WO2020131745A1 - Surface initiated polymerization of compositions having 1,1-disubstituted alkene compounds - Google Patents

Abstract

A coating method and system is provided. The system includes a substrate having an initiator for anionic polymerization and a polymerizable composition. The polymerizable composition comprises a multifunctional 1,1 -disubstituted alkene macromer that polymerizes to form a coating on the substrate.

Description

SURFACE INITIATED POLYMERIZATION OF COMPOSITIONS HAVING 1,1-DISUBSTITUTED ALKENE COMPOUNDS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims the priority of U.S. provisional patent application Serial No. 62/780,859, entitled SURFACE INITIATED POLYMERIZATION OF COMPOSITIONS HAVING 1 , 1 -DI SUB S TITUTED ALKENE COMPOUNDS, filed December 17, 2018, and hereby incorporates the same application herein by reference in its entirety.

TECHNICAL FIELD

[0002] The present disclosure generally relates to systems and methods to initiate surface polymerization of compositions including 1, 1-di substituted alkene compounds.

BACKGROUND

[0003] Polymerizable compositions are useful components in a number of applications and products and can be used, for example, as an adhesive, a coating, a sealant, a molding, a film, or as a composite binder. Known polymerizable compositions, however, have suffered from the need to use external polymerization initiators to initiate polymerization. External polymerization initiators have a number of drawbacks. For example, polymerization initiators cannot be removed after polymerization and remain in the cured composition affecting various attributes of the cured composition. Additionally, systems with external polymerization initiators are difficult to control. It would therefore be advantageous to provide a polymerizable system that can be easily cured on a variety of substrates without the addition of an external polymerization initiator while retaining excellent mechanical and coating properties.

SUMMARY

[0004] According to one embodiment, a method of initiating polymerization and forming a coating substrate includes providing a substrate, treating at least a portion of the substrate with an anionic initiator to form an initiator treated substrate, and applying a polymerization composition to the at least a portion of the initiator treated substrate to provide a coating on the substrate. The polymerization composition includes a multifunctional 1,1-di substituted alkene macromer. [0005] According to another embodiment, a coated system includes: a substrate comprising an anionic initiator; and a cured polymerizable composition in contact with the substrate, the polymerizable composition including a multifunctional 1,1 -di substituted alkene macromer having the formula:

wherein each X can independently be O or a direct bond; R3 and Rs can be the same or different and can each represent a hydrocarbyl group; R4 can be a hydrocarbyl group having n + 1 valences; and n is an integer from 2 to 20. The anionic initiator initiates polymerization of the polymerizable composition.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] FIG. 1 depicts a schematic view of an initiated system having a nucleophilic substrate and the propagation of the reactive macromers, according to one aspect.

DETATTED DESCRIPTION

Definitions

[0007] As used herein“essentially free of’ means that the system, method or composition contains about 5% or less, about 3% or less, about 1% or less, or about 0.5% or less, by weight, of the particular material or compound.

[0008] As will be appreciated, polymerizable compositions that can be cured on-demand without a polymerization initiator can be used in many applications where initiator-cured systems that require an external initiator are either unusable or undesirable. Such initiator-cured systems can refer to systems that require an additional component, external to the system, to initiate curing. Such additional components can be a chemical component (e.g., a chemical initiator) or an energy component (e.g., UV radiation or an electron beam). In contrast, polymerizable systems that can be cured without a polymerization initiator can refer to systems that can undergo polymerization without the introduction, or contact, of any additional components external to the system using instead, for example, anions generated in the polymerizable composition.

[0009] Certain initiator-cured systems are disadvantageous because they are two-part polymerization systems. Two-part polymerization systems generally refer to polymerization systems that require the addition of at least a second component to the system to initiate polymerization.

[0010] Addition-type polymerization systems are examples of a two-part polymerization system. Generally, such systems are disadvantageous as a result of the cost and environmental hazards of the initiator components, the energy and time required to mix the initiator components into the polymerizable composition, the time-sensitive application and use of the mixed system, and the continued presence of the initiator components in the cured composition. For example, addition- type acrylate and methacrylate systems require the discrete addition of a relatively large quantity (e.g., about 2% or more) of various initiator components and catalysts into a polymerizable composition to induce polymerization. In such systems, the relatively large quantity of initiator compounds must be meticulously mixed into the system and remain in the cured composition often compromising performance properties. These disadvantages are a fundamental consequence of two-part polymerization systems and cannot be alleviated by using techniques such as substrate priming or improved initiators.

[0011] Other initiator-cured systems include moisture curing systems, such as cyanoacrylate systems, that can be cured upon contact with water or moisture. Although sometimes classified as one-part systems by industry standards, such moisture-sensitive systems suffer from several consequences as a result of using an external initiator. For example, moisture-sensitive curing systems are difficult to control due to their rapid polymerization upon contact with commonly found surface moisture, which can vary widely in concentration both substrate to substrate and with seasonal atmospheric humidity. As such, they are unsuitable for use in certain applications such as those pertaining to various inorganic and/or acidic substrates. Additionally, cyanoacrylates also suffer from fairly limited physical and performance versatility. Attempts to improve cyanoacrylate systems through the addition of primers or additives have increased the complexity of use, as well as the expense of such systems.

[0012] A polymerizable system that can be cured without the addition of an external polymerization initiator, such as a system that uses substrate surface initiation of polymerization, can avoid these issues and can be used in a wide range of applications that are unsuitable for initiator-cured polymerization systems. For example, a polymerization system that can be cured without an external polymerization initiator can have improved stability and/or durability from the removal of the initiator in the cured system as well as improved usability by eliminating the addition and mixing steps necessary for secondary ex situ initiator-cured systems.

[0013] A polymerizable composition that can be cured without the addition of a polymerization initiator can generally be formed of combining and coating the polymerizable composition with a suitable substrate having embedded therein, a nucleophile that is an anionic initiator, for example an amine initiator, and in another aspect a tertiary amine initiator. Suitable substrates can vary widely and can include metal substrates, wood substrates, and leather substrates. Advantageously, such compositions can be cured without the addition of a polymerization initiator to the composition but by instead using the treated substrate to initiate polymerization.

[0014] In one aspect, the initiator can be a primary, secondary, or tertiary amine. Useful tertiary amine initiators include dimorpholinodialkyl ether, a di((dialkylmorpholino)alkyl) ether, bis-(2- dimethylaminoethyl)ether, triethylene diamine, pentamethyldiethylene triamine, N,N- dimethylcyclohexylamine, N,N-dimethyl piperazine 4-methoxyethyl morpholine, N- methylmorpholine, N-ethyl morpholine and mixtures thereof. A preferred dimorpholinodialkyl ether is dimorpholinodiethyl ether. A preferred di((dialkylmorpholino)alkyl) ether is (di-(2-(3,5- dimethyl-morpholino)ethyl)-ether) or 2,2’-dimorpholinodiethylether (DMDEE).

[0015] In certain aspects, an initiator can be added to a base coat, a dye, a wood stain or be introduced via plasma. Additionally, certain naturally initiating surfaces such as concrete and glass can also contain anionic initiators (e.g. non-amine initiators). [0016] In certain aspects, the initiator does not substantially permeate the substrate and is selected and applied so that a sufficient quantity of the initiator stays on, or near, the surface of the substrate. In certain aspects, the initiator is oriented on the surface of the substrate such that a sufficient number of the reactive initiator sites are available to react with the reactive alkene sites.

[0017] In contrast to known polymeric coatings, the polymer formed in the current disclosure is a crosslinked polymer. As can be appreciated, crosslinked polymers exhibit substantially improved durability, strength, and longevity compared to uncrosslinked polymers such as thermoplastic polymers. Additionally, known surface initiated polymers are conventionally utilized only as a functionalized surface and not as a final coating. In the present disclosure, the polymer formed from the surface initiated coating can be the final finish.

[0018] According to certain aspects, suitable macromers for the polymerizable compositions can be multifunctional 1,1 -di substituted alkene macromers. As used herein, 1, 1 -di substituted alkene compounds refer to compounds having two carbonyl groups bonded to the 1 carbon and a hydrocarbyl group bonded to each of the carbonyl groups. In such 1,1 -di substituted alkene compounds, the hydrocarbyl groups can be bonded to the carbonyl groups directly or through an oxygen atom.

[0019] According to certain aspects, suitable hydrocarbyl groups can include at least straight or branched chain alkyl groups, straight or branched chain alkyl alkenyl groups, straight or branched chain alkynyl groups, cycloalkyl groups, alkyl substituted cycloalkyl groups, aryl groups, aralkyl groups, and alkaryl groups. Additionally, suitable hydrocarbyl groups can also contain one or more heteroatoms in the backbone of the hydrocarbyl group.

[0020] In certain aspects, a suitable hydrocarbyl group can also, or alternatively, be substituted with a substituent group. Non-limiting examples of substituent groups can include one or more alkyl, halo, alkoxy, alkylthio, hydroxyl, nitro, cyano, azido, carboxy, acyloxy, and sulfonyl groups. In certain aspects, substituent groups can be selected from one or more alkyl, halo, alkoxy, alkylthio, and hydroxyl groups. In certain aspects, substituent groups can be selected from one or more halo, alkyl, and alkoxy groups. [0021] In certain aspects, suitable hydrocarbyl groups can be Ci-20 hydrocarbyl groups. For example, the hydrocarbyl group can be an alkyl ether having one or more alkyl ether groups or alkylene oxy groups. Suitable alkyl ether groups can include, without limitation, ethoxy, propoxy, and butoxy groups. In certain aspects, suitable hydrocarbyl groups can contain about 1 to about 100 alkylene oxy groups; in certain aspects, about 1 to about 40 alkylene oxy groups; and in certain aspects, about 1 to about 10 alkylene oxy groups. In certain aspects, suitable hydrocarbyl groups can contain one or more heteroatoms in the backbone.

[0022] Suitable examples of more specific hydrocarbyl groups can include, in certain aspects, Ci- 15 straight or branched chain alkyl groups, Ci-15 straight or branched chain alkenyl groups, C5-18 cycloalkyl groups, C6-24 alkyl substituted cycloalkyl groups, C4-18 aryl groups, C4-20 aralkyl groups, and C4-20 alkaryl groups. In certain aspects, the hydrocarbyl group can more preferably be Ci-8 straight or branched chain alkyl groups, C5-12 cycloalkyl groups, C6-12 alkyl substituted cycloalkyl groups, C4-18 aryl groups, C4-20 aralkyl groups, or C4-20 alkaryl groups.

[0023] As used herein, alkaryl can include an alkyl group bonded to an aryl group. Aralkyl can include an aryl group bonded to an alkyl group. Aralkyl can also include alkylene bridged aryl groups such as diphenyl methyl or propyl groups. As used herein, aryl can include groups containing more than one aromatic ring. Cycloalkyl can include groups containing one or more rings including bridge rings. Alkyl substituted cycloalkyl can include a cycloalkyl group having one or more alkyl groups bonded to the cycloalkyl ring.

[0024] In certain aspects, suitable alkyl groups can include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, hexyl, and ethyl hexyl. Similarly, examples of suitable cycloalkyl groups can include cyclohexyl and fenchyl and examples of suitable alkyl substituted groups can include menthyl and isobornyl.

[0025] According to certain aspects, suitable hydrocarbyl groups can include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, ethyl pentyl, hexyl, ethyl hexyl, fenchyl, menthyl, and isobornyl groups.

[0026] In certain aspects, illustrative examples of 1,1-di substituted alkene compounds can include methylene malonate compounds, methylene B-ketoester compounds, methylene B-di-ketone compounds, dialkyl disubstituted vinyl compounds, dihaloalkyl disubstituted vinyl compounds and any monofunctional, difunctional, or multifunctional monomers, oligomers, or polymers thereof. Compositions having one or more of such illustrative example compounds can be used as a suitable composition according to certain aspects.

[0027] Compositions having a 1, 1 -disubstituted alkene compound can have a variety of properties that make them particularly suitable for use in polymerizable systems. For example, a composition having a 1 , 1 -disubstituted alkene compound can be polymerized without the use of a solvent under ambient temperatures (e.g. at about room temperature or about 23 °C). Additionally, a composition having a 1, 1 -disubstituted alkene compound can exhibit water tolerance, be transparent in both cured and uncured states, and have excellent adhesion properties and cure times.

[0028] As can be appreciated, 1, 1 -disubstituted alkene compound can be monofunctional, difunctional, or multifunctional. Monofunctional compounds can refer to monomers that have a single addition polymerizable group. Difunctional compounds can refer to monomers, oligomers, resins, or polymers that contain two addition polymerizable groups. Multifunctional compounds can refer to any monomer, oligomer, resin, or polymer that contains three or more addition polymerizable groups. In contrast to monofunctional compounds, difunctional compounds and multifunctional compounds can undergo additional crosslinking, chain-extension, or both, when polymerized.

[0029] An illustrative example of a monofunctional 1, 1 -disubstituted alkene compound is depicted by general formula I:

wherein each X can independently be O or a direct bond and Ri and R2 can be the same or different and can each represent a hydrocarbyl group. [0030] An illustrative example of a multifunctional monomer having more than one methylene group connected by a multivalent hydrocarbyl group can be depicted by general formula II:

wherein each X can independently be O or a direct bond; R3 and Rs can be the same or different and can each represent a hydrocarbyl group; R.4 can be a hydrocarbyl group having n + 1 valences; and n is an integer of 1 or greater. In certain aspects, n can be 3 or fewer; and in certain aspects, n can be 2 or fewer or n can be 2 to 20 or 4 to 7.

[0031] According to certain aspects, specific examples of 1, 1 -di substituted alkene compounds can include methylene malonate compounds having general formula III:

wherein R.6 and R7 can be the same or different and can each represent a hydrocarbyl group. For example, methylene malonate compounds can include diethyl methylene malonate (“DEMM”), dimethyl methylene malonate (“DMMM” or “D3M”), hexyl methyl methylene malonate (“HMMM”), ethylethoxy ethyl methylene malonate (“EEOEMM”), fenchyl methyl methylene malonate (“FMMM”), dibutyl methylene malonate (“DBMM”), di-n-propyl methylene malonate, di-isopropyl methylene malonate, and dibenzyl methylene malonate. Additionally, in certain aspects, certain transesterification reaction products formed from the reaction of methylene malonate compounds with acetates, diacetates, alcohols, diols, and polyols can also be used to form 1, 1 -di substituted alkene macromers. [0032] According to certain aspects, examples of methylene beta ketoesters can be represented by general formula IV:

wherein Rx and R9 can be the same or different and can each represent a hydrocarbyl group.

[0033] According to certain aspects, examples of methylene beta diketones can be represented by general formula V:

wherein Rio and R can be the same or different and can each represent a hydrocarbyl group.

[0034] Additional details and methods of making suitable 1,1 -di substituted alkene compounds as well as other suitable compositions are disclosed in U.S. Patent No. 8,609,885; U.S. Patent No. 8,884,051; and WO 2014/110388 each of which are hereby incorporated by reference.

[0035] In certain aspects, 1,1-di substituted alkene compounds can also, or additionally, include polyester macromers. As can be appreciated, compositions containing polyester macromers can undergo polymerization when exposed to basic initiators. Polyester macromers are disclosed in U.S. Pat. No. 9,617,377, incorporated herein by reference in its entirely for all purposes.

[0036] Polymerization of a composition including a 1,1-di substituted alkene compound can be in one aspect, directly initiated without dissolving or solubilizing the compositions in a solvent. As can be appreciated, this advantageously eliminates the need to remove a solvent after polymerization and obviates any exposure to potentially hazardous solvents such as volatile organic compounds. In certain embodiments, the polymerizable compositions described herein can be substantially free of volatile organic compounds.

[0037] As can be appreciated, suitable substrates can generally include any substrates that can be treated to include anionic polymerization initiators including metal substrates, wood substrates, and leather substrates.

[0038] Suitable substrates can be produced in both a variety of shapes and with a variety of mechanical qualities. For example, suitable substrates can be provided in shapes that may be difficult to polymerize with polymerization systems requiring an external polymerization initiator such as, for example, 3D-printed parts, certain mechanical parts, leather and wood objects, and portions of machines and systems. The elimination of an external polymerization initiator can instead allow for a one-part application of the composition having a 1,1 -di substituted alkene compound and subsequent curing of the composition. For example, in certain aspects, a coating layer can be applied to a curved metallic part such as an automobile frame and then cured without time constraints imposed by any included polymerization initiators in the composition or alternatively without the need to subsequently supply any initiators. Mechanically, certain substrates and articles formed thereof can be supplied that demonstrate a variety of beneficial properties including, for example, transparently and flexibility.

[0039] Specific examples of suitable metals can include noble metals, steel, stainless steel, aluminum, copper, nickel, metal alloys, metal oxides, graphite, carbonized materials, and combinations thereof.

[0040] Generally, polymerization of a composition including a 1,1 -di substituted alkene compound can proceed through living anionic polymerization. As can be appreciated, living anionic polymerization is a process by which nucleophilic species initiate addition reactions with an electrophilic double or triple bond. Living anionic polymerization is not self-terminating and can proceed until quenched or until all of the reactive monomers are consumed. [0041] Initiation of living anionic polymerization can offer a number of benefits. For example, in certain aspects, additional polymerizable composition can be added to increase the thickness of a coating without requiring any additional initiator.

[0042] In certain aspects, an additional benefit of living anionic polymerization is the ability to quench polymerization before complete polymerization has occurred. For example, after polymerization has been initiated, a weak acid can be added to the composition to quench any additional polymerization. Quenching can allow for excess composition to be removed or can allow for the formation of weaker polymeric matrixes for targeted and consistent failure modes.

[0043] In certain aspects a weak acid can be added to the polymerizable composition to improve the pot life and thus workability of the composition during coating and processing of the substrate.

[0044] As shown in FIG. 1, in certain aspects, a polymerizable composition including a multifunctional 1,1 -di substituted alkene macromer can be bonded to a suitable substrate. A nucleophile on the substrate surface initiates polymerization of the multifunctional 1,1- disubstituted alkene macromer and can covalently bond the macromer to the substrate. Such bonding can generally be indicated by a change in the mechanical performance properties and substrate bonding failure modes.

[0045] FIG. 1 specifically illustrates the final molecular architecture of the bonding and shows an arrangement of polymer chains which can be considered to be a crosslinked polymer owing to the position of the reactive sites on the macromer molecule. This type of crosslinked polymer architecture can benefit applications which require durability and superior chemical and mechanical resistance.

[0046] Application of malonate-based multifunctional macromer directly onto a substrate having initiators on at least a portion of the surface can be a two-step process. The first step can involve incorporation of initiator to the substrate, followed by application of the final coat to form a crosslinked polymer coating. In certain aspects, the additional step of surface-initiated polymerization to introduce functionalities on the substrate is not needed.

[0047] In certain aspects, a polymerizable composition having a multifunctional 1,1 -di substituted alkene macromer can further include one or more additives including, for example, one or more dyes, pigments, toughening agents, impact modifiers, rheology modifiers, plasticizing agents, natural or synthetic rubbers, filler agents, reinforcing agents, thickening agents, opacifiers, inhibitors, fluorescence markers, thermal degradation reducers, thermal resistance conferring agents, surfactants, wetting agents, conductive synergists, or stabilizers. For example, thickening agents and plasticizers such as vinyl chloride terpolymer and dimethyl sebacate respectively, can be used to modify the viscosity, elasticity, and robustness of a system. Additives can additionally, or alternatively, provide mechanical reinforcement to the polymerized system.

[0048] In certain aspects, the polymerizable compositions can additionally include additional reactive macromers such as additional 1,1 -di substituted alkene monomers or acrylic amine. For example, a monofunctional 1,1 -di substituted alkene monomer can be included in addition to a multifunctional monomer in certain embodiments.

[0049] According to certain aspects, stabilizers can be included in the polymerizable compositions having a 1,1 -di substituted alkene compound to increase and improve the shelf life of the composition and to prevent spontaneous polymerization of the system. Generally, one or more anionic polymerization inhibitors such as liquid phase stabilizers (e.g., methanesulfonic acid (“MSA”)), vapor phase stabilizers (e.g., trifluoroacetic acid (“TFA”)), or free radical stabilizers (e.g., 4-methoxyphenol or mono methyl ether of hydroquinone (“MeHQ”)) can be used as a stabilizer package as disclosed in U.S. Patent No. 8,609,885 and U.S. Patent No. 8,884,051, each incorporated by reference. Additional free radical polymerization inhibitors are disclosed in U.S. Patent No. 6,458,956, and are hereby incorporated by reference. Anionic polymerization stabilizers are generally electrophilic compounds that scavenge electrons from the composition or growing polymer chain. The use of anionic polymerization stabilizers can terminate additional polymer chain propagation. Generally, only minimal quantities of a stabilizer are needed and, in certain aspects only about 150 parts-per-million (“ppm”) or less can be included. In certain aspects, a blend of multiple stabilizers can be included such as, for example, a blend of about 10 ppm MSA and 100 ppm MeHQ.

[0050] According to certain aspects, chelating agents can also be added to a composition having a 1, 1 -di substituted alkene compound. The inclusion of such chelating agents can be useful in a variety of roles and can act, for example, as a metal scavenger, moisture scavenger, synergistic initiation additive, polymerization additive, and/or as a surface compatibility agent. For example, a chelating agent may be useful to remove surface or substrate impurities and can allow for initiation and bonding to a wider range of such surfaces and substrates. Generally, any class of chelating agent can be suitable for inclusion provided the chelating agent does not induce polymerization of the 1,1-di substituted alkene compound. For example, nonionic chelating agents and oxidizing agents, such as hydroperoxides, can be suitable for inclusion in the polymerizable compositions. Specific examples of suitable chelating agents can include crown ethers, calixarenes, cyclodextrins, and polyethylene glycols. A specific example of an oxidizing agent can include cumene hydroperoxide. A suitable chelating agent, or oxidizing agent, can be added in quantities of about 3% or less, by weight, according to certain aspects; or at quantities of about 1% or less, by weight, according to certain aspects.

[0051] After curing and polymerization, the coating compositions herein have a coating thickness of about 1 micron to about 200 microns, in other aspects from about 5 microns to about 100 microns.

[0052] Test Methods

[0053] Cross-hatch adhesion is determined using ASTM D3359-09, gloss is determined according to ASTM D523-08 at 20, 60 or 85, °C, pencil hardness is determined according to ASTM D3363- 00; solvent resistance, methyl ethyl ketone (“MEK”) resistance, is determined according to ASTM D5402-93; and acid resistance and base resistance is determined according to GMW 14701. Clear coat thickness is determined by Positector 6000 Coating Thickness Gauge. Wet film thickness is determined by the Octagon Wet Film Thickness Gauge ranging from 10.2 pm to 10,160 pm, available from Gradco. Resistance to household products is determined by ASTM D1308. In certain aspects the MEK resistance is from about 40 double wipes to about 600 double wipes or from about 100 double wipes to 300 double wipes. [0054] Unless otherwise specified, the monomer used for each Example was:

[0055] Leveling agent was BYK-310, available from BYK Additives and Instruments (Wesel, DE). Light stabilizer was a hindered amine light stabilizer (“HALS”) and was Tinuvin 5060, available from BASF (Ludwigshafen, DE).

[0056] Examples

[0057] Example 1 - Clear Coat Formulations

Table 1

[0058] Table 1 depicts clear coat formulas for the formation of clear coatings on wood substrates including maple, oak, and cherry. The formulations in Table 1 were combined as follows. Monomer was first mixed together with butyl acetate in a tri-pour using a spatula by hand; for formulations of sizes greater than 25 grams, overhead mixing blades were implemented to ensure complete dispersion of all components for uniform formulation. BYK-310 and Tinuvin 5060 were mixed into the formulation until well dispersed. Formulas 4, 5, 6 and 7, were used to coat a wood sample in Examples 4-7 except that different solvent levels were used. Examples 4 and 5 contain a solvent level of about 5% and about 10%. Example 6, showed the best results, with a range of 10-15% solvent. Example 7 contained about 25% solvent to allow for the best application onto the wood substrate. Table 2

(IK Clear coat Formulations for Surface Initiation on Base coated Substrates)

[0059] Table 2 depicts clear coat formulations for surface initiation on base coats formed on metallic surfaces. The above formulation shows improved appearance with increased propylene glycol monomethyl ether acetate (“PM Acetate”) content up to 35%.

[0060] Example 2.

[0061] DMDEE as surface initiator for wood. To apply the Formulas of Table 1 to wood coatings, DMDEE was applied as a surface initiator to the wood substrates. DMDEE, or 2,2’- dimorpholinodiethylether, available from Huntsman, was applied to the surface neat and mixed in combination with solvent (butyl acetate, PM Acetate, etc.) or commercially available stain compositions, such as those available from Minwax. In all compositions (Formulas 4, 5, 6 and 7), the DMDEE successfully initiated the polymerization of the clear coat formulations of the formulations in Table 1. When the concentration of DMDEE was 10% of the solution the cure rate of the clear coat was 90 minutes. When concentrations were above 50%, the cure rates increased allowing for cure speeds of around 60 mins. Using concentrations of <10% cure rates decreased further, with a concentration of 1% in solution resulting in a cure rate of 120 minutes. Ideal physical and chemical properties (e.g. Examples 8 and 9) were observed with concentrations of at least 10% DMDEE.

[0062] Evaluation with a rheometer indicated that when using a 95:5 ratio of formulation to DMDEE, the gel time at room temperature was 400 secs. [0063] DMDEE as surface initiator for metallic surface. DMDEE was also used as a surface initiator for base coats sprayed on electrophoretic deposited (e-coated) metallic surfaces. DMDEE was incorporated in commercially available base coats (BASF Glasurit WA-8555 & WA-8554). Base coat formulations with and without DMDEE were sprayed onto e-coated metallic substrates dried at 60 °C for 10 min, followed by air dry in fume hood at room temperature prior to clear coat spray. Base coat formulations with various DMDEE loadings are detailed in Table 3 below.

Table 3

[0064] The clear coat formulation A described in Table 2 was sprayed onto base coats and cured at 80 °C for 60 min. Gloss performance was measured after wiping. Performance properties tested after 72 hours are summarized in Table 4.

Table 4

[0065] Table 4 demonstrates film formation of methylene malonate systems by surface initiated polymerization. Cure was also observed without the addition of DMDEE which would suggest inherent basicity of the base coat. However, increased DMDEE concentrations in base coats resulted in smoother finishes and reduced tack free times with no change in pencil hardness and MEK resistance. Clear coat formulation with increased solvent loading up to 35 wt.%, cured at low temperatures.

[0066] Formulation B, described in Table 2, with solvent content up to 35%, was sprayed onto base coats with 7.5 wt.% DMDEE. Gloss performance was measured after wiping. Performance properties tested after 24 hours are summarized in Table 5. Table 5

(Performance Properties of IK Clear on 7.5 wt.% DMDEE

in base coat at 22 °C, 65 °C and 80 °C)

[0067] Results summarized in Table 5 demonstrate the ability of methylene malonate systems to cure at lower temperatures with 60° gloss angles (after wiping) of greater than 90 gloss units (“GU”) and 20° gloss angles (after wiping) of greater than 80 GU with increased solvent loading. An optimum balance between low temperature cure and performance properties was obtained at a cure temperature of 65 °C.

[0068] Example 3. Method to obtain high gloss, haze-free surface-initiated coatings on base coated substrates without incorporating DMDEE

[0069] An inherently responsive base coat was formulated that did not require the incorporation of DMDEE. The inherently response base coat included including 0% DMDEE, 74% Glasurit WA 8555, and 26% deionized water and is depicted in Table 6.

Table 6

[0070] The base coat of Table 6 was inherently responsive due to the presence of 2- dimethylaminoethanol (tertiary amine) and other potentially nucleophilic formulation components such as melamine and Nickel, 5, 5’- azobis-2,4,6, (lH,3H,5H)-pyrimidinetrione complexes.

[0071] The concentration of 2-Dimethylaminoethanol (volatile initiator) was observed to impact the external appearance such as gloss, formation of haze and tack free time of IK surface-initiated methylene malonate clear coats. Experiments in the current example (Example 3) were aimed at optimizing drying conditions for the base coat in order to obtain haze-free, high gloss coatings without negatively affecting mechanical properties and adhesion.

[0072] (a) Gloss & Haze as a function of base coat drying time at 60 °C.

[0073] The inherently responsive base coat mixture of Table 6 was sprayed onto e-coated panels without incorporating DMDEE. Base coats were dried at 60 °C in a convection oven for 3 min, 10 min, and 30 min. Clear coat Formulation B, detailed in Table 2, were sprayed on the base coats and cured at 80 °C for a total of 20 min. [0074] A drying time of 3 min resulted in haze-free, surface-initiated coatings with enhanced gloss. The gloss remained constant over 7 days without wiping the haze off the panels. The magnitude of gloss difference before and after wiping was used as a metric to quantify surface haze. Difference in gloss; indicative of surface haze was seen to increase with base coat drying time.

[0075] (b) Gloss & Haze as a function of base coat drying temperature

[0076] The inherently reactive base coat mixture of Table 6 was sprayed onto e-coated panels without incorporating DMDEE. The base coated panels were dried at 60 °C for 3 min and at ambient temperature in the fumehood; set at an air flow of 130-140 ft/min for 13-20 min till the panels were touch-dry. Clear coat Formulation B, detailed in Table 2, were sprayed immediately thereafter and cured at 80 °C for a total duration of 20 min.

Table 7

(Gloss & Haze measurements for different base coat drying temperatures)

[0077] Clear coats sprayed on base coats dried at ambient temperature in the fumehood resulted in haze-free coatings with no significant changes in the gloss and reduced tack-free times at 80 °C. [0078] Coatings performance on base coats dried at ambient temperature is summarized for different macromer lots in Table 8 below.

Table 8

(Coatings performance for different macromer lots)

[0079] This method offers an advantage of reduced cycle time due to reduced clear coat tack free and base coat drying time.

[0080] Example 4. Shelf life of surface initiator’s activity on wood substrate. With the use of

DMDEE as a surface initiator, the clear coat formulation can be applied to the surface immediately after application of DMDEE and at least 2 weeks after application of surface initiator. The time to cure after immediate application is 90 mins to tack-free. The cure time for the clear coat applied after 24 hours of the DMDEE solution is 120 mins to tack-free and properties were still maintained for the coating. The cure time for the clear coat applied after both 1 week and 2 weeks (after the DMDEE solution is applied) is over three hours and took 24 hours for comparable properties to that of the immediate properties to be observed.

[0081] Example 5. Application method by Draw Down Bar on wood substrate. Formula 4 (Table 1) was applied to the wood substrate. Using a draw down bar, the coating was applied to the surface easily and allows for uniform application with controlled thickness. However, the bar tends to leave behind streaks due to difficultly with completely cleaning the bar. Increasing the amount of solvent did improve the wet out and led to a reduction in the amount of streaks across surface, but did not allow for complete removal of defects.

[0082] Example 6. Application method by Brush on wood substrate. Formula 5 (Table 1) was applied to the wood substrate. Using nylon or polyester/nylon blended brushes, a thicker coating (75 pm and greater) was applied, though a thinner coating (38-56 pm) is possible as well. There tends to be little to no streak marks across the surface. There is some difficultly with cleaning the applicator, if not done so promptly.

[0083] Example 7. Application method by lint-free cloth on wood substrate. Formula 6 (Table 1) was applied to the wood substrate. Using a lint-free cloth such as Kimwipes or Deluxe Paint and Staining Clothes from HDX, a thinner coating was achieved on the surface. Uniformity was difficult to maintain without a slight increase in solvent content to allow for better wet out of the surface. A lint-free cloth was required in order to prevent transfer of any fibers that may become entrapped in the coatings surface. There was a significant amount of formulation loss due to the absorption of the cloth during application, however the method allows for faster application and clean up.

[0084] Example 8. Application method by Spray Gun on wood substrate. Formula 7 (Table 1) was applied to the wood substrate. Using a spray gun, the thickness of coating can be controlled by the number of passes across the surface. The amount of solvent needs to be increased to allow for a spray application, however thin (e.g. 10 to 38 microns), and even coatings are easy to achieve via this method. This method allows for the most uniform coating thickness and tends to have the fastest tack-free time, as most of the additional solvent is lost during spray. This method does require higher amount of solvent, with at least 20-25% solvent in order to achieve optimum coating application and appearance. This method of application may be used for industrial setting for materials with non-uniform surfaces and edges (such as furniture, prefmished doors and window casings, etc.).

[0085] Example 9. Chemical and physical resistance of coatings on wood substrate.

Coatings with wet film thicknesses (WFT) greater than 35 pm were found to have resistance to MEK solvent wipes and show a resistance greater than 120 double wipes. Coatings of Formula 6 (Table 1), applied by brush or application by lint-free cloth, were tested for resistance to household products. These tests include water, 50% ethanol, isopropanol, vinegar, coffee, Formula 409^® cleaner, and mustard. The formulations are tested at periods of 1 hour after cure, 24 hours after cure, and 7 days after cure. The results are summarized in Table 9.

Table 9

*The coating showed improvement after 24 hrs.

[0086] ASTM D1308 was used to test the resistance to household products. The coating was then further evaluated after 24 hours for any self-healing properties. Testing on an uncoated wood surface resulted in all chemicals being absorbed into the surface and grey discoloration of the wood. Additionally, the coffee and mustard both caused staining of the wood surface.

[0087] The gloss of the clear coat formulation at 20° was 67.7 GU and at 60° was 88.5 GU. The coating develops hardness after 24 hrs and cannot be scratched by finger nail or when a nickel is run across the surface. The adhesion of the clear coat was 4B or higher.

[0088] Example 10. Two-Component System including Acrylic Amine on wood substrate.

Inclusion of an acrylic amine to a polymerizable composition was further evaluated. For a two- component system, 5% acrylic amine, (Setalux 17-1453, available from Nuplex Industries (Sydney, AU)), was added to a clear coat formulation. The complete clear coat formulation is depicted in Table 10.

Table 10

(2K Formulation for Clear Coats on Wood Substrate)

[0089] Components of Part A were combined and mixed until well dispersed. Part B was added and mixed for 1-2 minutes, to ensure dispersion of the initiator throughout the formulation, just before application onto the substrate to be coated.

[0090] The total workable pot life of the system was less than 10 mins, with the coating being tack-free after being applied to a wood substrate within 5 mins. The properties MEK and chemical resistance is the same as those of the surface initiated system using DMDEE as the initiator. Additionally, the gloss was within the same range, with the exception of samples cured at lower temperatures, where fewer defects occurred due to the slight reduction in cure speed.

[0091] Example 11. Low temperature cure on wood substrate. Clear coat Formulation 6 (Table 1) demonstrated the ability to cure across a range of temperatures with little to no negative impact on cure time. When cured on a wood surface (cherry, maple, oak) that had been treated with a solution containing 10% DMDEE at 10°C, the cure time was the same as the cured time at room temperature. Lower temperature cure rates allowed for less coating defects to appear as the solvent flashes off and surface wet out is better.

[0092] When using a two-component formula, the cure speed at 10°C were slightly increased, with a 95:5 ratio (Formulation to Initiator) and the gel time, via rheometer, was 95 secs at 25 °C and 55 secs at 10 °C. Upon further evaluation by rheometer, cure at lower temperatures allowed for a higher storage modulus to be attained by comparison to a temperature of 60 °C, as the lower temperature allowed for more solvent to escape producing a stronger coating. Additionally, cure speed and properties are still possible at 0 °C, as that of 10 °C.

[0093] Example 12. Swell Test. The clear coat of Formula 6 (Table 1), was applied to the surface of three separate panels and allowed to fully cure for 72 hrs. The panels were weighed, after which the panels were tested according to ASTM D4446. The panels were immersed in water for a total of 24 hrs at room temperature. Additionally, the coated panels were compared to an uncoated panel of the same wood type for comparison of the uptake of moisture into the wood surface. The coated panels had no weight change after 30 minutes and the test was extended to show a small percent increase in weight over the duration of 24 hours, and further shows less damage due to water exposure by comparison to the uncoated panel. This water uptake can be attributed to poor coverage across the entire surface due to limitations in application technique, as water damage can only be seen around these areas in which application was inferior to other areas. The results are shown in Table 11.

Table 11

[0094] Example 13: Methylene malonate clear coats on natural leather

[0095] Methylene malonate macromer was applied onto dyed vegetable tanned leather samples. A tertiary amine was incorporated into the dye for surface initiation of the applied macromer to form a protective coating. The coating was cured at room temperature for 24 hours to form a tack free film.

[0096] Incorporation of DMDEE in leather dyes:

[0097] Dye formulations detailed in table 1 were mixed prior to application onto vegetable tanned leather substrates. Table 12

(Dye formulations)

[0098] The above mixtures were applied onto the substrate with a gauze sponge in circular motion followed by 2 coats applied diagonally across the substrate. The coated samples were dried at 65 °C for 10 min till the substrates were touch dry.

[0099] Application of macromer

[0100] Three coats of monomer (unformulated) were applied onto the dried specimens with a gauze sponge. Specimens dyed with dye formulation 1 and 3 (without DMDEE) were coated with macromer and cured at ambient temperature and 70 °C for 1 hour. The specimen was observed to warp at 70 °C, therefore cure for subsequent samples was performed at ambient temperature in the fume hood.

[0101] Specimens dyed with dye formulation 2 and 4 (with 5% DMDEE) were coated with monomer with a gauze sponge and cured at ambient temperature in the fume hood.

[0102] Table 13 summarizes tack free times and some initial properties of the coated samples. Table 13

(Performance of coated specimens)

[0103] The results summarized in the table above demonstrate the ability of methylene malonate macromer to coat natural leather substrates by surface initiation at room temperature by incorporation of a tertiary amine initiator into the dye.

[0104] Exemplary embodiments [0105] Embodiment 1. A method of initiating polymerization and forming a coated substrate comprising: providing a substrate; treating at least a portion of the substrate with an anionic initiator to form an initiator treated substrate; and applying a polymerizable composition to the at least a portion of the initiator treated substrate to provide a coating on the substrate, the polymerizable composition comprising a multifunctional 1,1 -di substituted alkene macromer.

[0106] Embodiment 2. The method according to Embodiment 1 further comprises crosslinking the multifunctional macromer.

[0107] Embodiment 3. The method according to Embodiment 2, wherein the substrate is held at a temperature of: about -10 °C to about 140 °C for 10 minutes to about 180 minutes to crosslink the multifunctional macromer; or about 20°C to about 150 °C for about 10 minutes to about 120 minutes to crosslink the multifunctional macromer.

[0108] Embodiment 4. The method according to any preceding Embodiment, wherein the substrate comprises one or more of a wood substrate, a metal substrate, and a leather substrate.

[0109] Embodiment 5. The method according to any preceding Embodiment, wherein the multifunctional 1,1 -di substituted alkene macromer comprises the formula:

wherein each X is independently O or a direct bond; R3 and Rs are the same or different and each represents a hydrocarbyl group; R.4 is a hydrocarbyl group having n + 1 valences; and n is an integer from 2 to 20.

[0110] Embodiment 6. The method according to Embodiment 5, wherein n is from about 4 to about 7. [0111] Embodiment 7. The method according to any preceding Embodiment, wherein the anionic initiator comprises an amine initiator.

[0112] Embodiment 8. The method according to Embodiment 7, wherein the anionic initiator comprises 2,2’-dimorpholinodiethylether (DMDEE).

[0113] Embodiment 9. The method according to Embodiment 7, wherein the anionic initiator comprises 2-dimethylaminoethanol.

[0114] Embodiment 10. The method according to any preceding Embodiment, wherein treating the at least a portion of the substrate comprises application of a base coat, the base coat comprising the anionic initiator.

[0115] Embodiment 11. The method according to Embodiment 10, wherein the base coat comprises from about 0% to about 25% of the anionic initiator, by weight.

[0116] Embodiment 12. The method according to any preceding Embodiment, wherein the polymerizable composition is essentially free of a polymerization initiator.

[0117] Embodiment 13. The method according to any preceding Embodiment, wherein the coating exhibits gloss; and wherein the coating exhibits one or more of: about 60 Gloss Units (“GU”) to about 90 GU after wiping when measured at a 20° angle; and about 30 GU to about 100 GU after wiping when measured at a 60° angle.

[0118] Embodiment 14. The method according to any preceding Embodiment, wherein the methyl ethyl ketone (“MEK”) resistance is greater than about 40 double wipes.

[0119] Embodiment 15. The method according to any preceding Embodiment, wherein the polymerizable composition further comprises one or more members from the group including dyes, pigments, toughening agents, impact modifiers, rheology modifiers, plasticizing agents, natural or synthetic rubbers, filler agents, reinforcing agents, thickening agents, opacifiers, inhibitors, fluorescence markers, thermal degradation reducers, thermal resistance conferring agents, surfactants, and wetting agents. [0120] Embodiment 16. The method according to any preceding Embodiment, wherein the polymerizable composition further comprises one or more additional monomers.

[0121] Embodiment 17. The method according to any preceding Embodiment, wherein the polymerizable composition further comprises acrylic amine.

[0122] Embodiment 18. The method according to any preceding Embodiment, wherein the coating is substantially transparent.

[0123] Embodiment 19. A coated system comprising: a substrate comprising an anionic initiator; and a cured polymerizable composition in contact with the substrate, the polymerizable composition comprising a multifunctional 1, 1-di substituted alkene macromer having the formula:

wherein each X is independently O or a direct bond; R3 and Rs are the same or different and each represents a hydrocarbyl group; R.4 is a hydrocarbyl group having n + 1 valences; and n is an integer from 2 to 20; and wherein the anionic initiator initiates polymerization of the polymerizable composition.

[0124] Embodiment 20. The coated system according to Embodiment 19, wherein the cured polymerizable composition is crosslinked.

[0125] The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. [0126] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0127] Every document cited herein, including any cross-referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests, or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in the document shall govern.

[0128] The foregoing description of aspects and examples has been presented for purposes of description. It is not intended to be exhaustive or limiting to the forms described. Numerous modifications are possible in light of the above teachings. Some of those modifications have been discussed and others will be understood by those skilled in the art. The aspects were chosen and described for illustration of various aspects. The scope is, of course, not limited to the examples or aspects set forth herein, but can be employed in any number of applications and equivalent articles by those of ordinary skill in the art. Rather it is hereby intended the scope be defined by the claims appended hereto.

[0129] It should be understood that certain aspects, features, structures, or characteristics of the various aspects can be interchanged in whole or in part. Reference to certain aspects means that a particular aspect, feature, structure, or characteristic described in connection with certain aspects can be included in at least one aspect and may be interchanged with certain other aspects. The appearances of the phrase“in certain aspects” in various places in specification are not necessarily all referring to the same aspect, nor are certain aspects necessarily mutually exclusive of other certain aspects. It should also be understood that the steps of the methods set forth herein are not necessarily required to be performed in the orders described, and the order of the steps of such methods should be understood to be merely exemplary. Likewise, additional steps can be included in such methods, and certain steps may be omitted or combined, in methods consistent with certain aspects.

Claims

WHAT IS CLAIMED IS:

1. A method of initiating polymerization and forming a coated substrate comprising: providing a substrate; treating at least a portion of the substrate with an anionic initiator to form an initiator treated substrate; and applying a polymerizable composition to the at least a portion of the initiator treated substrate to provide a coating on the substrate, the polymerizable composition comprising a multifunctional 1,1 -di substituted alkene macromer.

2. The method according to claim 1 further comprises crosslinking the multifunctional macromer.

3. The method according to claim 2, wherein the substrate is held at a temperature of: about -10 °C to about 140 °C for 10 minutes to about 180 minutes to crosslink the multifunctional macromer; or about 20°C to about 150 °C for about 10 minutes to about 120 minutes to crosslink the multifunctional macromer.

4. The method according to any preceding claim, wherein the substrate comprises one or more of a wood substrate, a metal substrate, and a leather substrate.

5. The method according to any preceding claim, wherein the multifunctional 1,1- disubstituted alkene macromer comprises the formula:

wherein each X is independently O or a direct bond; R.3 and Rs are the same or different and each represents a hydrocarbyl group; R.4 is a hydrocarbyl group having n + 1 valences; and n is an integer from 2 to 20.

6. The method according to claim 5, wherein n is from about 4 to about 7.

7. The method according to any preceding claim, wherein the anionic initiator comprises an amine initiator.

8. The method according to claim 7, wherein the anionic initiator comprises 2,2’- dimorpholinodiethylether (DMDEE).

9. The method according to claim 7, wherein the anionic initiator comprises 2- dimethylaminoethanol.

10. The method according to any preceding claim, wherein treating the at least a portion of the substrate comprises application of a base coat, the base coat comprising the anionic initiator.

11. The method according to claim 10, wherein the base coat comprises from about 0% to about 25% of the anionic initiator, by weight.

12. The method according to any preceding claim, wherein the polymerizable composition is essentially free of a polymerization initiator.

13. The method according to any preceding claim, wherein the coating exhibits gloss; and wherein the coating exhibits one or more of: about 60 Gloss Units (“GU”) to about 90 GU after wiping when measured at a 20° angle; and about 30 GU to about 100 GU after wiping when measured at a 60° angle.

14. The method according to any preceding claim, wherein the methyl ethyl ketone (“MEK”) resistance is greater than about 40 double wipes.

15. The method according to any preceding claim, wherein the polymerizable composition further comprises one or more members from the group including dyes, pigments, toughening agents, impact modifiers, rheology modifiers, plasticizing agents, natural or synthetic rubbers, filler agents, reinforcing agents, thickening agents, opacifiers, inhibitors, fluorescence markers, thermal degradation reducers, thermal resistance conferring agents, surfactants, and wetting agents.

16. The method according to any preceding claim, wherein the polymerizable composition further comprises one or more additional monomers.

17. The method according to any preceding claim, wherein the polymerizable composition further comprises acrylic amine.

18. The method according to any preceding claim, wherein the coating is substantially transparent.

19. A coated system comprising: a substrate comprising an anionic initiator; and a cured polymerizable composition in contact with the substrate, the polymerizable composition comprising a multifunctional 1,1-di substituted alkene macromer having the formula:

wherein each X is independently O or a direct bond; R3 and Rs are the same or different and each represents a hydrocarbyl group; R.4 is a hydrocarbyl group having n + 1 valences; and n is an integer from 2 to 20; and wherein the anionic initiator initiates polymerization of the polymerizable composition.

20. The coated system according to claim 19, wherein the cured polymerizable composition is crosslinked.