Polyacrylates or other addition polymers are generally prepared by free-radical polymerization of monomers having ethylenically unsaturated groups such as acrylic groups, methacrylic groups or vinyl groups. Examples of such monomers include acrylic acid, methacrylic acid, (meth)acrylic acid alkyl esters, styrene, alkyl-substituted styrenes, vinyl esters and vinyl ethers. These monomers are generally prepared from petrochemical raw materials.

[0005] There is an increasing demand for chemical products prepared from renewable raw materials. Binder polymers prepared at least in part from renewable raw materials are known in the art. Alkyd resins, for example, contain a relatively high content of fatty acids derived from vegetable oils.

[0006] WO2009 / 080599 discloses a process for preparing polymerizable ethylenically unsaturated macromonomers from vegetable oils that can be used to prepare addition polymers for coating compositions.

[0007] Butenolides are ethylenically unsaturated furan compounds that can be prepared from carbohydrates, i.e., renewable raw materials. Carbohydrate raw materials such as starch, cellulose or carbohydrate-containing biological waste can be converted by dehydration into furfural, hydroxymethylfurfural or related furan derivatives and subsequently oxidized to lactones or other butenolides. The preparation of butenolides is described, for example, in Chapter II of J.C. de Jong, Asymmetric Diels-Alder reactions with 5-menthyloxy-2(5H)-furanones, Thesis University of Groningen, 2006, which is accessible https: / / www.rug.nl / research / portal / en / publications / asymmetric-dielsalder-reactions- wit h-5menthyloxy25hfuranones(f0ab6c00-8c6c-4ccc-90aa-3ef05f759fa4).html .

[0008] Poskonin et al. have disclosed in Russian Journal of Organic Chemistry 35(1999)721-726 copolymers prepared by free radical polymerization of 4-alkoxy-2-butenolides(5-alkoxy-2(5H)-furanones)with styrene, methyl methacrylate or vinyl acetate. The use of such copolymers in the synthesis of physiologically active substances has been proposed. Poskonin et al. have further disclosed in Russian Journal of Organic Chemistry 35(1997)520-523 oligomers prepared by free radical polymerization of 4-acetoxy-2-butenolide(5-acetoxy-2(5H)-furanone)with styrene, methyl methacrylate or vinyl acetate. A number average molecular weight of 1860-6460 was achieved.

[0009] WO2021 / 084066 describes the copolymerization of 5-alkoxy-2(5H)-furanone with a selected vinyl ether or vinyl ester and the use of the resulting copolymer as a binder in a polymer coating composition.

[0010] WO2021259819 A1 describes a radiation-curable coating composition comprising a 5-hydroxy- or 5-alkoxy-(5H)-furanone compound A and a compound B having at least two vinyl ether or vinyl ester groups such that the ratio of the vinyl moiety on compound B to the furanone moiety on compound A is at least 0.5.

[0011] Trost and Toste have disclosed in J.Am.Chem.Soc.2003, 125, 3090-3100 two butenolide compounds for introducing chirality into the synthesis of aflatoxins: 2-tert-butoxycarbonyloxy-5-oxo-2,5-dihydrofuran and 2-benzoyloxy-5-oxo-2,5-dihydrofuran.

[0012] Parijat Ray et al., “Synthesis of Bioacrylic Polymers from Dihydro-5-hydroxyl furan-2-one(2H-HBO)by Free and Controlled Radical Polymerization”, ACS OMEGA, Volume 3, Issue 2, February 20, 2018(2018-02-20), pages 2040-2048 describe the reaction of dihydro-5-hydroxyfuran-2-one with methacrylic anhydride to form the monomer dihydro-5-hydroxyfuran-2-one methacrylate. Homopolymerization and copolymerization were then carried out.

[0013] There is a need for coating compositions that utilize binder polymers obtainable from renewable raw materials and that have a higher reactivity and additional functional groups compared to known binder polymers. Summary of the Invention

[0015] Accordingly, in a first aspect, the present invention provides a coating composition comprising a binder polymer obtainable by copolymerizing a monomer mixture comprising a vinyl monomer M1 and a butenolide monomer M2,

[0016] wherein the vinyl monomer M1 has a 13 C chemical shift difference of at least 25 ppm between the α-C and β-C of the vinyl group, and

[0017] wherein the butenolide monomer M2 is a substituted 5-hydroxy-2(5H)-furanone of the general formula (I):

[0018]

[0019] wherein R 1 is -C(O)R 2 、-C(O)OR 2 、-C(O)NR 2 R 3 、-S(O)R 2 、-S(O2)R 2 、-C(O)SR 2 、-C(S)SR 2 and -C(S)NR 2 R 3 wherein R 2 is alkyl or aryl, and wherein R 3 is hydrogen, alkyl or aryl, or wherein R 2 and R 3 together with the nitrogen atom to which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl.

[0020] In a second aspect, the present invention provides a substrate coated with a coating deposited from a coating composition as defined herein.

[0021] In a third aspect, the present invention provides a binder polymer obtainable by copolymerizing a monomer mixture comprising a vinyl monomer M1 as defined herein and a butenolide monomer M2 as defined herein.

[0022] In a fourth aspect, the present invention provides a butenolide monomer which is a substituted 5-hydroxy-2(5H)-furanone of the general formula (III):

[0023]

[0024] wherein R 7 is C2-C 20 alkyl, -OCHR 8 R 9 , -NR 8 R 9 , -SR 9 wherein R 8 is alkyl or aryl, and wherein R 9 is hydrogen, alkyl or aryl, or when R 7 is -NR 8 R 9 , R 8 and R 9 together with the nitrogen atom to which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl.

[0025] It has been found that the binder polymer, when applied to a substrate and allowed to dry, provides a tack-free coating film having good hardness properties.

[0026] The binder polymer has a polymer backbone having functional groups that advantageously can provide crosslinking possibilities. Detailed Description of the Invention

[0028] The coating composition of the present invention comprises a binder polymer obtainable by copolymerizing a monomer mixture comprising a vinyl monomer M1 and a butenolide monomer M2.

[0029] The C chemical shift difference between the α-C and β-C of the vinyl used herein 13 can be determined from the chemical shifts reported in the spectral database of organic compounds ( https: / / sdbs.db.aist.go.jp / sdbs / cgi-bin / direct_frame_top.cgi ) managed by the National Institute of Advanced Industrial Science and Technology.

[0030] The alkyl used herein may be branched, unbranched, linear or cyclic. The alkyl may be saturated or unsaturated. It may be substituted or unsubstituted. The alkyl generally contains 1-20 carbon atoms, especially 1-12 carbon atoms, 1-6 carbon atoms or 1-4 carbon atoms. The alkyl may contain 2-20 carbon atoms, especially 2-12 carbon atoms, 2-6 carbon atoms or 2-4 carbon atoms. The alkyl may contain 1-3 carbon atoms, such as 1, 2 or 3 carbon atoms. Examples of alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, hexyl, lauryl, oleyl and cyclohexyl.

[0031] As used herein, cycloalkyl refers to a cyclic alkyl group. Cyclic heteroalkyl refers to a cyclic heteroalkyl group in which at least one carbon in the ring is replaced by a heteroatom. The heteroatom can be an atom other than nitrogen, oxygen or carbon. The cyclic heteroalkyl group can be a nitrogen-containing cyclic heteroalkyl group.

[0032] As used herein, aryl refers to an aromatic group. The aryl group can be substituted or unsubstituted. The aryl group usually contains 6 or 10 carbon atoms. The aryl group can be a phenyl group or a naphthyl group, especially a phenyl group. Heteroaryl refers to an aryl group containing a heteroatom, i.e., an atom other than carbon, in the aromatic ring. The heteroaryl group can be substituted or unsubstituted. The heteroaryl group usually contains 5 - 12 carbon atoms. Typical heteroatoms are oxygen or nitrogen.

[0033] M1 can have a 13 C chemical shift difference between the α-C and β-C of the vinyl group of at least 30 ppm, especially at least 35 ppm.

[0034] In the coating composition of the present invention, the vinyl monomer M1 can be a vinyl compound of the general formula (II):

[0035] R 4 CH=CH2 (II);

[0036] wherein R 4 is -OR 5 , -OC(O)R 5 , -N(R 6 )C(O)R 5 , -N(R 6 )C(O)OR 5 , -N(R 6 )C(S)R 5 , -N(R 6 )C(S)OR 5 , -N(R 6 )C(S)SR 5 and -SC(S)SR 5 any one of them, wherein R 5 is an alkyl group or an aryl group, and wherein R 6 is hydrogen, an alkyl group or an aryl group, or wherein R 5 and R 6 together with the atom to which they are attached form a nitrogen-containing cyclic heteroalkyl group or a nitrogen-containing heteroaryl group.

[0037] In one embodiment, R 4 is -OR 5 , -OC(O)R 5 or -N(R 6 )C(O)R 5 . Especially when R 4 is -OR 5 , R5 may be an alkyl group. When R 4 is -OR 5 , R 5 may in particular be a linear C1-C 12 alkyl group. When R 4 is -NR 6 C(O)R 5 , R 6 may be hydrogen and R 5 may be a C1-C 12 alkyl group, or R 5 and R 6 , together with the atom to which they are attached, in particular form a nitrogen-containing cyclic heteroalkyl group, in particular a C5-C7 nitrogen-containing cyclic heteroalkyl group.

[0038] In one embodiment, R 4 is -C(O)R 5 , where R 5 is a C2-C 12 alkyl group or an aryl group. R 5 may in particular be a C2-C6 alkyl group or a phenyl group.

[0039] In one embodiment, the vinyl monomer M1 is a vinyl ether, a vinyl ester or an N-vinyl monomer. M1 may be n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, 2-ethylhexyl vinyl ether, n-dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, vinyl neodecanoate, vinyl novate, N-vinylpyrrolidone, N-vinylimidazole, N-vinylformamide, N-vinylpyrrole, N-vinylcaprolactam or a mixture of two or more thereof. In one embodiment, the vinyl monomer M1 is vinyl neodecanoate or a mixture of vinyl neodecanoate and vinyl novate.

[0040] In the butenolide monomer M2 of the coating composition of the present invention, R 1 is -C(O)R 2 , -C(O)OR 2 , -C(O)NR 2 R 3 , -S(O)R 2 , -S(O2)R 2 , -C(O)SR 2 , -C(S)SR 2 and -C(S)NR 2 R 3 any one of them, where R 2 is an alkyl group or an aryl group, and where R 3 is hydrogen, an alkyl group or an aryl group, or where R 2 and R 3Together with the nitrogen atom to which they are attached, form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl. In one embodiment, R 1 can be -C(O)R 2 、-C(O)OR 2 、-C(O)NR 2 R 3 any one of.

[0041] In the butenolide monomer M2 of the coating composition of the present invention, R 2 can be C1-C 20 alkyl, C5-C7 cycloalkyl or phenyl. In one embodiment, R 2 can be C1-C 12 alkyl. In another embodiment, R 2 can be C5-C7 cycloalkyl. In another embodiment, R 2 can be phenyl.

[0042] In one embodiment, R 1 is -C(O)R 2 ; wherein R 2 is C2-C 12 alkyl or aryl. R 2 can especially be C2-C6 alkyl or phenyl.

[0043] In one embodiment, R 3 can be hydrogen or C1-C 20 alkyl. R 3 can especially be hydrogen or C1-C 12 alkyl, for example R 3 can be hydrogen.

[0044] In one embodiment, the base polymer of the present invention can be obtained by copolymerizing a monomer mixture comprising a vinyl monomer M1 and a butenolide monomer M2, wherein the vinyl monomer M1 has a 13 C chemical shift difference of at least 25 ppm between the α-C and β-C of the vinyl and wherein the butenolide monomer M2 is a substituted 5-hydroxy-2(5H)-furanone of the general formula (I):

[0045]

[0046] wherein R 1 is -C(O)OR 2 、-C(O)NR 2 R 3 、-S(O)R 2 、-S(O2)R 2 、-C(O)SR 2 、-C(S)SR2 , -C(S)NR 2 R 3 and -C(O)R 11 any one of, wherein R 2 is alkyl or aryl, R 3 is hydrogen, alkyl or aryl, or R 2 and R 3 together with the nitrogen atom to which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl, and wherein R 11 is aryl or C2-C 20 alkyl.

[0047] In one embodiment, R 1 can be -C(O)R 11 , -C(O)OR 2 , -C(O)NR 2 R 3 any one of.

[0048] In one embodiment of the base polymer of the present invention, R 2 is C1-C 12 alkyl, C5-C7 cycloalkyl or phenyl. In one embodiment, R 2 can be C2-C 12 alkyl. R 2 can be branched or unbranched, substituted or unsubstituted C1-C 12 alkyl. In another embodiment, R 2 can be C5-C7 cycloalkyl. In another embodiment, R 2 can be phenyl.

[0049] R 11 can be C2-C 12 alkyl, C5-C7 cycloalkyl or phenyl. In one embodiment, R 11 can be C2-C 12 alkyl. R 11 can be branched or unbranched, substituted or unsubstituted C2-C 12 alkyl. In another embodiment, R 11 can be C5-C7 cycloalkyl. In another embodiment, R 11 can be phenyl.

[0050] In one embodiment, R 1 is -C(O)R 11 ; wherein R 11 is aryl or C2-C 12 alkyl. R 11 can especially be C2-C6 alkyl or phenyl.

[0051] In one embodiment, R 3 can be hydrogen or C1-C 12 alkyl. R 3 can in particular be hydrogen.

[0052] In the base polymer of the present invention, the vinyl monomer M1 can be a vinyl compound of the general formula (II):

[0053] R 4 CH=CH2 (II);

[0054] wherein R 4 is -OR 5 , -N(R 6 )C(O)R 5 , -N(R 6 )C(O)OR 5 , -NR 6 C(S)R 5 , -NR 6 C(S)OR 5 , -NR 6 C(S)SR 5 , -SC(S)SR 5 and -OC(O)R 12 in any one of them, where R 5 is alkyl or aryl, R 6 is hydrogen, alkyl or aryl, or R 5 and R 6 together with the atoms to which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl, and wherein R 12 is aryl or C2-C 20 alkyl.

[0055] R 4 can be -OR 5 , -OC(O)R 12 or -N(R 6 )C(O)R 5 . In particular, when R 4 is -OR 5 , R 5 can be alkyl. When R 4 is -OR 5 , R 5 can in particular be linear C1-C 12 alkyl. When R 4 is -NR 6 C(O)R 5 , R 6 can be hydrogen and R 5 can be C1-C 12 alkyl, or R5 and R 6 Especially together with the atoms through which they are linked, they form a nitrogen-containing cyclic heteroalkyl group, especially a C5-C7 nitrogen-containing cyclic heteroalkyl group.

[0056] In one embodiment, R 4 is -OC(O)R 12 wherein R 12 is aryl or C2-C 12 alkyl. R 12 Especially can be C2-C6 alkyl or phenyl.

[0057] The monomer mixture can have any suitable molar ratio of vinyl monomer M1 to butenolide monomer M2. In one embodiment, the molar ratio of vinyl monomer M1 to butenolide monomer M2 can be in the range of 1:10 - 10:1, especially 1:5 - 5:1, for example 1:3 - 3:1, 1:2 - 2:1 or even 1:1.5 - 1.5:1. In one embodiment, the coating composition is an aqueous liquid coating composition comprising a base polymer emulsified in an aqueous phase.

[0058] In one embodiment, the monomer mixture can contain other ethylenically unsaturated monomers that can be copolymerized by free radical polymerization in addition to vinyl monomer M1 and butenolide monomer M2. Examples of such other monomers are acrylic acid, methacrylic acid, (meth)acrylic acid alkyl esters, styrene, methylene malonate, itaconic acid, vinyl acetate, divinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether and trivinyl ethers such as trimethylolpropane trivinyl ether. The presence of divinyl ether in the monomer mixture provides a base polymer with crosslinking functional groups.

[0059] In one embodiment, the monomer mixture contains less than 50 mol%, for example less than 30 mol%, less than 20 mol% or even less than 10 mol% of other ethylenically unsaturated monomers. In one embodiment, the monomer mixture contains 1 - 50 mol%, for example 2 - 30 mol%, especially 5 - 20 mol% of other ethylenically unsaturated monomers.

[0060] In another embodiment, the monomer mixture does not contain other ethylenically unsaturated monomers.

[0061] Copolymerization is a free radical polymerization method. The conditions that allow monomers to be copolymerized into an addition polymer by free radical polymerization are well known in the art. Suitable conditions generally include the presence of an initiator.

[0062] The copolymerization can be carried out in an organic solvent (solution polymerization). In solution polymerization, the monomer mixture is dissolved in a suitable organic solvent, heated to the desired reaction temperature and a suitable initiator is added in a suitable amount. During solution polymerization, the temperature is generally in the range of 50-180 °C, for example 70-160 °C. It should be understood that the optimum polymerization temperature depends on the decomposition temperature of the initiator used and the boiling point of any monomer under the pressure at which the polymerization is carried out. During the copolymerization, the monomer mixture can be dissolved in any suitable solvent. A suitable organic solvent is a solvent in which all the monomers in the monomer mixture and the resulting copolymer are soluble under the polymerization conditions. The organic solvent is usually an oxygen-containing organic solvent, such as an alcohol, a glycol ether, a glycol ester, an alkyl acetate, a ketone, an ester or a glycol ether / ester. For example, the solvent is a glycol ether or an alkyl acetate. 1-Methoxy-2-propanol and butyl acetate are specific solvents.

[0063] Alternatively, the copolymerization can be carried out as an emulsion polymerization process, in which the monomers are emulsified in an aqueous phase and then copolymerized. The emulsion polymerization can be carried out at a temperature in the range of 15-90 °C.

[0064] Any suitable initiator can be used. Suitable initiators are known in the art and include organic peroxides and azo initiators. Examples of azo initiators include azobisisobutyronitrile (AIBN) and 2,2'-azobis(2-methylbutyronitrile) (AMBN).

[0065] Examples of suitable organic peroxides include tert-butyl peroxy-3,5,5-trimethylhexanoate, benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, acetyl peroxide, tert-butyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxyoctanoate, tert-amyl peroxyoctanoate and tert-butyl peroxybenzoate. The initiator can be added in any suitable amount, generally up to 6 mol% based on the total molar amount of the ethylenically unsaturated monomers, for example in the range of 1-4 mol%. The total amount of the initiator can be added in two or three steps, i.e., a first amount is added at the start of the polymerization and additional amounts are added during the polymerization reaction.

[0066] Optionally, a chain transfer agent is used during the polymerization. Any suitable chain transfer agent can be used in a suitable amount. Suitable chain transfer agents are known in the art and include methyl 3-mercaptopropionate, 1-dodecanethiol, 1-octanethiol, mercaptoacetic acid, 2-hydroxy-1-ethanethiol and butenediol.

[0067] The copolymerization can be carried out batchwise, i.e., by charging all the monomers and the initiator at the start of the polymerization, or by gradually charging some of the monomers and / or the initiator during the copolymerization, i.e., under so-called starved-feed conditions.

[0068] It has been found that the copolymers thus obtained have properties that make them suitable for use as binder polymers in coating compositions. The binder polymer has a relatively high content of butenolide, which is a component that can be obtained from renewable raw materials. In particular, binder polymers can be obtained having a glass transition temperature measured by differential scanning calorimetry (DSC) according to ISO 11357-2 using a heating rate of 20 K / min in the range from -29 °C to +88 °C. Another advantageous property of the binder polymer is that it has a polymer backbone having functional groups (at the butenolide monomer) that can be used for crosslinking.

[0069] The coating composition can be a solvent-based or water-based liquid coating composition, or a powder coating composition, for example a liquid coating composition, in particular a water-based liquid coating composition in which the binder polymer is emulsified in the aqueous liquid phase.

[0070] The coating composition can contain other ingredients commonly used in coating compositions, such as color pigments, extender pigments, coalescing solvents and one or more additives, such as surfactants, defoamers, thickeners, leveling agents and biocides.

[0071] One aspect of the invention relates to a substrate coated with a coating deposited from the coating composition according to the invention. The substrate can be any suitable substrate, such as a wood, polymer, composite, metal or mineral substrate. The substrate can be a primed or bare substrate.

[0072] R 7 is any one of C2-C 20 alkyl, -OCHR 8 R 9 、-NR 8 R 9 、-SR 9 wherein R 8 is alkyl or aryl, and wherein R 9 is hydrogen, alkyl or aryl, or when R 7 is -NR 8 R 9 , R 8 and R 9 together with the nitrogen atom to which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl.

[0073] In one embodiment, in the butenolide compound of the invention R 7 is C2-C 12 alkyl. For example, R 7 can be C 12 H 23 、 i Pr or n Pr, in another embodiment R 7is -O-C1-C3 alkyl, such as O t Bu or OMe. In another embodiment, R 7 is -NHR 10 wherein R 10 is cycloalkyl or C1-C 12 alkyl. For example, R 10 is cyclohexane or C 12 H 25 .

[0074] The butenolides of the present invention may be compounds having any one of formulas (IV)-(XIII):

[0075]

[0076]

[0077]

[0078] The present invention is further illustrated by the following non-limiting examples. Example

[0079] Measurement Techniques

[0080] Monomer Conversion and Initial Reaction Rate

[0081] Method 1 (measuring monomer conversion and initial reaction rate by NMR):

[0082] 40 μL of the sample was diluted with CDCl3 (550 - 600 μL) in an NMR tube for reference. At different time points, 20 - 40 μL of the sample was taken from the reaction mixture with a microsyringe and diluted with CDCl3 (550 - 600 μL) in an NMR tube. All samples were analyzed by 1 1H NMR on a 400 MHz spectrometer (usually D1 = 5, ns = 8). After processing the spectra to correct the phase and baseline, the integration of the relevant peaks (one for each monomer) allowed the monitoring of the conversion. The initial reaction rate was calculated from the sampling over time according to the method described by Hermens et al., Sci. Adv. 2020; 6: eabe0026.

[0083] Method 2 (measuring monomer conversion by measuring the solid content):

[0084] The solid content of the polymer solution was determined according to ISO 3251 with an initial sample mass of 1.0 g, a test duration of 60 minutes at a temperature of 125 °C. The monomer conversion was calculated based on the measured solid content. The remaining monomer evaporated under the test conditions, while any formed polymer did not evaporate.

[0085] Number-average Molecular Weight (Mn) and Weight-average Molecular Weight (Mw) were Determined by GPC

[0086] The number-average and weight-average molecular weights were determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) (+1% acetic acid) or 2-MeTHF as the eluent (1 ml / min) on a styrene-divinylbenzene column calibrated with polystyrene standards.

[0087] The polydispersity index (PDI) was calculated by dividing the measured Mw by the measured Mn.

[0088] Glass Transition Temperature (Tg)

[0089] Tg was measured by differential scanning calorimetry (DSC) using a TA Instruments DSC Q2000 device in a modulation mode according to ASTM D3418.

[0090] A DSC cell filled with 6 + / - 1 mg of the sample and an empty DSC reference cell were heated from -80 °C to 110 °C at 5 °C / min in two consecutive runs in a differential scanning calorimeter (DSC) in a modulation mode (±1 °C every 40 seconds) using helium (50 ml / min) as the purge gas. Fourier transform enables the separation of the modulated heat flow into a heat capacity component (reversible heat flow) and a kinetic component (irreversible heat flow), which allows the separation of different simultaneous thermal events.

[0091] The heat capacity of the material changes rapidly at the Tg of the material (observed in the reversible heat flow curve), resulting in a significant drop in the reversible heat flow curve in a certain transition region. Tg was calculated at the inflection point (Tg(I)) for both runs.

[0092] The following vinyl ester and vinyl ether monomers were used:

[0093] - Dodecyl vinyl ether

[0094] - Vinyl neodecanoate (purchased from Hexion) VeoVa 10

[0095] - Vinyl neononanoate (purchased from Hexion) VeoVa 9

[0096] - N-Vinylpyrrolidone NVP

[0097] Butenolide monomers having the following R 1 groups were used:

[0098] - CH3 (5-methoxy-2(5H)-furanone or "methoxybutenolide")

[0099] - C(O)CH3 (5-acetoxy-2(5H)furanone or "acetoxybutenolide")

[0100] -C(O)CH(CH3)2 (5-isobutyryloxy-2(5H)-furanone or “isobutyryloxybutenolide”)

[0101] -C(O)C(CH3)3 (5-pivaloyloxy-2(5H)-furanone or “pivaloyloxybutenolide”)

[0102] -C(O)C6H5 (5-benzoyloxy-2(5H)-furanone or “benzoyloxybutenolide”)

[0103] -C(O)C 11 H 23 (5-dodecanoyloxy-2(5H)-furanone or “dodecanoyloxybutenolide”)

[0104] -C(O)C7H 14 C(H)=C(H)C8H 17 (5-oleyloxy-2(5H)-furanone or “oleyloxybutenolide”), where the double bond is cis

[0105] -C(O)CH2CH2C(O)OH (5-succinyloxy-2(5H)-furanone or “succinyloxybutenolide”)

[0106] -C(O)CH2CH2C(O)OCH3 (5-succinyloxy-2(5H)-furanone methyl ester)

[0107] -C(O)CH2CH2C(O) (bis(5-hydroxy-2(5H)-furanone) succinate)

[0108] -C(O)OCH3 (5-hydroxy-2(5H)-furanone methyl carbonate)

[0109] -C(O)OC(CH3) (5-hydroxy-2(5H)-furanone tert-butyl carbonate)

[0110] -C(O)NHC(H)C6H 10 (5-hydroxy-2(5H)-furanone cyclohexylcarbamate)

[0111] -C(O)NHC 12 H 25 (5-hydroxy-2(5H)-furanone dodecylcarbamate)

[0112] Use the following solvents and reagents:

[0113]

[0114] Use the following initiators:

[0115] tert-Butyl peroxy-3,5,5-trimethylhexanoate T42S

[0116] Comparative Preparation Example 1

[0117] Comparative Preparation Example 1

[0118] Methoxycrotonolactone

[0119] 5-Methoxy-2(5H)-furanone

[0120] Chemical formula: C5H5O3

[0121] Molecular weight: 114.1000

[0122] The product and its synthesis were previously described in Hermens et al., Sci. Adv. 2020; 6: eabe0026. 5-Hydroxy-2(5H)-furanone (100.0 g, 1 mol) was dissolved in 500 mL of anhydrous methanol and heated under reflux for 20 hours. The conversion was monitored by 1 1H NMR until all 5-hydroxy-2(5H)-furanone was consumed. The solvent was evaporated under reduced pressure and the crude product was distilled under reduced pressure (70 °C, 1.0×10 -2 mbar) to give 5-methoxy-2(5H)-furanone as a pale yellow oil (86.5 g, 0.76 mol, 76%).

[0123] Preparation Examples 1-13

[0124] Preparation Example 1

[0125] Acetoxycrotonolactone

[0126] 5-Oxo-2,5-dihydrofuran-2-yl acetate

[0127] Chemical formula: C6H5O4

[0128] Molecular weight: 142.1100

[0129] The product and its synthesis were previously described in G.C. Resende, E.S. Alvarenga, J.C.G. Galindo, F.A. Macias, J. Braz. Chem. Soc. 2012, 23(12), 2266 - 2270. In a flask under N2 atmosphere, hydroxybutenolide (1 equiv, 500 mg, 5.00 mmol, gray solid) was dissolved in anhydrous DCM (25 mL) and cooled to 0 °C with an ice bath. Acetic anhydride (1.6 equiv, 754 μL, 7.99 mmol) was added, and then a solution of DMAP (0.3 equiv, 183 mg, 1.50 mmol) in anhydrous DCM (1.5 mL) was added. The mixture was stirred at 0 °C for 1 h and then allowed to warm to room temperature. TLC (25% AcOEt / hexane, visualized with KMnO4) showed the formation of a new product at Rf = 0.37. The clear solution was washed with water (25 mL). After phase separation, the aqueous layer was further extracted with DCM (25 mL). The combined organic extracts were dried over sodium sulfate, filtered through cotton, and concentrated under reduced pressure. The residue was purified by automated column chromatography (15 g SiO2 column, 10 - 40% AcOEt / pentane, over 20 column volumes (CV)) with injection of the liquid using DCM. The collected fractions were concentrated to give pure acetyloxybutenolide (506 mg, 3.56 mmol, 71% yield) as a colorless liquid.

[0130] Preparation Example 2

[0131] Isobutyryloxycrotonolactone

[0132] 5 - Oxo - 2,5 - dihydrofuran - 2 - yl isobutyrate

[0133] Chemical formula: C8H 10 O4

[0134] Molecular weight: 170.1640

[0135] In a flask under N2 atmosphere, hydroxymaleic anhydride (90 wt% pure, 1.50 eq, 6.67 g, 4.00 mmol) was dissolved in anhydrous DCM (40 mL, [acid]=1 M). Isobutyric acid (1.00 eq, 3.70 mL, 40.0 mmol) and DMAP (5 mol%, 244 mg, 2.00 mmol) were added. The clear mixture (blue due to hydroxymaleic anhydride) was cooled to 0 °C with an ice bath. N,N'-Dicyclohexylcarbodiimide (DCC) (1.20 eq, 9.90 g, 48.0 mmol) was dissolved in anhydrous DCM (5 mL) and added dropwise at 0 °C over 5 min. After the addition, the ice bath was removed and the mixture was stirred at room temperature for 1 h. The mixture turned from blue to dark brown and had a precipitate. The reaction mixture was filtered through cotton wool, rinsed with DCM, to give a brown solid (urea) and a clear brown filtrate, which was concentrated in vacuo to a dark brown oil. The crude residue was purified by automated column chromatography (80 g SiO2 column, 5-30% AcOEt / pentane, over 15 CVs) with DCM injection of the liquid. The collected fractions were concentrated to give pure isobutyryloxymaleic anhydride (4.84 g, 28.4 mmol, 71% yield) as a yellow oil.

[0136] Preparation Example 3

[0137] Pivaloyloxycrotonolactone

[0138] 5-Oxo-2,5-dihydrofuran-2-yl pivalate

[0139] Chemical formula: C9H 12 O4

[0140] Molecular weight: 184.1910

[0141] Hydroxybutenolide (1 eq., 5.00 g, 50.0 mmol) was dissolved in anhydrous DCM (25 mL) and cooled to 0 °C in an ice bath. This caused (partial) precipitation of hydroxybutenolide. Trimethylacetic anhydride (1.2 eq., 12.2 mL, 60.0 mmol) was added, followed by a solution of DMAP (0.1 eq., 610 mg, 5.00 mmol) in anhydrous DCM (2.5 mL). The mixture was first stirred at 0 °C for 30 min and then allowed to warm to room temperature, which caused complete dissolution of the solid. The homogeneous mixture was further stirred at room temperature overnight (20 h total). During the reaction, the initial blue mixture turned dark green / brown. The reaction mixture was concentrated. The residue was purified by automated column chromatography (80 g SiO2 column, 5 - 30% AcOEt / pentane, 15 CVs) with DCM injection liquid. The collected fractions were concentrated to give pure pivaloyloxybutenolide (6.74 g, 36.6 mmol, 73% yield) as a pale yellow oil.

[0142] Preparation Example 4

[0143] Benzoyloxycrotonolactone

[0144] 5-oxo-2,5-dihydrofuran-2-yl benzoate

[0145] Chemical formula: C 11 H8O4

[0146] Molecular weight: 204.1810

[0147] The product was previously described in B.M. Trost, F.D. Toste, J. Am. Chem. Soc. 2003, 125(10), 3090 - 3100. Benzoyloxybutenolide was synthesized according to a procedure adapted from G.C. Resende, E.S. Alvarenga, J.C.G. Galindo, F.A. Macias, J. Braz. Chem. Soc. 2012, 23(12), 2266 - 2270. In a flask under N2 atmosphere, hydroxybutenolide (1 equiv, 160 mg, 1.60 mmol) was dissolved in anhydrous DCM (8 mL) and cooled to 0 °C with an ice bath. Benzoic anhydride (1.6 equiv, 579 mg, 2.56 mmol) was added, and then a solution of DMAP (0.3 equiv, 59 mg, 0.48 mmol) in anhydrous DCM (0.5 mL) was added. The mixture was stirred at 0 °C for 1 h and then allowed to warm to room temperature. Thin - layer chromatography (25% AcOEt / hexane, visualized with KMnO4) showed the formation of a new product at Rf = 0.47. The clear solution was washed with water (15 mL). After phase separation, the aqueous layer was further extracted with DCM (15 mL). The combined organic extracts were dried over sodium sulfate, filtered through cotton, and concentrated under reduced pressure. The residue was purified by automated column chromatography (15 g SiO2 column, 0 - 30% AcOEt / pentane, over 20 CV) with DCM injection liquid. The collected fractions were concentrated to give pure benzoyloxybutenolide as a white solid (236 mg, 1.16 mmol, 73% yield).

[0148] Preparation Example 5

[0149] Lauroyloxycrotonolactone

[0150] 5 - oxo - 2,5 - dihydrofuran - 2 - yl dodecanoate

[0151] Chemical formula: C 16 H 26 O4

[0152] Molecular weight: 282.3800

[0153] The lauroyloxybutenolide was synthesized according to the procedure adapted from Guo, Chin. J. Chem. 2005, 23, 1683. A solution of lauric acid (1 equiv, 1.00 g, 5.00 mmol) in anhydrous toluene (15 mL, [lauric acid]=0.33 M) was prepared in a reflux apparatus under N2 and stirring was initiated. Thionyl chloride (6.5 equiv, 2.4 mL, 3.9 g) was added to the clear colorless solution at room temperature. The mixture was heated to reflux for 4 h, during which the reaction mixture turned yellow. The reaction mixture was then concentrated under vacuum (water bath = 50 °C). The crude product was redissolved in anhydrous toluene (15 mL) and hydroxybutenolide (1 equiv, 500 mg, 5.00 mmol) was added to the resulting solution. The mixture was heated to reflux overnight. Upon heating, the initially insoluble hydroxybutenolide turned black and then dissolved. Thin layer chromatography [20% AcOEt / hexane, visualized with KMnO4] showed a distinct spot at Rf: 0.45 compared to hydroxybutenolide at Rf = 0.20. After cooling, the mixture was concentrated. The crude product was purified by automated column chromatography (15 g SiO2 column, AcOEt / pentane 0 - 25%, over 20 CV) using DCM as the eluent. The collected fractions were concentrated to give pure lauroyloxybutenolide as a white solid (925 mg, 3.28 mmol, 66% yield).

[0154] Preparation Example 6

[0155] Oleoyloxycrotonolactone

[0156] 5-Oxodihydrofuran-2-yl oleate

[0157] Chemical formula: C 22 H 36 O4

[0158] Molecular weight: 364.5260

[0159] In a flask under N2 atmosphere, hydroxybutenolide (1.00 equiv, 1.00 g, 10.0 mmol) was dissolved in anhydrous DCM (20 mL, [SM] = 0.5 M). Oleic acid (2.00 equiv, 5.64 g, 20.0 mmol) and DMAP (5 mol%, 61 mg, 0.50 mmol) in anhydrous DCM (2.5 mL) were added. The clear mixture was cooled to 0 °C with an ice bath. DCC (1.20 equiv, 2.47 g, 12.0 mmol) was dissolved in anhydrous DCM (2.5 mL) and added dropwise at 0 °C over 5 min. A white precipitate formed during the addition. The slurry then slowly turned brown over time. After 30 min, the ice bath was removed and the mixture was stirred at room temperature for 1 h until thin layer chromatography confirmed the complete consumption of hydroxybutenolide.

[0160] The reaction mixture was filtered, rinsed with DCM to give a white solid (urea) and a brown filtrate (ca. 50 mL), which was washed with saturated aqueous NaHCO3 (2 × 25 mL). The organic layer was dried over sodium sulfate, filtered, and then concentrated in vacuo to a brown oil. The residue was purified by automated column chromatography (40 g SiO2 column, 0 - 100% DCM / pentane, over 20 CV) using hexane injection. The collected fractions were concentrated to give pure oleoyloxybutenolide as a yellow oil that solidified at ca. 15 °C (950 mg, 2.61 mmol, 26% yield).

[0161] Preparation Example 7

[0162] Succinyloxycrotonolactone

[0163] 4 - oxo - 4 - ((5 - oxo - 2,5 - dihydrofuran - 2 - yl)oxy)butanoic acid

[0164] Chemical formula: C8H8O6

[0165] Molecular weight: 200.1460

[0166] Hydroxycrotonolide (1 equivalent, 1.00 g, 9.99 mmol) was dissolved in anhydrous DCM (20 mL) and cooled to 0 °C in an ice bath. Succinic anhydride (1.6 equivalents, 1.60 g, 16.0 mmol) was added, followed by a solution of DMAP (0.3 equivalent, 366 mg, 3.00 mmol) in anhydrous DCM (1 mL). The mixture was first stirred at 0 °C, during which time it changed from light blue to light green, and then allowed to warm to room temperature overnight. In the morning, the mixture became darker. Thin layer chromatography (50% AcOEt / hexane + 1 vol% AcOH, visualized with KMnO4) showed the formation of a new polar spot at Rf = 0.25. The reaction mixture was concentrated. The residue was purified by automated column chromatography (40 g SiO2 column, 10 - 60% AcOEt / pentane, over 25 CVs, then 60 - 100%, over 5 CVs) using DCM as the injection liquid solvent and adding 1 vol% AcOH in AcOEt. The collected fractions were concentrated to give succinyloxycrotonolide (1.37 g) as a white solid still containing trace amounts of succinic anhydride. Further purification by column chromatography (25 g SiO2 column, 10 - 60% AcOEt / pentane, over 25 CVs, then 60 - 100%, over 5 CVs) using solid injection (adsorbed on SiO2) and adding 1 vol% AcOH in AcOEt gave pure succinyloxycrotonolide (1.13 g, 5.63 mmol, 56% yield) as a white solid.

[0167] Preparation Example 8

[0168] Methyl Succinyloxycrotonolactone

[0169] Methyl (5-oxo-2,5-dihydrofuran-2-yl) succinate

[0170] Chemical formula: C9H 10 O6

[0171] Molecular weight: 214.1730

[0172] Succinyloxycrotonolide (1.00 equivalent, 200 mg, 1.00 mmol) was dissolved in anhydrous DCM (5 mL, [SM] = 0.2 M) in a flask under a N2 atmosphere. Methanol (3.00 equivalents, 121 μL, 3.00 mmol) and DMAP (5 mol%, 6 mg, 0.05 mmol) were added. The cloudy mixture was cooled to 0 °C in an ice bath. DCC (1.10 equivalents, 227 mg, 1.10 mmol) was added all at once at 0 °C. The mixture was stirred at 0 °C for 30 minutes and then at room temperature for 30 minutes.

[0173] The reaction mixture was filtered on a Büchner, rinsed with DCM, leaving a white solid and giving a brown filtrate, which was concentrated to a brown turbid oil. The residue was purified by automated column chromatography (15 g SiO2 column, 10 - 50% AcOEt / pentane, over 20 CV) under a liquid injection of DCM. The collected fractions were concentrated to give pure methyl succinyloxybutenolide as a colorless semi-solid (163 mg, 0.761 mmol, 76% yield).

[0174] Preparation Example 9

[0175] Succinyloxy Di-crotonolactone

[0176] Di(5-oxo-2,5-dihydrofuran-2-yl) succinate

[0177] Chemical formula: C 12 H 10 O8

[0178] Molecular weight: 282.2040

[0179] In a flask under a N2 atmosphere, succinyloxybutenolide (1.00 equiv, 500 mg, 2.50 mmol) and hydroxybutenolide (2.00 equiv, 500 mg, 5.00 mmol) were dissolved in anhydrous DCM (20 mL, [SM] = 0.125 M). DMAP (5 mol%, 15 mg, 0.13 mmol) was added. The clear mixture was cooled to 0 °C in an ice bath. DCC (1.20 equiv, 618 mg, 3.00 mmol) was dissolved in anhydrous DCM (2 mL) and added dropwise at 0 °C over 5 min. During the addition, the turbid pale yellow mixture first became clear pale yellow and then turned back to turbid with solid precipitation. The slurry then slowly turned brown over time. After 1 h, the ice bath was removed and the mixture was stirred at room temperature for 1 h. The reaction mixture was filtered, rinsed with DCM, giving a white solid (urea) and a clear brown filtrate, which was concentrated in vacuo to a brown solid. The residue was purified by automated column chromatography (25 g SiO2 column, 0 - 20% AcOEt / pentane, over 20 CV) under a solid injection with neutralized silica. The collected fractions were concentrated to give pure succinyloxy-di-butenolide as a white solid (532 mg, 1.88 mmol, 75% yield).

[0180] Preparation Example 10

[0181] Methylcarbonyloxycrotonolactone

[0182] Methyl (5-oxo-2,5-dihydrofuran-2-yl) carbonate

[0183] Chemical formula: C6H5O5

[0184] Molecular weight: 158.1090

[0185] Methyl carbonatoxycrotonolide was synthesized according to the procedure adapted from Zhang et al., Org. Lett. 2003, 5(26), 5015. Hydroxycrotonolide (1.00 equiv, 500 mg, 5.00 mmol) was introduced into a 25 mL round-bottom flask. An olive-shaped stir bar was added, and the flask was covered with a rubber septum and placed under vacuum. After 5 minutes, the flask was backfilled with nitrogen, and then two more vacuum-nitrogen cycles were performed. Anhydrous DCM (10 mL, [SM] = 0.5 M) was added, and the mixture was stirred vigorously (1000 rpm) at room temperature until the solid was completely dissolved. Then the clear solution was cooled to -10 °C using a saturated NH4Cl-ice bath. This made the solution turbid, probably because hydroxycrotonolide is less soluble in DCM at this temperature. Methyl chloroformate (1.10 equiv, 425 (1L, 5.50 mmol) was added to the mixture via syringe through the septum at -10 °C. Then DIPEA (1.20 equiv, 1.00 mL, 6.00 mmol) was added dropwise via syringe through the septum within 5 minutes. After the addition (during which the solution turned yellow), the mixture was stirred for 2 hours, during which the temperature rose from -10 °C to 0 °C and the color changed from yellow to dark red. Thin-layer chromatography (30% AcOEt / hexane, developed with KMnO4) showed a new spot at Rf = 0.45. The reaction mixture was diluted with DCM (10 mL) and washed twice with water (10 mL). The red organic layer was dried over sodium sulfate, filtered, and concentrated to give a red crude oil. It was purified by automated column chromatography (25 g SiO2 column, 10 - 50% AcOEt / pentane, over 40 CVs, then 50 - 100%, over 10 CVs) using DCM as the eluent. The collected fractions were concentrated to give a nearly colorless oil, a 2:1 mixture of the desired product and methoxycrotonolide. Thin-layer chromatography showed only one spot. The methoxycrotonolide was removed by distillation overnight on a rotary evaporator under high vacuum (<1 mbar) (water bath set at 60 °C). In the morning, the methoxycrotonolide had evaporated, leaving pure methyl carbonatoxycrotonolide (278 mg, 1.76 mmol, 35% yield) as a pale brown oil.

[0186] Preparation Example 11

[0187] tert-Butylcarbonyloxycrotonolactone

[0188] tert-Butyl (5-oxo-2,5-dihydrofuran-2-yl) carbonate

[0189] Chemical formula: C9H 12 O5

[0190] Molecular weight: 200.1900

[0191] Add hydroxybutenolide (1.0 equivalent, 1.00 g, 10.0 mmol) and an olive-shaped stir bar to a 50 mL round-bottom flask. Place the flask under vacuum and heat gently, which causes bubbling (presumably removal of residual solvent and water). Backfill the flask with N2 and add anhydrous DCM (20.0 mL, [SM] = 0.5 M). Add DMAP (25 mol%, 305 mg, 2.50 mmol) to the pale yellow solution, which dissolves rapidly. Cool the solution to 0 °C in an ice bath and add tert-butoxycarbonyl (Boc) anhydride (1.5 equivalents, 3.4 mL, 15.0 mmol) dropwise over 5 minutes. No gas evolution is observed. Stir the solution at 0 °C for 1 hour. Remove the ice bath and allow the temperature to rise to room temperature. A strong evolution of gas suddenly occurs during warming, along with a rapid color change from pale yellow to pink to red to brown. Gas evolution stops after only a few minutes.

[0192] Add saturated aqueous NH4Cl solution (25 mL) to the reaction mixture. Separate the layers and wash the organic layer again with saturated aqueous NH4Cl solution (25 mL). Extract the combined aqueous layers with DCM (25 mL). Wash the combined organic extracts with water (25 mL), dry over sodium sulfate, filter, and concentrate to a dark oil. The residue is purified by automated column chromatography (40 g SiO2 column, 0 - 30% AcOEt / pentane, over 15 CV) using DCM injection fluid. Concentrate the collected fractions to give pure tert-butoxycarbonyloxybutenolide (1.06 g, 5.27 mmol, 53% yield) as a light oil that solidifies overnight.

[0193] Preparation Example 12

[0194] Cyclohexylcarbamoyloxycrotonolactone

[0195] 5-Oxo-2,5-dihydrofuran-2-yl cyclohexylcarbamate

[0196] Chemical formula: C 11 H 15 NO4

[0197] Molecular weight: 225.2440

[0198] To a 25 mL round-bottom flask was added hydroxybutenolide (1.00 equiv, 1.00 g, 10.0 mmol) and an olive-shaped stir bar. The flask was placed under vacuum and gently heated, which caused bubbling (presumably removal of residual solvent and water). The flask was backfilled with N2 and anhydrous THF (10.0 mL, [SM] = 1.0 M) was added. To the pale yellow solution was added cyclohexyl isocyanate (1.10 equiv, 1.4 mL, 11.0 mmol) and dibutyltin dilaurate (1 mol%, 60 μL, 0.10 mmol) in sequence. The reaction mixture was stirred overnight at room temperature, during which time it became turbid brown. The reaction mixture was concentrated to a dark oil. The crude residue was purified twice by automated column chromatography (40 g SiO2 column, 10 - 50% AcOEt / pentane, over 20 CV) under DCM injection liquid. The collected fractions were concentrated to give pure cyclohexyl carbamoyloxybutenolide (820 mg, 3.64 mmol, 36% yield) as a colorless viscous oil.

[0199] Preparation Example 13

[0200] Dodecylcarbamoyloxycrotonolactone

[0201] 5-Oxo-2,5-dihydrofuran-2-yl dodecylcarbamate

[0202] Chemical formula: C 17 H 29 NO4

[0203] Molecular weight: 311.4220

[0204] Dodecylcarbamoyloxybutenolide (502 mg, 1.61 mmol) was prepared from hydroxybutenolide (500 mg, 5.00 mmol) in a manner similar to the preparation of Preparation Example 12 (cyclohexyl carbamoyloxybutenolide), with a yield of 32% after purifying the residue twice by automated column chromatography (25 g SiO2 column, 5 - 35% AcOEt / pentane, over 40 CV) under DCM injection liquid.

[0205] Examples 1-14 and Comparative Examples 1, 2

[0206] To a screw-cap 4-vial equipped with a 10 mm stir bar and septum was added one of Preparation Examples 1 - 13 and dodecyl vinyl ether (total 2 mmol), an internal standard (usually 1,3,5-trimethoxybenzene, 1 mmol), and a solvent (1-methoxypropan-2-ol, diethyl carbonate, or butyl acetate, 500 μL, [monomer] = 4 M).

[0207] Homogenize the mixture and, if necessary, heat briefly (e.g., in the case of insoluble monomers), then dilute 40 μL of the sample in an NMR tube with CDCl3 (550 - 600 μL) for reference. Then seal the vial and preheat it at 120 °C for 1 - 2 minutes. Add Trigonox 42S (60 μmol, 3 mol% relative to the monomer) to the hot mixture via a microsyringe through the septum, corresponding to t = 0. At different time points, take 20 - 40 μL of the sample from the reaction mixture with a microsyringe and dilute it in an NMR tube with CDCl3 (550 - 600 μL).

[0208] Analyze the polymer by gel permeation chromatography in THF or 2-MeTHF, detected by refractive index relative to polystyrene calibration.

[0209] The monomer conversion and the initial reaction rate are calculated according to Method 1 as described above.

[0210] Table 1

[0211]

[0212] The results show that a wide variety of butenolide monomers can be copolymerized using free radical initiation. In addition, the polymers of Examples 1 - 14 differently have a higher initial polymerization rate, higher conversion, higher number average molecular weight (M n ) or higher polydispersity index (PDI) than Comparative Example 1 or Comparative Example 2.

[0213] Examples 15, 16, 17 and Comparative Examples 3, 4

[0214] The base polymer is prepared by adding the butenolide monomer and Dowanol PM into a three-necked round-bottom flask equipped with a reflux condenser. Heat the mixture to a temperature of 125 °C and feed the vinyl monomer and tert-butyl peroxy-3,5,5-trimethylhexanoate (Trigonox 42S, purchased from Nouryon) in additional Dowanol PM under nitrogen protection at reflux conditions while maintaining the temperature at 125 °C over 2 hours. Then add some initiator and continue the reaction for 1 hour; then add more initiator and continue the reaction for another 1 hour. Cool the reaction mixture to room temperature. The calculated solids content (based on the total weight of the monomer, initiator, and solvent, the weight of the monomer and initiator) is 43 wt%. The molar ratio of the butenolide monomer to the vinyl monomer is 1:1 in each case.

[0215] The different base polymers prepared and the measured properties (monomer conversion, Tg, and molecular weight distribution) are shown in Table 2. The monomer conversion is measured according to Method 2 as described above.

[0216] Use a doctor blade to scrape a 200-μm wet film of Example 16 and Comparative Example 4 respectively on a glass plate. Dry the wet film at 23 °C and 50% relative humidity for 7 days. A transparent non-tacky coating is obtained. Determine the pendulum hardness (Persoz hardness) according to ISO 1522. Measure the time for the amplitude of the pendulum to decrease from 12 degrees to 4 degrees.

[0217] Table 2:

[0218]

[0219] *Formed a sticky film - Persoz hardness not tested

[0220] **Film formation did not occur - Persoz hardness not tested

[0221] These examples show that Examples 15 - 17 have increased monomer conversion without affecting the molecular weight distribution when using the same synthesis procedure as Comparative Examples 3 and 4. The base polymer film can form a non-tacky coating, and the hardness of the coating can be changed by selecting comonomers (blends). In addition, a non-tacky film can be produced from Example 16; it has sufficient Persoz hardness.

Claims

1. A coating composition comprising a binder polymer obtainable by copolymerizing a monomer mixture comprising a vinyl monomer M1 and a butenolide monomer M2, wherein the vinyl monomer M1 has a 13 chemical shift difference of at least 25 ppm between the α-C and β-C of the vinyl group, and wherein the butenolide monomer M2 is a substituted 5-hydroxy-2(5H)-furanone of the general formula (I): wherein R 1 is -C(O)R 2 、-C(O)OR 2 、-C(O)NR 2 R 3 、-S(O)R 2 、-S(O2)R 2 、-C(O)SR 2 、-C(S)SR 2 and -C(S)NR 2 R 3 is any one of, wherein R 2 is alkyl or aryl, and wherein R 3 is hydrogen, alkyl or aryl, or wherein R 2 and R 3 together with the nitrogen atom to which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl; and Among them, the 13 C chemical shift difference between the α-C and β-C of vinyl is determined by the chemical shifts reported in the organic compound spectral database managed by the National Institute of https: / / sdbs.db.aist.go.jp / sdbs / cgi-bin / direct_frame_top.cgi ) 2. The coating composition according to claim 1, wherein the vinyl monomer M1 is a vinyl compound of the general formula (II): R 4 CH=CH2 (II); wherein R 4 is -OR 5 、-OC(O)R 5 、-N(R 6 )C(O)R 5 、-N(R 6 )C(O)OR 5 、-NR 6 C(S)R 5 、-NR 6 C(S)OR 5 、-NR 6 C(S)SR 5 and -SC(S)SR 5 and wherein R 5 is alkyl or aryl, and wherein R 6 is hydrogen, alkyl or aryl, or wherein R 5 and R 6 together with the atoms to which they are attached form a nitrogen-containing cyclic heteroalkyl or a nitrogen-containing heteroaryl.

3. The coating composition according to claim 2, wherein R 4 is -OR 5 , -OC(O)R 5 or -N(R 6 )C(O)R 5 .

4. The coating composition according to any one of claims 1-3, wherein M1 is n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, 2-ethylhexyl vinyl ether, n-dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, vinyl neodecanoate, vinyl neodecanoate, N-vinylpyrrolidone, N-vinylimidazole, N-vinylformamide, N-vinylpyrrole, N-vinylcaprolactam or a mixture of two or more thereof.

5. The coating composition according to any one of claims 1-4, wherein R 1 is -C(O)R 2 -C(O)OR 2 -C(O)NR 2 R 3 or any one of them.

6. The coating composition according to any one of claims 1-5, wherein R 2 is C1-C 20 alkyl, C5-C7 cycloalkyl or phenyl.

7. A coating composition according to any one of claims 1-6, wherein R 3 is hydrogen.

8. The coating composition according to any one of claims 1-7, wherein the monomer mixture comprises the vinyl monomer M1 and the butenolide M2 in a molar ratio in the range of 1:5 - 5:

1.

9. The coating composition according to any one of claims 1-8, which is an aqueous liquid coating composition comprising a binder polymer emulsified in an aqueous phase.

10. A substrate coated with a coating deposited from a coating composition as defined in any one of claims 1-9.

11. A binder polymer obtainable by copolymerizing a monomer mixture comprising a vinyl monomer M1 as defined in any one of claims 1-9 and a butenolide monomer M2 as defined in any one of claims 1-9.

12. The base polymer according to claim 11, wherein the vinyl monomer M1 has a 13 C chemical shift difference of at least 25 ppm between the α-C and β-C of the vinyl group, and wherein the butenolide monomer M2 is a substituted 5-hydroxy-2(5H)-furanone of the general formula (I): wherein R 1 is -C(O)OR 2 、-C(O)NR 2 R 3 、-S(O)R 2 、-S(O2)R 2 、-C(O)SR 2 、-C(S)SR 2 、-C(S)NR 2 R 3 and -C(O)R 11 wherein R 2 is alkyl or aryl, R 3 is hydrogen, alkyl or aryl, or wherein R 2 and R 3 together with the nitrogen atom to which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl, and wherein R 11 is aryl or C2-C 20 alkyl.

13. The binder polymer according to claim 12, wherein the vinyl monomer M1 is a vinyl compound of the general formula (II): R 4 CH=CH2 (II); wherein R 4 is -OR 5 , -N(R 6 )C(O)R 5 , -N(R 6 )C(O)OR 5 , -NR 6 C(S)R 5 , -NR 6 C(S)OR 5 , -NR 6 C(S)SR 5 , -SC(S)SR 5 and -OC(O)R 12 , wherein R 5 is alkyl or aryl, R 6 is hydrogen, alkyl or aryl, or wherein R 5 and R 6 together with the atoms to which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl, and wherein R 12 is aryl or C2-C 20 alkyl.

14. A butenolide monomer which is a substituted 5-hydroxy-2(5H)-furanone of the general formula (III): wherein R 7 is C2-C 20 alkyl, -OCHR 8 R 9 , -NR 8 R 9 , -SR 9 any one of, wherein R 8 is alkyl or aryl, and wherein R 9 is hydrogen, alkyl or aryl, or when R 7 is -NR 8 R 9 , R 8 and R 9 together with the nitrogen atom to which they are attached form a nitrogen-containing cyclic heteroalkyl or nitrogen-containing heteroaryl.

15. The butenolide monomer according to claim 14, which is a compound having any one of the formulas (IV)-(XIII):

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