WO2021162938A1

WO2021162938A1 - Copolymers of dicarbonyl substituted-1-alkene and olefins and methods to make them

Info

Publication number: WO2021162938A1
Application number: PCT/US2021/016707
Authority: WO
Inventors: Alexander Y. Polykarpov; Jeffrey M. Sullivan; Mark HOLZER; Michael Powers
Original assignee: Sirrus, Inc.
Priority date: 2020-02-10
Filing date: 2021-02-05
Publication date: 2021-08-19

Abstract

A copolymer is formed by contacting an olefin and a 1,1-dicarbonyl substituted alkene and reacting the olefin and 1,1-dicarbonyl substituted alkene under a pressure greater than atmospheric pressure in the presence of a free radical initiator. The copolymer may be useful for packaging films and may be used in the absence of compatibilizers in combination with other plastics such as in laminate structures (films having at least two layers). The polymers may also improve the recyclability and biodegradability of polyolefins such as polyethylene and polypropylene.

Description

COPOLYMERS OF DICARBONYL SUBSTITUTED-l-ALKENE AND OLEFINS AND

METHODS TO MAKE THEM,

FIELD

[001] The invention relates to copolymers of 1,1-dicarbonyl substituted-l-alkenes and olefins. In particular, the invention relates to forming copolymers of methylene malonates and ethylene, propylene or other alpha olefin or combination thereof.

BACKGROUND

[002] Polyolefins, as a class of materials, have poor adhesion and compatibility with more polar polymeric materials and surfaces. In most instances, a separate adhesive is required to adhere polyolefins to polar substrates. Likewise, a compatibilizer is almost always required when blending a polyolefin with other polar thermoplastic polymers such as polyesters, polyamides and polycarbonates.

[003] Grafted polyolefins have been made providing for incorporation of polar groups on polyolefin backbones, but these typically involve the radically initiated grafting onto polyolefins polymers such as described in U.S. Pat. No. 3,177,269. Likewise, the amount of grafting has tended to be limited due to reductions of molecular weight when grafting and degradation of the polymer arising from the use of a radical initiator or formation of radicals (see, for example, U.S. Pat. No. 4.888,394). The grafting may also result in rheological properties that are undesirable arising from the amount of grafting, graft length and undesired cross-linking (see, for example, U.S. Pat. Nos. 3,884,882 and 5,140,074)

[004] It would be desirable to provide an olefin copolymer having polar functionality that avoids one or more of the problems in the art such as those described above. It would also be useful to provide such copolymer for applications such as packaging and laminate or layer structures and the like. SUMMARY

[005] A first aspect of the invention is a copolymer comprised of an olefin and 1,1-dicarbonyl substituted alkene. The polymer may be useful for improving the adhesion between packaging layers and separate flexible packaging layers using hydrolytic techniques.

[006] A second aspect of the invention is a method to form the polymer of the first aspect comprising, contacting an olefin monomer and a 1,1-dicarbonyl substituted alkene and reacting the olefin and 1,1-dicarbonyl substituted alkene under a pressure greater than atmospheric pressure in the presence of a free radical initiator at a reaction temperature. In an embodiment the reacting may take place using a solvent. Typically, when preparing a copolymer 1,1- dicarbonyl substituted alkene and ethylene, the pressure of the reaction is greater than about 50 bar to about 100 bar ethylene.

[007] A third aspect of the invention is an article comprised of the polymer in contact with a substrate. The substrate may be a film of a differing plastic such as known plastics useful in the packaging industry such as polyethylene (LDPE, HDPE and the like), polypropylene or functional polyolefins such as those known in the art containing maleic acid or anhydride groups (e.g., PRIMACOR available from The Dow Chemical Co.). In an embodiment, the copolymer is a layer in a laminate film having layers of differing plastics as just described.

[008] The properties of the polymer may vary widely depending on the 1,1-dicarbonyl substituted alkene and olefin used as well as the reaction conditions to realize desired weight average molecular weights (Mw), number average molecular weight (Mn) or z average molecular weight (Mz) such as those typically found in linear low density and high density polyethylene and polypropylene. Desirably, the olefin is ethylene, propylene or an alpha olefin and the copolymer has an Mw, Mn or Mz of 500 to 1,000,000.

[009] The copolymer of the olefin (e.g., ethylene, propylene or combination thereof) and 1,1-dicarbonyl substituted alkene may be useful in applications such as laminate structures, coatings, lubricants, waxes, rheological modifiers (e.g., thickeners in paints), adhesion promoter, adhesives including components in adhesives (e.g., pressure adhesive compositions and hot melt adhesives), surfactants for use in organic solvents, packaging, gas barrier films, additive manufactures articles and the like. DESCRIPTION OF THE DRAWING

[0010] Figure 1 is ¹³C NMR spectra of the copolymer of this invention and of a poly(diethyl methylenemalonate).

[0011] Figure 2 is an expanded region of the ¹³C NMR spectra of the copolymer of this invention and of a poly(diethyl methylene malonate) in the carbonyl region.

[0012] Figure 3 is thermogravimetric analysis graphs of the copolymer of this invention, poly(diethylmethylenemalonate) and a mechanical blend of polyethylene and poly(diethyl methylenemalonate (herein "pDEMM" or "poly(diethyl methylenemalonate).

DETAILED DESCRIPTION

[0013] 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 disclosure as set forth are not intended to be exhaustive or limit the scope of the disclosure.

[0014] The method to form polymer may be performed under any conditions or apparatus known in the art performing high pressure reactions. In some embodiments, a solvent may be used to dissolve the 1,1-dicarbonyl substituted alkene and free radical initiator. Useful solvents may include any solvent that dissolves the 1,1-dicarbonyl substituted alkene and the free radical initiator. Exemplary solvents include tetrahydrofuran, toluene, dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.

[0015] The reaction is carried out by contacting the olefin and 1,1-dicarbonyl substituted alkene and reacting at an elevated pressure in the presence of a free radical initiator at a sufficient reaction temperature. The pressure may vary from greater than 1 bar to 100 bar or any practicable or useful pressure of ethylene, for example. The reaction temperature may be any useful temperature, but typically is from about 25°C to about 100°C.

[0016] The free radical initiator may be any known or suitable free radical initiator that initiates the free radical polymerization of polyolefins such as ethylene. Desirably the free radical initiator is one that is soluble in the solvent when used. Depending on the desired characteristics differing free radical initiators or combinations of initiators may be used. For example, an initiator that does not cause substantial grafting and tends to form polymers having greater Mw may be desired (e.g. an azo initiator) such as those known in the art (e.g., U.S. Pat. No. 2,471,959, incorporated herein by reference). Likewise, if greater Mw is desired a chain extender may also be employed. In other instances, greater grafting and lower Mw may be desired and a peroxide initiator may be more suitable.

[0017] The amount of olefin/1, 1-dicarbonyl substituted alkene may be any useful molar ratio depending on the copolymer desired. For example, the ratio may be from 0.01, 0.05 or 0.1 to 100, 95, 90, 50, 20 or 10. The particular ratio may be adjusted to realize particular desired characteristics or properties of the polymer. For example, the ratio may be high (e.g., greater than 10) to realize flexible films that may have higher molecular weights or layers of flexible films for use in packaging or the ratio may be closer to 1 or lower to realize polymers that may useful for applications such as pressure sensitive adhesives, hot melt adhesives, surfactants and the like. [0018] Free radical initiators are generally used to produce the copolymers. Exemplary free radical initiators include organic peroxides including, but are not limited to, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, and peroxyketals. Examples of peroxides include, but are not limited to an alkyl peroxide, an aryl peroxide, an acyl peroxide, an aroyl peroxide, a ketone peroxide, a peroxycarbonate, a peroxycarboxylate, a hydroperoxide, and other organic peroxides. Examples of an alkyl peroxide inlcude diisopropyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl 2,5-(di- tert-butylperoxy)hexyne-3; 4,4'-bis(tert-butylperoxy)diisopropyl benzene; and 2,5-dimethyl-2,5- (ditert-butylperoxy)hexane. An example of an aryl peroxide is dicumyl peroxide. An example of an acyl peroxide is dilauroyl peroxide. An example of an aroyl peroxide is dibenzoyl peroxide. Examples of a ketone peroxide include methyl ethyl ketone peroxide and cyclohexanone peroxide. Examples of hydroperoxide include tert-butyl hydroperoxide and cumene hydroperoxide. Preferred examples of a free-radical initiator are di-tert-butyl peroxide; 2,5- dimethyl-2,5-(di-tert-butylperoxy)-hexyne-3; 2,5-dimethyl-2,5-(di-tert-butyl-peroxy)hexane, dicumyl peroxide; dibenzoyl peroxide; 4,4'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof. Higher molecular weight organic peroxide compounds are preferred because they are safer and easier to handle and store, as well as being more stable at higher temperatures. Preferred initiators are t-butyl peroxy pivalate, di-t-butyl peroxide, t-butyl peroxy acetate and t-butyl peroxy-2-hexanoate, or mixtures thereof.

[0019] In one embodiment, the free radical initiator may be azobisisobutyronitrile. The amount of free radical initiator may be any useful amount. Illustratively, the free radical initiators are generally used in an amount from 0.001%, 0.01%, 0.05% to 5%, 4%, 3%, 2%, or 1% by weight of polymerizable monomers and initiator. Combinations of initiators may be used.

[0020] Examples of known process reactors include agitated autoclave vessel having one or more reaction zones is used. The autoclave reactor normally has several injection points for initiator or monomer feeds, or both. In the second type, a jacketed tube is used as a reactor, which has one or more reaction zones. Suitable, but not limiting, reactor lengths may be from 100 to 3000 meters (m), or from 1000 to 2000 meters. The beginning of a reaction zone, for either type of reactor, is typically defined by the side injection of either initiator of the reaction, ethylene, chain transfer agent (or telomer), comonomer(s), as well as any combination thereof. A high pressure process can be carried out in autoclave or tubular reactors having one or more reaction zones, or in a combination of autoclave and tubular reactors, each comprising one or more reaction zones.

[0021] The 1,1-dicarbonyl alkenes are compounds wherein a central carbon atom is doubly bonded to another carbon atom to form a double bond. The central carbon atom is further bonded to two carbonyl groups. Each carbonyl group is bonded to a hydrocarbyl group either directly or through an oxygen atom. Where the hydrocarbyl group is bonded to the carbonyl group, a ketone group is formed. Where the hydrocarbyl group is bonded to the carbonyl group through an oxygen atom, an ester group is formed. The 1,1-dicarbonyl alkene may have a structure as shown below in Formula I, where X¹ and X² are an oxygen atom or a direct bond, and where R¹ and R² are each hydrocarbyl groups that may be the same or different. Both X¹ and X² may be oxygen atoms, such as illustrated in Formula IIA, one of X¹ and X² may be an oxygen atom and the other may be a direct bond, such as shown in Formula MB, or both X¹ and X² are direct bonds, such as illustrated in Formula 11C. The 1,1-dicarbonyl alkene compounds used herein may have all ester groups (such as illustrated in Formula IIA), all keto groups (such as illustrated in Formula IIC) or a mixture thereof (such as illustrated in Formula MB). Compounds with all ester groups may be preferred in some applications due to the flexibility of synthesizing a variety of such compounds.

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. Heteroatom means nitrogen, oxygen, sulfur and phosphorus, more preferred heteroatoms include nitrogen and oxygen. 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. One or both hydrocarbyl groups may consist of one or more carbon atoms and one or more hydrogen atoms. As used herein percent by weight or parts by weight refer to, or are based on, the weight of the solution composition unless otherwise specified.

[0022] A preferred class of 1,1-dicarbonyl alkene compounds is methylene malonates, the core structural unit/formula for which is shown in Formula IIA above. The term "monofunctional" refers to 1,1-dicarbonyl alkene compounds or a methylene malonate having only one core unit or one carbon-carbon double bond. The term "difunctional" refers to 1,1-dicarbonyl alkene compounds or a methylene malonate having two core unit bound through a hydrocarbyl linkage between one oxygen atom on each of two core formulas. The term "multifunctional" refers to 1,1-dicarbonyl alkene compounds or methylene malonates having more than one core formula which forms a chain through a hydrocarbyl linkage between one oxygen atom on each of two adjacent core formulas. When a thermoplastic copolymer is desired, monofunctional 1,1- dicarbonyl alkene compounds are used with little or no multifunctional 1,1-dicarbonyl alkene compounds. Some small amount may be desirable to cause branching or limited cross-linking so long as the thermoplastic nature is maintained. Desirably the 1,1-dicarbonyl alkene compound contains at least one ester and more desirably is a methylene malonate, wherein the estergroups may be hydrolyzed to improve adhesion as described below between film layers.

[0023] The hydrocarbyl groups (e.g., R¹ and R²), each may comprise straight or branched chain alkyl, straight or branched chain alkyl alkenyl, straight or branched chain alkynyl, cycloalkyl, alkyl substituted cycloalkyl, aryl, aralkyl, or alkaryl. The hydrocarbyl group may optionally include one or more heteroatoms in the backbone of the hydrocarbyl group. The hydrocarbyl group may be substituted with a substituent that does not negatively impact the ultimate function of the 1,1-dicarbonyl alkene or the polymer prepared from the 1,1-dicarbonyl alkene. Preferred substituents include alkyl, halo, alkoxy, alkylthio, hydroxyl, nitro, cyano, azido, carboxy, acyloxy, and sulfonyl groups. More preferred substituents include alkyl, halogen, alkoxy, allylthio, and hydroxyl groups. Most preferred substituents include halogen, alkyl, and alkoxy groups.

[0024] As used herein, alkaryl means an alkyl group with an aryl group bonded thereto. As used herein, aralkyl means an aryl group with an alkyl group bonded thereto and include alkylene bridged aryl groups such as diphenyl methyl groups or diphenyl propyl groups. As used herein, an aryl group may include one or more aromatic rings. Cycloalkyl groups include groups containing one or more rings, optionally including bridged rings. As used herein, alkyl substituted cycloalkyl means a cycloalkyl group having one or more alkyl groups bonded to the cycloalkyl ring.

[0025] The hydrocarbyl groups may include 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 12 carbon atoms. Hydrocarbyl groups with heteroatoms in the backbone may be alkyl ethers having one or more alkyl ether groups or one or more alkylene oxy groups. Alkyl ether groups may be ethoxy, propoxy, and butoxy. Such compounds may contain from about 1 to about 100 alkylene oxy groups, about 1 to about 40 alkylene oxy groups, about 1 to about 12 alkylene oxy groups, or about 1 to about 6 alkylene oxy groups.

[0026] One or more of the hydrocarbyl groups (e.g., R¹, R², or both) may include a C1-C15 straight or branched chain alkyl, a C1-C15 straight or branched chain alkenyl, a C5-C18 cycloalkyl, a C6-C24 alkyl substituted cycloalkyl, a C4-C18 aryl, a C4-C20 aralkyl, or a C4-C20 aralkyl. The hydrocarbyl group may include a Ci-Cs straight or branched chain alkyl, a C5-C12 cycloalkyl, a C6-C12 alkyl substituted cycloalkyl, a C4-C18 aryl, a C4-C20 aralkyl, or a C4-C20 aralkyl.

[0027] Alkyl groups may include methyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, ethyl pentyl, and hexyl groups. More preferred alkyl groups include methyl and ethyl. Cycloalkyl groups may include cyclohexyl and fenchyl. Alkyl substituted groups may include menthyl and isobornyl, norbornyl as well as any other bicyclic, tricyclic or polycyclic structure.

[0028] Hydrocarbyl groups attached to the carbonyl group may include methyl, ethyl, propyl, isopropyl, butyl, tertiary, pentyl, hexyl, octyl, fenchyl, menthyl, and isobornyl, cyclic, bicyclic or a tricyclic group such as cyclohexyl, norbornyl, or tricyclodecanyl.

[0029] The 1,1-dicarbonyl alkene may be comprised of one or more of methyl propyl methylene malonate, dihexyl methylene malonate, di-isopropyl methylene malonate, butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate, methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethylmethoxy methylene malonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxy ethyl methylene malonate, dimethyl methylene malonate, di-N-propyl methylene malonate, ethyl hexyl methylene malonate, methyl fenchyl methylene malonate, ethyl fenchyl methylene malonate, 2 phenylpropyl ethyl methylene malonate, 3 phenylpropyl ethyl methylene malonate, ethyl cyclohexyl methylene malonate, and dimethoxy ethyl methylene malonate.

[0030] When desired to make a crosslinked copolymer, a portion or all of the 1,1-dicarbonyl alkene may be multifunctional, having more than one core unit and thus more than one alkene group. Exemplary multifunctional 1,1-dicarbonyl alkenes are illustrated by the formula:

[0031] wherein R1 and R2 are as previously defined; X is, separately in each occurrence, an oxygen atom or a direct bond; n is an integer of 1 or greater to any useful amount such as a polymer of 1,000 or 10,000 Daltons or more to typically at most about 1,000,000 or 100,000 and R is hydrogen or a hydrocarbyl group having 1 to 30 carbons, so long as at least one R is hydrogen (i.e., =CH2) and preferably every R is hydrogen. Typically, n is 1 or 2 to 20 or 10. Typically, the amount of multifunctional 1,1-dicarbonyl alkene, when present, is at most about 5%, 2% or 1% to about 0.001% by weight of all the monomers or of all of the 1,1-dicarbonyl alkene used to make copolymer of this invention.

[0032] In exemplary embodiments R² may be, separately in each occurrence, straight or branched chain alkyl, straight or branched chain alkenyl, straight or branched chain alkynyl, cycloalkyl, alkyl substituted cycloalkyl, aryl, aralkyl, or alkaryl, wherein the hydrocarbyl groups may contain one or more heteroatoms in the backbone of the hydrocarbyl group and may be substituted with a substituent that does not negatively impact the ultimate function of the compounds or polymers prepared from the compounds. Exemplary substituents may be those disclosed as useful with respect to Rl. In certain embodiments R² may be, separately in each occurrence, C 1-15 straight or branched chain alkyl, C 2-15 straight or branched chain alkenyl, C 5-18 cycloalkyl, C 6-24 alkyl substituted cycloalkyl, C 4-18 aryl, C 4- 20 aralkyl or C 4-20 aralkyl groups. In certain embodiments R² may be separately in each occurrence C 1-8 straight or branched chain alkyl, C 5-12 cycloalkyl, C 6-12 alkyl substituted cycloalkyl, C 4-18 aryl, C 4- 20 aralkyl or C 4-20 alkaryl groups. [0033] In an embodiment, X is O and R² is the residue of a diol, wherein a polyester is formed. The polyesters may be formed from any suitable 1,1-dicarbonyl alkene such as the malonates described above and as described in U.S. Pat. No. 9,969,822 from col. 19, line 49 to col. 20, line 3 and a polyol incorporated herein by reference. Examples of suitable polyol include, for example, those described in U.S. Pat. No. 9,969,822 from col. 20, line 18 to col. 21, line 26, incorporated herein by reference. Examples of diols may include ethylene diol 1,3-propylene diol, 1,2 propylene diol, 1-4-butanediol, 1 ,2-butane diol, 1 ,3-butane diol, 2,3-butane diol, 1,5-pentane diol, 1,3- and 1,4-cyclohexanedimethanols or combinations thereof. Examples of triols may include 1,2,3-propane triol, 1,2,3-butane triol, trimethylolpropane, 1,2,4-butane triol or combination thereof. Likewise, the polyol may be even higher functional, for example, di(trimethylolpropane), pentaerythritol, dipentaerythritol or combination thereof. Any combination of polyols such as multiple diols, triols, tetraols, pentaols, hexaols or mixtures thereof may be used.

[0034] The 1,1-dicarbonyl alkene may be produced and purified by the methods described in U.S. Pat. Nos. 8,609,8985; 8,884,051; 9,108,914 and 9,518,001 and Int. Pub. WO 2017/197212. Examples of such 1,1-dicarbonyl alkenes are available under the tradenames CHEMILIAN and FORZA and include, for example, methylene malonate, dihexyl methylene malonate, dicyclohexyl methylene malonate and multifunctional polyester methylene malonates available from Sirrus, Inc., Loveland, OH.

[0035] The olefin may be any known olefin that will radically polymerize with the 1,1- dicarbonyl alkene and typically may be ethylene, propylene or any linear or cyclic alpha olefin having generally less than 12, 10 or 8 carbons.

[0036] In an embodiment other radically polymerizable monomers may be polymerized with the 1,1-dicarbonyl alkene and olefin. The other radically polymerizable monomer may be any known to copolymerize with olefins (e.g., ethylene and propylene) such as vinyl acetate, vinyl alcohol, and maleic anhydride. The amount of other monomers may be any useful amount to impart some desired characteristic, but typically is less than 50%, 30%, 10% or 5% to greater than 0.1% or 1 % by weight of the polymer.

[0037] Because of the unique geminal structure of methylene malonates where two ester groups are attached to one carbon such polymers may possess higher polarity over the acrylate or maleate/maleic anhydride analogs. The copolymer may be used directly as compatibilizers or for improvement of interlayer adhesion in laminate structures such as packaging films. The ester groups may also be readily hydrolyzed to produce carboxylic acid functionality to achieve the same for systems with higher incompatibility or further improve the adhesion.

[0038] Additionally, decarboxylation of such copolymers may be used to create bubble filled films with low density that can be used as insulators and for other applications.

[0039] The copolymers may be used to make biodegradable or recyclable LDPE-type or HDPE- type containers and bags. The copolymer can be used in the ester or the hydrolyzed acid form or a partially hydrolyzed form where some ester groups remain. The copolymer can either be used alone if the mechanical properties are sufficient or in combination with LDPE or other plastics such as ethylene vinyl acetate copolymer or polyvinylacetate.

[0040] The introduction of two carboxylate or carboxylic ester groups on the same carbon into the main chain of LDPE may reduce the strength of the adjacent carbon-carbon bond of the main chain and thus provide an opportunity for easier bond scission due to weathering or by thermomechanical processing. Such copolymer may also become biocompatible and improve biocompatibility of the LDPE/HDPE it is coextruded with, which can lead to easier digestion and degradation by microorganisms along with the decrease of the hydrophobicity and better compatibility with the living organs and tissues so that the microparticles of such copolymer are less harmful if swallowed by the living organisms.

[0041] The geminal esters may also induce crystallinity into the copolymers allowing for improved barrier properties as a stand-alone barrier or one coextruded with other plastics.

ILLUSTRATIVE EMBODIMENTS

[0042] The following examples are provided to illustrate the curable compositions and the copolymers formed from them, but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise noted. Table 1 shows the reagents used to make Example 1 and Comparative Example 1. Table 1

Example 1 and Comparative Examples 1 and 2

Comparative Example 1: Formation of pDEMM:

[0043] A 300 ml Parr reactor equipped with a 250 ml quartz liner, mechanical stirring assembly, 400 W Parr heating mantle, and thermocouple was used for the synthesis of poly(diethyl methylidenemalonate). The quartz reactor liner was passivated with 1 wt% solution of methane sulfonic acid (MSA) in dimethyl carbonate (DMC) followed by a rinse with methanol and air drying for 5 min. The passivation process was repeated a second time. All sample containers were also passivated using the same procedure.

[0044] The quartz liner was placed into the reactor and charged with: DMC (50.4 ml), DEMM (25.4 g, 0.15 mol), and AIBN (1.0 g, 0.006 mol). The reactor stirrer was turned on and set to 100 rpm. A continuous flow of argon was maintained with the pressure between 50 and 150 psi for 30 min followed by pressurization to 500 psi. The temperature was then increased at 2 °C/min rate to 70 °C using the heating mantle. The reaction pressure was then increased to 1100 psi once the temperature reached 70 °C. The reaction was stirred at this temperature and pressure for 1.5 h followed by cooling the reactor and reducing the pressure to ambient once the temperature reached 35 °C. The reaction products (solids impregnated with solvent) were added ca. 50 ml of hot (>80 °C) methanol. The slurry was allowed to settle, and the methanol was decanted. The solids were dried in a vacuum oven at 115 °C over 4 h. The opaque white polymer was then analyzed. With initial DEMM input of 25g this process yields between 15g and 23g of the polymer. [0045] Molecular weight was measured by GPC (using THF (tetrahydrofuran) mobile phase, PMMA (polymethylmethacrylate) standards). For the polymer sample prepared by this procedure molecular weight was measured to be: Mn=2163 g/mol, Mw=8295 g/mol, PD=3.835. The ¹³CNMR (in CDCU, 100MHz) showed the carbonyl carbon peak of the malonate ester groups at 167.7ppm (see Fig. 2).

Example 1: Formation of diethyl methylidenemalonate-ethylene copolymer:

[0046] The same reactor and passivation were used as described in Comparative Example 1. The quartz reactor liner was placed into the reactor and was charged with: DMC (50.4 ml), DEMM (25.4 g, 0.15 mol), and AIBN (1.0 g, 0.006 mol). The reactor stirrer was turned on and set to 100 rpm. A continuous flow of argon was maintained with the pressure between 50 and 150 psi for BOmin followed by evacuation to ambient pressure and then pressurization to 500 psi of ethylene. The temperature was then increased at 2 °C/min rate to 70 °C using the Parr heating mantle. Once the temperature reached 70 °C the ethylene pressure was increased to 1100 psi. The reaction was stirred at this temperature and pressure for 1.5 h followed by cooling the reactor and reducing the pressure to ambient once the temperature reached 35 °C. The polymer gel was dissolved in ca. 50 ml of hot (>80 °C) methanol. The solution thus formed was mixed into water and the solid precipitated and was separated. The solid was dried in the vacuum oven at 115 °C over 4 h. The semi opaque polymer was then analyzed. With initial DEMM input of 25g this process yields between lOg and 18g of polymer.

[0047] The molecular weight of the copolymer was measured by GPC (THF mobile phase, PMMA standard): Mn=20775 g/mol, Mw=38793 g/mol, PD=1.867. ¹³CNMR (CDCI₃, 150MHz) showed multiple carbonyl carbon peaks at: 167.75, 167.83, 168.12, 168.31, 168.78, 168.91, 169.33, 169.37ppm. (see Fig. 2).

Comparative Example 2: Blend of Polyethylene and pDEMM

[0048] Approximately equal weights of polyethylene powder and made as described below and the pDEMM powder of Comparative Example 1 were mechanically mixing by hand shaking in a vial for about 30 seconds.

[0049] Polyethylene used to make this Comparative Example 2 was made as follows. The same reactor was used as Example 1 and Comparative Example 1. The quartz reactor liner was placed into the reactor and was charged with: DMC (75 ml) and AIBN (0.15 g). The reactor stirrer was turned on and set to 100 rpm. A continuous flow of argon was maintained with the pressure between 50 and 150 psi for 30min followed by evacuation to ambient pressure and then pressurization to 500 psi of ethylene. The temperature was then increased at 2 °C/min rate to 70 2C using the Parr heating mantle. Once the temperature reached 70 °C the ethylene pressure was increased to 1100 psi. The reaction was stirred at this temperature and pressure for 1.5 h followed by cooling the reactor and reducing the pressure to ambient once the temperature reached 35 ^c. The solid polymer was then isolated, placed into the vacuum oven and dried to constant weight.

[0050] ¹³C NMR (nuclear magnetic resonance) spectroscopy was performed on the Example

1 copolymer and pDEMM of Comparative Example 1 using chloroform-d solvent and hexamethyldisiloxane standard. For the Example 1 copolymer a Bruker 600MHz spectrometer was used. For the pDEMM a Bruker 400MHz spectrometer was used.The NMR spectra for both are shown in Figures 1 and 2. The single peak for the carbonyl carbon in pDEMM was no longer observed in the 13C NMR spectrum of the copolymer. Instead multiple carbonyl carbon signals were observed shifted down field. This is consistent with the incorporation of methylene groups from ethylene into the polymer chains.

[0051] Thermogravimetric analysis (TGA) was performed on Example 1 and Comparative Examples 1 and 2. The TGA analysis was performed using a TA Instruments TGA Q50 using 5 °C/min heating rate under nitrogen atmosphere. The TGA graphs are shown in Fig. 3. From these graphs it is readily apparent the copolymer of Ex. 1 decomposes differently than the pDEMM of Comp. Ex. 1 and the blend of polyethylene and pDEMM of Comp. Ex. 2 indicating that a copolymer of DEMM and ethylene has been made.

[0052] Differential scanning calorimetry was performed on Example 1 and Comparative Examples 1 and 2. DSC was run on TA Instruments DSC 250 using a 5 °C/min heating rate.

[0053] The DSC Analysis of pDEMM of C. Ex. 1 demonstrated a melting transition between 140-153 °C with Tg between 4.7-15.6 °C. The mechanical blend of polyethylene and pDEMM of C. Ex. 2 showed two melting transitions: one for pDEMM (~140 °C) and one for polyethylene (~102.3 °C) while in the Ex. 1 of the copolymer of this invention the melting transition observed for pDEMM was not found (see initial heating DSC curve in Fig. 4). Therefore, the copolymer structure is further confirmed as the melting transition due to the DEMM segments has disappeared, (i.e., these segments are connected to ethylene segments). The copolymer has a melting transition at a temperature closer to that of ethylene, with crystallization observed upon cooling also at lower temperature (~63.8C) than the mechanical blend of pDEMM and PE (i.e., a broad arc with the peak at ~97.5C).

Claims

What is claimed is:

Claim 1. A copolymer comprising the reaction product of a 1,1-dicarbonyl substituted alkene and an olefin.

Claim 2. The copolymer of claim 1, wherein the olefin is ethylene, propylene, alpha olefin having 3 to 12 carbons that is linear or cyclic or mixture thereof.

Claim 3. The copolymer of Claim 2, wherein the olefin is ethylene, propylene or combination thereof.

Claim 4. The copolymer of claim 3, wherein the olefin is ethylene.

Claim 5. The copolymer of any of the preceding claims wherein the ratio of the olefin/1, 1-dicarbonyl substituted alkene is 0.01 to 100.

Claim 6. The copolymer of any one of the preceding claims, wherein the ratio of the olefin/1, 1-dicarbonyl substituted alkene is at least 0.1 to 10.

Claim 7. The copolymer of any one of the preceding claims, wherein the copolymer has a weight average molecular weight (Mw) of 200 g/moles to 1,000,000.

Claim 8. The copolymer of 7, wherein the Mw is at least 1,000 g/moles to 500,000 g/moles.

Claim 9. The copolymer of any one of the preceding claims, wherein the 1,1- dicarbonyl substituted alkene is represented by:

wherein X, X¹ and X² are an oxygen atom or a direct bond, and where R¹ and R² are each hydrocarbyl groups having from 1 to 30 carbons and R is hydrogen or a hydrocarbyl group having from 1 to 30 carbons, so long as at least one R is hydrogen.

Claim 10. The copolymer of Claim 9, wherein X is an oxygen atom and R² is the residue of a polyol.

Claim 11. The copolymer of any one of preceding claims , wherein the 1,1- dicarbonyl substituted alkene is comprised of one or more of methyl propyl methylene malonate, dihexyl methylene malonate, di-isopropyl methylene malonate, butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate, methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethylmethoxy methylene malonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxy ethyl methylene malonate, dimethyl methylene malonate, di-N- propyl methylene malonate, ethyl hexyl methylene malonate, methyl fenchyl methylene malonate, ethyl fenchyl methylene malonate, 2 phenylpropyl ethyl methylene malonate, 3 phenylpropyl ethyl methylene malonate, ethyl cyclohexyl methylene malonate, and dimethoxy ethyl methylene malonate.

Claim 12. The copolymer of any one of the preceding claims, wherein the 1,1- dicarbonyl substituted alkene monofunctional methylene malonate.

Claim 13. A method of forming a copolymer comprising, contacting an olefin and a 1,1-dicarbonyl substituted alkene and reacting the olefin and 1,1-dicarbonyl substituted alkene under a pressure greater than atmospheric pressure in the presence of a free radical initiator at a reaction temperature.

Claim 14. The method of claim 13, wherein the reaction temperature is above about 20°C to about 100°C.

Claim 15. The method of either claim 12 or 13, wherein the olefin is an ethylene, propylene or combination thereof and the pressure is greater than 50 bar to 200 bar of the olefin.

Claim 16. The method of 15, wherein the reaction pressure is greater than 10 bar.

Claim 17. The method of any one of the preceding claims IB to 16, wherein the radical initiator is azobisisobutyronitrile.

Claim 18. The method of any one of claims 13 to 17, wherein a solvent is used.

Claim 19. The method of claim 18, wherein the solvent is tetrahydrofuran, toluene and dimethyl carbonate or combination thereof.

Claim 20. An article comprised of the copolymer of any one of claims 1-12.

Claim 21. The article of Claim 20, wherein the copolymer is in contact with a substrate.

Claim 22. The article of claim 21, wherein the substate is comprised of a metal, ceramic, polymer, composite thereof or combination thereof.

Claim 23. The article of claim 22, wherein substrate is a polymer and the article is a laminate film having at least two layers.

Claim 24. The polymer of any one of claims 1 to 12, wherein the polymer is further comprised of the reaction product of another radically polymerizable monomer other than the 1,1-dicarbonyl substituted alkene and olefin.

Claim 25. The polymer of claim 23, wherein the another radically polymerizable monomer is vinyl acetate.

Claim 26. The article of claim 20, wherein the article is a laminate, coating, lubricant, wax, rheological modifier (e.g., thickeners in paints), adhesion promoter, adhesive composition, surfactant, package, film, or additive manufactured article.

Claim 27. The copolymer of claim 9, wherein the 1,1-dicarbonyl substituted alkene is represented by:

Claim 28. The copolymer of claim 9, wherein the 1,1-dicarbonyl substituted alkene is represented by:

present in an amount of at most about 5% by weight of the 1,1-dicarbonyl substituted alkene.