Bio-based monomers and polymers made from them

Abstract

This document discloses monomers of hydroxyphenyl butanone methacrylate (FMA) or raspberry ketone methacrylate (RKMA) having the following structures: and gingerone methacrylate (ZMA) having the following structures. Homopolymers and copolymers using the same monomers are also disclosed. Categories of methacrylate monomers comprising bio-based and reactive ketone moieties are also disclosed. Paint compositions made from copolymers including FMA and / or ZMA are also disclosed.

Description

Invention Field

[0001] This invention relates to a novel class of bio-based monomers and homopolymers, as well as novel copolymers made from said bio-based monomers. The invention also relates to a novel class of crosslinkable bio-based monomers, which, when polymerized with other monomers, produce film-forming polymers that can be used in building compositions. When said building composition is applied to a substrate and evaporates in a liquid phase, the film-forming polymer crosslinks with a crosslinking agent in the liquid phase to form a solid film. Background of the Invention

[0003] Biological and / or renewable compounds such as vanillin and vanillyl alcohol (originally extracted from vanilla plantifolia beans and more recently from lignin) have been used in the cosmetics and fragrance industries and have been used to flavor foods and beverages. Vanillin and vanillyl alcohol have been synthesized as monomers having hydroxyl and aldehyde reactive sites. These monomers can be homopolymerized or copolymerized, as discussed in U.S. Patent Application Publication No. US2018 / 0201703 (Methacrylated Vanillin (MV) and Methacrylated Vanillyl Alcohol (MVA)) by Kessler et al. and U.S. Patent Application Publication No. US2014 / 0275435 by Holmberg et al., which are incorporated herein by reference in their entirety.

[0004] To form a more robust solid film from waterborne architectural compositions, crosslinkable monomers (such as diacetone acrylamide (DAAM)) are copolymerized with other monomers (such as acrylic monomers, vinyl monomers, styrene monomers, and / or urethane monomers) to form a latex adhesive. After the architectural composition is applied to a substrate and the aqueous phase evaporates, the DAAM portion utilizes its ketone reactive sites to react in the aqueous phase with crosslinking compounds (such as diamines) or dihydrazides (such as adipic acid dihydrazides (ADH)), causing the latex resin to self-crosslink to form a more robust film, such as a film with higher scrub resistance. Such crosslinking or self-crosslinking mechanisms are discussed in commonly owned U.S. Patent No. 9,040,617 B2, which is incorporated herein by reference in its entirety.

[0005] Due to the difference between the aldehyde reaction site and the ketone reaction site on DAAM monomers, the use of MV monomers as crosslinkable monomers in film-forming latex resins in building compositions remains unclear. Therefore, other crosslinkable monomers, preferably bio-based crosslinkable monomers, are still needed, whose function in building compositions is similar to or superior to that of DAAM. Invention Overview

[0007] Therefore, this invention relates to a novel class of bio-based monomers and homopolymers, as well as novel copolymers made from said novel bio-based monomers and other monomers. The invention also relates to a novel class of crosslinkable bio-based monomers, which, when copolymerized with other monomers, form film-forming polymers for use in building compositions. When said building composition is applied to a substrate and evaporates in a liquid phase, the film-forming polymer crosslinks with a crosslinking agent in the liquid phase to form a solid film.

[0008] The present invention also relates to a class of methacrylate monomers comprising a bio-based moiety and a reactive ketone moiety.

[0009] The present invention also relates to hydroxyphenyl butanone methacrylate or raspberry ketone methacrylate monomers having the following structures:

[0010]

[0011] The present invention also relates to homopolymers made from the aforementioned hydroxyphenyl butyl ketone methacrylate monomer, and to copolymers made from monomers including hydroxyphenyl butyl ketone methacrylate monomer. The copolymer is capable of forming a film on a substrate upon evaporation of the aqueous or solvent-based monomer. A portion of the copolymer formed from the hydroxyphenyl butyl ketone methacrylate monomer is capable of crosslinking with dihydrazide, diamine, or other suitable crosslinking agents in an aqueous phase, preferably upon / as the aqueous phase evaporates.

[0012] The present invention also relates to gingerone methacrylate having the following structure:

[0013]

[0014] The present invention also relates to homopolymers made from the gingerone methacrylate monomer, and to copolymers made from monomers including gingerone methacrylate monomer. The copolymer is capable of forming a film on a substrate upon evaporation of the aqueous or solvent base. A portion of the copolymer formed from the gingerone methacrylate monomer is capable of crosslinking with dihydrazide, diamine, or other suitable crosslinking agents in an aqueous phase, preferably upon / as the aqueous phase evaporates. Brief description of the attached diagram

[0016] In the accompanying drawings, which form part of and are to be read in conjunction with the specification, the same reference numerals are used to indicate the same parts in the various views:

[0017] Figure 1 These are photographs of TLC tests on samples of raspberry ketone and the hydroxyphenyl butyl ketone methacrylate (FMA) monomer of the present invention, as well as mixtures thereof.

[0018] Figure 2 The hydroxyphenyl butyl ketone methacrylate monomer of the present invention is shown. 13C-NMR spectrum.

[0019] Figure 3 The hydroxyphenyl butyl ketone methacrylate monomer of the present invention is shown. 1 H-NMR spectrum.

[0020] Figure 4 The FTIR spectrum of raspberry ketone is shown.

[0021] Figure 5 The FTIR spectrum of the hydroxyphenyl butyl ketone methacrylate monomer of the present invention is shown;

[0022] Figure 6 Showing Figure 4 and 5 The FTIR spectrum.

[0023] Figures 7(a)-(b) show the results of GC-MS analysis of the crude hydroxyphenyl methyl ketone methacrylate monomer mixture.

[0024] Figures 8(a)-(c) show the MS results of some impurities present in the crude product mixture of Figure 7(a); these were identified as methacrylic anhydride, raspberry ketone and raspberry ketone acetate components, respectively.

[0025] Figure 9 The FTIR spectra of the monomers hydroxyphenyl methyl ketone methacrylate and hydroxyphenyl methyl ketone methacrylate homopolymers of the present invention are shown.

[0026] Figure 10 The image shows the DSC plot of the homopolymer of hydroxyphenyl methyl ethyl ketone methacrylate, displaying its glass transition temperature (Tg).

[0027] Figure 11 (A)-(D) are photographs of dried film samples of the FMA-containing copolymer and the comparative copolymer of the present invention, respectively, with and without ADH, after the swelling ratio test.

[0028] Figure 12 These are TLC photographs of samples of gingerone, the gingerone methacrylate (ZMA) monomer of the present invention, and mixtures thereof.

[0029] Figure 13 The gingerone methacrylate monomer of the present invention is shown. 13 C-NMR spectrum.

[0030] Figure 14 The gingerone methacrylate monomer of the present invention is shown. 1 H-NMR spectrum.

[0031] Figure 15 The FTIR spectrum of gingerone is shown.

[0032] Figure 16 The FTIR spectrum of the gingerone methacrylate monomer of the present invention is shown.

[0033] Figure 17 Showing Figure 15 and 16 The FTIR spectrum.

[0034] Figure 18 This is a DSC plot showing the glass transition temperature (Tg) of the ZMA monomer.

[0035] Figure 19 (A)-(F) are photographs of dried film samples containing copolymers of DAAM, FMA, and ZMA after swelling ratio tests, with and without ADH.

[0036] Detailed description of the preferred implementation scheme

[0037] Compounds with ketone reaction sites similar to DAAM were studied and synthesized, including, but not limited to, biologically based or renewable compounds.

[0038]

[0039] This produces monomers that can be polymerized into homopolymers, copolymers, and crosslinkable portions of copolymers. Exemplary compounds having ketone reactive sites include, but are not limited to, raspberry ketone and gingerone. Other suitable compounds are discussed below.

[0040] In one embodiment, raspberry ketone is used as a starting material. Raspberry ketone is a naturally occurring compound and is the main aromatic compound of red raspberries. It is also found in cranberries and blackberries and can be extracted from these fruits. Raspberry ketone can also be synthesized from non-biological sources. Raspberry ketone is also known as 4-(4-hydroxyphenyl)butane-2-one (IUPAC); p-hydroxybenzylacetone; 4-(p-hydroxyphenyl)-2-butanone; hydroxyphenylbutanone; oxyphenylon; raspberry ketone; and rasketone.

[0041] Structurally, raspberry ketones contain an aromatic benzene ring, which is attached to a reactive hydroxyl (-OH) site at one end and to a ketone site at the other end, although connected by spacer groups or intermediate atoms, as shown below:

[0042]

[0043] The inventors of this invention believe that the hydroxyl reaction site allows raspberry ketone to react with another compound or monomer to synthesize a new monomer. A preferred compound or monomer is methacrylic anhydride, which is a reactive monomer that can be used to prepare other monomers. Methacrylic anhydride has two acyl groups bonded to a single oxygen atom and has the following structure,

[0044]

[0045] Example 1: Two-phase reaction between raspberry ketone and methacrylic anhydride

[0046] A 16 wt% aqueous solution of sodium hydroxide (NaOH) was added to a solution of raspberry ketone, methacrylic anhydride, and dimethylaminopyridine (DMAP) catalyst in dichloromethane (CH2Cl2) solvent. Dichloromethane is immiscible with water and is heavier than water (density 1.33 g / ml). The mixture was stirred at room temperature (RT or about 77°F) for about 1 / 2 hour. This procedure is much more efficient than the following reactions (close to the quantitative consumption of raspberry ketone starting material): the pure reaction of raspberry ketone with acetic anhydride at elevated temperature in the presence of DMAP, or the solvent-free two-phase reaction of raspberry ketone and acetic anhydride with 16 wt% aqueous NaOH at room temperature. The organic phase was separated and washed with deionized (DI) water, 10 wt% aqueous hydrochloric acid (HCl), deionized water, 10 wt% aqueous sodium bicarbonate (NaHCO3), and deionized water, respectively. The organic phase was separated and dried over magnesium sulfate (MgSO4). The solution is then filtered and evaporated to produce new monomers, hydroxyphenyl methyl ketone methacrylate (FMA) or raspberry ketone methacrylate (RKMA), which are transparent, colorless liquids at room temperature. Upon aging, the material may undergo a phase transformation into a waxy, off-white solid.

[0047]

[0048] As confirmed, the hydroxyl reaction site of raspberry ketone was used to react and bond with the acyl moiety of methacrylic anhydride. In this example, 1.1 moles of methacrylic anhydride were reacted with 1 mole of raspberry ketone. Besides the resulting hydroxyphenylbutanone methacrylate monomer, other compounds remaining in the mixture included residual starting materials raspberry ketone and methacrylic anhydride.

[0049] As described below, analytical tools such as thin-layer chromatography (TLC) are used to focus on hydrogen and carbon-13, respectively. 1 H-NMR and 13 The synthesis of hydroxyphenylbutanone methacrylate was confirmed by C-NMR (nuclear magnetic resonance) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and gas chromatography-mass spectrometry (GC-MS).

[0050] Thin-layer chromatography (TLC): A sample containing a mixture of hydroxyphenyl methyl ketone methacrylate and raspberry ketone, or only hydroxyphenyl methyl ketone methacrylate and only raspberry ketone, is spotted or deposited near the bottom of a supporting substrate (e.g., aluminum or glass) and covered with a stationary phase, typically silica gel. TLC tests measure the affinity of each composition in the sample for the stationary phase and for the mobile phase (which is a solvent or a mixture of solvents). The supporting substrate on which the sample is spotted is held vertically with its bottom end in the solvent, and the solvent moves upward along the supporting substrate by capillary action. Different compounds will move upward along the supporting substrate at different rates or distances depending on their polarity. Generally, more polar compounds move upward along the supporting substrate more slowly than less polar compounds.

[0051] As in Figure 1 To best illustrate, the raspberry ketone spot is deposited on the left, and the hydroxyphenyl butyl ketone methacrylate labeled "171" is deposited on the right. A spot containing a mixture of both is deposited between them. The supporting substrate is rotated vertically to bring the spots close to the bottom, and then the spots are eluted, i.e., by washing with a solvent mixture containing approximately 90% toluene and approximately 10% acetone to remove or move the adsorbed material upwards. Figure 1 The results showed that the raspberry ketone spot shifted upwards by a first short distance, while the hydroxyphenyl methyl ketone methacrylate spot shifted upwards by a second, longer distance. Intriguingly, the mixture's spots separated into two: one at the first distance for raspberry ketone and the other at the second distance for hydroxyphenyl methyl ketone. TLC experiments indicated that hydroxyphenyl methyl ketone methacrylate differed from, or at least possessed a different polarity (more hydrophobic) from, the starting material raspberry ketone.

[0052] Retention factor (R) f It can be used for quantitative TLC analysis, which is the ratio of the distance that hydroxyphenyl methyl ketone methacrylate moves upward along the supporting substrate to the distance that the solvent mixture moves upward. Figure 1 R of hydroxyphenyl methyl ketone methacrylate f It is approximately 0.55, and the R of raspberry ketone is... f The value is approximately 0.25.

[0053] Nuclear Magnetic Resonance (NMR) spectroscopy: NMR spectroscopy measures the selective absorption of high-frequency radio waves by certain atomic nuclei affected by an external magnetic field. The sample is placed in this magnetic field; when nuclei aligned with the external magnetic field are excited to the opposite state by radio frequency (RF) waves, an NMR signal is generated, and the subsequent emission of the absorbed RF energy is measured. The intramolecular magnetic field of atoms in a molecule alters the resonance frequency required for this magnetic field to "flip," thus providing information about molecular structure and functional groups. Two NMR experiments were performed on hydroxyphenylbutanone methacrylate.13 C-NMR is tuned to carbon-13. Although the most common carbon isotope is carbon-12 (which does not appear in NMR), a sufficient number of carbon-13 atoms present in organic molecules can reveal information about their structure. 1 H-NMR is tuned to the hydrogen nucleus (commonly called the proton). The structures of hydroxyphenyl butanone methacrylate with carbon labeled from "a" to "l" and those with hydrogen labeled from "a" to "h" are shown below:

[0054]

[0055] NMR analysis is typically performed on samples dissolved in a solvent. Due to the hydrophobicity of the monomers in this invention, deuterated chloroform (CDCl3) was used as the solvent in the experiments. In CDCl3, hydrogen is replaced by its isotope deuterium to avoid signals from the hydrogen nuclei. Figure 2 The NMR instrument is rated at 100 MHz, which means that the instrument has a magnetic field in which hydrogen atoms resonate at 100 MHz. Figure 3 The NMR spectroscopy is rated at 400 MHz. Two peaks 100 Hz apart on an NMR spectrum at 100 MHz will be 300 Hz apart on a 300 MHz instrument, 400 Hz apart on a 400 MHz instrument, and so on. To normalize the horizontal axis on the NMR spectrum, the frequency range of the peaks is divided by the fundamental resonance frequency to produce a ratio, which is then multiplied by 10. 6 The value of ppm (parts per million) is generated at that time.

[0056] Figure 2 It shows the peaks of all carbon nuclei “a”-“l” and the characteristic triplet of deuterated chloroform at 77 ppm. 13 CNMR data (CDCl3, 100MHz): δ 207.6 (k), 165.9 (d), 149.1 (h), 138.4 (b), 135.8 (e), 129.2, 127.1, and 121.5 (a, f, and g), 77.3, 77.0, and 76.7 (CDCl3), 45.0 (i), 30.0 and 29.0 (c and j), 18.3 (l).

[0057] Figure 3 The peaks for all proton / hydrogen nuclei "a"-"h" are shown, along with a small peak at 7.3 ppm for chloroform present in deuterated chloroform. 13 In C-NMR, the order of signal intensity (from strongest to weakest) is: CH3>CH2>CH>C-quaternary or carbonyl. In proton spectra, the integral is directly related to the amount of protons present. Signal splitting reveals information about the number of adjacent protons and the chemical structure. 1¹H NMR data (CDCl₃, 400 MHz): δ 7.27 (CHCl₃), 7.19 and 7.02 (2x multiplets, CH phenyl, d and e), 6.33 (multiplets, CH vinyl, b), 5.74 (multiplets, CH vinyl, a), 2.89 (triplet, CH₂, f / g, J). f,g 7.6 Hz), 2.75 (triple peak, CH2, f / g, J) f,g 7.6Hz), 2.13 (single peak, CH3, h), 2.05 (single peak, CH3, c).

[0058] Fourier Transform Infrared (FTIR) Spectroscopy: FTIR spectroscopy measures the absorption of electromagnetic radiation in the infrared range (wavelengths from approximately 760 nm to approximately 10 nm). 3 The sample containing the test composition is exposed to broadband electromagnetic radiation covering the IR range. An interferometer (such as a Michelson interferometer) receives the absorbed signal from the sample, and a computer using Fourier transform technology converts the data into information about various segments or portions of the test composition. Various portions and functional groups (e.g., OH, CH, NH, O=C=O, etc.) are present at various frequencies (cm²). -1 A lookup table of absorption data is used to identify various portions of the test composition. It is known that frequency (also known as wavenumber) and wavelength are inverse functions of each other. An exemplary lookup table is available at sigmaaldrich.com / technical-documents / articles / biology / ir-spectrum-table.html.

[0059] Figure 4 This is the FTIR spectrum of raspberry ketone, showing various frequencies in their respective portions. Notably, at 3358 cm⁻¹... -1 The depression at 1688 cm (which represents the phenol-hydroxyl moiety) and the depression at 1688 cm -1 The ketone portion at that location. Figure 5 This is the FTIR spectrum of the hydroxyphenyl butyl ketone methacrylate of the present invention, and Figure 6 It comes from Figure 4 and 5 The two spectra are superimposed, in which the spectrum of hydroxyphenyl methyl ketone methacrylate is essentially above the spectrum of raspberry ketone. Figure 6 The disappearance of the phenolic hydroxyl moiety in the hydroxyl-butanone methacrylate monomer is shown, confirming the use of the hydroxyl reaction site in the reaction. The ester-ketone peak shifts slightly to 1713 cm⁻¹. -1 Furthermore, the carbonyl group of methacrylate is at 1734 cm⁻¹ -1 And C=C vinyl at 1638cm -1The presence of [a certain element] indicates the synthesis of a new composition. FTIR data (in cm⁻¹) -1 (in units): 3105-2929 (broad, multiple peaks), 1899 (weak), 1734, 1713, 1638, 1510, 1449, 1403, 1367, 1324, 1296, 1203, 1167, 1131, 1017, 949, 885, 807, 650 (weak), 569, 553, 518, 450 (weak).

[0060] Gas Chromatography-Mass Spectrometry (GC-MS): GC-MS is a combination of gas chromatography (GC) and mass spectrometry (MS). In the GC section, a carrier gas (usually helium, nitrogen, or hydrogen, containing the sample mixture to be analyzed, called the mobile phase) passes through a glass or metal segment or column called the stationary phase, which contains a microlayer of liquid or polymer deposited on an insert support. The gaseous mobile phase interacts with the stationary phase, and each component of the sample mixture will elute at different times, called retention times. The components are ionized by electron bombardment in the MS section. The molecules of the components and their fragments become charged and are separated according to their mass-to-charge ratio (m / z) by placing them in an electric or magnetic field. Their mass-to-charge ratio is related to the path of the charged molecule to the detector. The relative signal intensity is plotted as a function of m / z. The combination of GC and MS improves the accuracy of identifying the analyte because if MS identifies a molecule with a corresponding GC retention time, the identification of that molecule is more confident.

[0061] Figure 7(a) shows the retention times of various components in a gas sample containing a strong signal at 13.865 min. The percentage of total abundance represents the percentage of the area of ​​one peak to the total area under all peaks. Other minor components (e.g., less than 3%) include the original reactants (methacrylic anhydride at 6.131 min and raspberry ketone at 14.965 min) and even smaller amounts (e.g., less than 1%) of raspberry ketone acetate (at 12.942 min) and methacrylic acid (at 6.139 min). A peak at 0.876 min is considered to be oxygen and nitrogen, which, as discussed below, are the major components of air. The inventors of this invention believe that this peak is caused by the air introduced into the test. When the oxygen and nitrogen peaks are discounted, the abundance of the peak at 13.865 min accounts for approximately 94% of the total abundance of all components in the sample.

[0062] Figure 7(b) shows the mass spectrum of the GC peak at 13.865 min; here, the molecular ion peak at 232.2 corresponds to the molecular weight of hydroxyphenylbutanone methacrylate, and the fragmentation pattern is shown at peaks at 69.1 and 41.1, indicating the methacrylate portion of the molecule. The mass spectra of the GC peaks at 6.139, 14.971, and 12.948 min in Figure 7(a) are shown in Figures 8(a)-(c), and are found to be comparable to the reference spectra of methacrylic anhydride, raspberry ketone, and raspberry ketone acetate, respectively. Figure 1 The mass spectrum of methacrylic anhydride in Figure 8(a) matches the standard mass spectrum published on PubChem.ncbi.nlm.nih.com, with peaks at 39, 41, and 69 on the m / z axis. The mass spectrum of raspberry ketone shown in Figure 8(b) matches the standard mass spectrum of the same compound from the same source, with peaks at 43, 77, 94, 107, and 164 on the m / z axis. The mass spectrum of raspberry ketone acetate in Figure 8(c) is similar to that of raspberry ketone shown in Figure 8(b), with the same peaks, as the two compounds are structurally similar, and has an additional small peak at 206, which indicates the molecular ion. The mass spectra of nitrogen and oxygen from the same PubChem source have peaks at 28 and 32, respectively, while the mass spectrum of methacrylic acid has peaks at 39, 40.5, and 86 on the m / z axis. None of these compounds have a strong peak above 164 on the m / z axis.

[0063] Referring back to Figure 7(b), the strong peaks at m / z 41.1 and 69.1 are primarily associated with the methacrylic acid moiety of hydroxyphenyl butyl ketone methacrylate and with methacrylic anhydride impurities or fragments thereof. The peaks at 43 and 107.1 are mainly associated with the raspberry ketone moiety of hydroxyphenyl butyl ketone methacrylate and with raspberry ketone and raspberry ketone acetate impurities. The peak at m / z = 232.2 at 13.865 minutes represents the molecular ion of the novel hydroxyphenyl butyl ketone methacrylate monomer.

[0064] TLC test ( Figure 1 ), NMR spectroscopy ( Figure 2-3 FTIR spectroscopy Figure 4-6 GC-MS experiments (Figures 7-8 and sub-parts) confirmed the synthesis of a novel monomer, hydroxyphenylbutanone methacrylate.

[0065] Example 2: Homopolymer of hydroxyphenyl butyl ketone methacrylate

[0066] A novel hydroxyphenyl butyl ketone methacrylate monomer was polymerized using solution polymerization. A 1% by weight initiator solution of hydroxyphenyl butyl ketone methacrylate and azobisisobutyronitrile (AIBN) was mixed in tert-butanol solvent. The mixture was sealed and stored at 65°C for 48 hours. Subsequently, the formed solid was separated, washed with isopropanol (IPA), and dried in a forced-air oven at 65°C. The homopolymer was separated into a white solid at room temperature and ground into a white powder.

[0067] Figure 9 The FTIR spectrum of the hydroxyphenyl methyl ketone methacrylate monomer is shown, substantially above the FTIR spectrum of the homopolymer of this monomer. At 1638 cm⁻¹ -1 The sharp drop in temperature (indicating the C=C vinyl moiety in the hydroxyphenyl methyl ketone methacrylate monomer) is not present in the spectrum of the homopolymer, which is expected during homopolymer formation. The Tg of the hydroxyphenyl methyl ketone methacrylate homopolymer was measured using experimental differential scanning calorimetry (DSC) and found to be 95°C, as in... Figure 10 As shown in the image.

[0068] Example 3: Copolymers including hydroxyphenyl butyl ketone methacrylate

[0069] Emulsion polymerization was used to copolymerize hydroxyphenyl methyl ketone methacrylate with methyl methacrylate (MMA), butyl methacrylate (BA), and methacrylic acid (MAA). The hydroxyphenyl methyl ketone methacrylate was ready for use without further purification, except for the removal of dichloromethane (CH2Cl2) solvent. Aqueous emulsions of MMA, BA, MAA (1 wt%, based on total monomer solids or BOTMS), wet-adhesive monomer (1 wt%, BOTMS), and hydroxyphenyl methyl ketone methacrylate (5 wt%, BOTMS) were prepared. Approximately 5 wt% of the monomer emulsion was fed into the round-bottom flask, and polymerization was initiated by adding sodium persulfate initiator at approximately 80°C. After stirring for 15 minutes, more monomer emulsion was fed into the mixture, and the feed rate was increased after 30 minutes. After 3 hours, all monomer emulsions were added to the mixture. The mixture was held at approximately 80°C for 30 minutes, then cooled to approximately 60°C. The mixture was monitored by dropwise addition of an oxidizing agent solution of tert-butyl hydroperoxide (tBHP) and a reducing agent solution of a sodium salt of an organic sulfinic acid derivative over 15 minutes. The mixture was then cooled to approximately 35°C and neutralized with a 3.5% by weight sodium hydroxide (NaOH) solution. The mixture was further cooled, and a biocide was added.

[0070] The copolymers of the present invention have the following properties:

[0071] pH = 9.1

[0072] % solids = 48.9%

[0073] Particle size = 146.8 nm (volume average).

[0074] MFFT = 3.4℃, according to ISO 2115 (April 2001), used to measure the minimum film-forming temperature. Brookfield viscosity = 110 cP.

[0075] Swelling ratio test

[0076] The tests were conducted using the copolymer of the present invention from Example 3, and compared with a comparative similar copolymer without hydroxyphenyl methyl ketone methacrylate. Both the comparative samples with and without ADH crosslinking agent, and the samples from Example 3 of the present invention, were coated onto a transparent substrate in an aqueous phase, allowing evaporation and polymerization. Figure 11 The samples are arranged as follows: Sample A is Example 3 without ADH; Sample B is Example 3 with ADH; Sample C is a comparative copolymer without ADH; and Sample D is a comparative copolymer with ADH.

[0077] In this experiment, a resin film was applied to a glass plate using a wet-dip coating method to a thickness of 20 mils (20 per 1 inch). The film was dried at constant humidity and temperature (70% RH and room temperature). The dried film was peeled off and cut into the desired sample cubes. The cut samples were developed in a sealed petri dish in a 1:1 solvent mixture of methyl ethyl ketone / toluene for 2 hours. The size of the gel samples was measured on graph paper. 10 units equal 25 mm (1 inch); 8 units equal 20 mm. Swelling was isotropic, meaning the length and width of the sample expanded to the same extent. Reduced swelling of the sample was an indication of cross-linking.

[0078] A square of 8x8 units per side was cut from the dried membrane. It was expected that ADH-free samples A of the present invention and comparative samples C and D would not undergo crosslinking, and after immersion in MEK / toluene solvent, samples A and C swelled or swelled to a 27x27 unit square. Sample D partially dissolved. In contrast, sample B of the present invention, containing the crosslinking agent ADH, only swelled or swelled to a 16x16 unit square. The swelling ratio was 16. 2 :27 2 The ratios of 256:729 or 1:2.85 indicate that the copolymers of the present invention self-crosslink through ADH, thereby forming a stronger film resistant to solvent swelling. The amount of crosslinking can be determined from the swelling ratio by applying ASTM D2765 or ASTM F2214.

[0079] It should be noted that, as discussed above, Example 3 was neutralized with NaOH after polymerization, but it was still able to resist swelling, indicating significant crosslinking, which is surprising, since it is known that ketone-hydrazide crosslinking is promoted by pH changes in acidic regions.

[0080] As disclosed above, a novel monomer, hydroxyphenyl methyl ketone methacrylate (FMA) or raspberry ketone methacrylate (RKMA), was synthesized. The homopolymers of FMA or RKMA were measured by DSC to have an experimental Tg of approximately 95°C. When copolymerized with other monomers to form latex copolymer resins, FMA or RKMA can form paint / dye films that can self-crosslink with hydrazine.

[0081] In another embodiment, gingerone is used as a starting material. Gingerone is a ketone derived from the ginger plant and is generally produced from gingerol (a volatile oil) during the drying process. Gingerone is also known as vanillylacetone, 4-(4-hydroxy-3-methoxyphenyl)-2-butanone, or 4-(4-hydroxy-3-methoxyphenyl)butane-2-one or 4-phenylbutane-2-one. Structurally, gingerone is similar to raspberry ketone described above, except that it has a methoxy group attached to a benzene ring, as shown below:

[0082]

[0083] Similar to raspberry ketone, the hydroxyl (OH) moiety in gingerone reacts with another compound or monomer to synthesize another novel monomer. A preferred compound or monomer is methacrylic anhydride, which is a reactive monomer that can be used to prepare other monomers, as described above.

[0084] Example 4: Two-phase reaction between gingerone and methacrylic anhydride

[0085] Similar to Example 1, gingerone was used instead of raspberry ketone, but with a larger solvent, to synthesize a novel gingerone methacrylate monomer from gingerone and methacrylic anhydride via a two-phase reaction. Gingerone methacrylate exhibits a high precipitation tendency due to the methoxy substituent on the benzene ring, which increases the crystallinity of the monomer. A 10% by weight aqueous solution of sodium hydroxide (NaOH) was added to a solution of gingerone and methacrylic anhydride in dichloromethane (CH2Cl2) solvent. The mixture was stirred at room temperature (RT or about 77°F) for about 1 hour. The organic phase was separated and washed with deionized (DI) water. The organic phase was then separated and concentrated to yield gingerone methacrylate as a grayish-white crystalline solid. Gingerone methacrylate has the following structure:

[0086]

[0087] As confirmed, the hydroxyl reaction site of gingerone was used to react and bond with the acyl moiety of methacrylic anhydride. In this example, 1 mole of methacrylic anhydride was used to react with 1 mole of gingerone. Besides the resulting gingerone methacrylate monomer, other compounds remaining in the mixture included trace amounts of residual starting materials gingerone and methacrylic anhydride.

[0088] Thin-layer chromatography (TLC): A mixture containing gingerone methacrylate and gingerone, gingerone methacrylate alone, or gingerone alone is spotted or deposited near the bottom of a supporting substrate (e.g., aluminum or glass) and covered with a stationary phase, typically silica gel. Figure 12 To best illustrate, gingerone spots are deposited on the left and gingerone methacrylate labeled "ZMA" is deposited on the right. Spots containing a mixture of both are deposited between them. The supporting substrate is rotated vertically to bring the spots close to the bottom, and then the spots are eluted, i.e., by washing with a solvent mixture containing approximately 90% toluene and approximately 10% acetone to remove or remove adsorbed material. Figure 12 This indicates that the gingerone spot shifted upwards a first short distance, and the gingerone methacrylate spot shifted upwards a second, longer distance. Intriguingly, the mixture's spots separated into two spots: one at the first distance for gingerone and the other at the second distance for gingerone methacrylate. Figure 12 R of gingerone methacrylate f It is approximately 0.58, and the R of gingerone is... f The value is approximately 0.36. TLC tests indicate that gingerone methacrylate differs from, or at least has a different polarity (more hydrophobic) from, the starting material gingerone.

[0089] NMR spectroscopy analysis was also performed on gingerone methacrylate. The structures of gingerone methacrylate with carbons labeled from "a" to "l" and hydrogens labeled from "a" to "h" are shown below. Figure 13 Showing 13 C-NMR spectrum, and Figure 14 The gingerone methacrylate was shown. 1 H-NMR spectrum. Figure 13-14 The NMR instrument is rated at 400 MHz.

[0090]

[0091] Figure 13 The peaks for carbon nuclei “a” to “l” are shown, as well as the characteristic triplet of CDCl3 at approximately 77 ppm. 13C-NMR data (CDCl3 400MHz): δ 207.6 (k), 165.4 (d), 150.9 (h), 139.8, 138.0 and 135.5 (b, e and n), 126.9 (a), 122.5, 120.2 and 112.6 (f, g and m), 77.3, 77.0 and 76.7 (CDCl3), 55.7 (o), 45.0 (i), 29.9 (c), 29.4 (j) and 18.3 (l).

[0092] Figure 14 The peaks for proton / hydrogen nuclei “a” to “h” are shown, with a small peak of chloroform present in CDCl3 at approximately 7.3 ppm. 1 ¹H NMR data (CDCl₃, 400 MHz): δ 7.27 (CHCl₃), 6.94 (double peak, CH phenyl, d, J) d,e 8.0Hz), 6.80 (double peak, CH phenyl, i, J) i,e 2.0 Hz,), 6.75 (doublet, CH phenyl, e, J) e,d 8.0Hz, J e,i 2.0 Hz), 6.34 (multiplet, CH vinyl, b), 5.73 (multiplet, CH vinyl, a), 3.79 (singlet, OCH3, j), 2.87 (triplet, CH2, f / g, J) f,g (approximately 7.2 Hz), 2.76 (triple peak, CH2, f / g, J) f,g (Approximately 7.2 Hz), 2.13 (single peak, CH3, h), 2.05 (multiple peak, CH3, c). NMR data indicate that the synthesis of gingerone methacrylate was successful.

[0093] Figure 15 These are the FTIR spectra of gingerone, showing various portions at their respective frequencies. Notably, at 3379 cm⁻¹... -1 The depression at 1708 cm (which represents the phenol-hydroxyl moiety) and the depression at 1708 cm -1 The ketone portion at that location. Figure 16 This is the FTIR spectrum of gingerone methacrylate of the present invention, and Figure 17 yes Figure 15 and 16 The two spectra are superimposed, with the spectrum of gingerone methacrylate essentially above that of gingerone. Figure xx shows the disappearance of the phenolic-hydroxyl moiety in the gingerone methacrylate monomer, confirming the use of a hydroxyl reaction site in the reaction. The ester-ketone peak is slightly shifted towards 1704 cm⁻¹. -1 The movement, and the carbonyl group of methacrylate at 1729 cm -1 At 1636 cm and C=C vinyl at 1636 cm-1 The presence of this feature indicates the synthesis of a new composition. FTIR data (in cm⁻¹) -1 (Units): 3200-2850 (broad, multiple peaks), 1729, 1704, 1636 (weak), 1605, 1510, 1470, 1448, 1427, 1410, 1368, 1352, 1315, 1271, 1202, 1334, 1119, 1029, 1003 (weak), 954, 879, 804, 797, 733, 647, 548).

[0094] Example 5: Homopolymer of gingerone methacrylate

[0095] Ginger ketone methacrylate homopolymer was prepared in a manner similar to that of the hydroxyphenyl butyl ketone methacrylate homopolymer from Example 2.

[0096] The Tg of gingerone methacrylate homopolymer was measured using experimental differential scanning calorimetry (DSC) and found to be approximately 56 °C. Figure 18 As shown in the image.

[0097] Example 6: Copolymers including gingerone methacrylate

[0098] Gingerone methacrylate was copolymerized with methyl methacrylate (MMA), butyl acrylate (BA), and methacrylic acid (MAA) using emulsion polymerization. Gingerone methacrylate was ready for use without further purification, except for the removal of dichloromethane (CH2Cl2) solvent. Aqueous emulsions of MMA, BA, MAA (1 wt%, based on total monomer solids or BOTMS), wet-adhesive monomer (1 wt%, BOTMS), and gingerone methacrylate (5 wt%, BOTMS) were prepared in a 1-liter four-necked round-bottom flask equipped with a thermocouple, feed tube, nitrogen inlet, and reflux condenser. Approximately 5 wt% of the monomer emulsion was fed into the round-bottom flask, and polymerization was initiated by adding sodium persulfate initiator at approximately 80°C. After stirring for 15 minutes, more monomer emulsion was fed into the mixture, and the feed rate was increased after 30 minutes. After 3 hours, all monomer emulsions were added to the mixture. The mixture was held at approximately 80°C for 30 minutes, then cooled to approximately 60°C. The mixture was monitored by dropwise addition of an oxidizing agent solution of tert-butyl hydroperoxide (tBHP) and a reducing agent solution of a sodium salt of an organic sulfinic acid derivative over 15 minutes. The mixture was then cooled to approximately 35°C and neutralized with a 3.5% by weight sodium hydroxide (NaOH) solution. The mixture was further cooled, and a biocide was added.

[0099] The copolymers of the present invention have the following properties:

[0100] pH = 8.4

[0101] % solids = 49.5%

[0102] Particle size = 140 nm (volume average).

[0103] MFFT = 3℃, according to ISO 2115 (April 2001), is used to measure the minimum film-forming temperature.

[0104] Brookfield viscosity = 90 cP

[0105] Swelling ratio test: The tests were conducted using the copolymer of the present invention containing gingerone methacrylate from Example 6, and compared with a similar copolymer containing hydroxyphenyl butyl ketone methacrylate from Example 3, and a comparative similar copolymer containing reactive diacetone acrylamide (DAAM) monomer. These three polymer samples were tested with and without ADH. Samples were prepared in the same manner as described above. Figure 19 (A)-(F) are photographs of 8x8 unit dried film samples that have been developed and swollen in MEK / toluene solvent for 2 hours. Figure 19 (A) and (D) are samples containing 5% DAAM by weight. The sample without ADH partially dissolved, while the sample containing ADH swelled to 15 x 15 units. 2 (3.5 times swelling). Figure 19 (B) and (E) are samples containing 5% FMA by weight. The sample without ADH was partially damaged but remained intact, while the sample containing ADH swelled to 14x14 units. 2 (3.1 times swelling). Figure 19 (C) and (F) are samples containing 5% ZMA by weight. The ADH-free sample remained intact and swelled to 25 x 25 units. 2 (Swelling by 9.8 times), while the sample containing ADH swelled to 13x13 units. 2 (2.6 times swelling). As mentioned above, the amount of crosslinking can be determined from the swelling ratio by applying ASTM D2765 or ASTM F2214.

[0106] Paints containing FMA, without FMA, and containing conventional crosslinkable monomer DAAM acrylic copolymer resins were prepared and compared with each other, as shown in the experiments below.

[0107] Example 7 of the present invention: Acrylic latex copolymer prepared using hydroxyphenyl butyl ketone methacrylate monomer

[0108] Table 1 provides the components used to form an acrylic latex polymer containing self-crosslinking FMA. To produce the adhesive, reactor seed was added to a nitrogen-purged 4-necked reactor, and the temperature was then raised to 75-80°C. Next, 50 g of the premixed monomer emulsion was added to the reactor, followed by initiator solution I. The mixture was then allowed to react for 15 minutes. The remaining monomer emulsion and initiator solution II were then added to the reactor simultaneously over 3.5 hours. The latex formed in the reactor was maintained at 80°C for 1 hour. The reactor was cooled to 60°C, and then oxidant and reducing agent solutions were added simultaneously in a 30-minute phase. The reactor was cooled to room temperature (e.g., 25°C), and a biocidal solution was added to obtain a latex adhesive with a Flory-Fox glass transition temperature of 16°C and a solids content of 51.2%. The latex was free of grit and had a particle size of 128 nm (volume average).

[0109] Table 1

[0110]

[0111]

[0112] Comparative Example 8: Acrylic latex copolymer prepared without self-crosslinking monomers

[0113] This comparative polymer example was prepared using the same components and methods as in Example 7 of the present invention, except that FMA was omitted from the monomer emulsion. The latex polymer has a similar Flory-Fox glass transition temperature of 16°C and a solids content of 51.1%. The latex is free of grit and has a particle size of 116 nanometers (volume average).

[0114] Comparative Example 9: Acrylic latex polymer prepared using diacetone acrylamide (DAAM) monomer

[0115] This comparative polymer example was prepared using the same components and methods as in Example 7 of the present invention, except that 5.6 grams (equivalent to 0.024 moles) of FMA in the monomer emulsion was replaced with 4 grams (equivalent to 0.024 moles) of DAAM. By making the two crosslinking monomers have the same molar number, the number of crosslinking functional groups (e.g., ketone groups) will remain the same in both latex polymers.

[0116] Comparative polymer Example 9 has a similar Flory-Fox glass transition temperature of 16°C and a solids content of 51.2%. The latex is free of grit and has a particle size of 133 nanometers (volume average).

[0117] Paint compositions were produced using binders from the latex polymers of Examples 7, 8, and 9. The components of the paint compositions are provided in Table 2. The milled components were mixed for 10 minutes after the addition of all milled components while stirring at high speed. The stirring was then reduced to a mixing speed, and the Stage 1 diluent was added and mixed for 20 minutes. The Stage 2 diluent was then added, and the mixture was mixed again.

[0118] Table 2

[0119]

[0120]

[0121]

[0122] Results and discussion of Examples 7–9

[0123] Test the stain-cleaning properties, anti-blocking properties, adhesiveness, and scrubbability of the paint.

[0124]

[0125] Compared to Comparative Example 8, which lacks crosslinking monomers, Paint Example 7 of the present invention exhibits improved tack, anti-blocking properties, and washability. The inventors of the present invention believe that these improved properties are due to the crosslinking effect of the acrylic monomers with FMA in Paint Example 7 of the present invention.

[0126] Compared to Comparative Example 9 with DAAM, Paint Example 7 of the present invention also has improved adhesion and anti-blocking properties, as well as equal or better stain removal properties, especially for wine and graphite.

[0127] Compared to Comparative Example 8, which does not contain crosslinking monomers in the resin, Paint Example 7 of the present invention exhibits better scrubbability. Comparative Example 9 exhibits even higher scrubbability than Paint Example 7 of the present invention.

[0128] Preferably, based on the swelling ratio tests of Examples 6 and 7, FMA or ZMA or bio-based monomers having ketone reaction sites are present in the resin copolymer in amounts from about 0.25% to about 10% by weight, preferably from about 0.40% to about 8% by weight, and more preferably from about 0.5% to about 6% by weight.

[0129] Cleanliness test: Cleanliness tests were conducted on a 7-mil (wet) coating on a Leneta matte plastic scrubbing board (P-121-10N) in a room with constant temperature and humidity of 73℉ and 50% relative humidity. The coating was allowed to dry for 7 days.

[0130] Household stains, graphite, ketchup, yellow mustard, red cooking wine, and coffee were applied to the surface of the coated scrubber. After 10 minutes, the board was rinsed with tap water and gently wiped dry with a cellulose sponge. The scrubber was then mounted on a TQC AB5000 Washability machine and washed for 500 cycles with a sponge soaked in soap / water solution. After washing, the board was rinsed with water and dried for 24 hours. The color difference δE(DE) between the contaminated and washed area and the uncontaminated and washed area was measured using a spectrophotometer. A smaller DE indicates better cleanability of the stains on the paint.

[0131] Adhesive properties: The tackiness of the paint film was tested on a 3-mil (wet) coating using a Brookfield CT3 Texture Analyzer on BYK Byko-charts Plaint White Sealing Chart #2837. The coating was allowed to dry for 1 or 7 days in a constant temperature and humidity room at 77℉ and 50% relative humidity. The tack strength was recorded numerically in grams. Three readings were recorded for each sample. The average of the three readings was reported as the tackiness number. A lower tackiness number indicates lower tackiness and better anti-tack properties of the paint.

[0132] Anti-adhesion test: Anti-adhesion testing was performed using a modified ASTM D4946. A paint coating was prepared on a white Leneta WK card sealed in a vacuum plate. The coating was dried for 1 day and 7 days in a constant temperature and humidity room at 25°C and 50% humidity. A one-inch square was cut from the plate, and two squares were placed face-to-face. A 100-gram cubic weight was placed on top and the plate was placed at 120°F for 24 hours. The sample was removed from the oven and the plate was allowed to cool for 1 / 2 hour. The fusion of the sample was examined by pulling the two plates apart with a slow and steady force. Anti-adhesion grades are given as follows: 5 - no tack; 4 - slightly tacky; 3 - moderate tack; 2 - poor tack; 1 - transfer (record the percentage of film removed).

[0133] Performed using ASTM D2486 Method B Scrub resistance test The test was conducted on a 7-mil paint coating that had been dried for 7 days. A TQC scrub abrasion and washability tester with a 340-gram boat was used for the test. The number of scrub cycles at which failure occurred (when the paint film was removed and the underlying substrate surface was exposed) was recorded. A higher reading indicates better scrub resistance of the paint.

[0134] The results showed that, compared with the conventional DAAM / ADH crosslinking mechanism, FMA / ADH and ZMA / ADH exhibited high membrane integrity through crosslinking.

[0135] Alternative implementation plan :

[0136] This invention is not limited to the embodiments described above. Other starting materials may be used instead of ketone compounds or methacrylic anhydride or both.

[0137] Methacrylic anhydride belongs to the acid anhydride class. An acid anhydride is a compound having two acyl groups bonded to the same oxygen atom. Acid anhydrides have the following general structure:

[0138]

[0139] Other suitable anhydrides are vinyl structures containing an unsaturated olefin chemical composition, and include, but are not limited to, acrylic anhydrides, maleic anhydrides, and other unsaturated anhydrides.

[0140] Another suitable compound that can replace methacrylic anhydride is glycidyl methacrylate, which has the following structure:

[0141]

[0142] The etherification synthesis of glycidyl methacrylate is discussed in Al-Odayni, A.-B. et al., New Monomer Based on Eugenol Methacrylate, Synthesis, Polymerization and Copolymerization with Methyl Methacrylate-Characterization and Thermal Properties, Polymers 2020, 12, 160, 1-20; doi:10.3390 / polym12010160 (in its entirety incorporated herein by reference).

[0143] Other phenolic compounds with ketone and hydroxyl reaction sites can be used instead of raspberry ketone or gingerol. Azadirachtin is another suitable compound, found in the needles and mycorrhizae of Norway spruce. Azadirachtin methacrylate can also be synthesized using the same technique.

[0144]

[0145] 4-Hydroxyphenylacetone is another suitable phenolic compound with both ketone and hydroxyl reaction sites.

[0146]

[0147] Other suitable bio-based phenolic compounds that can be synthesized into monomers and polymers are discussed in Lochab, B. et al., Naturally occurring phenolic sources: monomers and polymers, RSC Adv. 2014, 4, 21712-21752 (which is incorporated herein by reference in its entirety).

[0148] Alternative Synthesis Technology

[0149] Typically, (meth)acrylic acid monomers, including FMA and ZMA, can be produced directly from (meth)acrylic acid in an esterification reaction, or from an activated form of (meth)acrylic acid, such as anhydrides, acyl chlorides, N-hydroxysuccinimides, etc. FMA and ZMA can also be synthesized by other means, i.e., techniques different from those discussed in Example 1.

[0150] In the presence of strong Lewis or FMA and ZMA can be synthesized in the presence of an acid catalyst via Fisher or Fisher-Speier esterification between (meth)acrylic acid (or its short alkyl chain ester, such as methyl or ethyl ester) and raspberry ketone. The reaction is preferably carried out in a pure atmosphere, but can also be carried out in the presence of a solvent that facilitates the azeotropic removal of water (or methanol / ethanol) formed during the reaction. Examples of Fisher-type phenol esterification can be found in Batra, PC, Rozdon, ON, Acetylation of phenols using acetic acid, Proc. Indian Acad. Sci. (Math. Sci.) 1949, 29, 349-351; Offenhauer, RD, The direct esterification of phenols, J. Chem. Ed. 1964, 41(1), 39; Konwar, D. et al., Esterification of carboxylicacids by acid activated Kaolinite clay, Ind. J. Chem. Techn. 2008, 15, 75-78. These references are incorporated into this paper in their entirety through citation.

[0151] Alternatively, methacrylic acid (or its short alkyl chain esters, such as methyl or ethyl esters) can be reacted in the presence of a lipase B enzyme (such as Novozym 435) as a catalyst. This reaction is preferably heated and can be carried out purely / undiluted or in an organic solvent. Preferably, the organic solvent facilitates the azeotropic removal of water (or methanol / ethanol) formed during the reaction. Examples of lipase-catalyzed synthesis are described in V. Athawale et al., Lipase-Catalyzed Synthesis of Geranyl Methacrylate by Transesterification: Study of Reaction Parameters, Tetrahedron Letters 2020, 43(27), 4797-4800, and Roby, MH et al., Enzymatic Production of Bioactive Docohexaenoic Acid Phenolic Ester, Food Chemistry 2015, 171, 397-404. These references are incorporated herein by reference in their entirety.

[0152] Alternatively, FMA and ZMA can be prepared from the activated form of the acid. For example, it can be prepared in a variety of ways by reaction between (meth)acrylic anhydride and raspberry ketone or gingerone, as described in the following literature: Anbu, N. et al., Acetylation of alcohols, amines, phenols, thiols under catalyst and solvent-free conditions, Chemistry 2019, 1, 69-79; Jin, T.-S. et al., Rapid and efficient method for acetylation of alcohols and phenols with acetic anhydride catalyzed by silica sulfate, Synthetic Communications 2006, 36, 1221-1227; Haddadin, MJ et al., Acylation of phenol by cyclic and acyclic anhydrides in anhydrous aceticacid, J. Pharm. Sci. 1975, 64(11), 1766-1770; Yue, C. et al., Acetylation of alcohols and phenols with acetic anhydride under solvent-free conditions using an Ionic liquid based on morpholine as a coverable and reusable catalyst, Monatsheftefür Chemie-Chemical Monthly 2010, 141, 975-978; Meshram, GA and Patil, VD, Simple and efficient method for acetylation of alcohols, phenols, amines, and thiols using anhydrous NiCl2 under solvent-free conditions, Synth. Commun. 2009, 39(14), 2516-2528. These references are incorporated herein by reference in their entirety.

[0153] FMA and ZMA can also be synthesized by the methods described in US 2018 / 0201703 or US 2014 / 0275435 to synthesize methacrylated vanillin and / or methacrylated vanillyl alcohol. Other syntheses are disclosed in Al-Odayni, A.-B. et al., New Monomer Based on Eugenol Methacrylate, Synthesis, Polymerization and Copolymerization with Methyl Methacrylate-Characterization and Thermal Properties, Polymers 2020, 12, 160, 1-20; Tale, NV, Jagtap, RN, Synthesis of Diacetone Acrylamide Monomer and the Film Properties of Its Copolymers, Iranian Polym. J. 2010, 19(10), 801-810; Rupavani, J. et al., Synthesis, Characterization and End Use Evaluation of 2-Allyl-3(5)-pentadecyl Phenol and Their Acrylic / Methacrylic Esters, Eur. Polym. J. 1993, 29(6), 863-869. All of these references are incorporated herein by reference in their entirety.

[0154] While the exemplary embodiments of the invention disclosed herein clearly achieve the above objectives, it should be understood that numerous modifications and other embodiments can be devised by those skilled in the art. Therefore, it should be understood that the appended claims are intended to cover all such modifications and embodiments that fall within the spirit and scope of the invention.

Claims

1. The component dispersed in the aqueous phase of the aqueous composition has the following structure (A). Or the following structure (B) A copolymer formed by polymerizing a monomer and at least one other monomer. The monomer having structure (A) or structure (B) is capable of crosslinking, and The copolymer is able to form a film on the substrate after the aqueous composition is applied to the substrate and the aqueous phase evaporates.

2. The copolymer of claim 1, wherein the portion formed by said copolymer is capable of crosslinking with hydrazide in an aqueous phase.

3. The copolymer of claim 1 or 2, wherein the at least one monomer comprises an acrylic, vinyl, or urethane monomer.

4. The copolymer of claim 1 or 2, wherein the at least one monomer comprises a styrene monomer.

5. A paint composition comprising the aqueous composition according to any one of claims 1 to 4.

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