Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes

Abstract

Compositions comprising a) one or more polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chain and a portion of the diesters are 1,1-diester-1-alkenes and at least one terminal end comprises the residue of one of the 1,1-diester-1 alkenes and wherein one or more terminal ends may comprise the residue of one or more diols; and b) one or more polymers having pendant Michael Addition donor groups. Disclosed are coating prepared from these compositions.

Description

FIELD

Disclosed are novel compositions containing polyester macromers containing the residue of 1,1-diester-1-alkene compounds and polymers containing pendant Michael Addition donors. Further disclosed are coatings containing the compositions and methods for using the compositions as coatings.

BACKGROUND

Polyesters are utilized in a number of applications due to their properties and their ease of synthesis. Exemplary uses include coatings, films, fibers, and resins. Due to their properties polyesters are also utilized in blends with other polymers to improve certain property limitations of the other polymers, such polymers include polycarbonates, polyamides, styrenic polymers, and polyolefins, and the like. Polyesters are typically prepared by reacting diacids with dialcohols, and generally are linear in structure. It is somewhat challenging to cross-link these polyesters due to the structure. Some crosslinking processes require special catalysts or high temperatures.

1,1-diester-1-alkenes, such as methylene malonates, contain two diester groups, and an alkylene group disposed between the two diester groups. Recent developments in synthesis of these compounds facilitate the synthesis of these compounds and their use in a variety of applications, see Malofsky U.S. Pat. No. 8,609,885; U.S. Pat. No. 8,884,051; and U.S. Pat. No. 9,108,914; incorporated herein by reference in their entireties for all purposes. Processes for transesterifying these compounds have also been recently developed. Malofsky et al. WO 2013/059473 and US 2014/0329980, incorporated herein by reference in their entirety for all purposes, discloses the preparation of multifunctional methylene malonates by multiple synthetic schemes. One disclosed process involves reacting a methylene malonate with a polyol in the presence of a catalyst to prepare compounds wherein at least one of the ester groups on the methylene malonates undergoes transesterification to react with the polyol and form multifunctional compounds (multifunctional meaning the presence of more than one methylene malonate core unit). The use of enzyme catalysis is disclosed. Sullivan, U.S. Pat. No. 9,416,091 discloses transesterification of 1,1-disubstituted-1-alkenes using certain acid catalysts, incorporated herein by reference in its entirety for all purposes.

Commonly owned application titled POLYESTER MACROMERS CONTAINING 1,1-DICARBONYL-SUBSTITUTED 1 ALKENES having a Ser. No. 15/234,191 filed Aug. 11, 2016 discloses compositions containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes useful in preparing polyesters containing compositions which can be crosslinked elegantly without the need for problematic catalysts and use relatively mild conditions. Disclosed are coatings prepared from such compositions that exhibit enhanced properties, wherein such enhanced properties include flexibility, adhesion to substrates, pencil hardness, solvent resistance, abrasion resistance, ultraviolet radiation resistance, acid and base resistance, and the like. Processes that prepare the components for such coatings and the coatings are also disclosed. The compositions and processes disclosed provide significant improvements in coating technology. In order to meet customer expectations additional enhancement to this technology is desirable.

What is needed are polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes compositions useful in preparing coating compositions which can be crosslinked elegantly without the need for problematic catalysts and use relatively mild conditions. What is also needed are coatings prepared from such compositions that exhibit enhanced properties, such as flexibility, adhesion to substrates, pencil hardness, solvent resistance, abrasion resistance, ultraviolet radiation resistance, high temperature acid and base resistance, fuel resistance. Processes that prepare the coatings are needed.

SUMMARY

Disclosed are compositions comprising a) one or more polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chain and a portion of the diesters are 1,1-diester-1-alkenes and at least one terminal end comprises the residue of one of the 1,1-diester-1-alkenes and wherein one or more terminal ends may comprise the residue of one or more diols; and b) one or more polymers having pendant Michael Addition donor groups. The pendant Michael Addition donor groups may comprise functional groups containing active hydrogen atoms. The one or more polymers having pendant Michael Addition donor groups may comprise one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyether amines, polyester polyols, polyether polyols and siloxane polyols. The composition may contain three or more alternating chains of the residue of one or more diols and one or more diesters, wherein at least some of the diesters are 1,1-diester-1-alkenes, and each of the chains are bonded at one end to an oxygen of the residue of a polyol having three or more of the oxygen atoms. The polyester macromers may correspond to Formula 1

wherein Z is separately in each occurrence —R²OH or —R¹; R¹ is separately in each occurrence a hydrocarbyl group which may contain one or more heteroatoms; R² is separately in each occurrence a hydrocarbylene group having two or more bonds to oxygen atoms, wherein the hydrocarbylene group may contain one or more heteroatoms; c is an integer of 1 or more; and n is an integer of about 1 to 3. c may be an integer of about 2 to about 8 or about 3 to about 6. The polyester macromers may contain one chain of the residue of one or more diols and one or more diesters, wherein at least some of the diesters are 1,1-diester-1-alkenes. The polyester macromers disclosed may exhibit number average molecular weights of about 400, or about 700 to about 3000.

The one or more diesters may comprise 1,1-diester-1-alkenes. In addition to the one or more 1,1-diester-1-alkenes, the one or more diesters may comprise one or more dihydrocarbyl dicarboxylates. The polyester macromers contain the residue of one or more 1,1-diester-1-alkenes and may contain the residue of one or more dihydrocarbyl dicarboxylates. The one or more dihydrocarbyl dicarboxylates may comprise one or more of aromatic dicarboxylates, aliphatic dicarboxylates, cycloaliphatic dicarboxylates and/or a dicarboxylate containing two different hydrocarbyl groups selected from aromatic, aliphatic and cycloaliphatic.

Disclosed is a composition comprising i) a plurality of polyester macromers as described herein; ii) one or more multifunctional monomers containing the residue of one or more polyols and one or more 1,1-diester-1-alkenes, wherein the multifunctional monomers have substantially all of the hydroxyl groups of the polyols replaced with the 1,1-diester-1-alkenes; and iii) one or more 1,1-diester-1-alkenes. The one or more polyols may be diols. The one or more multifunctional monomers may be difunctional monomers. This composition may be combined with one or more polymers having pendant Michael Addition donor groups.

Disclosed is a composition comprising a) i) a plurality of polyester macromers as described herein; ii) one or more multifunctional monomers containing the residue of one or more polyols and one or more 1,1-diester-1-alkenes, wherein the multifunctional monomers have substantially all of the hydroxyl groups of the polyols replaced with the 1,1-diester-1-alkenes; and iii) one or more 1,1-diester-1-alkenes; b) a volatile solvent; c) an additional amount of one or more 1,1-diester-1-alkenes if so desired; d) one or more leveling and wetting agents; e) one or more UV stabilizers f) one or more additives to improve abrasion resistance and g) one or more additives to provide surface slip and anticratering properties. The solvent may be an alkoxy alkanol or an alkoxy alkyl acetate. The wetting agent may be a polyether modified polydimethyl siloxane. UV stabilizer may be a benzotriazole based or a hindered amine based compound. The composition may contain an additive to improve scratch resistance which may be a nanometer sized silica filler. An additive to improve surface slip properties may be a polyether modified polydimethyl siloxane. This composition may be combined with one or more polymers having pendant Michael Addition donor groups.

Disclosed is a composition comprising one or more polyester macromers and one or more of the polyols endcapped with one or more 1,1-diester-1-alkenes or multifunctional monomers, that is the terminal ends of the chains contain the residue of one or more 1,1-diester-1-alkenes and/or multifunctional monomers. The composition may contain a solvent. The one or more polyols may be one or more polyether polyols, polysiloxane polyols, polycarbonate polyols, polyester polyols, acrylic polyols, or polybutadiene polyols. The one or more polyols may be one or more polycarbonate polyols. The one or more polyols may be di or tri functional. The one or more polyols may have Michael Donor groups, such as hydroxyl, thiol or amino groups, pendant from their backbone.

The compositions containing polyester macromers disclosed herein and one or more polymers having pendant Michael Addition donor groups may be fabricated into films or coatings. The coatings or films may have a thickness of about 0.001 micrometers or greater, or about 10 micrometers or greater. The coatings or films may have a thickness of about 160 micrometers or less or about 140 micrometers or less. Compositions containing a plurality of one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups disclosed herein may be cured. Compositions containing a plurality of one or more polyester macromers disclosed herein may be crosslinked after cure.

Disclosed is a composition comprising a) a plurality of polyester macromers according to the preceding description and b) one or more polymers having pendant Michael Addition donor groups wherein a portion of or all of the polyester macromers are crosslinked through the 1,1-alkene groups. Disclosed is a composition comprising a) a plurality of polyester macromers according to the preceding description and b) one or more polymers having pendant Michael Addition donor groups wherein a portion of or all of the polyester macromers are crosslinked by Michael Addition of the Michael Addition Donors pendant from the polymers to the 1 alkene groups of the polyester macromers.

Disclosed is a composition comprising one or more polyester macromers as disclosed herein in one part and in a second part one or more compounds having basic character sufficient to initiate anionic polymerization of the polyester macromers; wherein when the two parts are combined the polyester macromers undergo curing. The one or more compounds having basic character may comprise one or more amines or polyamines. The one or more compounds having basic character may comprise one or more polyalkyleneimines. These compositions may be combined with one or more polymers having pendant Michael Addition donor groups.

Disclosed is an article having a coating containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups as part of the composition disposed on all or a portion of one or more of the surfaces of the article. The article may have a base coat upon which the coating formulation is deposited. The base coat may contain pigments. The base coat may have a basic pH at the surface. The pigments may be basic. The base coat may have amine groups or hydroxyl groups on the surface that may help with the cure process and adhe-sion of the coating to the substrate. The polyester macromer coating may be clear. The polyester macromer coating may contain pigments or other known ingredients used in coatings.

Disclosed is a method comprising contacting a composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups according to the preceding description with a surface of a substrate wherein the surface is at least mildly basic and forming a coating on the surface of the substrate comprising the composition containing the one or more polyester macromers. The substrate may be comprised of one or more of a material that is at least mildly basic, nucleophilic and/or contains a plurality of Michael Addition donor groups on its surface.

Disclosed is a method comprising contacting a composition containing one or more polyester macromers as disclosed herein and one or more polymers having pendant Michael Addition donor groups with a surface of a substrate wherein the surface is at least mildly basic, contains nucleophiles and/or Michael Addition donors and forming a coating on the surface. The substrate may be comprised of material that is at least mildly basic, nucleophilic and/or contains Michael Addition donors. A composition that contains a basic, nucleophilic, or a Michael Addition donor compound that initiates anionic polymerization for 1,1-disubstituted alkenes or Michael adds to the alkene groups of the polyester macromers may be applied to the surface of the substrate before applying the composition containing one or more polyester macromers and macromers and one or more polymers having pendant Michael Addition donor groups. Exemplary basic compounds comprise one or more amines, polyamine, basic pigments; polyalkyleneamine polyethylene amines and carboxylate salts. The methods for forming coatings may further comprise exposing the substrate with the composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups to a temperature of about 20° C. to about 150° C. for about 10 minutes to about 120 minutes under conditions such that the coating containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups disposed on the surface of the substrate is crosslinked. The coatings may also be cured with no heat input, at ambient temperatures, which requires greater cure times, or example up to about 24 hours.

The compositions containing polyester macromers and one or more polymers having pendant Michael Addition donor groups can be used to prepare coating formulations that can be cured and crosslinked using relatively mild conditions. The polyester macromers allow the tailoring of properties of polyester containing compositions. Specifically the polyester macromers allow the preparation of polyester compositions that have improved mechanical properties and elasticity. The cured coatings disclosed exhibit one or more of the following properties of a gloss according to ASTM D523-08 at 20° of 50 GU or greater; a pencil hardness according to ASTM D3363-00 of 4H or greater; a solvent resistance according to ASTM D5402-93 to 80 rubs of methyl ethyl ketone or greater; mandrel flexibility according to ASTM D522-93 of 80 percent or greater; cross hatch adhesion of 4B or higher and 100 percent according to ASTM D3359-09 and acid resistance up to 70° C. and base resistance at greater than 70° C. according to GMW 14701. The methods of preparing coatings and films allow the preparation of coatings with the above-described enhanced properties in an efficient manner.

DETAILED DESCRIPTION

The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the invention, its principles, and its practical application. The specific embodiments of the present invention as set forth are not intended to be exhaustive or limiting of the invention. The scope of the disclosure should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible as will be gleaned from the following claims, which are also hereby incorporated by reference into this written description.

Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by a person skilled in the art to which this disclosure belongs. The following references provide one of skill with a general definition of many of the terms used in this disclosure: Singleton et al., Dictionary of Microbiology and Molecular Biology (2nd ed. 1994); The Cambridge Dictionary of Science and Technology (Walker ed., 1988); The Glossary of Genetics, 5th Ed., R. Rieger et al. (eds.), Springer Verlag (1991); and Hale & Marham, The Harper Collins Dictionary of Biology (1991). The following terms have the meanings ascribed to them below, unless specified otherwise.

Disclosed are compositions comprising a) polyester macromers containing in one or more chains the residue of one or more diols and one or more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chain and a portion of the diesters are 1,1-diester-1-alkenes and at least one terminal end comprises the residue of one of the 1,1-diester-1-alkenes and wherein one or more terminal ends may comprise the residue of one or more diols and b) one or more polymers having pendant Michael Addition donor groups. The macromers may have two or greater of such chains. The chains may include the residue or one or more dihydrocarbyl dicarboxylates. The chains may contain the residue of one or more diols and one or more diesters wherein the diesters comprise one or more 1-diester-1-alkenes, the residue of the one or more diols and the one or more 1,1-diester-1 alkenes and optionally one or more dihydrocarbyl dicarboxylates may be randomly disposed along the chains. The polyester macromers may be used to form polyesters, blended with polyesters and/or other polymeric compounds to provide enhanced properties. Disclosed are methods of preparing the polyester macromers and incorporating them in a variety of polyester containing compositions. Further disclosed are methods of preparing structures from polyester macromer containing compositions such as coatings.

As used herein, diester refers to any compound having two ester groups which can be subjected to transesterification. A 1,1-diester-1-alkene is a compound that contains two ester groups and a double bond bonded to a single carbon atom referred to as the one carbon atom. Dihydrocarbyl dicarboxylates are diesters having a hydrocarbylene group between the ester groups wherein a double bond is not bonded to a carbon atom which is bonded to two carbonyl groups of the diester.

The term “monofunctional” refers to the 1,1-diester-1-alkenes having only one core unit. The core unit comprises two carbonyl groups and a double bond bonded to a single carbon atom. The term “difunctional” refers to the 1,1-diester-1-alkenes having two core units (each including the reactive alkene functionality) bound through a hydrocarbylene linkage between one oxygen atom on each of two core formulas. The term “multifunctional” refers to the 1,1-diester-1-alkenes having two or more core units (each core unit including the reactive alkene functionality) bound together through a hydrocarbylene linkage between one oxygen atom on each of two or more core formulas.

Acid catalyst, as used herein, is an acidic species that catalyzes the transesterification reaction while minimizing or not contributing to side reactions. One or more as used herein means that at least one, or more than one, of the recited components may be used as disclosed. Nominal as used with respect to functionality refers to the theoretical functionality; generally this can be calculated from the stoichiometry of the ingredients used. Heteroatom refer to atoms that are not carbon or hydrogen such as nitrogen, oxygen, sulfur, and phosphorus; heteroatoms may include nitrogen and oxygen. Hydrocarbyl, as used herein, refers to a group containing one or more carbon atom backbones and hydrogen atoms, which may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups well-known to one skilled in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic, or any combination of such segments. The aliphatic segments can be straight or branched. The aliphatic and cycloaliphatic segments may include one or more double and/or triple bonds. Included in hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl, and aralkyl groups. Cycloaliphatic groups may contain both cyclic portions and noncyclic portions. Hydrocarbylene means a hydrocarbyl group or any of the described subsets having more than one valence, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene. As used herein percent by weight or parts by weight refer to, or are based on, the weight or the compounds or compositions described unless otherwise specified. Unless otherwise stated parts by weight are based 100 parts of the relevant composition.

The terms “volatile” refers to compounds which are capable of evaporating readily at normal temperatures and pressures. “Non-volatile” refers to compounds which are not capable of evaporating readily at normal temperatures and pressures. The term “stabilized” (e.g., in the context of “stabilized” 1,1-diester-1-alkenes, or compositions comprising the same,) refers to the tendency of the compounds (or their compositions) to substantially not polymerize with time, to substantially not harden, form a gel, thicken, or otherwise increase in viscosity with time, and/or to substantially show minimal loss in cure speed (i.e., cure speed is maintained) with time. Residue with respect to an ingredient used to prepare the polyester macromers disclosed herein means that portion of the ingredient, such as a polyol, such as a diol, a diester, such as a 1,1-diester-1-alkene and/or a dihydrocarbyl dicarboxylate, that remains in the compound after inclusion as a result of the methods disclosed herein. Substantially all as used herein that greater than 95 percent of the referenced parameter, composition or compound meet the defined criteria, greater than 99 percent of the referenced parameter, composition or compound meet the defined criteria, or greater than 99.5 percent of the referenced parameter, composition or compound meet the defined criteria.

Disclosed are polyester macromers which contain one or more chains containing the residue of one or more diols and one or more diesters wherein a portion of the diesters comprise 1,1-diester-1-alkenes. The residue of the diols and the diesters can alternate along the chains or can be disposed randomly along the chains. The diesters may further comprise any diester compound that will undergo transesterification with a polyol or diol. Among diester compounds are dihydrocarbyl dicarboxylates. The polyester macromers may have three or more chains as described. The polyester macromers having three or more chains contain the residue of a polyol originally having three or greater hydroxyl groups. The three or more chains propagate from each of the three or more hydroxyl groups. The polyols having three or more chains function as initiators from which each of the chains of the polyester macromers propagate. If the polyol is a diol a single chain is produced because the macromer formed is linear. Where a polyol having three or more hydroxyls is used to prepare the macromer, it may have two or more chains as not all of the hydroxyls may propagate chains. The macromers may contain one or more chains, may contain two or more chains, or may contain three or more chains. The macromers may contain eight or less chains, six or less chains, four or less chains or three or less chains. The chains may comprise the residue of one or more polyols, one or more diols and one or more diesters, including one or more 1,1-diester-1-alkenes and optionally one or more dihydrocarbyl dicarboxylates. The chains may comprise the residue of one or more diols and one or more diesters, including one or more 1,1-diester-1-alkenes and optionally one or more dihydrocarbyl dicarboxylates. The polyester macromers contain the residue of at least one 1,1-diester-1-alkenes at the terminal end of one of the chains. The polyester macromers may further comprise one or more diols or dihydrocarbyl dicarboxylates at the terminal end of one or more of the chains. Substantially all of the terminal ends of chains may be 1,1-diester-substituted alkenes.

The polyester macromers may comprise sufficient amount of the residue of one or more polyols, in this context the polyols have 3 or greater hydroxyl groups, to initiate the desired number of chains. The residue of the polyols in the polyester macromers may be about 20 mole percent or greater of the macromer; 30 mole percent or greater or about 40 mole percent or greater. The residue of the polyols in the polyester macromers may be about 50 mole percent or less; or about 40 mole percent or less. The polyester macromers may comprise sufficient amount of the residue of one or more diols, in this context the polyols have 2 hydroxyl groups, to prepare polyester macromers having the desired chain length and number average molecular weight. The residue of the diols in the polyester macromers may be about 20 mole percent or greater of the macromer; 40 mole percent or greater or about 50 mole percent or greater. The residue of the diols in the polyester macromers may be about 50 mole percent or less; 40 mole percent or less or about 30 mole percent or less. The polyester macromers may comprise sufficient amount of the residue of the 1,1-diester-substituted-1-alkenes to provide the desired crosslink density to compositions containing the polyester macromers. The residue of the 1,1-diester-substituted-1-alkenes in the polyester macromers may be about 20 mole percent or greater of the macromer; 30 mole percent or greater or about 40 mole percent or greater. The residue of the 1,1-diester-substituted-1-alkenes in the polyester macromers may be about 60 mole percent or less of the macromer; about 50 mole percent or less of the macromer; about 40 mole percent or less or about 30 mole percent or less. The polyester macromers may comprise sufficient amount of the residue of the dihydrocarbyl dicarboxylates to provide the desired space between crosslinks to compositions containing the polyester macromers to provide the desired flexibility and/or elasticity to the structures containing the polyester macromers. The residue of the dihydrocarbyl dicarboxylates in the polyester macromers may be about 10 mole percent or greater of the polyester macromer; 20 mole percent or greater or about 30 mole percent or greater. The residue of the dihydrocarbyl dicarboxylates in the polyester macromers may be about 30 mole percent or less of the polyester macromer; 20 mole percent or less or about 10 mole percent or less.

The polyester macromers may correspond to Formula 1

wherein Z is separately in each occurrence —R²OH or —R¹; R¹ is separately in each occurrence a hydrocarbyl group which may contain one or more heteroatoms; R² is separately in each occurrence a hydrocarbylene group having two or more bonds to oxygen atoms; c is an integer of 1 or more; and n is an integer of about 1 to 3. With respect to R² the bonds to oxygen atoms may include bonds to the oxygen of a polyol, a diol, or a diester or the residue thereof depending on the context of use of R².

The polyester macromers may contain one chain of the residue of one or more diols and one or more diesters. These polyester macromers may correspond to Formula 2,

wherein Z, R¹ and R² are as previously defined; and m is an integer of about 1 to 3.

The polyester macromers containing the residue of one or more 1,1-diester-1-alkenes and the residue of one or more dihydrocarbyl dicarboxylates may correspond to one of Formulas 3 to 6:

wherein D corresponds to the formula

wherein E corresponds to the formula,

wherein Z, R¹, R² and m are as previously defined; R³ is separately in each occurrence a hydrocarbylene group having two bonds to the carbonyl groups of one or more of the diesters or to the residue of such diesters depending on the context, wherein the hydrocarbylene group may contain one or more heteroatoms; c is an integer of 1, or 2 or more; d is an integer of 0 or 1; e is an integer of 0 or 1; f is the integer 1; n is an integer of about 1 to 3; p is an integer of 2 or more; and q is an integer of 1 or more; wherein each pair of d and e must equal 1. p may be an integer of 3 or greater. p may be an integer of 8 or less, 6 or less or 3 less. q may be an integer of 4 or less or 3 or less.

The polyester macromers may contain in their backbone repeating units comprising the residue of at least one diester and one diol. A significant portion of the diesters are 1,1-diestersubstituted-1-alkenes. A portion of the diesters may be 1,1-dihydrocarbyl dicarboxylates. The backbone of polyester macromers contain a sufficient number of repeating units comprising the residue of at least one diester and one diol to facilitate the use of the polyester macromers as disclosed herein such as in coatings. The number of repeating units comprising the residue of at least one diester and one diol in polyester macromers may be 2 or greater, 4 or greater or 6 or greater. The number of repeating units comprising the residue of at least one diester and one diol in polyester macromers may be 8 or less, 6 or less, or 4 or less. The diesters in some polyester macromers can be all 1,1-diester-1-alkenes. The diesters in some polyester macromers can be 1,1-diester-1-alkenes and dihydrocarbyl dicarboxylates. The molar ratio of 1,1-diester-1-alkenes and dihydrocarbyl dicarboxylates in some polyester macromers is selected to provide the desired degree of crosslinking in structures prepared from the polyester macromers. The molar ratio of 1,1-diester-1-alkenes and dihydrocarbyl dicarboxylates in some polyester macromers may be 1:1 or greater, 6:1 or greater or 10:1 or greater. The molar ratio of 1,1-diestersubstituted-1-alkenes and dihydrocarbyl dicarboxylates in some polyester macromers may be 15:1 or less, 10:1 or less, 6:1 or less or 4:1 or less. The polyester macromers may exhibit a number average molecular weight of about 700 or greater, about 900 or greater, about 1000 or greater or about 1200 or greater. The polyester macromers may exhibit a number average molecular weight of about 3000 or less, about 2000 or less or about 1600 or less. Number average molecular weight as used herein is determined dividing total weight of all the polymer molecules in a sample, by the total number of polymer molecules in a sample. The polydispersity of the polyester macromers may be about 1.05 or greater or about 1.5 or greater. The polydispersity of the polyester macromers may be about 2.5 or less or about 1.5 or less. For calculating the poly-dispersity the weight average molecular weight is determined using gel permeation chromatography using polymethylmethacrylate standards. Polydispersity is calculated by dividing the measured weight average molecular weight (M_v) by the number average molecular weight (M_n), that is M_v/M_n.

The polyester macromers disclosed may be prepared from 1,1-diester-1-alkenes, diols, polyols and/or dihydrocarbyl dicarboxylates. The choice of specific ingredients, ratios of ingredients and sequence of process steps impact the final structure and content of the polyester macromers. The presence of polyols having greater than two hydroxyl groups function to initiate the chains and their use results in the formation of polyester macromers having more than two chains, that is the macromer exhibits branching and the polymer is not linear. The 1,1-diester-1-alkenes help form the chains and introduce pendant alkene groups capable of crosslinking via anionic and/or free radical polymerization and/or Michael addition. The diols may initiate a single chain and chain extend the polyester macromers. The dihydrocarbyl dicarboxylates help form the chains and function to space the pendant alkene groups from one another, thereby increasing the distance between crosslinks and the average molecular weight per crosslink.

The 1,1-diester-1-alkenes comprise a central carbon atom referred to as the 1 carbon atom. Bonded to the 1 carbon atom are the carbonyl groups of two ester groups and another carbon atom via a double bond. The double bond, due to it being bonded to two carbonyl groups, is highly reactive. The doubly bonded carbons may be part of an alkenyl group which is highly reactive. The alkenyl group may be a C_2-4 alkenyl group, or a methylene group (C═C). The esters contain hydrocarbyl groups bonded to the oxygen bonded to the carbonyl group wherein the hydrocarbyl groups may contain one or more heteroatoms, including heteroatom containing functional groups. The hydrocarbyl groups can be any hydrocarbyl groups that can undergo transesterification under the conditions disclosed herein. The hydrocarbyl groups on the ester may be separately in each occurrence alkyl, alkenyl, cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, or alkheteroaryl, or polyoxyalkylene, or both of the hydrocarbyl groups may form a 5-7 membered cyclic or heterocyclic ring. The hydrocarbyl groups on the ester may be separately in each occurrence C₁-C₁₅ alkyl, C₂-C₁₅ alkenyl, C₃-C₉ cycloalkyl, C_2-20 heterocyclyl, C_3-20 alkheterocyclyl, C_6-18 aryl, C_7-25 alkaryl, C_7-25 aralkyl, C_5-18 heteroaryl or C_6-25 alkyl heteroaryl, or polyoxyalkylene, or both of the hydrocarbyl groups form a 5-7 membered cyclic or heterocyclic ring. The recited groups may be substituted with one or more substituents, which do not interfere with the transesterification reaction. Exemplary substituents include halo, alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester. The hydrocarbyl groups on the ester may be separately in each occurrence C₁-C₁₅ alkyl, C₃-C₆ cycloalkyl, C_4-18 heterocyclyl, C_4-18 alkheterocyclyl, C_6-18 aryl, C_7-25 alkaryl, C_7-25 aralkyl, C_5-18 heteroaryl or C_6-25 alkyl heteroaryl, or polyoxyalkylene. The hydrocarbyl groups on the ester may be separately in each occurrence a C_1-4 alkyl. The hydrocarbyl groups on the ester may be separately in each occurrence methyl or ethyl. The hydrocarbyl groups on the ester may be the same for each ester group on the 1,1-di-1-alkene compounds. Exemplary compounds are dimethyl, diethyl, ethylmethyl, dipropyl, dibutyl, diphenyl, and ethyl-ethylgluconate malonates. The compounds may be dimethyl and diethyl methylene malonate. The 1,1-diester-1-alkenes can be prepared as disclosed in Malofsky et al., U.S. Pat. Nos. 8,609,885 and 8,884,051; and Malofsky et al. U.S. Pat. No. 9,108,914.

The 1,1-diester-1-alkene compounds may correspond to formula 7:

R¹ is separately in each occurrence a group that can undergo replacement or transesterification under the conditions of the methods disclosed herein. R¹ may be separately in each occurrence alkyl, alkenyl, cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, or alkheteroaryl, or polyoxyalkylene, or both of the R¹s form a 5-7 membered cyclic or heterocyclic ring. R¹ may be separately in each occurrence C₁-C₁₅ alkyl, C₂-C₁₅ alkenyl, C₃-C₉ cycloalkyl, C_2-20 heterocyclyl, C_3-20 alkheterocyclyl, C_6-18 aryl, C_7-25 alkaryl, C_7-25 aralkyl, C_5-18 heteroaryl or C_6-25 alkyl heteroaryl, or polyoxyalkylene, or both of the R₁ groups form a 5-7 membered cyclic or heterocyclic ring. The recited groups may be substituted with one or more substituents, which do not interfere with the transesterification reaction. Exemplary substituents include halo alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester. R¹ may be separately in each occurrence C₁-C₁₅ alkyl, C₃-C₆ cycloalkyl, C_4-18 heterocyclyl, C_4-18 alkheterocyclyl, C_6-18 aryl, C_7-25 alkaryl, C_7-25 aralkyl, C_5-18 heteroaryl or C_6-25 alkyl heteroaryl, or polyoxyalkylene. R¹ may be separately in each occurrence a C_1-4 alkyl. R¹ may be separately in each occurrence methyl or ethyl. R¹ may be the same or different for each ester group on the 1,1-disubstituted alkene compounds.

A preferred class of 1,1-disubstituted alkene compounds are the methylene malonates which may correspond to formula 8:

wherein R¹ is as described herein before.

The 1,1-diester-alkenes may be prepared using a method which results in a sufficiently high purity so that they can be included into polyester macromers that can be polymerized and/or crosslinked. The purity of the 1,1-diester-1-alkenes may be sufficiently high so that 70 mole percent or more, 80 mole percent or more, 90 mole percent or more, 95 mole percent or more, or 99 mole percent or more of the polyester macromers containing 1,1-diester-1-alkenes may be converted to polymer during a polymerization or curing process. The purity of the 1,1-diester-1-alkenes may be about 85 mole percent or more, about 90 mole percent or more, about 93 mole percent or more, about 95 mole percent or more, about 97 mole percent or more, or about 99 mole percent or more, based on the total moles of the 1,1-diester-1-alkenes. If the 1,1-diester-1-alkenes includes the analogous 1,1-diester alkane it may be about 10 mole percent or less, or about 1 mole percent or less. The concentration of any impurities containing a dioxane group may be about 2 mole percent or less, about 1 mole percent or less, about 0.2 mole percent or less, or about 0.05 mole percent or less, based on the total moles of the 1,1-diester-1-alkenes. The total concentration of any impurity having the alkene group replaced by an analogous hydroxyalkyl group (e.g., by a Michael addition of the alkene with water) may be about 3 mole percent or less, about 1 mole percent or less, about 0.1 mole percent or less, or about 0.01 mole percent or less, based on the total moles in the 1,1-diester-1-alkenes. The 1,1-diester-1-alkenes may be prepared by a process including one or more (e.g., two or more) steps of distilling a reaction product or an intermediate reaction product (e.g., a reaction product or intermediate reaction product of a source of formaldehyde and a malonic acid ester).

Polyols useful in preparing polyester macromers disclosed herein are compounds having a hydrocarbylene backbone with two or more hydroxyl groups bonded to the hydrocarbylene backbone and which may be capable of transesterifying ester compounds under the transesterification conditions disclosed herein. Polyols useful herein fall in two groups. The first group are diols which have two hydroxyl groups bonded to a hydrocarbylene backbone and which function both to initiate and extend the chains of the polyester macromers. Polyols with greater than two hydroxyl groups bonded to the hydrocarbylene backbone function to initiate more than two chains. Diols may also function to extend the more than two chains. The polyols may have from 2 to 10 hydroxyl groups, from 2 to 4 hydroxyl groups or from 2 to 3 hydroxyl groups. The backbone for the polyols, including diols, may be alkylene, alkenylene, cycloalkylene, heterocyclylene, alkyl heterocyclylene, arylene, aralkylene, alkarylene, heteroarylene, alkheteroarylene, or polyoxyalkylene. The backbone may be C₁-C₁₅ alkylene, C₂-C₁₅ alkenylene, C₃-C₉ cycloalkylene, C_2-20 heterocyclylene, C_3-20 alkheterocyclylene, C_8-18 arylene, C_7-25 alkarylene, C_7-25 aralkylene, C_5-18 heteroarylene, C_8-25 alkyl heteroarylene or polyoxyalkylene. The alkylene sections may be straight or branched. The recited groups may be substituted with one or more substituents which do not interfere with the transesterification reaction. Exemplary substituents include halo alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester. The backbone may be C_2-10 alkylene groups. The backbone may be a C_2-8 alkylene group, which may be straight or branched, such as ethylene, propylene, butylene, pentylene, hexylene, 2-ethyl hexylene, heptylene, 2,2-methyl, 1,3-propylene, 2-methyl 1,3 propylene or octylene. The diols having a methyl group at the 2 position of an alkylene chain may be used. Exemplary diols include ethane diol, propane diol, butane diol, pentane diol, hexane diol, 2 ethyl hexane diol, heptane diol, octane diol, neopentyl glycol (2,2-methyl, 1,3-propane diol), 2-methyl 1,3 propane diol, 2-butyl-1,3-propane diol, 2-ethyl-1,3-propane diol and 1,4-cyclohexanol. The polyol may correspond to formula 9 R²OH)_c;

the diol may correspond to formula 10: HO—R²—OH

wherein R² is separately in each occurrence a hydrocarbylene group having two or more bonds to the hydroxyl groups of a polyol. R² may be separately in each occurrence alkylene, alkenylene, cycloalkylene, heterocyclylene, alkyl heterocyclylene, arylene, aralkylene, alkarylene, heteroarylene, alkheteroarylene, or polyoxyalkylene. R² may be separately in each occurrence C₁-C₁₅ alkylene, C₂-C₁₅ alkenylene, C₃-C₉ cycloalkylene, C_2-20 heterocyclylene, C_3-20 alkheterocyclylene, C_6-18 arylene, C_7-25 alkarylene, C_7-25 aralkylene, C_5-18 heteroarylene, C_6-25 alkyl heteroarylene or polyoxyalkylene. The recited groups may be substituted with one or more substituents which do not interfere with the transesterification reaction. Exemplary substituents include halo alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester. R² may be separately in each occurrence a C_2-8 alkylene group, such as ethylene, propylene, butylene, pentylene, hexylene, 2-ethyl hexylene, heptylene, 2-methyl 1,3 propylene or octylene. Exemplary C₃-C₉ cycloalkylenes include cyclohexylene. The alkylene groups may be branched or straight and may have a methyl group on the 2 carbon. Among preferred alkarylene polyols are polyols with the structure of -aryl-alkyl-aryl- (such as -phenyl-methyl-phenyl- or -phenyl-propyl-phenyl-) and the like. Among preferred alkyl cycloalkylene poly-yls are those with the structure of -cycloalkyl-alkyl-cycloalkyl- (such as -cyclohexyl-methyl-cyclohexyl- or -cyclohexyl-propyl-cyclohexyl-) and the like. The polyalkylene oxy groups may have alkylene groups of ethylene, propylene or butylene and the butylene groups may be derived from butylene oxides or tetrahydrofuran. c may be an integer of 8 or less, 6 or less, 4 or less or 3 or less. c may be an integer of 2 or greater or 3 or greater.

The one or more dihydrocarbyl dicarboxylates are compounds with two ester groups having a hydrocarbylene group disposed between the ester groups. The one or more dihydrocarbyl dicarboxylates comprise one or more of aromatic dicarboxylates, aliphatic dicarboxylates and cycloaliphatic dicarboxylates or may one or more dihydrocarbyl dicarboxylates wherein one of the hydrocarbyl groups is aliphatic, cycloaliphatic or aromatic and the other is selected from another class of aliphatic, cycloaliphatic or aromatic group. The one or more dihydrocarbyl dicarboxylates comprise one or more of aromatic dicarboxylates having 8 to 14 carbon atoms in the backbone, aliphatic dicarboxylates having 1 to 12 carbon atoms in the backbone and cycloaliphatic dicarboxylates having 8 to 12 carbon atoms in the backbone. The one or more dihydrocarbyl dicarboxylates comprise one or more malonates, terephthalates, phthalates, isophthalates, naphthalene-2,6-dicarboxylates, 1,3-pheny-lenedioxy diacetates, cyclohexanedicarboxylates, cyclohexanediacetates, diphenyl-4,4′-dicarboxylates, succinates, glutarates, adipates, azelates, sebacates, or mixtures thereof. The one or more dihydrocarbyl dicarboxylates may comprise one or more malonates isophthalates, terephthalates or sebacates. The one or more dihydrocarbyl dicarboxylates correspond to formula 11:

wherein R¹ is as previously described; andR³ is separately in each occurrence a hydrocarbylene group having two bonds to the carbonyl groups of the diester wherein the hydrocarbylene group may contain one or more heteroatoms. R³ may be separately in each occurrence arylene, cycloalkylene, alkylene or alkenylene. R³ may be separately in each occurrence C_8-14 arylene, C_8-12 cycloalkylene, C_1-12 alkylene or C_2-12 alkenylene.

Some of the methods for the preparation of the polyester macromers involve the preparation of intermediate compounds. One class intermediate compounds is the multifunctional monomers. The multifunctional monomers may be prepared from 1,1-diester-1-alkenes and polyols, including diols. Where the polyol has greater than two hydroxyl groups, preparation of a multifunctional monomer is desired before chain extension. Multifunctional monomers comprise a polyol wherein at least two of the hydroxyl groups are replaced by the residue of 1,1-diester-1-alkenes. Where there are greater than two hydroxyl groups on the polyol it is possible that not all of the hydroxyl groups react with 1,1-diester-1-alkenes. It is desirable to react substantially all of the hydroxyl groups with the 1,1-diester-1-alkenes. The alternatives discussed hereinbefore for the polyols and 1,1-diester-1-alkenes as far as structure are also applicable to the multifunctional monomers. Where a polyol with 3 or greater hydroxyl groups are used to prepare the multifunctional monomers they correspond to formula 12

where a diol is used to initiate the multifunctional monomers they correspond to formula 13;

wherein R¹, R² and c are as defined hereinbefore. The multifunctional monomers can be prepared as disclosed hereinafter and as disclosed in Malofsky US 2014/0329980 and in Sullivan U.S. Pat. No. 9,416,091 both incorporated herein in their entirety for all purposes.

Another intermediate which may be used in the preparation of polyester macromers is one or more compounds comprising the one or more dihydrocarbyl dicarboxylates having the residue of a polyol, such as a diol, bonded to each of the carbonyl groups. These compounds may be referred to a polyol capped dihydrocarbyl dicarboxylates. Some of them may be called diol capped dihydrocarbyl dicarboxylates. Each ester group of the dihydrocarbyl dicarboxylates is subjected to transesterification to replace the hydrocarbyl groups with polyols, such as diols. The resulting polyol capped dihydrocarbyl dicarboxylates have terminal hydroxyl groups. The polyol capped dihydrocarbyl dicarboxylates may correspond to formula 14;

the diol capped dihydrocarbyl dicarboxylates may correspond to formula 15;

wherein R², R³ and c are as described hereinbefore. In this context the hydrocarbylene of R³ is bonded to the carbonyl groups of the residue of a diester in the polyol capped dihydrocarbyl dicarboxylates.

The polyester macromers may be used in compositions that are useful in preparing polymers and structures from the polymers. The compositions may be assembled by blending the polyester macromers with desired components. The compositions may comprise or include mixtures of compounds formed in the preparation of the polyester macromers. Other ingredients may be added to the mixtures of compounds formed in the preparation of the polyester macromers to form compositions which are designed to be used in the preparation of polymers containing the polyester macromers or structures formed from the polymers or polyester macromers. One composition comprises i) a plurality of polyester macromers disclosed herein; ii) one or more multifunctional monomers containing the residue of one or more polyols and one or more 1,1-diester-1-alkenes, wherein the multifunctional monomers have substantially all of the hydroxyl groups of the polyols replaced with the 1,1-diester-1-alkenes; and iii) one or more 1,1-diester-1-alkenes. Each of these ingredients are disclosed hereinbefore. This composition can be taken from the reaction mixture formed when the polyester macromers are prepared. The resulting reaction mixture can be subjected to a separation process, such as distillation to remove an excess one or more of the more volatile species, such as alcohols, polyols or unreacted dihycrocarbyl dicarboxylates, to achieve the desired concentrations of components. One or more of the recited compounds may be added to achieve the desired component concentrations. Plurality with respect to the polyester macromers mean that a number of polyester macromer units which may be the same or different polyester macromers are present. The polyester macromers are present in sufficient amount to prepare the desired polymers and structures from the polymers and introduce a desired level of crosslinking. Any one or more of the polyester macromers disclosed herein may be used in the compositions. Polyester macromers containing the residue of one or more dihydrocarbyl dicarboxylates in the backbone may be utilized. Polyester macromers used in the compositions may comprise the residue of one or more polyols and one or more 1,1-diester-1-alkenes. The 1,1-diester-1-alkenes are present to function as a reactive diluent and to facilitate forming a composition that exhibits a target viscosity. The 1,1-diester-1-alkenes may provide rapid reactivity to form the polymer or structures prepared. The one or more multifunctional monomers are present to enhance crosslinking of the polymer or structures prepared. The components are present in sufficient amounts to achieve their recited purpose. The plurality of polyester macromers are present in an amount of about 10 percent by weight or greater of the composition, about 30 percent by weight or greater or about 60 percent by weight or greater. The plurality of polyester macromers are present in an amount of about 80 percent by weight or less of the composition, about 70 percent by weight or less or about 40 percent by weight or less. The multifunctional monomers are present in an amount of about 5 percent by weight or greater of the composition, about 10 percent by weight or greater, about 20 percent by weight or greater or 30 percent by weight or greater. The multifunctional monomers are present in an amount of about 50 percent by weight or less of the composition, about 40 percent by weight or less, about 30 percent by weight or less or about 20 percent by weight or less. The 1,1-diester-1-alkenes are present in an amount of about 0 percent by weight or greater of the composition, about 1 percent by weight or greater, about 5 percent by weight or greater, about 10 percent by weight or greater or about 20 percent by weight or greater. The 1,1-diester-1-alkenes are present in an amount of about 40 percent by weight or less of the composition, about 30 percent by weight or less or about 20 percent by weight or less. The one or more polyols may be diols. The multifunctional monomer may be a difunctional monomer.

The composition comprising i) a plurality of polyester macromers disclosed herein; ii) one or more multifunctional monomers containing the residue of one or more polyols and one or more 1,1-diester-1-alkenes, wherein the multifunctional monomers have substantially all of the hydroxyl groups of the polyols replaced with the 1,1-diester-1-alkenes; and iii) one or more 1,1-diester-1-alkenes may be used as the basis for preparing additional compositions. This composition may be used in such other compositions in sufficient amount to function as desired. This composition may be present in an amount of about 10 percent by weight or greater of the formed composition, about 20 percent by weight or greater, about 30 percent by weight or greater, about 60 percent by weight or greater or about 70 percent by weight or greater. This composition may present in an amount of about 80 percent by weight or less of the composition, about 60 percent by weight or less or about 30 percent by weight or less. Such compositions may contain a volatile solvent. The volatile solvent may be any solvent that does not react with the components or interfere in the curing of the compositions. The solvents may be volatile at about 50° C. or greater. The solvents may be volatile polar solvents. The solvent may be volatile polar aprotic solvents. The polar aprotic solvent may volatilize away from the other components once the coating is applied to a substrate. Any polar aprotic solvent which volatilizes away from the other components once applied to the surface of a substrate may be utilized herein. The polar aprotic solvents may exhibit a boiling point of about 100° C. or greater, about 110° C. or greater or about 130° C. or greater. The polar aprotic solvents may exhibit a boiling point of about 200° C. or less, about 190° C. or less or about 170° C. or less. The polar aprotic solvent may be an alkylene glycol ether, an acetate modified alkylene glycol ether, a ketone, or a mixture of any of these solvents, and the like. The volatile solvents are present in sufficient amount to facilitate use of the compositions as desired, that is the solvents facilitate delivery of the compositions and allow wet-out of the composition on the surface. The volatile solvents are present in an amount of about 0 percent by weight or greater of the composition, about 1 percent by weight or greater, about 5 percent by weight or greater, about 10 percent by weight or greater or about 20 percent by weight or greater. The volatile solvents are present in an amount of about 50 percent by weight or less of the composition, about 40 percent by weight or less of the composition, about 20 percent by weight or less or about 10 percent by weight or less. The compositions formed may contain an additional amount of 1,1-diester-1-alkenes. The additional 1,1-diester-1-alkenes are present in the compositions formed to function as reactive diluents and to accelerate polymerization. The additional 1,1-diester-1-alkenes may be present in an amount of 0 percent by weight or greater of the composition, about 1 percent by weight or greater, about 5 percent by weight or greater, about 10 percent by weight or greater or about 30 percent by weight or greater. The additional 1,1-diester-1-alkenes may be present in an amount of about 50 percent by weight or less of the composition, about 40 percent by weight or less or about 30 percent by weight or less. The formed compositions may further contain one or more wetting agents which facilitate the application of such compositions to substrates. Any wetting and or levelling agent which enhances the application of the compositions to a substrate may be used. Exemplary classes of wetting agents include polyether modified polydimethyl siloxanes, fluorinated hydrocarbons and the like. The wetting agents may be polyether modified polydimethyl siloxanes. The wetting and/or levelling agents are present in sufficient amount to facilitate application of the compositions to a substrates surface. The wetting agents may be present in an amount of about 0.01 percent by weight or greater of the composition, about 0.5 percent by weight or greater or about 1 percent by weight or greater. The wetting agents may be present in an amount of about 5 percent by weight or less of the composition, about 2 percent by weight or less or about 1 percent by weight or less. The formed compositions may further contain one or more UV stabilizers which inhibit the degradation of structures containing the polyester macromers. Any UV stabilizer which inhibits degradation due to exposure to UV radiation may be used. Exemplary classes of ultraviolet light stabilizers include benzophenones, benzotriazoles and hindered amines (commonly known as hindered amine light stabilizers (HALS). Exemplary UV light stabilizers include Cyasorb UV-531 2-hydroxy-4-n-octoxybenzophenone, Tinuvin 571 2-(2 H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, branched and linear Tinuvin 1,2,3 bis(1-octyloxy-2,2,6,6, tetramethyl-4-piperidinyl) sebacate and Tinuvin 765, bis(1,2,2,6,6,-pentamethyl-4-piperidinyl) sebacate. The UV light stabilizers are present in sufficient amount to enhance long-term durability of the compositions containing polyester macromers. The UV light stabilizers should be selected so as to not affect the stability or pot life of the composition by premature polymerization, either by initiating or catalyzing free radical polymerization, anionic polymerization or Michael addition across the alkene double bond. The UV light stabilizers may be present in an amount of about 0.01 percent by weight or greater of the composition, about 0.1 percent by weight or greater or about 0.2 percent by weight or greater. The UV light stabilizers may be present in an amount of about 5 percent by weight or less of the composition, about 3 percent by weight or less, about 2 percent by weight or less or about 1 percent by weight or less. The composition may further comprise defoamers and/or deaerators. The compositions containing polyester macromers may foam during processing which can cause problems with respect to surface and appearance of the coating. Any defoamer and/or deaerator which prevents foaming or the formation of bubbles and which does not negatively impact the properties of the composition may be used. Exemplary defoamers are silicone defoamers, silicone free defoamers, polyacrylate defoamers, mixtures thereof and the like. Exemplary defoamers include FOAM BLAST™ 20F, FOAM BLAST™ 30 silicone defoaming compounds and FOAM BLAST™ 550 polyacrylate defoamers available from Emerald; TEGO AIREX™ 920 polyacrylate defoamer and TEGO AIREX™ 980 from Degussa, SILMER ACR™ Di-10 and ACR™ Mo-8 polydimethylsiloxane acrylate copolymer from Siltech Corporation, FOAMEX N™ or TEGO AIREX™ 900 silicone based defoamers available from Degussa or BYK™ 1790 silicone-free defoamer from BYK Chemie. The defoamer/deaerator is present in the polyester macromer compositions in a sufficient amount to prevent formation of bubbles and/or foam. If too much is used, adhesion to the desired surfaces and adhesives may be negatively impacted. The defoamer and/or deaerator may be present in an amount of about 0.01 percent by weight or greater based on the weight of the composition, about 0.05 percent by weight or greater or about 0.1 percent by weight or greater. The defoamer/deaerator may be present in an amount of about 2.0 percent by weight or less or about 1.0 percent by weight or less based on the weight of the composition.

These compositions may contain an additive to improve scratch resistance. Any additive which improves scratch resistance may be utilized. Exemplary scratch resistance additives may include silicates, aluminas, zirconias, carbides, oxides, nitrides or any other fillers with high hardness. Exemplary scratch resistance additives may include alumina (e.g., alpha alumina), silica, zirconia, boron carbide, silicon carbide, cerium oxide, glass, diamond, aluminum nitride, silicon nitride, yttrium oxide, titanium diboride, aluminosilicates (i.e. “Zeeospheres” from 3M), titanium carbide, combinations thereof, and the like. Exemplary scratch resistance additives may be silicates and aluminas. Exemplary scratch resistance additives may include nanometer sized silica fillers. The scratch resistance additives may have a particle size of about 10 micrometers or less or about 5 micrometers or less. The scratch resistance additives may be present in a sufficient amount to enhance the surface hardness and abrasion resistance of the coating and in an amount such that a homogeneous dispersion can be prepared. The scratch resistance additives may be present in an amount of about 0.1 percent by weight or greater of the composition or about 0.5 percent by weight or greater. The scratch resistance additives may be present in an amount of about 5 percent by weight or less of the composition, about 2 percent by weight or less or about 1 percent by weight or less.

These compositions may comprise an additive to improve surface slip properties. Any known composition that improves surface slip properties may be used. Exemplary surface slip additives may be a polyester modified polydimethyl siloxanes, waxes and the like. Exemplary waxes include those based on polyethylene, polytetrafluoroethylene or polypropylene wax dispersions in acrylate monomers, such as the EVERGLIDE™ or S-395 or SST series of products from Shamrock Technologies, or polyamide particles such as ORGASOL™ from Arkema, or montan wax with reactive acrylate groups, such as CERIDUST™ TP 5091 from Clariant, or CERAFLOUR™ wax powders from Byk-Chemie. The wax may be in powder form having a particle size which is smaller than the desired thickness of the coating prepared from the composition. The maximum particle size may be about 30 microns or less, about 25 microns or less, about 20 microns or less or about 15 microns or less. The wax may be highly crystalline. Exemplary waxes comprise a polyethylene, polypropylene, polyamide, polytetrafluoroethylene, or blends and/copolymers thereof. The wax may be crystalline polyethylene or polytetrafluoroethylene or blends of polyethylene with polytetrafluoroethylene. The surface slip additives may be present in an amount of about 0.1 percent by weight or greater of the composition or about 0.5 percent by weight or greater. The surface slip additives may be present in an amount of about 5 percent by weight or less of the composition, about 2 percent by weight or less or about 5 percent by weight or less.

The compositions disclosed herein contain one or more polymers having pendant Michael Addition donor groups. Any polymers having pendant Michael Addition donor groups that improve the properties of coatings prepared from compositions containing a plurality of polyester macromers may be used in the compositions disclosed herein. A Michael Addition donor is a functional group that reacts with an electrophilic unsaturated group such as the alkene groups on the polyester macromers. The Michael Addition donors may be functional groups containing at least one active hydrogen atom. The Michael Addition donor groups may comprise amines, hydroxyl, thiol, or mixtures thereof. The Michael Addition donor groups may comprise amines and/or hydroxyl. The polymer which contains the pendant Michael Addition Donor groups can be any polymer backbone that facilitates preparation of coatings with the desired properties, such as those described herein. It is desirable that the polymers enhance the gloss, flexibility and outdoor resistance in the form of improved UV and moisture resistance, of coatings prepared from polyester macromere compositions and polymers having pendant Michael Addition donor groups. The polymers having pendant Michael Addition donor groups may be acrylic, polycarbonate, styrene acrylonitrile, siloxane polyester or polyether backbones and the like. Exemplary polymers having pendant Michael Addition donor groups include one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, seed oil polyols, polyether polyols, polyester polyols and siloxane polyols. The one or more polymers having pendant Michael Addition donor groups comprise one or more acrylic polyols or amine modified acrylic polyols, and the like. Polymers containing pendant Michael Addition donor groups may comprise compounds containing polyacrylate backbones which are prepared from one or more acrylate containing compounds provided at least one of the acrylate containing compounds contain a Michael Addition donor, for instance a hydroxyl, amino, or thiol group. Such polymers may be prepared via free radical polymerization as is well known to those skilled in the art. Exemplary acrylate compounds containing Michael donor groups include hydroxylethyl methacrylate, hydroxy butylacrylate, hydroxyethyl acrylate, and the like. Styrene acrylonitrile based polymers containing Michael Addition Donors may be prepared by reacting styrene, acrylonitrile and a polyalkylene oxide containing an active hydrogen containing functional group such as an amine, hydroxyl or thiol group. The polyalkylene oxide may be a polypropylene oxide. The active hydrogen containing functional groups may be amino or hydroxyl, or may be hydroxyl. Polycarbonate based polymers containing Michael addition donors may be prepared by the steps of: (A) reacting (i) phosgene, (ii) a branched-chain polyhydric alcohol having about 4 to 12 carbon atoms, and (iii) about 3 to 40 mole percent, based upon the total amount of polyhydric alcohol, of a straight-chain polyhydric alcohol having about 5 to 20 carbon atoms in the presence of a solvent and in the absence of a catalyst at a temperature of about 60° C. to 100° C., and (B) contacting the amorphous polycarbonate product in the reaction mixture with a catalytic amount of a tertiary amine at reflux temperature for a period of time of at least about 30 minutes.

Polymers containing pendant Michael Addition donor groups may have a hydroxyl number which enhances the properties of coatings prepared from the compositions disclosed. The hydroxyl number of the polymers containing pendant Michael Addition donor groups may be about 40 or greater measured in terms of the KOH number, about 60 or greater or about 100 or greater. The hydroxyl number of the polymers containing pendant Michael Addition donor groups may be about 220 or less measured in terms of the KOH number, about 200 or less or about 150 or less. Hydroxyl number (OH) is the measure of the active hydrogen group content, such as hydroxyl group content, of gram of polyol. Hydroxyl value is measured by titrating a known mass of polyol against potassium hydroxide (KOH), and is expressed as mg KOH/g. Lower hydroxyl values indicates lower active hydrogen content, hydroxyl content, and a higher molecular weight for the overall polyol. OH equivalent weight is the number of grams of a given product that contains one equivalent of hydroxyl groups (OH), Equivalent weight=56100/OH. Molecular Weight is determined by multiplying the equivalent weight by the polyol functionality.

The composition comprising a) a composition containing a plurality of polyester macromers and b) polymers containing pendant Michael Addition donor groups may contain a sufficient amount of each so as to provide the desired properties of coatings prepared therefrom, as disclosed herein. Such compositions may contain an amount of a composition containing a plurality of polyester macromers based on the total weight of a coating composition of about 40 percent by weight or greater, about 50 percent by weight or greater or about 60 percent by weight or greater. Such compositions may contain an amount of a composition containing a plurality of polyester macromers based on the total weight of a coating composition of about 90 percent by weight or less, about 70 percent by weight or less or about 50 percent by weight or less. Such compositions may contain an amount of polymers containing pendant Michael Addition donor groups based on the total weight of a coating composition of about 10 percent by weight or greater, about 30 percent by weight or greater or about 40 percent by weight or greater. Such compositions may contain an amount of polymers containing pendant Michael Addition donor groups based on the total weight of a coating composition of about 60 percent by weight or less, about 50 percent by weight or less or about 40 percent by weight or less.

The composition comprising a) a composition containing a plurality of polyester macromers and b) polymers containing pendant Michael Addition donor groups may further comprise c) one or more polar aprotic solvents. The polar aprotic solvent may volatileize away from the other components once the coating is applied to a substrate. Any polar aprotic solvent which volatilizes away from the other components once applied to the surface of a substrate may be utilized herein. The polar aprotic solvents may exhibit a boiling point of about 100° C. or greater, about 110° C. or greater or about 130° C. or greater. The polar aprotic solvents may exhibit a boiling point of about 200° C. or less, about 190° C. or less or about 170° C. or less. The polar aprotic solvent may be an alkylene glycol ether, an acetate modified alkylene glycol ether, a ketone, or a mixture of any of these solvents and the like. The polar aprotic solvent may be present in sufficient amount to adjust the viscosity of the composition to facilitate application of the composition to a substrate and to allow appropriate wet-out of the composition on the surface to be coated. Such compositions may contain an amount of solvent based on the total weight of a coating composition of about 0 percent by weight or greater, about 1 percent by weight or greater or about 10 percent by weight or greater. Such compositions may contain an amount of solvents based on the total weight of a coating composition of about 30 percent by weight or less, about 20 percent by weight or less or about 15 percent by weight or less.

The polyester macromer compositions disclosed herein can be used to prepare coatings. Such structures may be cured and/or crosslinked. The crosslinked compositions may be crosslinked through the alkene groups pendant from the macromer chains. The crosslink may be a direct bond between the alkene groups of adjacent macromer chains. The macromer chains may be included in prepolymer or polymer chains. The macromer chains may be crosslinked through any compound having unsaturation that polymerizes by anionic or free radical polymerization. The polyester macromer chains may be crosslinked through 1,1-diester alkenes wherein the crosslinks comprise the residue of the 1,1-diester alkenes. The polyester macromer chains may be crosslinked through multifunctional monomers wherein the crosslinks comprise the residue of the multifunctional monomers. The crosslinks between chains may be illustrated by formula 16:

wherein F is separately in each occurrence a direct bond, the residue of a compound that polymerizes with an unsaturated group by anionic polymerization or free radical polymerization. F may be separately in each occurrence a direct bond, the residue of a 1,1-diester-1-alkene or a multifunctional monomer. The dotted lines refer to the backbone of the polymerized macromer. The crosslink density of a crosslinked composition containing the polyester macromers may be any such density that provides the desired properties of the composition. A portion of or all of the polyester macromers may be crosslinked by Michael Addition of the Michael Addition donors pendant from the polymers to the 1 alkene groups of the polyester macromers. The crosslinks by Michael Addition of the Michael Addition donors pendant from the polyols to the 1 alkene groups of the polyester macromer may correspond to Formula 18

Wherein X is the residue of a Michael Addition donor; and R^x is the polymer or the substrate to which the residue of the Michael Addition donor is bonded. X may be independently in each occurrence O, NR^y, or S. R^x may be independently in each occurrence a polymer comprising an acrylic polyol, amine modified acrylic polyol, polycarbonate polyol, modified acrylic copolymer polyol, polyether amines, polyester polyols, polyether polyols or siloxane polyol or a substrate. R^y may be H or a hydrocarbyl group as described hereinbefore. The polyester macromers may be crosslinked through the 1,1-alkene groups and by Michael Addition of the Michael Addition donors pendant from the polymers to the 1 alkene groups. Alternatively, the polyester macromers may be crosslinked by unsaturated groups of compounds, including 1,1-disubstituted alkenes and/or multifunctional monomers, via free radical or anionic addition processes as are well known to those skilled in the art.

The polyester macromers and compositions containing them may undergo polymerization when exposed to basic initiators. If applied to the surface of a substrate that is basic the polyester macromers will cure via anionic polymerization. Polyester macromers and compositions containing the polyester macromers can undergo cure if contacted with a composition containing basic materials as a polymerization activator. The polymerization activator and methods of delivering the polymerization activator are disclosed in Malofsky U.S. Pat. No. 9,181,365, incorporated herein by reference in its entirety for all purposes. The polymerization activator may be at least one of a base, a base enhancer, a base creator, or a base precursor. In certain embodiments, the polymerization activator comprises a basic material selected from a strong base (pH over 9), a moderately strong base (pH from 8-9), or a (mildly basic) weak base (pH from over 7 to 8), or a combination thereof. In other embodiments, the polymerization activator comprises a basic material selected from an organic material, an inorganic material or an organometallic material, or a combination thereof. The polymerization activator is at least one member selected from: sodium acetate; potassium acetate; acid salts of sodium, potassium, lithium, copper, and cobalt; tetrabutyl ammonium fluoride, chloride, and hydroxide; an amine whether primary, secondary or tertiary; an amide; salts of polymer bound acids; benzoate salts; 2,4-pentanedionate salts; sorbate salts; propionate salts; secondary aliphatic amines; piperidine, piperazine, N-methylpiperazine, dibutylamine, morpholine, diethylamine, pyridine, tri-ethylamine, tripropylamine, triethylenediamine, N,N-dimethylpiperazine, butylamine, pentylamine, hexylamine, heptylamine, nonylamine, decylamine; salts of amines with organic monocarboxylic acids; piperidine acetate; metal salt of a lower monocarboxylic acid; copper(II) acetate, cupric acetate monohydrate, potassium acetate, zinc acetate, zinc chloracetate, magnesium chloracetate, magnesium acetate; salts of acid containing polymers; salts of polyacrylic acid co-polymers, or pigments having a basic character. In certain embodiments, the polymerization activator is encapsulated in a wax, or is provided in inactive engagement with the polymerizable composition by chemical inactivation.

Disclosed is a polymerizable system comprising: a polymerizable composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups; and polymerization activator physically separated from the polymerizable composition; wherein the polymerization activator is able to initiate polymerization upon contact with the polymerizable composition without substantial mixing. The polymerization activator may be physically separated from the polymerizable composition, the physical separation is achieved by storing the activating agent and the polymerizable composition in separate locations within an applicator means. In exemplary embodiments, the applicator means is an aerosol spray device. In other embodiments, the physical separation is achieved by initially applying the polymerization activator to at least a portion of a substrate, followed by applying the polymerizable composition to the portion of the substrate. In still other embodiments, the physical separation is achieved by providing the polymerization activator in or on at least a portion of a substrate. The polymerization activator may be physically separated from the polymerizable composition, the polymerization activator is in an inert state and wherein the polymerizable system further comprises a converting agent able to convert the polymerization activator from the inert state to an active state. The basic polymerization initiator may be encapsulated in a composition that can be subjected to a process that releases the initiator. An encapsulated initiator particle includes an initiator matrix. The initiator matrix includes a first cured composition formed of one or more 1,1-disubstituted alkene compounds and one or more polymerization initiators substantially encapsulated by the first cured composition. Exemplary compositions are disclosed in U.S. Pat. No. 9,334,430 incorporated herein by reference in its entirety for all purposes.

Disclosed is a composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups as disclosed herein in one part and in a second part one or more compounds having basic character sufficient to initiate anionic polymerization of the polyester macromers or one or more compound that catalyzes Michael Addition; wherein when the two parts are combined the polyester macromers undergo curing. Any of the basic materials disclosed herein may be used. The one or more compounds having basic character may be one or more amines or polyamines. The one or more compounds having basic character may be one or more polyalkyleneimines, such as polyethyleneimines. Compounds that catalyze Michael Addition include acids and bases. Compounds that catalyze Michael Addition may be present in an amount of about 0.01 percent by weight or greater based on the weight of the formulation, about 0.05 percent by weight or greater, about 0.1 percent by weight or greater or about 0.3 percent by weight or greater. Compounds that catalyze Michael Addition may be present in an amount of about 1 percent by weight or less based on weight of the formulation, about 0.5 percent by weight or less or about 0.2 percent by weight or less.

The polyester macromers and compositions containing them may be used in the preparation of polyester based structures including one or more polymers having pendant Michael Addition donor groups, such as coatings on substrates and the like. Disclosed are coatings containing polyester macromers or the residue of the polyester macromers and one or more polymers having pendant Michael Addition donor groups. A coating containing polyester macromers or the residue of the polyester macromers and one or more polymers having pendant Michael Addition donor groups can be disposed on one or more surfaces or a portion thereof of a substrate. The coatings may be cured and/or crosslinked. The films or coatings may have a thickness of about 0.01 micrometers or greater, about 0.04 micrometers or greater or about 0.1 micrometers or greater. The coating may be cured and/or crosslinked. The coating may have a thickness of about 160 micrometers or less, about 140 micrometers or less, about 100 micrometers or less, about 60 micrometers or less, about 40 micrometers or less, about 10 micrometers or less, about 2 micrometers or less or about 1 micrometers or less. Disclosed are articles comprising a substrate with a coating comprising one or more polyester macromers or a composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups applied to one or more surfaces.

Disclosed are articles comprising substrates containing pigmented base coats on the substrates with coatings containing polyester macromers disclosed herein and one or more polymers having pendant Michael Addition donor groups disposed on the base coats. The base coats may have a basic character which is sufficient to cure and/or crosslink the polyester macromers and one or more polymers having pendant Michael Addition donor groups. The coatings containing the polyester macromers and one or more polymers having pendant Michael Addition donor groups may be clear and function as clear coats. The coatings disclosed may contain any additional components utilized in coating such as pigments, adhesion promotors, fire retardants, and ingredients as disclosed herein and the like. Coatings disclosed herein may contain pigments and function as stand-alone coatings of base coats with a clear coat disposed above such base coats. Disclosed is a system which comprises a base coat and a clear coat containing a composition as disclosed herein, that is the composition contains one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups.

The polyester macromers or compositions containing them may be added to any composition containing the ingredients to prepare polyesters so as to introduce alkene units into the backbone. The compositions comprise diols and diesters known to those skilled in the art of preparing polyesters. The polyester macromers or compositions containing them may be added to blends containing polyesters to add the alkene functionality. The compositions containing the polyester macromers or compositions containing them may be crosslinked as disclosed herein.

The polyester macromers may be prepared from polyols, diols, and diesters. The di-esters include one or more 1,1-diester-1-alkenes and may include dihydrocarbyl dicarboxylates. The final structure of the polyester macromers may be determined by the ratios of reactants and the sequence of synthesis of intermediates which are disclosed hereinbefore. The intermediates and the polyester macromers may be prepared by transesterification. The polyols having greater than two hydroxyl groups and diols function to initiate the polyester macromer chains. The diols also function to react with the diesters to form the macromer chains. The 1,1-diester-1-alkenes react with the polyols and diols to form the macromer chains and to introduce pendant alkene groups into the macromer chains. The dihydrocarbyl dicarboxylates function to react with the polyols and diols to form the macromer chains and to spread out the pendant alkene groups on the macromer chains. The polyester macromers may be prepared by contacting the polyol, diols and diesters and subjecting them to transesterification conditions. The resulting polyester macromers may have somewhat random and uncontrolled structure. It may be desirable to prepare intermediates and use the intermediates to prepare the polyester macromers as the use of intermediates allow for control of the final structure.

The multifunctional monomers may be prepared by contacting one or more polyols with an equivalents excess of one or more 1,1-diester 1-alkenes in the presence of a transesterification catalyst under conditions such that one or more multifunctional monomers are formed wherein the multifunctional monomers contain the one or more polyols having two or more of their hydroxyl groups replaced with the residue of the one or more 1,1-diester 1-alkenes. The ratio of equivalents of one or more 1,1-diester 1-alkenes to one or more polyols maybe about 2:1 or greater or about 4:1 or greater. The ratio of equivalents of one or more 1,1-diester 1-alkenes to one or more polyols maybe about 5:1 or less or about 3:1 or less. The multifunctional monomers may be used to control the number of chains in the polyester macromers and/or to form the polyester macromer chains in a controlled manner. The polyol capped dihydrocarbyl dicarboxylates may be prepared by contacting the one or more dihydrocarbyl dicarboxylates with an excess of one or more polyols in the presence of a transesterification catalyst under conditions such that one or more dihydrocarbyl dicarboxylates having the residue of a polyol bonded to each of the carbonyl groups is prepared. The ratio of equivalents of one or more diols to one or more dihydrocarbyl dicarboxylates maybe about 2:1 or greater. The ratio of equivalents of one or more diols to one or more dihydrocarbyl dicarboxylates maybe about 4:1 or less or about 3:1 or less.

Disclosed is a method comprising: contacting one or more polyols with an equivalents excess of one or more 1,1-diester 1-alkenes in the presence of a transesterification catalyst under conditions such that one or more multifunctional monomers are formed wherein the multifunctional monomers contain the one or more polyols having two or more of their hydroxyl groups replaced with the residue of the one or more 1,1-diester 1-alkenes; and contacting the multifunctional monomers with an additional amount of the one or more polyols, with the proviso that the polyols are diols, or with one or more second polyols which are diols, in the presence of a transesterification catalyst under conditions such that one or more polyester macromers are prepared which contain one or more chains of the residue of one or more diols and one or more 1,1-diester-1-alkenes wherein the residue of the one or more diols and the one or more 1,1-diester-1 alkenes alternate along the chain and at least one terminal end comprises the residue of one of the 1,1-diester-1 alkenes and wherein one or more terminal ends may comprise the residue of one or more diols. The multifunctional monomers and an additional amount of the one or more polyols or with one or more second polyols are contacted with one or more compounds comprising one or more dihydrocarbyl dicarboxylates having the residue of a polyol bonded to each of the carbonyl groups such that one or more polyester macromers are prepared wherein at least some to the polyester macromers contain the residue of the one or more the dihydrocarbyl dicarboxylates in their backbone. The one or more compounds comprising the one or more dihydrocarbyl dicarboxylates having the residue of a polyol bonded to each of the carbonyl groups is prepared by contacting the one or more dihydrocarbyl dicarboxylates with an excess of one or more polyols in the presence of a transesterification catalyst under conditions such that one or more dihydrocarbyl dicarboxylates having the residue of a polyol bonded to each of the carbonyl groups is prepared.

Disclosed a method comprising: contacting one or more diols, one or more 1,1-diester 1-alkenes, and one or more dihydrocarbyl dicarboxylates in the presence of a transesterification catalyst under conditions that one or more polyester macromers are prepared which contain one or more chains of the residue of one or more diols, one or more dihydrocarbyl dicarboxylates and one or more 1,1-diester-1-alkenes wherein the residues of each are disposed in a random manner along the chain and at least one terminal end comprises the residue of one of the 1,1-diester-1 alkenes and wherein one or more terminal ends may comprise the residue of one or more diols and/or one or more dihydrocarbyl dicarboxylates.

Disclosed is a method comprising: contacting one or more polyols with an equivalents excess of one or more 1,1-diester 1-alkenes in the presence of a transesterification catalyst under conditions such that one or more multifunctional monomers are formed wherein the multifunctional monomers contain the one or more polyols having at least two of their hydroxyl groups replaced with the residue of the one or more 1,1-diester 1-alkenes; and contacting the one or more multifunctional monomers one or more diols, one or more 1,1-diester 1-alkenes, and one or more dihydrocarbyl dicarboxylates in the presence of a transesterification catalyst under conditions that one or more polyester macromers are prepared which contain one or more chains of the residue of one or more diols, one or more dihydrocarbyl dicarboxylates and one or more 1,1-diester-1-alkenes wherein the residues of each are disposed in a random manner along the chain and at least one terminal end comprises the residue of one of the 1,1-diester-1 alkenes and wherein one or more terminal ends may comprise the residue of one or more diols and/or one or more dihydrocarbyl dicarboxylates.

Disclosed is a method comprising: contacting one or more multifunctional monomers which contain the one or more polyols having their hydroxyl groups replaced with the residue of the one or more 1,1-diester 1-alkenes; one or more compounds comprising a dihydrocarbyl dicarboxylates having the residue of a polyol bonded to each of the carbonyl groups; and one or more polyols in the presence of a transesterification catalyst under conditions such that one or more polyester macromers are prepared which contain one or more chains of the residue of the one or more polyols, the one or more 1,1-diester-1-alkenes, and the one or more compounds comprising a dihydrocarbyl dicarboxylates having the residue of a polyol bonded to each of the carbonyl groups and at least one terminal end comprises the residue of one of the 1,1-diester-1 alkenes and wherein one or more terminal ends may comprise the residue of one or more diols and/or one or more dihydrocarbyl dicarboxylates.

In the methods disclosed wherein the one or more polyols or second polyols may be diols. The one or more dihydrocarbyl dicarboxylates comprise one or more of aromatic dicarboxylates, aliphatic dicarboxylates, cycloaliphatic dicarboxylates, or a dihydrocarbyl dicarboxylates having different hydrocarbyl groups selected from aromatic, aliphatic and cycloaliphatic groups. The oxygens from the hydroxyl groups on the diols and polyols are bonded to aliphatic carbon atoms.

Transesterification is an equilibrium process and is typically performed under conditions to remove the byproduct formed during the exchange, meaning the product formed by the hydrocarbyl moieties leaving the esters undergoing transesterification. In some desired embodiments the hydrocarbyl moieties leaving the ester group of the ester compounds are smaller than the hydrocarbyl moieties replacing them so as to make the byproducts more volatile than the transesterified ester compounds. The smaller byproducts will generally be more volatile than the transesterified ester compound, which facilitates removal of the byproduct due to their volatile nature. The process disclosed can be used with any process conditions that remove the byproduct formed from the leaving hydrocarbyl moieties. Exemplary process conditions or steps that may be used to remove the byproduct formed from the leaving hydrocarbyl moieties may include one or more of the following: distillation, membrane transport, inert gas purge, and the like.

The transesterification reactions may be performed in the presence of a catalyst, such as an acid, an ester of such acid or an enzyme. The transesterification catalyst may be an enzyme. The transesterification catalyst may be a lipase enzyme. A transesterification process utilizing an enzyme is disclosed in US 2014/0329980, incorporated herein by reference for all purposes in its entirety.

The catalyst may be an acid or an ester thereof. The transesterification process using an acid or ester is disclosed in co-owned U.S. Pat. No. 9,416,091, incorporated herein by reference for all purposes in its entirety. Any acid or ester thereof that catalyzes transesterification while minimizing side reactions may be used. In some embodiments the acid or acid utilized to form an ester is an acid having a pKa in a polar aprotic solvent, such as acetonitrile or dioxane, as disclosed hereinafter. The pKa may be chosen to efficiently catalyze the transesterification reaction while minimizing side reactions and the concentration of catalyst in a reaction mixture. The acid used may have a pKa of about −5 or greater, about −3 or greater, or about 1.0 or greater. The acid used may have a pKa of about 14 or less, about 11 or less, or about 9 or less. The acid can be a Bronsted acid having a pKa as disclosed. The catalyst may be a superacid or an ester thereof. Superacid means an acid having an acidic strength greater than the strength of 100 percent sulfuric acid. Ester thereof, in the context of the acid catalysts, refer to compounds wherein the hydrogen on the acid is replaced with a hydrocarbyl group, preferably an alkyl group. Superacids are acids having a strength greater than the strength of 100 percent sulfuric acid, a pKa less than 100 percent sulfuric acid, that is less than 8, more preferably less than about 5, and most preferably less than about 2. The measurement of acid strength is based on Kutt et al. “Equilibrium Acidities of Super Acids,” Journal of Organic Chemistry Vol 76 pages 391 to 395, 2011, published on the Web Dec. 17, 2010, which is incorporated herein by reference. Exemplary super acids include trifluoromethanesulfonic acid (triflic acid), sulfated tin oxide, triflated tin oxide, sulfated zirconia, triflated zirconia, and triflated HZSM-5. The most preferred super acids are triflic and fluorosulfonic acid.

Exemplary acid catalysts include triflic acid, fluorosulfonic acid, and sulfuric acid. For reactions requiring monosubstitution (only one hydroxyl group on the alcohol or one ester group on the second ester is being replaced by transesterification), weaker acids with pKa values equal to or higher than sulfuric acid may be desired. Examples of such acids include sulfuric acid or methanesulfonic acid. For reactions requiring disubstitution (two hydroxyl groups on the alcohol or two ester groups on the second ester are being replaced by transesterification), stronger acids with pKa values equal to or lower than sulfuric acid may be desired. Examples of such acids include sulfuric acid, fluorosulfonic acid, and triflic acid. For reactions requiring polysubstitution (more than 2 hydroxyl groups on the alcohol and more than 2 ester groups on another ester compound), choice of acid catalysts can be similar to that for disubstitution reactions but reaction time may need to be increased. Esters of acids useful as catalysts include alkyl triflates.

The catalyst can be mixed with the reactants or can be supported on a substrate such as a membrane or an inert carrier such as a porous support structure (the catalysts can be heterogeneous). Catalysts which are not supported are commonly referred to as homogeneous. The catalyst can be used in any concentration that catalyzes the transesterification reaction. The amount of catalyst utilized for the reaction depends on the type of catalyst being chosen. The concentration of homogeneous catalyst is about 1 molar equivalents or less per equivalent of the ester compounds undergoing transesterification; about 0.1 molar equivalents or less; about 0.05 molar equivalents or less; about 0.005 molar equivalents or less. The concentration of catalyst is about 0.001 molar equivalents or greater per equivalent of the ester compounds undergoing transesterification; and most preferably about 0.0015 molar equivalents or greater. Higher concentrations of catalysts than recited may be utilized. As disclosed in Malofsky et al., U.S. Pat. Nos. 8,609,885 and 8,884,051; and Malofsky et al. WO 2013/059473 the presence of acid in the 1,1-disubstituted alkene compounds recovered can present problems with respect to use of the compounds and low concentrations of acid in the products in use is desired. If high levels of acid are contained in the final product, additional purification or removal steps may be required. The amounts recited achieve the balance between efficient catalysis and the need for low acid concentrations in the product for use. In embodiments when the catalyst is selected from sulfuric acid or those acids having pKa values less than that of sulfuric acid, the concentration of such catalysts in the reaction mixture is preferably at the upper end of the ranges recited herein. The choice of polyol and/or diester compound and the relative moles of the polyol and the diester will impact the product of the process.

Where the reactants are liquid under reaction conditions it is desired to contact the reactants and catalysts in neat form (i.e., without a solvent or dispersant). If the use of a solvent is desired, a solvent that does not react with the reactants or the catalyst is preferred. Another consideration in the choice of solvents is the boiling point of the solvent chosen. It is desired that the solvent have a boiling point of about 15° C. or higher, preferably about 20° C. or higher than the temperature at which the reaction is conducted. Aprotic solvents are preferred and more preferred solvents are long chain alkanes having a boiling point above the reaction temperature as described herein; exemplary solvents are decane or dodecane. The reactants are contacted at any temperature at which the transesterification will proceed. Preferably the reactants are contacted at a temperature of about 80° C. or greater or about 100° C. or greater. The reactants may be contacted at a temperature of about 160° C. or less, 140° C. or less or about 130° C. or less. The reactants are contacted for a sufficient time to prepare the desired transesterified product. It is preferred to perform the process such that the starting first ester compound, such as a 1,1-disubstituted alkene compound, is substantially completely reacted with the alcohol or a second ester compound to prepare the desired product. Preferably the reactants are contacted for about 1 hour or greater. The reactants are contacted may be 4 hours or less or about 2 hour or less.

It is desired to perform the process under conditions that enhance contact of the diesters and polyol to allow the replacement of the original hydrocarbyl moieties on the ester groups of the diester. Some form of agitation is desired to enhance this contact. Exemplary methods of agitation include the use of stirrers, sparging with an inert gas, and the like. A preferred method is to use vigorous stirring and/or vigorous sparging with nitrogen. The transesterification reaction is believed to be an equilibrium reaction. Performing the process under conditions to drive the reaction in the direction of the desired product is recommended. Exemplary ways to achieve this include adding an excess of one reactant, removing the alcohol formed by the leaving hydrocarbyl moiety, and the like. Where the compound formed from the leaving hydrocarbyl moiety is volatile it can be removed through the use of a vacuum, use of conditions at which the leaving alcohol can be distilled off and the other reactants and products do not distill away.

The catalyst may be an enzyme. The transesterification reaction conditions comprise room temperature and atmospheric pressure; elevated temperature and atmospheric pressure; room temperature and under vacuum; elevated temperature and under vacuum; or any combination thereof. The transesterification step may be performed at a temperature of about 20° C. or greater, about 35° C. or greater or about 40° C. or greater. The transesterification step may be performed at a temperature of about 85° C. or less or about 70° C. or less.

The transesterification reaction may be performed in the presence of free radical stabilizers and anionic polymerization inhibitors as described in Malofsky et al., U.S. Pat. Nos. 8,609,885 and 8,884,051; and Malofsky et al. WO 2013/059473, relevant parts incorporated herein by reference. To prevent production of polymeric products, it is desirable to include an acid which inhibits polymerization but does not significantly participate in catalysis of the transesterification. The acid used to inhibit polymerization may have a pKa less than 100 percent sulfuric acid. According to certain embodiments, stabilizers can be included in compositions containing the transesterified products to increase and improve the shelf life and to prevent spontaneous polymerization. One or more anionic polymerization stabilizers and/or free-radical stabilizers may be added to the compositions. Anionic polymerization stabilizers are generally electrophilic compounds that scavenge nucleophiles from the composition or growing polymer chain. The use of anionic polymerization stabilizers can terminate additional polymer chain propagation. Exemplary anionic polymerization stabilizers are acids, exemplary acids are carboxylic acids, sulfonic acids, phosphoric acids, and the like. Exemplary stabilizers include liquid phase stabilizers (e.g., methanesulfonic acid (“MSA”)) and vapor phase stabilizers (e.g., trifluoroacetic acid (“TFA”)). it may be desirable to utilize relatively weak acids to inhibit polymerization. Generally such weak acids exhibit a pKa in acetonitrile of about −1.5 or about 2 or less. Exemplary acids used to inhibit anionic polymerization are alkyl substituted aryl sulfonic acids, such as dodecylbenzenesulfonic acid, p-toluenesulfonic acid, and the like. As the catalyst in the method of the invention is an acid a second anionic polymerization inhibitor may not be required in performing the method disclosed herein. It is desired to include a free radical stabilizer or polymerization inhibitor in performing the method disclosed herein. The concentrations of the stabilizers, or polymerization inhibitors, useful in the method are disclosed hereinafter.

Free radical stabilizers preferably include phenolic compounds (e.g., 4-methoxyphenol, mono methyl ether of hydroquinone (“MeHQ”) butylated hydroxytoluene (“BHT”)). Stabilizer packages for 1,1-disubstituted alkenes are disclosed in U.S. Pat. No. 8,609,885 and U.S. Pat. No. 8,884,051, each incorporated by reference. Additional free radical polymerization inhibitors are disclosed in U.S. Pat. No. 6,458,956 and are hereby incorporated by reference. Generally, only minimal quantities of a stabilizer are needed and, in certain embodiments only about 5000 parts-per-million (“ppm”) or less can be included. In certain embodiments, a blend of multiple stabilizers can be included; for example, a blend of anionic stabilizers (MSA) and free radical stabilizers (MeHQ).

The one or more anionic polymerization stabilizers are present in sufficient amount to prevent premature polymerization. The anionic polymerization stabilizers may be present in an amount of about 1 ppm or less based on the weight of the first ester compound (1,1-disubstituted alkene), about 5 ppm by weight or greater, or about 10 ppm by weight or greater. The anionic polymerization stabilizers may be present in an amount of about 500 ppm by weight or less based on the weight of the ester compound (1,1-disubstituted alkene), about 250 ppm by weight or less, or about 100 ppm by weight or less. The one or more free radical stabilizers are present in sufficient amount to prevent premature polymerization. The free radical polymerization stabilizers may be present in an amount of about 10 ppm or less based on the weight of the ester compound (1,1-disubstituted alkene), about 100 ppm by weight or greater or about 1000 ppm by weight or greater. The free radical polymerization stabilizers may be present in an amount of about 10,000 ppm by weight or less based on the weight of the ester compound (1,1-disubstituted alkene), about 8000 ppm by weight or lessor about 5000 ppm by weight or less.

Disclosed is a method comprising contacting a composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups with a surface of a substrate wherein the surface is at least mildly basic and forming a coating on the surface of the substrate comprising the composition containing the one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups. The substrate is comprised of material that is basic. The composition that contains a basic compound may be applied to the surface of the substrate before applying the composition containing one or more polyester macromers. The composition that contains a basic compound may comprise any compound disclosed herein as an anionic polymerization inhibitor useful with 1,1-diester-1-alkenes. Exemplary basic compounds include an amine, polyamine basic pigments or carboxylate salts. The composition that contains a basic compound may comprise a polyalkyleneimine. The method may further include exposing the substrate with the composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups to a temperature of about 20° C. or greater or about 50° C. or greater. The method may further include exposing the substrate to with a composition containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups to a temperature of about to 150° C. or less or about 120° C. or less. The time period for such exposure may be about 10 minutes or greater or about 20 minutes or greater. The time period for such exposure may be 120 minutes or less, about 60 minutes or less or about 30 minutes or less. The exposure is performed under conditions such that the coating containing one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups disposed on the surface of the substrate is cured and/or crosslinked.

The polyester macromer containing coatings or films may cure and/or crosslink when exposed to certain conditions. When the coating or film are exposed to relatively strong bases and or elevated temperatures they cure and crosslink at the same time. If they are exposed to mildly basic materials at relatively low temperatures, less than about 50° C. or less than about 40° C. they may not completely cure or crosslink. Such coatings or films may be cured by exposure to elevated temperatures to cure as disclosed herein.

The coatings prepared from one or more polyester macromers and one or more polymers having pendant Michael Addition donor groups may exhibit one or more of the following properties listed below. A gloss according to ASTM D523-08 at 20° of 40 GU or greater, 50 GU or greater or 60 GU or greater. A pencil hardness according to ASTM D3363-00 of 3H or greater, 4H or greater or 5H or greater. A solvent resistance according to ASTM D5402-93 of about 80 double rubs of methyl ethyl ketone or greater, 100 rubs or greater or 200 rubs or greater. A mandrel flexibility according to ASTM D522-93 of 70 percent or greater, 80 percent of greater or 90 percent; A cross hatch adhesion of 4B or higher 100 percent according to ASTM D3359-09. An acid resistance according to GMW 14701 up to 40° C., up to 50° C. or up to 60° C. A base resistance according to GMW 14701 40° C. or greater, 50° C. or greater or of 60° C. or greater. Coatings are able to withstand 500 hours, 1000 hours, of Xenon arc UV/moisture exposure according to ASTM D7869 with no loss in gloss or color and 500 hours of salt spray testing according to GMW 3286-11 with no change in gloss or no signs of blistering and corrosion.

The articles/compositions disclosed may further comprise any one or more of the features described in this specification in any combination, including the preferences and examples listed in this specification, and includes one or more of the following features: wherein the pendant Michael Addition donor groups comprise functional groups containing active hydrogen atoms; wherein the pendant Michael Addition donor groups comprise amines, hydroxyl, thiol, or mixtures thereof; wherein the Michael Addition donor groups comprise amines and/or hydroxyl wherein the composition contains one or more alternating chains of the residue of one or more diols and one or more diesters wherein each of the chains are bonded at one end to an oxygen of the residue of a polyol having three or more of the oxygen atoms; wherein the polyester macromer corresponds to Formula 1; wherein c as used in a number of formulas may be an integer of about 3 to about 6; wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyester polyols, polyether polyols and siloxane polyols; wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more acrylic polyols or amine modified acrylic polyols; a composition according to any one of the preceding claims which comprises a) from about 40 to about 90 percent by weight of one or more polyester macromers and from about 10 to 60 percent by weight of one or more one or more polymers having pendant Michael Addition donor groups wherein the amounts are based on the weight of the composition, which may optionally contain a solvent; the solvent may comprise one or more polar aprotic solvents; the solvent may comprise one or more one or more alkylene glycol ethers, acetate modified alkylene glycol ethers, or ketones, having a boiling point of about 80° C. to about 200° C.; the solvent is present in an amount of about 5 to about 40 percent by weight wherein the amounts are based on the weight of the composition; the polyester macromer may contain one chain of the residue of one or more diols and one or more diesters; the polyester macromers may correspond to Formula 2; the polyester macromers may exhibit a number average molecular weight of about 400 to about 3000; the oxygens from the hydroxyl groups on the diols and polyols of the polyester macromers may be bonded to aliphatic carbon atoms; the one or more chains of the polyester macromers may comprise a residue of one or more dihydrocarbyl dicarboxylates; the one or more dihydrocarbyl dicarboxylates may comprise one or more of aromatic dicarboxylates having 8 to 14 carbon atoms in the backbone, aliphatic dicarboxylates having 1 to 12 carbon atoms in the backbone and cycloaliphatic dicarboxylates having 8 to 12 carbon atoms in the backbone; the one or more dihydrocarbyl dicarboxylates may comprise one or more malonates, terephthalates, phthalates, isophthalates, naphthalene-2,6-dicarboxylates, 1,3-phenylenedioxy diacetates, cyclohexanedicarboxylates, cyclohexanediacetates, diphenyl-4,4′-dicarboxylates, succinates, glutarates, adipates, azelates, sebacates, or mixtures thereof; the one or more dihydrocarbyl dicarboxylates comprise one or more malonates, isophthalates, terephthalates or sebacates; the polyols used to prepare the polyester macromers correspond to Formula 9, the 1,1-diester-1-alkenes correspond to Formula 7 and the one or more dihydrocarbyl dicarboxylates correspond to Formula 11; c is 2 and the polyols used to prepare the polyester macromers correspond to the formula HO—R²—OH wherein R² is as previously described; the polyols used to prepare the polyester macromers may comprise one or more aliphatic backbones that are branched; the one or more polyols used to prepare the polyester macromers may comprise one or more branched aliphatic chains having at least one branch on the 2 carbon atom and cycloaliphatic backbones; the one or more polyols may comprise pentane diol, hexane diol, neopentyl glycol, 2-methyl-1,3-propane diol, 2-butyl-1,3-propane diol, 2-ethyl-1,3-propane diol or cyclohexane dimethanol; the polyester macromers correspond to Formula 3; the polyester macromers correspond to Formula 4; the polyester macromers correspond to Formula 5; polyester macromers according to Formula 4 or 5 wherein the ratio of d to e in the macromer is about 1:1 to about 4:1; a polyester macromer having from about 1 to about 4 dihydrocarbyl dicarboxylates are contained in each chain; the polyester macromers correspond to Formula 6; a composition comprising i) a plurality of polyester macromers described herein, ii) one or more multifunctional monomers containing the residue of one or more polyols and one or more 1,1-diester-1-alkenes, wherein the multifunctional monomers have substantially all of the hydroxyl groups of the polyols replaced with the 1,1-diester-1-alkenes, and iii) one or more 1,1-diester-1-alkenes, wherein such composition may comprise i) from about 10 to about 90 percent by weight of a plurality of polyester macromers, ii) from about 1 to about 50 percent by weight of one or more multifunctional monomers, and iii) from about 1 to about 30 percent by weight of one or more 1,1-diester-1-alkenes wherein the percentages are based on the amounts of the ingredients listed; the one or more polyols used to prepare the polyester macromers may be diols; the one or more multifunctional monomers used to prepare the polyester macromers may be difunctional monomers; a composition comprising a) a polyester macromer containing composition as disclosed herein, b) a volatile solvent, c) optionally, an additional amount of one or more 1,1-diester-1-alkenes, d) one or more wetting and levelling agents, e) one or more UV stabilizers and/or UV absorbers, and, f) one or more defoamers, wherein such composition may comprise a) from about 10 to about 90 percent by weight of a polyester macromer containing composition as disclosed herein, b) from about 1 to about 50 percent by weight of a volatile solvent, c) from about 0 to about 40 percent by weight of one or more 1,1-diester-1-alkenes, d) from about 0.01 to about 2 percent by weight of one or more wetting and levelling agents, e) from about 0.01 to about 3 percent by weight of one or more UV stabilizers and/or UV absorbers, and, f) from about 0.01 to about 2 percent by weight of one or more defoamers, wherein the percentages are based on the weight of components a, b, c, d, e and f; a composition as disclosed herein which is cured and in the form of a coating; wherein the coating exhibits a thickness of about 1 micrometers to about 100 micrometers; wherein the coating exhibits a thickness of about 2-160 microns; a composition containing a plurality of polyester macromers wherein a portion of or all of the polyester macromers are crosslinked through the 1,1-alkene groups; a composition wherein the crosslinks between chains may be illustrated by formula 17; a composition according to Formula 17 wherein F may be separately in each occurrence a direct bond, the residue of a 1,1-diester-1-alkene or a multifunctional monomer; a composition wherein a portion of or all of the polyester macromers are crosslinked by Michael Addition of the Michael Addition Donors pendant from the polymers to the 1 alkene groups of the polyester macromers; a composition wherein the crosslinks by Michael Addition of the Michael Addition Donors pendant from the polyols to the 1 alkene groups of the polyester macromer correspond to Formula 18; a composition according to Formula 18 wherein X is independently in each occurrence O, NR^y, or S; and R^x is independently in each occurrence a polymer comprising an acrylic polyol, amine modified acrylic polyol, polycarbonate polyol, modified acrylic copolymer polyol, polyester polyol, polyether polyol or siloxane polyol or a substrate; the polyester macromers are crosslinked through the 1,1-alkene groups and/or by Michael Addition of the Michael Addition Donors pendant from the polymers to the 1 alkene groups; the cured coating exhibits one or more of the following properties of a gloss according to ASTM D523-08 at 20°, or 60°, or 85° of 40 GU or greater; a pencil hardness according to ASTM D3363-00 of 3H or greater; a solvent resistance according to ASTM D5402-93 to 80 rubs of methyl ethyl ketone or greater; mandrel flexibility according to ASTM D522-93 of 80 percent or greater; cross hatch adhesion of 4B or higher and 100 percent according to ASTM D3359-09 and acid resistance up to 70° C. and base resistance at greater than 70° C. according to GMW 14701; the polymers having pendant Michael Donor groups exhibit a hydroxyl number of about 50 to about 200; and a composition as described herein which further comprises one or more of the following components: pigments, fillers, reinforcing agents, anti-slip additives, and additves to improve abrasion resistance.

The methods disclosed may further comprise any one or more of the features described in this specification in any combination, including the preferences and examples listed in this specification, and includes any one or more of the following features; the substrate is comprised of one or more of a material that is at least mildly basic, nucleophilic and/or contains a plurality of Michael Addition Donor groups on its surface; the pendant Michael Addition donor groups comprise functional groups containing active hydrogen atoms; the pendant Michael Addition donor groups comprise amines, hydroxyl, thiol, or mixtures thereof; the Michael Addition donor groups comprise amines and/or hydroxyl; the substrate has a pigmented coating deposited on its surface wherein the pigmented coating is mildly basic or nucleophilic; the coating comprising the composition containing the one or more polyester macromers forms a clear coating; which includes exposing the substrate with the composition containing one or more polyester macromers deposited on the substrate to a temperature of about 20° C. to about 150° C. for about 10 minutes to about 120 minutes under conditions such that the coating containing one or more polyester macromers disposed on the surface of the substrate is crosslinked; wherein the coating or the surface of the substrate contains a catalyst for Michael Addition; and the coating or the surface of the substrate contains an initiator for anionic polymerization.

Illustrative Embodiments of the Invention

The following examples are provided to illustrate the invention, but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated.

The reaction procedure is described as follows: a three neck 100 mL round bottom flask with a distillation head, thermometer, vacuum adapter, and collection flask are assembled using high vacuum grade grease along with a heating mantle, thermocouple, and a magnetic stir bar. The reaction mixture is subjected to agitation typically ranging from 400-600 rpm. Vacuum is used to remove subsequent byproducts from the reaction mixture and the various pressures are indicated below along with the mix time in each case. In some cases, nitrogen gas is used to purge the mixture in lieu of vacuum and, if applicable, is indicated below. In each case, the mole equivalent is relative to the diethyl methylene malonate (“DEMM”) monomer used.

NMR spectroscopy is employed using a 300 MHz NMR to analyze reaction mixtures. Samples were prepared using chloroform-d (CDCl₃) and hexamethyldisiloxane as an internal standard appearing at about 0 ppm. For 1,1-disubstituted alkene compounds with symmetrical substituents (e.g., DEMM), the reactive alkene functionality (i.e., the double bond) appears at about 6.45 ppm. For 1,1-disubstituted alkene compounds with asymmetrical substituents, the reactive alkene functionality appears as a doublet at about 6.45 ppm. In most cases, four NMR scans are run on each samples specimen with a 20 second delay between scans.

GC-MS is employed to determine conversion of starting materials to the desired transesterified product(s) and detect the presence of any byproducts. A helium gas (carrier gas) purge of about 1 mL/min is employed to aid the ionized in sample reaching the MS detector. Typical sample injection volumes of 1-2 μL of about 2-5% of the reaction mixture in dichloromethane (CH₂Cl₂) are used for injecting into the GC-MS instrument. The GC-MS profile method involves maintaining the oven at 100° C., followed by a ramp of 15° C./min to 250° C. Typical run times range from 18-23 minutes. Retention times of 1,1-disubstituted alkene compounds, based on the above mentioned method, range from 4.5-17 min and are strongly dependent on the substituents and the ease of ionization of the particular molecule in the GC chamber.

Gel permeation chromatography (GPC) is used to determine the molecular weight of the polyester macromers formed after transesterification. Polymethylmethacrylate standards (PMMA), covering a range of 500 to 1.08 million in number average molecular weight (Mn) were used to plot the calibration curve. Samples were dissolved in THF and filtered before injection. A 10 μL injection volume was utilized at 1 ml/min. Columns were maintained at 35° C. and 75 bar pressure. A refractive index detector is utilized downstream and is also maintained at 75 bar pressure. The amount of different species in the composition were calculated based on the percent area of the molecular weight peak on the chromatogram.

Ingredients and Products

Pentane Diol
DEM      Diethyl malonate
DEMM     Diethyl methylene malonate
         (diethyl 1-methylene-1,1-dicarboxylate)
MeHQ     Mono methyl ether hydroquinone
MSA      Methanesulfonic acid
Catalyst CALB Lipase Enzyme

Testing and Test procedures—coatings prepared as described herein are tested for a number of properties according to the following procedures.

Crosshatch tape adhesion   ASTM D3359-09
Specular gloss             ASTM D523-08
Pencil hardness            ASTM D3363-00
MEK rub resistance         ASTM D5402-93
Mandrel                    ASTM D522-93
Abrasion                   ASTM D4060-95 (modified for Linear Taber)
Moisture                   GMW 14729
Acid/Base resistance       GMW 14701
Weathering (UV + moisture) SAE J2020
Salt spray                 GMW 3286-11 Neutral salt spray

Example 1—Preparation of Di-functional Monomer from Pentane Diol and DEMM

A round bottom flask is charged with DEMM (172 g, 1 mol), pentanediol (26 g, 0.25 mol) and CALB lipase enzyme (8.6 g) (purchased from CLEA) 5 weight percent based on DEMM. The round bottom flask is placed on a rotovap preheated to 45° C. and pressure of 150 mm Hg is applied. After 1 hour the reaction is checked for completion by GCMS and HNMR. Once the pentanediol has been consumed, the reaction has gone to completion. The product mixture is about a 65/35 mixture of difunctional monomer and DEMM according to GCMS analysis. The reaction mixture is filtered to remove enzyme. A 3 neck round bottom flask equipped with mechanical agitator, thermometer and a condenser is charged with the reaction mixture formed. The reaction mixture is distilled at 65° C. and a pressure <0.800 mm Hg for 2 hours or until the amount of difunctional monomer is greater than 65 percent by weight of the solution. The typical product composition is: 67% DEMM-pentanediol multifunctional monomer and 33% DEMM.

Example 2—Endcapping Diethyl Malonate with Pentane Diol

A round bottom flask is charged with pentanediol (260 g 2.5 mol), DEM (159 g, 1 mol) and CALB lipase enzyme (18 g) (purchased from CLEA), 7 weight percent based on pentanediol. The round bottom flask is placed on a rotovap and preheated to 45° C. and a pressure of 150 mm Hg is applied. After 1 hour the reaction is checked for completion by GCMS and HNMR. Once the DEM has been consumed, the reaction has gone to completion. The reaction mixture is filtered to remove enzyme. A 3 neck round bottom flask equipped with mechanical agitator, thermometer and a condenser is charged with the reaction mixture which is distilled at 100° C. and less than 0.800 mmHg for 2 hours or until the amount of pentanediol is about 10 weight percent of the reaction mixture (as determined by GCMS). The typical product composition is about 90 percent by weight or pentanediol capped diethyl malonate and about 10 percent by weight pentanediol.

Example 3—Preparation of Polyester Macromer

A round bottom flask is charged with DEMM-pentanediol difunctional monomer (142 g, 0.4 mol) and pentanediol capped diethyl malonate (27.6 g 0.1 mol), diethyl methylene malonate, (70 g, 0.4 mol), pentane diol (2.7 g, 0.025 mol) and CALB lipase enzyme (10 g) 7 weight percent based on DEMM-pentanediol difunctional monomer. The round bottom flask is placed on a rotovap preheated to 45° C. and at a pressure of 150 mm Hg. After 1 hour the reaction mixture is checked for completion (disappearance of pentanediol-difunctional monomer) by GCMS. The reaction mixture is filtered to remove the enzyme. The resulting solution is examined by GPC. The product composition is generally comprised of the following: 60-75 weight percent of polyester macromer, 20-30 weight percent of pentanediol-difunctional monomer, 0-10 weight percent of DEMM. 100 ppm MEHQ and 10 ppm MSA are added to the final product. MSA is accurately measured out from a 1 percent by weight MSA: DEMM solution. This reaction is illustrated by the equation:

Example 4—Preparation of Polyester Macromer

A round bottom flask is charged with DEMM-pentanediol difunctional monomer (142 g, 0.4 mol), diethyl methylene malonate, (70 g, 0.4 mol), pentane diol (10.8 g, 0.10 mol) and CALB lipase enzyme (10 g) 7 weight percent based on DEMM-pentanediol difunctional monomer. The round bottom flask is placed on a rotovap preheated to 45° C. at a pressure of 150 mm Hg. After 1 hour the reaction mixture is checked for completion (disappearance of pentanediol-difunctional monomer) by GCMS. The reaction mixture is filtered to remove the enzyme. The resulting solution is examined by GPC. The product composition is generally comprised of the following: 60-75 weight percent of polyester macromer, 20-30 weight percent of pentanediol-difunctional monomer, 0-10 weight percent of DEMM. 100 ppm MEHQ and 10 ppm MSA are added to the final product. MSA is accurately measured out from a 1 percent by weight MSA DEMM solution. This reaction is illustrated by the equation:

For most of the experiments the composition is 60-70% of polyester macromers having a molecular weight of 800, 30-35% DEMM-pentane diol difunctional molecule and 5-10% DEMM. References to polyester composition refers to this general composition. Any deviations from this will be specifically mentioned.

Example 6: Testing the Polyester Composition on Cold Rolled Steel

The cold rolled steel panels are from Q-Panel (4″×6″ steel). The steel panels require an initiator to be used to adhere to the substrate. Pyridyl ethyl trimethoxysilane (PETS), and Polyethylenimine branched (PEI) are used as initiators as 1% solution in butyl cellosolve. The initiator solution is drawn down using a 2.5 Meyer rod and solvent is flashed off at 80° C. for 5 minutes. A solution of the polyester composition is drawn down using a 20 Meyer rod resulting in a wet film thickness of 40 microns. The cure temperature used is 80° C. The coated panels are cured within 20-30 minutes. Properties of the resultant coating after full cure are summarized in Table 2. To pass the Cross Hatch test the result must be 5B. To pass the mandrel test the sample must show no detected cracks at all bend angles on the mandrel.

TABLE 2
Properties of the polyester composition on cold rolled steel
initiated by 1% PEI (250K MW) in butyl cellosolve
Parameter or test
Cure Time          20 minutes @ 80° C.
Pencil Hardness    >9H
Gloss Reading      80 GU @ 20° C.
Solvent Resistance >80 double MEK wipes
Cross Hatch        Pass
Mandrel            Fail

The polyester composition, having a molecular weight of 800 is also cured using a branched PEI initiator with a molecular weight of 800. The results of the testing are summarized in Table 3. The improved flexibility of this polyester composition on a Mandrel test is attributed to the higher molecular weight of this polyester composition.

TABLE 3
Properties of a polyester on cold rolled steel initiated by
branched 1% PEI (800 MW) in butyl cellosolve.
Parameter or test  Results
Cure Time          20 minutes @ 120° C.
Pencil Hardness    7H to 8H
Gloss Reading      131.3 GU @ 20° C.
Solvent Resistance >100 double MEK wipes
Cross Hatch        Pass
Mandrel            Pass

Example 7: Spray Coating on Base Coated Steel Panels

BASF R-M Onyx HD™ base coat is professionally sprayed on the panels. There is some variation in the color of the coated base coats across different tests. This shows the robustness of the chemistry being able to cure on base coats of different colors.

The clear coat is also sprayed on the base coated panels. Each formulation is sprayed using an automotive refinish HVLP gun (Anest Iwata model number WS-400). Each round of spraying is conducted in a forced air laboratory hood with 100 ft/min air flow. Before first use, the gun is pacified by spraying a solution of 1% methanesulfonic acid in acetone. The gun is connected to a shop compressed air source of 90 psi which is stepped down with a regulator to 25 psi at the gauge. During spraying, the active pressure reading is 20 psi. Spray coatings are applied in two coats with each pass overlapping the one above it 50%. After each formulation, the gun is cleaned by spraying acetone through it twice.

The polyester composition is adjusted by formulation according to Table 4 below. BYK 333 is a polyether modified silicone additive which is used for improving wet out on base coats. 40% butyl cellosolve solvent is used to dilute the polyester composition to improve spray capabilities and to assist with wet out. Formulation 1 using polyester and solvent comprises the polyester composition having a molecular weight of 60 weight percent; 0.1 wt % BYK 333 polyether modified silicone and 40 wt % Butyl cellosolve.

TABLE 5
Properties of the formulation on base coat
Parameter or test  Results
Cure Time          30 minutes @ 120° C.
Pencil Hardness    8H to 9H
Gloss Reading      73.7 GU @ 20° C.
Solvent Resistance >100 double MEK wipes
Cross Hatch        Pass
Mandrel            Pass

This demonstrates that the cure of the polyester based formulation using the base coat at elevated temperatures results in good coating properties.

Example 8

Example 7 is repeated except the cure temperature chosen is 82° C. Properties of the resultant coating are not affected as shown in Table 6 below.

TABLE 6
Coating properties for Formulation 1
after cure at 82° C.
Parameter or test  Results
Cure Time          30 minutes @ 82° C.
Pencil Hardness    8H to 9H
Gloss Reading      75.7 GU @ 20° C.
Solvent Resistance >100 double MEK wipes
Cross Hatch        Pass
Mandrel            Pass

Example 9: Replacing Solvent with Reactive Diluent (DEMM)

DEMM (dimethyl methylene malonate) is added at 20% to decrease the weight percentage of butyl cellosolve to 20 percent. DEMM reacts rapidly to form crosslinks with the di and multi-functional components at lower temperatures. The formulation comprises 60 weight percent of a polyester macromer having a molecular weight of 800, 0.1 wt % BYK 333 polyether modified silicone, 20 wt % Butyl cellosolve and 20 wt % DEMM

The coating procedure is similar to that described in Example 6. The Coatings are cured at 50° C. for 25 minutes and complete cure is obtained. Coatings appeared aesthetically pleasing and showed good properties as shown in Table 7.

Parameter or test
Cure Time          25 minutes @ 50° C.
Pencil Hardness    9H
Gloss Reading      60.4 GU @ 20° C.
Solvent Resistance >100 double MEK wipes
Cross Hatch        Pass
Mandrel            Pass

Acid and base resistance testing is conducted using GM method GMW14701. The results are summarized in Table 8.

	Test Conditions	Acid Resistance	Base Resistance
	Room Temperature	Pass	Pass
	for 24 hours
	50° C. for 25 minutes	Pass	Pass
	70° C. for 25 minutes	Pass	Pass
	82° C. for 25 minutes	Fail	Pass

This demonstrates that the coatings have good acid and base resistance after full crosslinking where the only failures are occurring at elevated temperatures.

Example 10: Formulations with Polyester and Acrylic Polyols

Acrylic polyols are chosen to be used with polyesters in varying amounts to improve flexibility, resistance properties and long term aging characteristics. Acrylic polyols made by BASF under the trade name Joncryl and those made by Dow under the trade name Paraloid are utilized. Several formulation attempts have been made to test the ratio of acrylic polyol to polyester that provides the desired flexibility and to improve coating properties. Two ratios of polyester to acrylic polyol are chosen based on an evaluation of the cure speed and conditions and the properties of the coatings after cure. Formulations are sprayed on to steel panels coated with a base coat and cured as described above.

The formulation may be curing using Anionic polymerization and Michael addition reactions. The hydroxyl groups present on the surface of the base coat and scattered across the chain length of the acrylic polyol undergo Michael addition with the reactive methylene groups present in the polyol, thus incorporating the polyol into the crosslinked matrix.

TABLE 9
Formulation 3 utilizing polyester and acrylic polyol
Ingredient                       Weight percent
Polyester Macromer               68
Joncryl 935 Acrylic polyol       12
BYK 333 polyether modified silicone 0.1
Glycol Ether PM Acetate          20

Formulation 3 is spray coated on a Car Star Base Coat.

TABLE 10
Performance Results for Formulation 3
Parameter or test                Results
Cure Time                        25 minutes @ 60° C.
Pencil Hardness                  6H
Gloss Reading                    82 GU @ 20° C.
Solvent Resistance               200 double MEK wipes
Cross Hatch                      5B Pass
Mandrel                          6/10
Acid Base at Room Temp           Acid 10/10 Base 10/10
Acid Base at 50° C.              Acid 10/10 Base 10/10
Acid Base at 70° C.              Acid 6/10 Base 10/10
Fuel (Dip Test Method A) GMW 14333 10 cycles No scratch
Fuel (Method B) GMW 14333        100% removed
Abrasion                         Wear Index 1.3
UV/Moisture for 168 hours        100% gloss retained
Salt Spray for 168 hours         100% gloss retained

Example 11

Formulation 4 is spray coated on a Car Star Base Coat. Formulation 4 demonstrates a lower flexibility on the Mandrel test.

TABLE 11
Formulation 4 using polyester and acrylic polyol
Ingredient                       Weight percent
Polyester Macromer               56
Joncryl 935 Acrylic polyol       24
BYK 333 polyether modified silicone 0.1
Glycol Ether PM Acetate          20

TABLE 13
Performance Data for Formulation 4
Parameter or test
Cure Time                        25 minutes @ 60° C.
Pencil Hardness                  6H
Gloss Reading                    84 GU @ 20° C.
Solvent Resistance               200 double MEK wipes
Cross Hatch                      5B Pass
Mandrel                          8/10
Acid Base at Room Temp           Acid 10/10 Base 10/10
Acid Base at 50° C.              Acid 10/10 Base 10/10
Acid Base at 70° C.              Acid 8/10 Base 10/10
Fuel (Dip Test Method A) GMW 14333 10 cycles No scratch
Fuel (Method B) GMW 14333        100% removed
Abrasion                         Wear Index 1.45
UV/Moisture 500 hours            100% gloss retained
Salt Spray 500 hours             100% gloss retained

Example 11 demonstrates that coatings made utilizing formulation 4 have 168 hours resistance to an accelerated test utilizing UV/moisture exposure and 168 hours resistance to corrosion by salt spray exposure.

Example 12: Utilization of Other Polyesters in Formulations

The polyester prepared from pentane diol and DEM according to the following structure is used in Formulation 5, described below.

TABLE 13
Formulation 5
Ingredient                       Weight percent
Polyester Macromer               68
Joncryl 935 Acrylic polyol       12
BYK 333 polyether modified silicone 0.1
Glycol Ether PM Acetate          20

The spray and cure process is as described in the examples above. A longer cure time is needed and this is attributed to the reduced electron withdrawing capability of the methylene groups due to the spacing effect. Properties of the coating after full cure can be summarized in Table 14 below.

TABLE 14
Properties of Formulation 5
Parameter or test                Results
Cure Time                        25 minutes @ 60° C.
Pencil Hardness                  5H
Gloss Reading                    67 GU @ 20° C.
Solvent Resistance               100 double MEK wipes
Cross Hatch                      5B Pass
Mandrel                          8/10
Acid Base at Room Temp           Acid 10/10 Base 10/10
Acid Base at 50° C.              Acid 8/10 Base 10/10
Acid Base at 70° C.              Acid 4/10 Base 10/10
Fuel (Dip Test Method A) GMW 14333 5 cycles Easy to scratch
Fuel (Method B) GMW 14333        100% removed
Abrasion                         Wear Index 0.65
UV/Moisture-168 hours            100% gloss retained
Salt Spray-168 hours             100% gloss retained

Cure Time 25 minutes @ 60° C. followed by 15 min @ 120° C.

Formulation 5 has much better flexibility on the Mandrel test due to the spaced structure of the base polyester. It has a lower pencil hardness before aging. After UV/moisture and salt spray testing, this formulation is able to maintain gloss, adhesion and flexibility. Thus spacing the methylene groups in the polyester may provide a useful strategy for improved flexibility after resistance testing although initial testing may not reflect the best possible combination of properties.

Example 13: Coatings Made with Polyester Having Cyclic Structures

Inclusion of cyclic aliphatic ring in the diol to make the polyester by using diols like cyclohexane dimethanol (CDM) reduces the free volume in the system, improves the overall moisture resistance and UV resistance and imparts rigidity to the resultant polymer. The structure for the polyester is as shown in the formula provided below.

TABLE 15
Formulation 6
Ingredient                       Weight percent
CDM based Polyester Macromer     56
Joncryl 935 Acrylic polyol       24
BYK 333 polyether modified silicone 0.1
Glycol Ether PM Acetate          20

The spray and cure process is as described in the examples above. A longer cure time is needed and this was attributed to the reduced electron withdrawing capability of the methylene groups due to the CDM groups. Properties of the coating after full cure are summarized in Table 16 below.

TABLE 16
Properties of Formulation 6
Parameter or test                Results
Cure Time                        25 minutes @ 60° C.
Pencil Hardness                  6H
Gloss Reading                    79 GU @ 20° C.
Solvent Resistance               >100 double MEK wipes
Cross Hatch                      5B Pass
Mandrel                          10/10
Acid Base at Room Temp           Acid 10/10 Base 10/10
Acid Base at 50° C.              Acid 10/10 Base 10/10
Acid Base at 70° C.              Acid 4/10 Base 10/10
Fuel (Dip Test Method A) GMW 14333 10 cycles Easy to scratch
Fuel (Method B) GMW 14333        100% removed
Abrasion                         Wear Index 0.95
UV/Moisture-500 hours            100% gloss retained
Salt Spray-500 hours             100% gloss retained

Cure Time 25 minutes @ 60° C. followed by 15 min @ 120° C.

Formulation 6 demonstrates a lower flexibility on the Mandrel test due to the cyclic structure of the base polyester. It has a higher pencil hardness before aging. After UV/moisture and salt spray testing, this formulation is able to maintain gloss and adhesion. Formulation is also able to maintain gloss 100% after exposure to 99% relative humidity in a humidity chamber for 3 weeks. This shows the improved moisture resistance due to the cyclic structures present in the polyester.

Parts by weight as used herein refers to 100 parts by weight of the composition specifically referred to. Any numerical values recited in the above application include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc., are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value, and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of “about” or “approximately” in connection with a range applies to both ends of the range. Thus, “about 20 to 30” is intended to cover “about 20 to about 30”, inclusive of at least the specified endpoints. The term “consisting essentially of” to describe a combination shall include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms “comprising” or “including” to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist essentially of the elements, ingredients, components or steps. Plural elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step might be divided into separate plural elements, ingredients, components or steps. The disclosure of “a” or “one” to describe an element, ingredient, component or step is not intended to foreclose additional elements, ingredients, components or steps.

Claims

1. A composition comprising a) one or more polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chain and a portion of the diesters ore 1,1-diester-1-alkenes and at least one terminal end comprises the residue of one of the 1,1-diester-1-alkenes and wherein one or more terminal ends may comprise the residue of one or more diols: and b) one or more polymers having pendant Michael Addition donor groups wherein a portion of or all of the polyester macromers are crosslinked by Michael Addition of the Michael Addition Donors pendant from the polymers to the 1-alkene groups of the polyester macromers

2. A composition according to claim 1 wherein X is independently in each occurrence O, NRy, or S;

3. A composition according to claim 1 wherein the pendant Michael Addition donor groups comprise functional groups containing active hydrogen atoms.

4. A composition according to claim 1 wherein the pendant Michael Addition donor groups comprise amines, hydroxyl, thiol, or mixtures thereof.

5. A composition according to claim 1 wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyester polyols, polyether polyols and siloxane polyols.

6. A composition according to claim 1 wherein the one or more polymers having Pendant Michael Addition donor groups comprise one or more acrylic polyols or amine modified acrylic polyols.

7. A composition according to claim 1 wherein the polyester macromer exhibits a number average molecular weight of about 400 to about 3000.

8. A composition comprising i) a plurality of polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more dole and the one or more diesters alternate along the chain and a portion of the diesters are 1,1-diester-1-alkenes and at least one terminal end comprises the residue of one of the 1,1-diester-1-alkenes and wherein one or more terminal ends may comprise the residue of one or morn diols;ii) one or more multifunctional monomers containing the residue of one or more polyols and one or more 1,1-diester-1-alkenes, wherein the multifunctional monomers have substantially all of the hydroxyl groups of the polyols replaced with the 1,1-diester-1-alkenes;iii) one or more 1,1-diester-1-alkenes; andiv) one or more polymers having pendant Michael Addition donor groups;wherein a portion of or all of the polyester macromers are crosslinked through the 1,1-alkene groups by Michael Addition of the Michael Addition Donors pendant from the polymers;wherein the crosslinks by Michael Addition of the Michael Addition Donors pendant from the polyols to the 1-alkene groups of the polyester macromer correspond to the formula

9. A composition according to claim 8 wherein the pendant Michael Addition donor groups comprise functional groups containing active hydrogen atoms.

10. A composition according to claim 8 wherein the pendant Michael Addition donor groups comprise amines, hydroxyl, thiol, or mixtures thereof.

11. A composition according to claim 8 wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyester polyols, polyether polyols and siloxane polyols.

12. A composition according to claim 8 wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more acrylic polyols or amine modified acrylic polyols.

13. A composition according to claim 8 wherein X is independently in each occurrence O, NRy, or S; and Rx is independently in each occurrence a polymer comprising an acrylic polyol, amine modified acrylic polyol, polycarbonate polyol, modified acrylic copolymer polyol, polyester polyol, polyether polyol or silane polyol or a substrate; and,Ry is H or a hydrocarbyl group.

14. A composition according to claim 8 wherein a portion of the polyester macromers are crosslinked through some of the 1,1-alkene groups wherein the crosslinks between chains are represented by formula 17:

15. A composition according to claim 14 wherein F is separately in each occurrence a direct bond or the residue of a 1,1-diester-1-alkene or a multifunctional monomer.

16. A composition according to claim 8 wherein the polyester macromer exhibits a number average molecular weight of about 400 to about 3000.

17. A composition according to claim 1 wherein a portion of the polyester macromers are crosslinked through some of the 1,1-alkene groups wherein the crosslinks between chains are represented by formula 17:

18. A composition according to claim 17 wherein F is separately in each occurrence a direct bond or the residue of a 1,1-diester-1-alkene or a multifunctional monomer.