阅读说明：本技术 亚甲基丙二酸酯的uv固化工艺 (UV curing process of methylene malonate ) 是由 A·R·霍尔泽 A·德史潘德 A·S·帕苏利 J·M·萨利文 于 2018-07-13 设计创作，主要内容包括：一种方法,其包括通过将一种以上的光引发剂与包括一种以上的1,1-二取代烯烃化合物的组合物接触而形成配混物,所述1,1-二取代烯烃化合物的纯度相对于1,1-二取代烯烃化合物的总重量为约85摩尔％以上；并且将所述配混物暴露于紫外辐射下而引发自由基聚合、阴离子聚合、或两者,从而固化所述配混物以形成非粘性表面。本教导还涉及了根据所公开的方法制备的一种聚合物。(A method comprising forming a compound by contacting one or more photoinitiators with a composition comprising one or more 1, 1-disubstituted alkene compounds, the 1, 1-disubstituted alkene compounds having a purity of about 85 mole% or more relative to the total weight of the 1, 1-disubstituted alkene compounds; and exposing the compound to ultraviolet radiation to initiate free radical polymerization, anionic polymerization, or both, thereby curing the compound to form a non-tacky surface. The present teachings also relate to a polymer made according to the disclosed method.)

1. A method comprising forming a compound by contacting one or more photoinitiators with a composition comprising one or more 1, 1-disubstituted alkene compounds, the 1, 1-disubstituted alkene compounds having a purity of about 85 mole percent or more relative to the total weight of the 1, 1-disubstituted alkene compounds; and exposing the compound to ultraviolet radiation to initiate free radical polymerization, anionic polymerization, or both, thereby curing the compound to form a non-tacky surface.

2. The method of claim 1, wherein the one or more 1, 1-disubstituted alkene compounds correspond to formula 1 below:

wherein X¹And X²Independently at each occurrence is an oxygen atom or a direct bond; and is

Wherein R is¹And R²Independently at each occurrence, is the same or different hydrocarbyl group.

3. The method of claim 2, wherein the one or more 1, 1-disubstituted alkene compounds comprise an ester group corresponding to formula 1A below:

wherein R is¹And R²Independently at each occurrence, is the same or different hydrocarbyl group.

4. The method of claim 2, wherein the one or more 1, 1-disubstituted alkene compounds comprise a ketone group corresponding to formula 1B below:

wherein R is¹And R²Independently at each occurrence, is the same or different hydrocarbyl group.

5. The method of claim 2, wherein the one or more 1, 1-disubstituted alkene compounds comprise one or more ester groups and one or more ketone groups corresponding to formula 1C below:

wherein R is¹And R²Independently at each occurrence, is the same or different hydrocarbyl group.

6. The method of claim 2, wherein the one or more 1, 1-disubstituted alkene compounds are multifunctional monomers corresponding to formula 1D below:

wherein X, at each occurrence, is independently an oxygen atom or a direct bond;

wherein R is¹And R²Independently at each occurrence, is the same or different hydrocarbyl group; and is

n is an integer of 1 or more.

7. The method of any one of claims 1 to 3, wherein the one or more 1, 1-disubstituted alkene compounds are methylene malonate monomers.

8. The method of any one of the preceding claims, wherein the one or more photoinitiators comprise α aminoketones, α hydroxyketones, phosphine oxides, phenylglyoxylates, thioxanthones, benzophenones, benzoin ethers, oxime esters, amine synergists, maleimides, or mixtures thereof.

9. The method of any one of the preceding claims, wherein the one or more photoinitiators are selected from 1, 1-dibenzoyl ferrocene, 2-methyl-4' - (methylthio) -2-morpholinopropiophenone, a salt of tributylamine and tetraphenyl boronic acid, isopropyl thioxanthone, or a combination thereof.

10. The method of any preceding claim, wherein the photoinitiator is added to the composition comprising a 1, 1-disubstituted alkene compound in an amount of from about 0.1% to about 6% by weight.

11. The method of any one of the preceding claims, wherein the composition comprises a 1, 1-disubstituted alkene compound having two or more core units linked together by a hydrocarbylene bond between one oxygen atom on each of two or more core formulae.

12. The method of any preceding claim, wherein the composition comprises one or more (meth) acrylates or any other olefin containing unsaturated molecules that can be polymerized by free radicals.

13. The method of any one of the preceding claims, wherein the method is performed at ambient temperature.

14. The method of any of the preceding claims, wherein the irradiance of the ultraviolet light is at about 1 watt/cm²And about 5 watts/cm²And a wavelength of from about 250 nanometers to about 400 nanometers.

15. The method of claim 9, wherein the ultraviolet light is emitted at about 325 nanometers to about 375 nanometers.

16. The method of any preceding claim, wherein the compound is cured in the form of a film or coating.

17. The method of claim 16, wherein the film or coating is a tack-free film when exposed to ultraviolet light.

18. The method of any of the preceding claims, wherein the compound is exposed to ultraviolet light for less than about 3 minutes.

19. The method of claim 18, wherein the compound is exposed to ultraviolet light for less than about 60 seconds.

20. A method comprising contacting the compound of any of the preceding claims with a surface of a substrate, wherein the surface is at least mildly nucleophilic; and exposing the compound to ultraviolet light; wherein the compound cures throughout its thickness.

21. The method of claim 20, wherein the compound is cured by a combination of free radical curing and anionic curing.

22. The method of claim 20 or 21, wherein the substrate has a colored coating deposited on a surface thereof, wherein the colored coating is mildly alkaline or nucleophilic.

23. The method of any one of the preceding claims, wherein the purity is about 90 mole% or greater relative to the total weight of the 1, 1-disubstituted alkene compound.

24. The method of any one of the preceding claims, wherein the purity is about 97 mole% or greater relative to the total weight of the 1, 1-disubstituted alkene compound.

25. A polymer prepared according to the method of any one of the preceding claims.

Technical Field

The present teachings relate to a compound that includes more than one 1, 1-disubstituted alkene compound. Further disclosed are methods of forming a compound including more than one initiator and curing the compound, including using ultraviolet radiation.

Background

1, 1-disubstituted alkene compounds, such as methylene malonates, comprise two ester groups, and an alkylene group positioned between the two ester groups. Recent developments have facilitated the synthesis of these compounds and their use in a variety of applications, see Malofsky U.S. patent No. 8,609,885; 8,884,051, respectively; and 9,108,914; which is incorporated herein by reference in its entirety for all purposes. More recently, methods have also been developed for transesterifying these compounds. WO2013/059473 to Malofsky et al, U.S. Pat. No. 2014/0329980; and 9,512,058 are incorporated herein by reference in their entirety for all purposes, disclosing the preparation of multifunctional methylene malonates by various synthetic schemes. One disclosed method involves reacting a methylene malonate with a polyol in the presence of a catalyst to produce a compound, wherein one of the ester groups on the methylene malonate undergoes transesterification to react with the polyol and form a polyfunctional compound (polyfunctional meaning the presence of more than one methylene malonate core unit). The use of enzymatic catalysts is disclosed. U.S. patent No. 9,416,091 to Sullivan, which is incorporated herein by reference in its entirety for all purposes, discloses the transesterification of 1, 1-disubstituted-1-olefins using specific acid catalysts.

The polymerization of the 1, 1-disubstituted alkene compound may be carried out in bulk. The resulting polymerization process can be difficult to control, resulting in variations in properties or mechanical properties, or incomplete or uneven curing. Typically, the resulting polymer may be characterized by one or more of the following: typically high levels of branching, high polydispersity index, high concentrations of non-polymeric reaction products, high concentrations of monomers and/or oligomers, or typically high viscosity.

As used herein, bulk polymerization refers to the polymerization of a polymerizable composition comprising one or more monomers at a concentration of about 80 weight percent or more, preferably about 90 weight percent or more (e.g., about 100 weight percent), relative to the total weight of compounds in the polymerizable composition that is liquid at room temperature. These polymerizations also typically require an input of energy in the form of heat or radiation to initiate the polymerization.

In U.S. patent nos. 2,330,033; and 2,403,791, both of which are incorporated herein by reference, describe free radical polymerization of dialkylmethylene malonate monomers using heat, UV light, and a peroxide. In these patents, the monomers are prepared using conventional methods, which results in low purity monomers. The polymer examples in these patents are all prepared via bulk polymerization. It would therefore not be desirable for bulk polymerization to be able to control polymer properties such as molecular weight and molecular weight distribution.

Commercially available UV curing systems are mainly based on the radical chemistry of polyurethanes and epoxy acrylates. However, a limitation of these types of technologies is the susceptibility to oxygen inhibition by free radicals, resulting in a sticky exposed surface in some potting and encapsulation type applications.

Polymerization of 1, 1-disubstituted alkene compounds using an anionic polymerization process is useful for bulk polymerization of 1, 1-disubstituted alkene compounds and processes have been disclosed that can be operated at or near ambient conditions (starting conditions). Such anionic bulk polymerization can be initiated using a wide range of initiators, and can even be initiated by contact with a particular substrate. However, compounds that decompose to basic analogues upon exposure to UV radiation have limited commercial appeal.

What is needed is a composition that is capable of curing upon exposure to a UV light source, and related methods of formulating the composition and curing the composition. What is also needed is a composition, which may be a coating, that exhibits enhanced properties such as flexibility, adhesion to a substrate, pencil hardness, solvent resistance, abrasion resistance, ultraviolet resistance, high temperature acid and base resistance, and the like. There is also a need for a method of making such a coating composition and coating.

Disclosure of Invention

One aspect of the present disclosure is directed to a method comprising: forming a compound by contacting one or more photoinitiators with a composition comprising one or more 1, 1-disubstituted alkene compounds; and exposing the compound to ultraviolet radiation to initiate free radical polymerization, anionic polymerization, or both, thereby curing the compound to form a non-tacky surface. The purity of the 1, 1-disubstituted alkene compound may be about 85 mol% or more, about 90 mol% or more, about 93 mol% or more, about 97 mol% or more, or about 99 mol% or more, relative to the total weight of the 1, 1-disubstituted alkene compound. The one or more 1, 1-disubstituted alkene compounds may correspond to formula 1 below:

wherein X¹And X²Independently at each occurrence is an oxygen atom or a direct bond; and is

Wherein R is¹And R²Independently at each occurrenceAre the same or different hydrocarbyl groups. The one or more 1, 1-disubstituted alkene compounds may include an ester group corresponding to formula 1A below:

wherein R is¹And R²Independently at each occurrence, is the same or different hydrocarbyl group. The one or more 1, 1-disubstituted alkene compounds may include a keto group corresponding to formula 1B below:

wherein R is¹And R²Independently at each occurrence, is the same or different hydrocarbyl group. The one or more 1, 1-disubstituted alkene compounds may include one or more ester groups and one or more ketone groups corresponding to formula 1C below:

wherein R is¹And R²Independently at each occurrence, is the same or different hydrocarbyl group. The one or more 1, 1-disubstituted alkene compounds may be multifunctional monomers corresponding to formula 1D below:

wherein X, at each occurrence, is independently an oxygen atom or a direct bond; wherein R is¹And R²Independently at each occurrence, is the same or different hydrocarbyl group; and n is an integer of 1 or more.

The one or more 1, 1-disubstituted alkene compounds may be methylene malonate monomers. The composition may include a 1, 1-disubstituted alkene compound having two or more core units linked together by a hydrocarbylene bond between one oxygen atom on each of two or more core formulas. The composition may include more than one (meth) acrylate or any other olefin containing unsaturated molecules that can be polymerized by free radicals.

The one or more photoinitiators may include α aminoketones, α hydroxyketones, phosphine oxides, phenylglyoxylates, thioxanthones, benzophenones, benzoin ethers, oxime esters, amine synergists (aminosynergists), maleimides, or mixtures thereof, the one or more photoinitiators may be selected from 1, 1-dibenzoyl ferrocene, 2-methyl-4' - (methylthio) -2-morpholinophenyl propanone, salts of tributylamine and tetraphenyl boronic acid, isopropyl thioxanthone, or combinations thereof, the photoinitiator may be added to the composition comprising a 1, 1-disubstituted alkene compound in an amount of from about 0.1 to about 6 weight percent.

The methods as disclosed herein may be performed at ambient temperature. The irradiance of the ultraviolet light may be at about 1 watt/cm²And about 5 watts/cm²In the meantime. The wavelength of the ultraviolet light may be from about 250 nanometers to about 400 nanometers. For example, the wavelength may be from about 325 nanometers to about 375 nanometers. The compound may be applied and cured in the form of a film or coating. The film or coating may be a tack-free film when exposed to ultraviolet light. The compound may be exposed to ultraviolet light for less than about 3 minutes. The compound may be exposed to ultraviolet light for less than about 60 seconds.

A method according to the teachings herein may include contacting a compound as disclosed with a surface of a substrate. The substrate may be at least slightly nucleophilic. The method may include exposing the compound to ultraviolet light. The compound may be cured throughout at least a portion of its thickness, or throughout its entire thickness. The compound may be cured by a combination of free radical curing and anionic curing. The substrate may have a colored coating deposited on its surface, wherein the colored coating may be mildly alkaline or nucleophilic.

The methods according to the teachings herein can be used to make polymers comprising more than one 1, 1-disubstituted olefin monomer.

The present teachings thus relate to a method and polymers produced by the method that are capable of being cured by free radical photoinitiator chemistry and/or anionic photolatent base chemistry. The present teachings demonstrate that the combination of free radical and anionic chemistries can help overcome the limitations of existing free radical chemistries, thereby improving cure depth while reducing or eliminating the oxygen inhibition effect on the surface of the cured material.

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 particular embodiments of the present invention as set forth are not intended to be exhaustive or limiting of the invention. The scope of the invention 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 derived from the appended claims, which are also incorporated into the written description by reference.

Disclosed are compositions formed by contacting one or more initiators, such as photoinitiators and/or photobase generators, with a composition comprising one or more 1, 1-disubstituted alkene compounds. Surprisingly, it has been found that monomers comprising 1, 1-disubstituted olefins can polymerize free-radically, anionically, or both upon exposure to ultraviolet radiation to form a non-tacky surface of the polymer. The composition can be cured by both UV radiation and anionic surface initiation, wherein the composition is applied to the alkaline surface of a substrate.

A compound as disclosed herein may comprise more than one monomer. The monomer typically includes more than one 1, 1-disubstituted alkene compound (e.g., more than one 1, 1-disubstituted ethylene compound). The 1, 1-disubstituted olefin may be the principal monomer (i.e., a monomer present in greater than 50 weight percent of the polymer block or the entire polymer). 1, 1-disubstituted alkene compounds are those in which a central carbon atom is double-bonded to another carbon atom to form a vinyl group (e.g.Monomer). The central carbon atom is further bonded to two carbonyl groups. Each carbonyl group is bonded to the hydrocarbon group through a direct bond or an oxygen atom. When a hydrocarbyl group is bonded to a carbonyl group through a direct bond, a keto group is formed. When a hydrocarbyl group is bonded to a carbonyl group through an oxygen atom, an ester group is formed. The 1, 1-disubstituted olefins may have the structure shown in formula I below, wherein X is¹And X²Is an oxygen atom or a direct bond, and wherein R¹And R²Each is a hydrocarbon group which may be the same or different. X¹And X²Can all be oxygen atoms as shown in formula IIA, X¹And X²One of which may be an oxygen atom and the other may be a direct bond, as shown in formula IIB, or X¹And X²May both be direct bonds as shown in formula IIC. The 1, 1-disubstituted alkene compounds used herein may have: all are ester groups (as shown in formula IIA), all are ketone groups (as shown in formula IIC) or a mixture thereof (as shown in formula IIB). Due to the flexibility of synthesizing various such compounds, all ester-based compounds may be preferred in some applications.

Formula I

Formula IIA

Formula IIB

Formula IIC

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

One or more as used herein means that at least one, or more than one, of the components can be used as disclosed. The nominal (nominal) used in relation to the functionality refers to the theoretical functionality, which can generally be calculated from the stoichiometry of the ingredients used. In general, the actual functionality is different due to imperfections in the starting materials, incomplete conversion of the reactants and formation of by-products. Durability in this context means that the composition, once cured, retains sufficient strength to perform its designed function, in embodiments where the cured composition is an adhesive that holds the substrates together for the lifetime or most of the lifetime of the structure containing the cured composition. When the cured composition is a film, coating, or sealant, the film or sealant adheres to more than one substrate for the lifetime or most of the lifetime of the structure containing the cured composition. As an indicator of this durability, curable compositions (e.g., adhesives, films, coatings, or sealants) can exhibit excellent results during accelerated aging. The residual content of a component refers to the amount of the component that is present in free form or reacted with other materials such as polymers. Generally, the residual content of a component can be calculated from the ingredients used to prepare the component or composition. Alternatively, it may be determined using known analytical techniques. Heteroatoms refer to nitrogen, oxygen, sulfur and phosphorus, more preferred heteroatoms include nitrogen and oxygen. Hydrocarbyl as used herein refers to a group containing more than one backbone of carbon atoms (backbones) and hydrogen atoms, which may optionally contain more than one heteroatom. When the hydrocarbyl group contains heteroatoms, the heteroatoms may form more than one functional group as is well known to those skilled in the art. The hydrocarbon group may comprise cycloaliphatic segments, aliphatic segments, aromatic segments, or any combination of such segments. The aliphatic segment may be straight or branched. The aliphatic and cycloaliphatic segments may include more than one double and/or triple bond. Included among the hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl, and aralkyl groups. An alicyclic group may comprise both cyclic and acyclic moieties. Hydrocarbylene refers to a hydrocarbyl group or any subset thereof having more than one valence, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene, and aralkylene. One or both hydrocarbyl groups may be composed of more than one carbon atom and more than one hydrogen atom. As used herein, weight% or parts by weight refers to or is based on the weight of the solution composition, unless otherwise specified.

The 1, 1-disubstituted alkene compound refers to a compound having a carbon to which a double bond is attached and which is further bonded to two carbon atoms of a carbonyl group. A preferred class of 1, 1-disubstituted alkene compounds are methylene malonates, which refer to compounds having the following core formula:

the term "monofunctional" refers to having only one core compound or methylene malonate. Is intended to mean a 1, 1-disubstituted alkene compound of the formula or a methylene group, said formulae being linked by a hydrocarbyl bond between one oxygen atom on each of the two core formulae. The term "multifunctional" refers to a 1, 1-disubstituted alkene compound or methylene malonate having more than one core formula that forms a chain through a hydrocarbyl bond between one oxygen atom on each of two adjacent core formulas. The 1, 1-disubstituted alkene compound may be a 1, 1-diester-1-alkene. As used herein, diester refers to any compound having two ester groups. A 1, 1-diester-1-alkene is a compound containing two ester groups and a double bond bonded to a single carbon atom, referred to as the one carbon atom. A dihydrocarbyl dicarboxylate is a diester with a hydrocarbylene group between ester groups, where the double bond is not bonded to a carbon atom of two carbonyl groups bonded to the diester. The term "ketal" refers to a molecule having ketal functionality-i.e., a molecule comprising carbon bonded to two-OR groups, wherein O is oxygen and R represents any alkyl group. The terms "volatile" and "non-volatile" refer to compounds that can be easily evaporated at normal temperature and pressure in the case of volatility, or compounds that cannot be easily evaporated at normal temperature and pressure in the case of non-volatility. As used herein, the term "stable" (e.g., in the context of a "stable" 1, 1-disubstituted alkene compound or a monomer composition comprising the same) refers to the tendency of the compound (or monomer composition) to substantially not polymerize over time, to substantially not harden, form a gel, thicken, or otherwise increase in viscosity over time and/or to substantially exhibit minimal loss of cure speed over time (i.e., to maintain cure speed) prior to activation with an activator. As used herein, the term "shelf life" (e.g., in the context of 1, 1-disubstituted alkene compounds having improved "shelf life") means that the 1, 1-disubstituted alkene compounds are stable over a given period of time; e.g. 1 month, 6 months, even more than 1 year.

Hydrocarbyl (e.g., R)¹And R²) May each comprise a linear or branched alkyl group, a linear or branched alkylalkenyl group, a linear or branched alkynyl group, a cycloalkyl group, an alkyl substituted cycloalkyl group, an aryl group, an aralkyl group, or an alkaryl group. The hydrocarbyl group may optionally contain more than one heteroatom in the backbone of the hydrocarbyl group. The hydrocarbyl group may be substituted with a substituent that does not adversely affect the ultimate function of the monomer or the polymer prepared from the monomer. Preferred substituents include alkyl, halogen, alkoxy, alkylthio, hydroxy, nitro, cyano, azido, carboxy, acyloxy, and sulfonyl. More preferred substituents include alkyl, halo, alkoxy, alkylthio, and hydroxy. Most preferred substituents include halogen, alkyl, and alkoxy.

As used herein, alkaryl refers to an alkyl group to which an aryl group is bonded. As used herein, aralkyl refers to an aryl group having an alkyl group bonded thereto and includes alkylene bridged aryl groups such as diphenylmethyl or diphenylpropyl. As used herein, an aryl group may include more than one aromatic ring. Cycloalkyl groups include groups containing more than one ring, optionally including bridged rings. As used herein, alkyl-substituted cycloalkyl refers to a cycloalkyl group having more than one alkyl group bonded to the cycloalkyl ring.

The hydrocarbon group may include 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 12 carbon atoms. The hydrocarbon group having a hetero atom in the main chain may be an alkyl ether having one or more alkyl ether groups or one or more alkyleneoxy groups. The alkyl ether group can be ethoxy, propoxy, and butoxy. Such compounds may contain from about 1 to about 100 alkyleneoxy groups, from about 1 to about 40 alkyleneoxy groups, from about 1 to about 12 alkyleneoxy groups, or from about 1 to about 6 alkyleneoxy groups.

More than one hydrocarbyl radical (e.g. R)¹、R²Or both) may include C_1-15Straight or branched alkyl, C_1-15Straight-chain or branched alkenyl, C_5-18Cycloalkyl radical, C_6-24Alkyl-substituted cycloalkyl, C_4-18Aryl radical, C_4-20Aralkyl, or C_4-20An aralkyl group. The hydrocarbyl group may comprise C_1-8Straight or branched alkyl, C_5-12Cycloalkyl radical, C_6-12Alkyl-substituted cycloalkyl, C_4-18Aryl radical, C_4-20Aralkyl, or C_4-20An aralkyl group.

The alkyl group may include methyl, propyl, isopropyl, butyl, t-butyl, hexyl, ethylpentyl, and hexyl groups. More preferred alkyl groups include methyl and ethyl. The cycloalkyl group may include cyclohexyl and fenchyl. Alkyl substituents may include menthyl and isobornyl.

The hydrocarbon group attached to the carbonyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a fenchyl group, a menthyl group (menthyl group), and an isobornyl group.

The monomer may include methyl propyl methylene malonate, dihexyl methylene malonate, diisopropyl methylene malonate, butyl methyl methylene malonate, ethoxyethyl methylene malonate, methoxyethyl methylene malonate, hexyl methyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, pentyl methyl methylene malonate, ethyl methoxy methylene malonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxyethyl methylene malonate, dimethyl methylene malonate, di-n-propyl methylene malonate, hexyl methylene malonate, methyl fenchyl methylene malonate, ethyl fenchyl methylene malonate, 2 phenyl propyl methylene malonate, ethyl phenyl propyl methylene malonate, butyl methyl ester fenchyl methylene malonate, ethyl phenyl malonate, ethyl methyl ester methyl malonate, ethyl methyl ester of dimethyl methylene malonate, ethyl ester of dimethyl malonate, ethyl ester of, 3-phenylpropyl methylenomalonate ethyl ester, and dimethoxyethyl methylenomalonate.

Some or all of the 1, 1-disubstituted olefins may also be multifunctional, having more than one core unit and thus more than one olefinic group. Exemplary multifunctional 1, 1-disubstituted olefins are represented by the formula:

wherein R is¹And R²As previously defined; x, at each occurrence, is independently an oxygen atom or a direct bond; n is an integer of 1 or more; and R is a hydrocarbyl group, and the 1, 1-disubstituted alkene has n +1 alkenes. In the formula, n may be 1 to about 7, 1 to about 3, or 1. In exemplary embodiments, R²Independently at each occurrence, may be a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, cycloalkyl, alkyl-substituted cycloalkyl, aryl, aralkyl, or alkaryl group, wherein the hydrocarbyl group may contain more than one heteroatom in the backbone of the hydrocarbyl group and may be substituted with substituents that do not adversely affect the ultimate function of the compound or the polymer prepared from the compound. Exemplary substituents may be those with respect to R¹Useful are those disclosed. In certain embodiments, R²Independently at each occurrence may be C_1-15Straight or branched alkyl, C_2-15Straight-chain or branched alkenyl, C_5-18Cycloalkyl of, C_6-24Alkyl-substituted cycloalkyl, C_4-18Aryl radical, C_4-20Aralkyl or C_4-20An aralkyl group. In certain embodiments, R²Independently at each occurrence may be C_1-8Straight or branched alkyl, C_5-12Cycloalkyl radical, C_6-12Alkyl-substituted cycloalkyl, C_4-18Aryl radical, C_4-20Aralkyl or C_4-20An alkaryl group.

In accordance with the teachings herein, one or more monomers may include as a comonomer a 1, 1-disubstituted alkene compound having a hydrocarbyl group bonded to each carbonyl group by a direct bond (e.g., a carbon-carbon bond) or an oxygen atom, such as a monomer having one or more of the features described above. If included, the comonomer can optionally be a monomer other than a 1, 1-disubstituted alkene compound. Any comonomer capable of anionic or free radical polymerization may be employed. For example, the comonomer may be capable of forming a random copolymer with the 1, 1-disubstituted alkene compound, capable of forming a block copolymer with the 1, 1-disubstituted alkene compound, or both.

The 1, 1-disubstituted alkene compounds can be prepared using a process that results in a sufficiently high purity so that they can be polymerized. The purity of the 1, 1-disubstituted alkene compound may be sufficiently high such that 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more of the 1, 1-disubstituted alkene compound is converted into a polymer during the polymerization process. The purity of the 1, 1-disubstituted alkene compound may be about 85 mol% or more, about 90 mol% or more, about 93 mol% or more, about 95 mol% or more, about 97 mol% or more, or about 99 mol% or more, relative to the total weight of the 1, 1-disubstituted alkene compound. If the 1, 1-disubstituted alkene compound comprises an impurity, greater than about 40 mole%, or greater than about 50 mole% of the impurity molecules are analogous 1, 1-disubstituted alkane compounds. The concentration of any impurity having a dioxanyl group may be about 2 mol% or less, about 1 mol% or less, about 0.2 mol% or less, or about 0.05 mol% or less, relative to the total weight of the 1, 1-disubstituted alkene compound. The total concentration of any impurities having an olefinic group replaced with a similar hydroxyalkyl group (e.g., by michael addition of an alkene to water) can be about 3 mol% or less, about 1 mol% or less, about 0.1 mol% or less, or about 0.01 mol% or less, relative to the total moles of the 1, 1-disubstituted alkene compound. The 1, 1-disubstituted alkene compounds can be prepared by a process comprising more than one (e.g., more than two) steps of distilling a reaction product or an intermediate reaction product (e.g., a reaction product or an intermediate reaction product of formaldehyde and a malonate source).

The 1, 1-disubstituted alkene compounds may include monomers made according to the teachings of U.S. patent No. 8,609,885(Malofsky et al), which is incorporated by reference in its entirety. Other examples of monomers that may be employed include international patent application publication nos. WO 2013/066629 and WO2013/059473, and U.S. patent No. 9,221,739; 9,512,058, respectively; 9,527,795, which are all incorporated by reference in their entirety.

The disclosed compositions may comprise 1, 1-disubstituted alkene containing structures comprising a polyester macromer, which may comprise more than one chain comprising residues of more than one diol and more than one diester, wherein a portion of the diester may comprise a 1, 1-diester-1-alkene. The residues of the diols and diesters may alternate along the chain or may be randomly disposed along the chain. Diesters may further include any diester compound that will undergo transesterification with a polyol or diol. Among the diester compounds are dihydrocarbyl dicarboxylic acids. The 1, 1-disubstituted alkene containing compounds, such as polyester macromers, may have more than three of said chains. Compounds containing 1, 1-disubstituted olefins, such as polyester macromers, having more than three chains comprise residues of polyols initially having more than three hydroxyl groups. More than three chains may each extend from more than three hydroxyl groups. Polyols having more than three chains can act as initiators by which the chains of 1, 1-disubstituted alkene containing compounds, such as polyester macromers, are each extended. If the polyol is a diol, a single chain is formed because the macromer formed is linear. When a polyol having three or more hydroxyl groups is used to prepare the macromer, it may have two or more chains, since not all hydroxyl groups may propagate a chain. The macromer may comprise more than one chain, may comprise more than two chains, or may comprise more than three chains. The macromer may comprise fewer than eight chains, fewer than six chains, fewer than four chains, or fewer than three chains. The chain may comprise the residues of more than one polyol, more than one diol and more than one diester, including more than one 1, 1-diester-1-alkene and optionally more than one dihydrocarbyl dicarboxylate. The chain may comprise the residues of more than one diol and more than one diester, including more than one 1, 1-diester-1-alkene and optionally more than one dihydrocarbyl dicarboxylate. Compounds containing 1, 1-disubstituted olefins, such as polyester macromers, comprise a residue of at least one 1, 1-diester-1-olefin at the end of one chain. The 1, 1-disubstituted alkene containing compounds, such as polyester macromers, may further comprise one or more diols or dihydrocarbyl dicarboxylates at the end of one or more chains. Substantially all of the ends of the chain may be 1, 1-diester substituted olefins.

The 1, 1-disubstituted alkene compounds and compounds formed comprising these 1, 1-disubstituted alkene compounds may comprise repeat units in their backbones comprising residues of at least one diester and one diol. A significant portion of the diester may be a 1, 1-diester substituted-1-alkene. A portion of the diester may be a dihydrocarbyl 1, 1-dicarboxylate. The backbone of the 1, 1-disubstituted alkene containing compound, such as a polyester macromer, comprises a sufficient amount of repeating units comprising residues of at least one diester and one diol to facilitate the use of the 1, 1-disubstituted alkene containing compound, such as a polyester macromer, as disclosed herein, for example, in coatings, films, fibers, particles, and the like. The number of repeating units comprising residues of at least one diester and one diol in the 1, 1-disubstituted alkene containing compound may be 2 or more, 4 or more, or 6 or more. The number of repeating units comprising residues of at least one diester and one diol in the 1, 1-disubstituted alkene containing compound may be 10 or less, 8 or less, or 6 or less. The diesters in some of the 1, 1-disubstituted olefin containing compounds may all be 1, 1-diester-1-olefins. Diesters in some compounds containing a 1, 1-disubstituted alkene may be 1, 1-diester-1-alkene and dihydrocarbyl dicarboxylate. The ratio of 1, 1-diester-1-alkenes and dihydrocarbyl dicarboxylates in some 1, 1-disubstituted alkene containing compounds is selected to provide a desired degree of crosslinking in structures prepared from the 1, 1-disubstituted alkene containing compounds. The ratio of 1, 1-diester-1-alkenes to dihydrocarbyl dicarboxylates in some 1, 1-disubstituted alkene containing compounds may be 1:1 or greater, 6:1 or greater, or 10:1 or greater. The ratio of 1, 1-diester substituted-1-alkenes to dihydrocarbyl dicarboxylates in some 1, 1-disubstituted alkene containing compounds may be 15:1 or less, 10:1 or less, 6:1 or less, or 4:1 or less. The 1, 1-disubstituted alkene containing compounds, such as polyester macromers, may exhibit a number average molecular weight of about 600 or more, about 900 or more, about 1000 or more, or about 1200 or more. 1, 1-disubstituted alkene containing compounds such as 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 by the total weight of all polymer molecules in the sample divided by the total number of polymer molecules in the sample. The polydispersity of 1, 1-disubstituted alkene containing compounds, such as polyester macromers, may be about 1.05 or greater or about 1.5 or greater. The polydispersity of 1, 1-disubstituted alkene containing compounds, such as polyester macromers, may be about 5 or less or about 3.5 or less. To calculate the polydispersity, gel permeation chromatography using polymethyl methacrylate standards was used to determine the weight average molecular weight.

The disclosed 1, 1-disubstituted alkene containing compounds, such as polyester macromers, can be prepared from 1, 1-diester-1-alkenes, diols, polyols, and/or dihydrocarbyl dicarboxylates. The selection of specific ingredients, the proportions of the ingredients, and the order of the process steps affect the final structure and content of the 1, 1-disubstituted alkene containing compound. The presence of a polyol having more than two hydroxyl groups acts as an initiating chain, resulting in the formation of a polyester macromer having more than two chains, i.e., the macromer exhibits branching and the polymer is not linear. The 1, 1-diester-1-olefins contribute to chain formation and introduce pendant (pendant) olefinic groups that can be crosslinked via anionic and/or free radical polymerization. Diols can initiate single chains and extend chains out of compounds containing 1, 1-disubstituted olefins. The dihydrocarbyl dicarboxylate helps form chains and acts to space the pendant olefinic groups from each other, thereby increasing the distance between crosslinks (crosslinks) and the average molecular weight relative to each crosslink.

Compounds containing 1, 1-disubstituted alkenes, such as polyester macromers, may comprise a sufficient amount of the residue of one or more polyols, in this context polyols having 3 or more hydroxyl groups to initiate the desired number of chains. The residue of the polyol in the polyester macromer may be greater than about 20 mole% of the macromer; 30 mol% or more or about 40 mol% or more. The residue of the polyol in the polyester macromer may be about 50 mole% or less; or about 40 mol% or less. The polyester macromer may comprise a sufficient amount of residues of more than one diol, in this context a polyol having 2 hydroxyl groups to produce a polyester macromer having the desired chain length and number average molecular weight. The residue of the diol in the polyester macromer may be greater than about 20 mole% of the macromer; 40 mol% or more or about 50 mol% or more. The residue of the diol in the polyester macromer may be about 50 mole% or less; 40 mol% or less or about 30 mol% or less. The polyester macromonomer may comprise a sufficient amount of residues of 1, 1-diester substituted-1-olefin to provide a desired crosslink density to a composition comprising the polyester macromonomer. The residue of the 1, 1-diester substituted-1-olefin in the polyester macromonomer can be greater than about 20 mole% of the macromonomer; 30 mol% or more or about 40 mol% or more. The residue of the 1, 1-diester substituted-1-olefin in the polyester macromonomer can be less than about 60 mole% of the macromonomer; less than about 50 mole% of the macromer; about 40 mol% or less or about 30 mol% or less. The polyester macromer may comprise a sufficient amount of residues of dihydrocarbyl dicarboxylate to provide the desired space between cross-linked portions to the composition comprising the polyester macromer, thereby providing flexibility and/or elasticity to the structure comprising the polyester macromer. The residue of the dihydrocarbyl dicarboxylate in the polyester macromonomer can be greater than about 10 mole% of the polyester macromonomer; 20 mol% or more or about 30 mol% or more. The residue of the dihydrocarbyl dicarboxylate in the polyester macromonomer can be less than about 30 mole% of the polyester macromonomer; 20 mol% or less or about 10 mol% or less.

Polyols that can be used are compounds that possess a hydrocarbylene backbone having two or more hydroxyl groups bonded to the hydrocarbylene backbone and may be capable of transesterifying an ester compound under the transesterification conditions disclosed herein. The polyols used herein are divided into two groups. The first group is diols, which have two hydroxyl groups bonded to the alkylene backbone and both function to initiate and extend the chain of the polyester macromonomer. Polyols having more than two hydroxyl groups bonded to the alkylene backbone function to initiate more than two chains. The diol may also serve to extend more than two chains. The polyol may have 2 to 10 hydroxyl groups, 2 to 4 hydroxyl groups, or 2 to 3 hydroxyl groups. The backbone of the polyol including the diol may be an alkylene, alkenylene, cycloalkylene, heterocyclylene, alkylheterocyclylene, arylene, aralkylene, alkarylene, heteroarylene, alkylheteroarylene, or polyoxyalkylene. The main chain may be C₁-C₁₅Alkylene radical, C₂-C₁₅Alkenylene radical, C₃-C₉Cycloalkylene radical, C_2-20Heterocyclylene radical, C_3-20Alkylheterocyclylene radical, C_6-18Arylene radical, C_7-25Alkarylene radical, C_7-25Aralkylene, C_5-18Heteroarylene group, C_6-25An alkylheteroarylene or polyoxyalkylene. The alkylene moiety may be linear or branched. The group may be substituted with one or more substituents that do not interfere with the transesterification reaction. Exemplary substituents include haloalkylthio, alkoxy, hydroxy, nitro, azido, cyano, acyloxy, carboxy, or ester. The main chain may be C_2-10An alkylene group. The main chain may be C which may be straight or branched_2-8Alkylene radicals, e.g. ethylene, propylene, butylene, pentylene, hexylene, 2-ethylhexylene, heptylene2-methyl-1, 3-propylene or octylene. Diols having a methyl group at the 2-position of the alkylene chain may be used. Exemplary diols include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, 2-ethylhexylene glycol, heptylene glycol, octylene glycol, 2-methyl 1,3 propanediol, neopentyl glycol, and 1, 4-cyclohexanol. The polyol may correspond to the formula:the diol may correspond to the formula: HO-R²-OH；

Wherein R is²Independently at each occurrence, is an alkylene group having more than two bonds to the hydroxyl groups of the polyol. R²Independently at each occurrence can be an alkylene, alkenylene, cycloalkylene, heterocyclylene, alkylheterocyclylene, arylene, aralkylene, alkarylene, heteroarylene, alkylheteroarylene, or polyoxyalkylene. R²Independently at each occurrence may be C₁-C₁₅Alkylene radical, C₂-C₁₅Alkenylene radical, C₃-C₉Cycloalkylene radical, C_2-20Heterocyclylene radical, C_3-20Alkylheterocyclylene radical, C_6-18Arylene radical, C_7-25Alkarylene radical, C_7-25Aralkylene, C_5-18Heteroarylene group, C_6-25An alkylheteroarylene or polyoxyalkylene. The group may be substituted with one or more substituents that do not interfere with the transesterification reaction. Exemplary substituents include halogen, alkylthio, alkoxy, hydroxy, nitro, azido, cyano, acyloxy, carboxy, or ester. R²Independently at each occurrence may be C_2-8Alkylene, such as ethylene, propylene, butylene, pentylene, hexylene, 2-ethylhexylene, heptylene, 2-methyl-1, 3-propylene or octylene. Exemplary C3-C9 cycloalkylene groups include cyclohexylene. The alkylene group may be branched or straight chain and may have a methyl group on the 2 carbon. Among the preferred alkylarylene polyols are polyols having a structure such as-aryl-alkyl-aryl- (e.g. -phenyl-methyl-phenyl-or-phenyl-propyl-phenyl-). Among them, preferred is an alkylcycloalkylene-polyPolyols are those having the structure-cycloalkyl-alkyl-cycloalkyl- (e.g. -cyclohexyl-methyl-cyclohexyl-or-cyclohexyl-propyl-cyclohexyl-), and the like. c may be an integer of 8 or less, 6 or less, 4 or less, or 3 or less and c may be an integer of 1 or more, 2 or more, or 3 or more.

One or more dicarboxylic acid dialkyl esters are compounds having two ester groups with alkylene groups disposed between the ester groups. The one or more dihydrocarbyl dicarboxylic acid esters include one or more aromatic dicarboxylic acid esters, aliphatic dicarboxylic acid esters, and alicyclic dicarboxylic acid esters, or may be one or more dihydrocarbyl dicarboxylic acid esters in which one of the hydrocarbon groups is aliphatic, alicyclic, or aromatic and the other is selected from another class of aliphatic, alicyclic, or aromatic. The one or more dihydrocarbyl dicarboxylates include one or more of an aromatic dicarboxylic acid ester having 8 to 14 carbon atoms in the main chain, an aliphatic dicarboxylic acid ester having 1 to 12 carbon atoms in the main chain, and an alicyclic dicarboxylic acid ester having 8 to 12 carbon atoms in the main chain. The one or more dihydrocarbyl dicarboxylates comprise one or more of malonate, terephthalate, phthalate, isophthalate, naphthalene-2, 6-dicarboxylate, 1, 3-phenylenedioxydiacetate, cyclohexanedicarboxylate, cyclohexanediacetate, diphenyl-4, 4' -dicarboxylate, succinate, glutarate, adipate, azelate, sebacate, or a mixture thereof. The one or more dihydrocarbyl dicarboxylates may comprise one or more malonates. One or more dihydrocarbyl dicarboxylic acid esters correspond to the formula:

wherein R is¹As previously described; and is

R³Independently at each occurrence is an alkylene group having two bonds to the carbonyl group of the diester, wherein the alkylene group may contain more than one heteroatom. R³Independently at each occurrence may be an arylene, cycloalkylene, alkylene, or alkenylene group. R³Independently at each occurrence canIs as C_8-14Arylene radical, C_8-12Cycloalkylene radical, C_1-12Alkylene or C_2-12An alkenylene group. R³May be a methylene group.

Some methods of preparing polyester macromers involve the preparation of intermediate compounds. One class of intermediate compounds is the polyfunctional monomers. The multifunctional monomer may be prepared from a 1, 1-diester-1-olefin and a polyol comprising a diol. When the polyol has more than two hydroxyl groups, preparation of the multifunctional monomer is desired prior to chain extension. The multifunctional monomer comprises a polyol in which at least two hydroxyl groups are replaced by residues of a 1, 1-diester-1-alkene. When more than two hydroxyl groups are present on the polyol, it is possible that not all of the hydroxyl groups are reacted with the 1, 1-diester-1-olefin.

Structures containing 1, 1-disubstituted olefins, such as polyester macromers, can be used in compositions useful for preparing polymers and structures derived from the polymers. The composition may be formed by blending a 1, 1-disubstituted olefin containing structure, such as a polyester macromer, with the desired components. The composition may comprise or include a mixture of compounds formed in the preparation of 1, 1-disubstituted olefin containing structures or polyester macromers. Other ingredients may be added to the mixture of compounds formed in the preparation of the 1, 1-disubstituted alkene containing structure or polyester macromer to form a composition designed for use in preparing a polymer comprising a 1, 1-disubstituted alkene containing compound, a polyester macromer, or a structure formed from the polymer or polyester macromer.

The resulting compositions may further comprise one or more wetting or leveling agents that aid in the application of such compositions to a substrate. Any wetting and/or leveling agent that enhances application of the composition to the substrate may be used. Exemplary classes of wetting or leveling agents include polyether modified polydimethylsiloxanes, fluorinated hydrocarbons, and the like. The wetting agent may be a polyether modified polydimethylsiloxane. The wetting and/or leveling agent is present in an amount sufficient to facilitate application of the composition to the surface of the substrate. The wetting agent may be present in an amount of about 0.01 weight percent of the compositionPresent in an amount of greater than or equal to the amount%, greater than or equal to about 0.5% by weight, or greater than or equal to about 5% by weight. The wetting agent may be present in an amount of about 5% or less, about 2% or less, or about 1% or less by weight of the composition. The resulting composition may further comprise one or more UV stabilizers that inhibit the degradation of structures comprising 1, 1-disubstituted alkene containing compounds such as polyester macromers. Any UV stabilizer that suppresses deterioration due to exposure to UV rays may be used. Exemplary classes of ultraviolet light stabilizers include benzophenones, benzotriazoles, and hindered amines (commonly referred to as Hindered Amine Light Stabilizers (HALS)). Exemplary UV light stabilizers include Cyasorb UV-5312-hydroxy-4-n-octyloxybenzophenone, Tinuvin 5712- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, branched and straight-chain 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 stabilizer is present in an amount sufficient to enhance the durability of the composition comprising the 1, 1-disubstituted alkene containing compound, such as a polyester macromer. The UV light stabilizer may be present in an amount of about 0.01% by weight or more, about 0.1% by weight or more, or about 0.2% by weight or more of the composition. The UV light stabilizer may be present in an amount of less than about 5 wt%, less than about 3 wt%, less than about 2 wt%, or less than about 1 wt% of the composition. The composition may further comprise an antifoaming agent and/or an air release agent. Compositions comprising compounds containing 1, 1-disubstituted olefins can foam during processing, which can cause problems with the surface and appearance of the coating. Any anti-foaming and/or air-release agent that prevents foaming or bubble formation and 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 antifoam agents include FOAM BLAST available from Emerald^TM20F、FOAM BLAST^TM30 Silicone antifoam Compounds and FOAM BLAST^TM550 polyacrylate defoamer; TEGO AIREX from Degussa^TM920 polyacrylate defoamer and TEGO AIREX^TM980. SILMER ACR available from Siltech Corporation^TMDi-10 and ACR^TMMo-8 polydimethylsiloxane acrylate copolymer, FOAMEX N available from Degussa^TMOr TEGO AIREX^TM900 Silicone based antifoam agent or BYK from BYK Chemie^TM1790 Silicone defoamer is absent. The defoaming agent and/or degassing agent may be present in the 1, 1-disubstituted alkene containing compound or polyester macromer composition in a sufficient amount to prevent the formation of bubbles and/or foaming. If used too much, adhesion to the desired surface and adhesive can be negatively affected. The anti-foaming agent and/or air release agent may be present in an amount of about 0.05 wt% or more, more preferably about 0.1 wt% or more, relative to the weight of the composition. The anti-foaming agent and/or air release agent may be present in an amount of about 2.0 wt% or less or about 1.0 wt% or less relative to the weight of the composition.

The scratch resistance additives may include alumina (e.g., α alumina), silica, zirconia, boron carbide, silicon carbide, ceria, glass, diamond, aluminum nitride, silicon nitride, yttria, titanium diboride, aluminosilicates (i.e., "Zeeospheres" from 3M), titanium carbide, combinations thereof, and the like.

The polymer composition may contain one or more other fillers such as filler particles (e.g., fibers, powders, beads, flakes, particulates, etc.). The filler particles may be fibers (e.g., have an aspect ratio of greater than 10 for the longest direction relative to each perpendicular direction). The filler particles can be particles that are not fibers (e.g., have an aspect ratio of the longest direction relative to each perpendicular direction of less than 10, less than 8, or less than 5). The filler may be formed of an organic material and/or an inorganic material. Examples of organic fillers include biomass-derived fillers and polymer-derived fillers. The inorganic filler includes: non-metallic materials, and semiconductor materials. For example, the filler particles may include aluminum silicate, aluminum hydroxide, aluminum oxide, silicon oxide, barium sulfate, bentonite, boron nitride, calcium carbonate (e.g., activated calcium carbonate, light calcium carbonate, or ground calcium carbonate), calcium hydroxide, calcium silicate, calcium sulfate, carbon black, clay, cotton linters, cork flour, diatomaceous earth, dolomite, hard rubber powder (ebonite powder), glass, graphite, hydrotalcite, iron oxide, iron metal particles, kaolin, mica, magnesium carbonate, magnesium hydroxide, magnesium oxide, phosphide, pumice, pyrophyllite, sericite, silica, silicon carbide, talc, titanium oxide, wollastonite, zeolite, zirconium oxide, or any combination thereof. The filler particles may be present at a concentration of about 0.1 wt% or more, about 1 wt% or more, about 5 wt% or more, or about 10 wt% or more. The filler particles may be present at a concentration of about 70 wt% or less, about 50 wt% or less, about 35 wt% or less, or about 25 wt% or less. The filler particles preferably have one dimension, two dimensions, or three dimensions of about 1mm or less, about 0.3mm or less, about 0.1mm, about 50 μm or less, about 10 μm or less. The filler particles preferably have one, two, or three dimensions of about 0.1 μm or more, about 0.3 μm or more, or about 1 μm or more.

The polymer compositions according to the teachings herein may include a plasticizer for adjusting the properties of the final polymer for the desired use. The plasticizer may be added before, during, or after polymerization. For example, in certain embodiments, a suitable plasticizer may be included with the 1, 1-disubstituted alkene monomer. In general, suitable plasticizers may include plasticizers for modifying the rheological properties of the adhesive system including, for example, straight and branched chain alkyl-phthalates such as diisononyl phthalate, dioctyl phthalate, and dibutyl phthalate, as well as partially hydrogenated terpenes, trioctyl phosphate, epoxy plasticizers, toluene sulfonamide, chloroparaffins, adipates, sebacates such as dimethyl sebacate, castor oil, xylene, 1-methyl-2-pyrrolidone, and toluene. Commercially available plasticizers such as HB-40 manufactured by Solutia Inc. (St. Louis, Mo.) may also be suitable.

These compositions may contain additives to improve surface slip characteristics. Any known composition that improves surface slip characteristics may be used. Exemplary surface slip additives may be polyester modified polydimethylsiloxanes, waxes, and the like. Exemplary waxes include those based on polyethylene, polytetrafluoroethylene, or polypropylene wax dispersions in acrylate monomers, such as EVERGLIDE from Shamrock Technologies^TMOr S-395 or SST series products; or as ORGASOL from Arkema^TMPolyamide particles, etc.; or CERIDUST, e.g. from Clariant^TMTP 5091 and the like montan wax having reactive acrylate groups, or CERAFLOUR from Byk-Chemie^TMWax powder. The wax may be in the form of a powder having a particle size less 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 include polyethylene, polypropylene, polyamide, polytetrafluoroethylene, or blends and/or copolymers thereof. The wax may be crystalline polyethylene or polytetrafluoroethylene, or a blend of polyethylene and polytetrafluoroethylene. The surface slip additive may be present in an amount of about 0.1% by weight or more or about 0.5% by weight or more of the composition. The surface slip additive may be present in an amount of about 5% by weight or less, about 2% by weight or less, or about 1% by weight or less of the composition.

The compositions as disclosed herein may include one or more initiators for initiating polymerization and/or curing under curing conditions. Curing conditions may result in the formation of free radicals. The initiator can initiate free radicals when exposed to radiationThe initiator may include compounds of the classes of phosphine oxides, ketones and derivatives thereof, benzophenones, carbocyanines and methines, polycyclic aromatic hydrocarbons such as anthracene, and dyes such as xanthene, safranines and acridine, these initiators may be chemical species belonging to one of the main classes of, e.g., pentanedione, benzil, piperonyl, benzophenone, and benzophenone, carbonyl containing compounds such as benzophenone, and carbonyl containing compounds such as selenophenyl, benzophenone, and selenophenyl containing compounds such as benzophenone, and selenophenyl, and carbonyl containing compounds such as selenophenyl, and selenophenyl-containing compounds such as selenophenyl, quinophthalocyanine, selenophenyl-containing compounds such as selenophenyl, quinophthalocyanine, selenophenyl-2-selenophenyl, quinophthalocyanine, selenophenyl, and selenophenyl-containing compounds such as benzophenone, naphthoxazines, selenophenyl, quinophthalocyanines, naphthoxazines, and selenophenyl-containing compounds such as xanthene, naphthoxazines, and benzoxazines, and benzoxaz]Nitrogen-containing compounds such as oxime esters; halogenated compounds such as halogenated ketones or aldehydes, methyl aryl halides, sulfonyl halides or dihalides; phosphine oxides and photoinitiator dyes such as diazonium salts, azoxybenzenes and derivatives, rhodamine, eosin, fluorescein, acriflavine, and the like. Initiators may include 1,1 dibenzoyl ferrocene, 2-methyl-4' - (methylthio) -2-morpholinopropiophenone, tributylamine and tetraphenylboronic acid (tetraphenylboronate) salts (tba. bph)₄) Isopropyl thioxanthone, or a combination thereof.

The initiator may be present in a sufficient amount to catalyze polymerization upon exposure to the appropriate polymerization conditions described below. The initiator may be present in an amount of about 0.05 wt% or more, about 0.1 wt% or more, or about 1 wt% or more, relative to the weight of the composition. The initiator may be present in an amount of about 20 wt% or less, about 10 wt% or less, or about 6 wt% or less, relative to the weight of the composition.

The polymers according to the teachings herein preferably adhere to one or more of the following substrates: aluminum, steel, glass, silicon, or wood. For example, when two substrates having a polymer disposed between the substrates are separated, the separation of the substrates can result in cohesive failure of the polymer, with some of the polymer remaining on the surface of the substrates.

The polymers according to the teachings herein may be used in extruded, blow molded, injection molded, thermoformed, or compression molded articles. The polymer may be used as a binder. For example, polymers may be used in the pressure sensitive adhesive composition. The polymers may be used as coatings, such as protective coatings. The polymer may be used as a primer on a substrate.

The 1, 1-disubstituted alkene containing compounds, which may be polyester macromers, and compositions comprising them may be used to prepare polyester systems such as coatings, films, fibers, adhesives on substrates. Although polyester macromers are disclosed, it is understood that any 1, 1-disubstituted alkene containing compound is within the scope of the present teachings. A coating comprising a 1, 1-disubstituted alkene containing compound, a polyester macromer, and/or residues of a polyester macromer may be disposed on more than one surface of a substrate or a portion thereof. The film, coating, or other structure may be cured and/or crosslinked. The crosslinking composition may be crosslinked by the pendant olefin groups from the macromonomer chains. The crosslinking may be a direct bond between the olefin groups of adjacent macromonomer chains. The macromer chain may be contained in a prepolymer or polymer chain. The macromonomer chains can be crosslinked by any compound having unsaturation which is polymerized by anionic or free radical polymerization. The 1, 1-disubstituted alkene containing compound or polyester macromonomer chain can be crosslinked by a 1, 1-diester alkene, wherein the crosslinking moiety comprises the residue of the 1, 1-diester alkene. The 1, 1-disubstituted alkene containing compound or polyester macromonomer chains can be crosslinked by a multifunctional monomer, wherein the crosslinked portion comprises the residue of the multifunctional monomer. The cross-linking portion between chains can be represented by the following formula:

wherein F is independently at each occurrence a direct bond, a residue of a compound polymerized with an unsaturated group by anionic polymerization or free radical polymerization. F may independently at each occurrence be a direct bond, a 1, 1-diester-1-alkene, or a residue of a multifunctional monomer. The crosslink density of the crosslinked composition comprising the 1, 1-disubstituted alkene containing compound or polyester macromer may be any such density that provides the desired properties of the composition.

The film or coating may have a thickness of about 0.01 microns or more, about 0.04 microns or more, about 0.1 microns or more, about 0.5 microns or more, or about 1 micron or more. The film or coating may be cured and/or crosslinked. The film or coating may have a thickness of about 500 microns or less, about 350 microns or less, about 160 microns or less, about 100 microns or less, about 80 microns or less, or about 60 microns or less, about 20 microns or less, or about 1 micron or less. An article is disclosed that includes a substrate having a coating comprising one or more 1, 1-disubstituted alkene compounds, which may be polyester macromers, or a composition comprising one or more 1, 1-disubstituted alkene compounds, applied to one or more surfaces.

Compounds containing 1, 1-disubstituted olefins and compositions comprising them can undergo polymerization upon exposure to a basic curing initiator. If applied to the surface of a basic substrate, the 1, 1-disubstituted alkene containing compound will cure via anionic polymerization. Accordingly, a method is disclosed that includes contacting a composition comprising one or more 1, 1-disubstituted alkene containing compounds as described herein 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. The substrate may comprise a material that is at least slightly alkaline. The substrate itself may be at least slightly alkaline. The substrate may include a pretreatment that is at least mildly alkaline. A composition comprising a basic compound that initiates anionic polymerization of a 1, 1-disubstituted olefin or polyester macromer may be applied to the surface of a substrate prior to applying the composition comprising one or more 1, 1-disubstituted olefin compounds or polyester macromers. Exemplary basic compounds include one or more amines; a polyamine basic pigment; a polyalkyleneamine; a polyethyleneimine; or a carboxylate. Anionic polymerization may be initiated upon contact between the coating or composition and the at least mildly alkaline substrate. The anionic polymerization can be initiated without exposing the coating or composition to further conditions. The anionic polymerization may occur at ambient temperature. The coating can also be cured at ambient temperature, such as with UV radiation, without heat input.

Also disclosed is an article comprising: a substrate comprising an undercoat layer on a substrate, having disposed on the undercoat layer a coating comprising a 1, 1-disubstituted alkene containing compound disclosed herein. The primer layer may have basic properties sufficient to cure and/or crosslink 1, 1-disubstituted alkene containing compounds such as polyester macromers. The coating comprising the 1, 1-disubstituted alkene containing compound may be transparent and used as a clear coating.

Also disclosed is a method comprising contacting a composition comprising one or more 1, 1-disubstituted alkene containing compounds with a surface of a substrate, wherein the surface is at least mildly basic; and forming a coating on a surface of a substrate comprising a composition comprising one or more 1, 1-disubstituted alkene containing compounds, which may comprise a polyester macromer. The substrate may comprise a basic material. The composition comprising the basic compound may be applied to the surface of the substrate prior to applying the composition comprising the one or more 1, 1-disubstituted alkene containing compounds. The composition comprising the basic compound may comprise any of the compounds disclosed herein as inhibitors of anionic polymerization for use with 1, 1-diester-1-olefins. Exemplary basic compounds include amines, polyamine basic pigments, or carboxylic acid salts. The composition comprising the basic compound may comprise a polyalkyleneimine. The method can further include exposing the substrate having the composition comprising the one or more 1, 1-disubstituted alkene containing compounds to a temperature of about 20 ℃ or greater or about 50 ℃ or greater. The method can further include exposing the substrate having the composition comprising one or more 1, 1-disubstituted alkene containing compounds to a temperature of about 150 ℃ or less or about 120 ℃ or less. Such exposure times may be about 10 minutes or more or 20 minutes or more. Such exposure time may be 120 minutes or less, about 60 minutes or less, or about 30 minutes or less. The exposing is performed under conditions such that a coating comprising one or more 1, 1-disubstituted alkene containing compounds disposed on the surface of the substrate is cured and/or crosslinked. Thus, contact of the composition with the surface of the basic substrate can initiate anionic polymerization or curing, particularly at the interface between the surface of the substrate and the composition. The coating or film may be cured and/or crosslinked when exposed to particular conditions. The coating or film may be cured and crosslinked simultaneously when exposed to a relatively strong base, elevated temperature, or both.

A compound as disclosed herein can include contacting one or more initiators, such as a photoinitiator and/or photobase generator, with a composition comprising one or more 1, 1-disubstituted alkene compounds. Upon exposure to ultraviolet radiation, one or more photoinitiators and/or photobase generators can induce free radical polymerization, anionic polymerization, or both. The polymerization may replace or supplement anionic polymerization or curing at the interface between the coating or film and the surface of the substrate. For example, anionic polymerization can occur at the interface between the coating or film and the surface of the substrate, and the opposite surface of the coating or film can undergo free radical or anionic polymerization upon exposure to ultraviolet radiation. This may provide surface curing at both surfaces of the coating or film, curing throughout the entire thickness of the coating or film, or both.

A method is disclosed of contacting one or more initiators, such as a photoinitiator or photobase generator, with a composition comprising one or more 1, 1-disubstituted alkene compounds as described herein, and exposing the compound to ultraviolet radiation. Compositions comprising more than one 1, 1-disubstituted alkene compounds can be exposed to radiationThe degree is about 0.5 watt/cm²Above, about 1 watt/cm²Above, or about 1.5 watts/cm²Under the above ultraviolet light. The ultraviolet light may have an irradiance of about 5 watts/cm²About 4.5 watts/cm²Less than, or about 4 watts/cm²The following. The ultraviolet light may have a wavelength of about 250 nanometers or more, about 300 nanometers or more, or about 325 nanometers or more. The ultraviolet light may have a wavelength of about 400 nanometers or less, about 390 nanometers or less, or about 375 nanometers or less. For example, the ultraviolet light may be emitted between about 325 nanometers and about 375 nanometers. The compound may be exposed to ultraviolet light for less than about 240 seconds, less than about 180 seconds, less than about 120 seconds, less than about 90 seconds, less than about 60 seconds, or less than about 30 seconds. Upon exposure to a source of ultraviolet light, either surface curing of the compound, or complete curing of the compound may be observed. The surface of the cured compound may be tack free. The ability to cure compositions comprising more than one 1, 1-disubstituted alkene compound by free radical photoinitiator chemistry and/or anionic photolatent base chemistry may provide advantages, particularly in thin coatings where the surface may be cured by UV radiation and the remaining coating may be cured by anionic surface initiation. The combination of free radical and anionic chemistry can help overcome the limitations of current free radical chemistry.

The composition or film may be capable of curing in a variety of ways. The composition may undergo dual cure. For example, the composition may undergo both anionic and free radical polymerization. The composition may be applied to a substrate having an at least mildly alkaline surface (e.g., as a property of the substrate or due to the application of an alkaline coating) to initiate anionic polymerization at the area contacting the alkaline surface or substrate. Free radical polymerization may be initiated on the opposite side of the composition or film. The surface of the composition or film facing away from the substrate to which it is applied may be exposed to radiation such as ultraviolet radiation. Upon exposure to radiation, free radical polymerization may be initiated. Dual curing of the composition or film may allow curing throughout at least a portion of the thickness of the composition. Dual curing may allow curing throughout the entire thickness of the composition or film to achieve a complete, tack-free cure.

Illustrative embodiments

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

A compound comprising diethyl methylene malonate monomer (DEMM) was contacted with one or more initiators as shown in table 1. The dual functionality was introduced into the system by the addition of 1,6 pentanediol DEMM crosslinker. Approximately 2g of each compound was dispensed with a plastic pipette in an aluminum pan and exposed to a UV LED light source emitting at 365nm for a period of less than 30 seconds. The thickness of the cured film was measured after full cure was observed.

TABLE 1

Upon exposure to UV radiation, an increase in the viscosity of the respective compound over time has been observed. Free radical polymerization was observed when 2-methyl-4' - (methylthio) -2-morpholinopropiophenone was used as an initiator. The results in table 1 show that methylene malonates can be cured by free radical photoinitiator chemistry, by anionic photolatent base chemistry, or both. Radical curing has shown better depth of cure. Anionic curing can be used to eliminate the oxygen inhibiting effect on the surface of the cured material.