WO2013013132A1

WO2013013132A1 - Aliphatic polycarbonate extrusion coatings

Info

Publication number: WO2013013132A1
Application number: PCT/US2012/047565
Authority: WO
Inventors: Peter SHEPARD; Sanjeev Naik; James Mahoney
Original assignee: Novomer, Inc.
Priority date: 2011-07-20
Filing date: 2012-07-20
Publication date: 2013-01-24

Abstract

A laminate includes paper or paperboard and at least one extrusion-coated layer including at least one aliphatic polycarbonate. In some embodiments, the extrusion-coated layer substantially includes only an aliphatic polycarbonate. In some embodiments, the extrusion-coated layer includes a polymer blend of an aliphatic polycarbonate and at least one other polymer, which may also be an aliphatic polycarbonate. In some embodiments, the extrusion-coated layer is applied without a tie layer. In some embodiments, the aliphatic polycarbonate is poly(ethylene carbonate). In some embodiments, the aliphatic polycarbonate is poly(propylene carbonate). In other embodiments, the aliphatic polycarbonate is not poly(propylene carbonate).

Description

ALIPHATIC POLYCARBONATE EXTRUSION COATINGS

REFERENCE TO RELATED APPLICATIONS

This application claims one or more inventions which were disclosed in

Provisional Application Number 61/509,738 filed July 20, 2011, entitled "ALIPHATIC POLYCARBONATE EXTRUSION COATINGS". The benefit under 35 USC § 119(e) of the United States provisional application is hereby claimed, and the aforementioned application is hereby incorporated herein by reference.

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION The invention pertains to the field of polymer extrusion coatings. More

particularly, the invention pertains to extrusion coatings including an aliphatic

polycarbonate.

DESCRIPTION OF RELATED ART

Lessening the carbon footprint of plastics used for consumer applications such as packaging is of increasing importance. Aliphatic polycarbonates are recognized as an attractive option in this regard since they have a very favorable carbon footprint. This is due in part to the fact that a significant portion of the mass of the polymer is derived from C0₂ which can be derived from waste sources. Additional factors, such as lower processing temperatures and lower use of energy in production, make these polymers even more favorable when compared to polymers derived exclusively from petroleum or natural gas feedstocks. Life cycle analyses of aliphatic polycarbonates also indicate they surpass bio-based polymers that require large amounts of energy and fresh water for production and in some instances compete for the same resources required for food production.

Lower permeability to oxygen is important in many packaging applications. Good oxygen barrier properties lead to an increased shelf-life as a result of less oxidation of food and beverages, thereby maintaining taste and quality for a longer time. This is particularly important as current trends in the packaging industry are to down-gauge films by reducing their thickness to provide light-weight packaging. Thus, an improvement in permeability at an equivalent thickness or an equivalent permeability at a much lower thickness can have significant commercial value. Improved oxygen barrier films are important for packaging a variety of foods and beverages, including meat, baked goods, snacks, juices in stand-up pouches, confectionaries, and a wide variety of moisture and oxygen sensitive nutraceuticals and health and beauty products. The food packaging industry is looking for new options as they move away from current materials like polyvinylidene chloride (PVDC) due to environmental regulatory pressures on chlorinated materials and ethylene vinyl alcohol (EVOH) due to sensitivity to moisture and higher oxygen permeability at higher humidity levels.

Coextrusion or lamination yielding multi-layer products is typically used to obtain films with high barrier properties for packaging applications. Three to five layers and sometimes up to nine layers are used to produce a film with the desired properties.

However, multi-layer products require high capital investment and complex process control. A single blend polymer with higher barrier properties can reduce the complexity of the packaging significantly, but low moisture sensitivity of commonly-used oxygen barrier polymers like EVOH requires them to be embedded between two polyolefm layers.

Alternatively, paper or paperboard is commonly used as a packaging material in the food industry, with one or more layers of polymer being coated or laminated onto either or both sides of the paper or paperboard. The polymer coatings provide better barrier properties to the packaging, thereby extending the life of the packaged material.

Aliphatic polycarbonates (APCs) are a class of polymers generally formed as a copolymer of an epoxide and carbon dioxide.

Poly(propylene carbonate) (PPC) is an aliphatic polycarbonate known since the late 1960's when it was first synthesized by Inoue and co-workers. Until recently, high molecular weight PPC has been predominantly synthesized using zinc carboxylate catalysts to copolymerize propylene oxide and C0₂. The resulting material was the focus of intense investigation and several companies have explored applications for the material as a commodity thermoplastic. To date, PPC has been commercialized only as a sacrificial polymer in applications where the clean thermal decomposition of PPC is advantageous. Commercialization of the material for thermoplastic applications has been complicated by poor thermal and processing properties. Recently, transition metal complexes have been developed for the copolymerization of C0₂ and epoxides, but such complexes have not been fully exploited and/or optimized in the preparation of improved PPC materials.

Poly(ethylene carbonate) (PEC) is an aliphatic polycarbonate formed from copolymerization of ethylene oxide and C0₂. PEC has a similar polymer backbone to PPC but differs in that it has unsubstituted ethylene groups in place of the methyl-substituted ethylene backbone found in PPC. Extrusion-coating of packaging materials with one or more polymer film layers is known in the art.

U.S. Patent No. 3,972,467, entitled "Paper-board Laminate" and issued August 3, 1976 to Whillock et al., discloses a paperboard laminate for containers for bulk packaging liquids, syrups, and pastes, which includes a layer of a high strength polymer film and which also may include a layer of aluminum foil.

U.S. Patent Application Publication No. 2011/0132975, entitled "Packaging Laminate, Method for Manufacturing of the Packaging Laminate and Packaging Container Produced Therefrom" by Toft et al. and published June 9, 2011, discloses a non-foil packaging laminate for liquid food packaging with a core layer of paper or paperboard, outermost liquid-tight, heat-sealable layers of polyolefm, and an oxygen gas barrier layer formed by liquid film coating of a liquid gas barrier composition and subsequent drying. The liquid composition includes a polymer binder dispersed or dissolved in a liquid medium.

U.S. Patent No. 5,059,459, entitled "Paperboard Laminate" and issued October 22, 1991 to Huffman, discloses extrusion-coated multilayer paperboard laminates with layers of low density polyethylene (LDPE) and ethylene vinyl alcohol (EVOH) copolymer and adhesive tie layers.

U.S. Patent No. 4,950,510, entitled "Multiple Layer Paperboard Laminate" and issued August 21, 1990 to Massouda, discloses extrusion-coated multilayer paperboard laminates with layers of LDPE and ethylene vinyl alcohol copolymer and a modified polyolefm such as Plexar® tie layer resin (LyondellBasell Industries, Rotterdam, NL).

U.S. Patent No. 5,552,002, entitled "Method for Making Paperboard Packaging Containing a PVOH Barrier" and issued September 3, 1996 to Farrell et al., discloses extrusion-coated multilayer paperboard packaging laminates with a buried polyvinyl alcohol (PVOH) barrier layer.

U.S. Patent No. 4,698,246, entitled "Novel Laminates for Paperboard Cartons and a Process of Forming Said Laminates" and issued October 6, 1987 to Gibbons et al., discloses extrusion-coated multilayer paperboard packaging laminates with layers of LDPE and glycol-modified polyethylene terephthalate.

U.S. Patent Application Publication No. 2010/0078465, entitled "Paperboard Extrusion Coating Processes and Polymers for Use Therein" by Le and published April 1, 2010, discloses extrusion-coated paperboard packaging laminates with one or more layers of linear LDPE, elastomer, plastomer, high density polyethylene (HDPE), LDPE, medium density polyethylene (MDPE), polypropylene, or polypropylene copolymer.

U.S. Patent No. 6,821,373, entitled "Method of Producing a Laminated Packaging Material" and issued November 23, 2004 to Berlin et al., discloses extrusion-coated multilayer paperboard packaging laminates with at least one layer of PVOH and a barrier layer of an inorganic laminar compound. U.S. Patent No. 4,142,021, entitled "Oxygen Barrier Laminate Films Including a

Polyalkylene Carbonate Adhesive" and issued February 27, 1979 to Dixon et al., discloses laminate films including a base layer and at least one adhesive layer of a polyalkylene carbonate. The polyalkylene carbonate is solvent-cast over a film of polyethylene, melt- coextruded with polyethylene, or melted and pressed against the base layer. U.S. Patent No. 5,536,806, entitled "Substantially Crystalline Poly(Alkylene

Carbonates), Laminate and Methods of Making" and issued July 16, 1996 to Sant'Angelo, discloses laminates including a layer of poly(alkylene carbonate) (APC) and more specifically a poly(propylene carbonate) (PPC) layer or a poly(ethylene carbonate) (PEC) layer. Sant'Angelo discloses that the APC is extruded in an amorphous sheet/film but by stretching the film, the APC allegedly becomes crystalline.

U.S. Patent Application Publication No. 2012/0052209, entitled "Composition for Paper Coating" by Jeon et al. and published March 1, 2012, discloses certain compositions of poly(propylene carbonate) and poly (propylene carbonate)-co-poly(cyclohexene carbonate) layers extrusion-coated onto paper.

SUMMARY OF THE INVENTION

DEFINITIONS

Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of

Chemistry and Physics, 75^th Ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March 's Advanced Organic Chemistry, 5^th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989;

Carruthers, Some Modern Methods of Organic Synthesis, 3^rd Edition, Cambridge

University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference. Certain compounds of the present invention can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers. Thus, inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers. In certain embodiments, the compounds of the invention are enantiopure compounds. In certain other embodiments, mixtures of enantiomers or diastereomers are provided.

Furthermore, certain compounds, as described herein may have one or more double bonds that can exist as either a Z or E isomer, unless otherwise indicated. The invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic mixtures of enantiomers. In addition to the above-mentioned compounds per se, this invention also encompasses compositions comprising one or more compounds.

As used herein, the term "isomers" includes any and all geometric isomers and stereoisomers. For example, "isomers" include cis- and trans-isomers, E- and Z- isomers, R- and ^-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention. For instance, a compound may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as "stereochemically enriched". The term "epoxide", as used herein, refers to a substituted oxirane. Such substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes,

trisubstituted oxiranes, and tetrasubstituted oxiranes. Such epoxides may be further optionally substituted as defined herein. In certain embodiments, epoxides comprise a single oxirane moiety. In certain embodiments, epoxides comprise two or more oxirane moieties.

The term "polymer", as used herein, refers to a molecule of high relative molecular mass, the structure of which comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass. In certain embodiments, a polymer is comprised of only one monomer species {e.g., polyethylene oxide). In certain embodiments, a polymer of the present invention is a copolymer, terpolymer,

heteropolymer, block copolymer, or tapered heteropolymer of one or more epoxides.

As used herein, the term "catalyst" refers to a substance the presence of which increases the rate and/or extent of a chemical reaction, while not being consumed or undergoing a permanent chemical change itself.

As used herein, the term "crystalline" refers to a polymer or polymer composition that possesses a first order transition or crystalline melting point (T_m) as determined by differential scanning calorimetry (DSC) or equivalent technique. The term may be used interchangeably with the term "semicrystalline". Relative to an amorphous polymer, a crystalline polymer or a composition thereof possesses higher degrees of ordered structure. In some embodiments, a crystalline polymer has characteristics that may be used to differentiate the material from amorphous material. In some embodiments, crystalline material is sufficiently crystalline such that is has a melting point.

As used herein, the term "crystallizable" refers to polymers or compositions thereof which are mainly amorphous in a certain state, but can crystallize upon being subjected to conditions and methods described herein.

As used herein, the term "amorphous" refers to a polymer lacking a melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.

The term "head-to-tail" ratio is used in its conventional sense with regard to poly(propylene carbonate). Such terms may be used to describe and/or quantify the regioregularity of a polymer or polymer composition. The head-to-tail ratio of

poly(propylene carbonate) can readily be determined by ¹³C-NMR spectroscopy, as described by, for example, Lednor, et al., J. Chem. Soc, Chem. Comm. 1985, 598-599.

The term "tacticity", as used herein, refers to the stereoregularity of the orientation of the propylene unit methyl groups in a polymer or polymer composition. Such stereoregularity may be considered apart from regioregularity {e.g., head-to-tail ratio), but for simplicity the definition below considers adjacent propylene units with the same regiochemistry. Pairs (diads) of methyl residues from adjacent {i.e., spaced apart by a carbonate unit) propylene units which have the same relative stereochemical orientation with respect to the polymer backbone are termed "meso" (m). Those of opposite stereochemical configuration are termed "racemic" (r). When three adjacent propylene units (triads) have methyl groups with the same orientation, the tacticity of the triad is "mm". If two adjacent propylene units in a three propylene unit sequence have the same stereochemical orientation, and that orientation is different from the relative configuration of the third unit, the tacticity of the triad is "mr". When the middle propylene unit has an opposite configuration from either propylene neighbor, the triad has "rr" tacticity. The fraction of each type of triad in the polymer bases on the total chain content can be determined and when multiplied by 100 indicates the percentage of that type found in the polymer. The tacticity as used herein is the percentage of isotactic "mm" triads.

The term "syndiotactic", as used herein, refers to a PPC polymer or polymer composition wherein the stereochemical orientation of propylene unit methyl groups alternates along the polymer chain. For example, a perfectly syndiotactic polymer has 100% racemic diads. A syndiotactic polymer or composition thereof need not be perfectly syndiotactic, but may contain a certain degree of syndiotacticity (e.g., slightly

syndiotactic).

The term "isotactic", as used herein, refers to a PPC polymer or polymer composition wherein the relative stereochemical orientation of propylene unit methyl groups is the same along the polymer chain. For example, a perfectly isotactic polymer has 100% meso diads. An isotactic polymer or composition thereof need not be perfectly isotactic, but may contain a certain degree of isotacticity (e.g., slightly isotactic).

The term "melting point" for a material as used herein is defined as the highest peak among principal and secondary melting peaks as determined by Differential

Scanning Calorimetry (DSC). The term "barrier polymer", as used herein, is defined as any polymer having a low permeability to a molecule of interest. In some embodiments, the molecule of interest is oxygen. In some embodiments, the molecule of interest is water.

The term "structural polymer", as used herein, is defined as any polymer having a predetermined value for at least one mechanical or structural property other than permeability such as, for example, density, hardness, rigidity, impact resistance, strength, and toughness.

The term "polycarbonate", as used herein, is defined as any polymer containing carbonate groups. The term "aliphatic polycarbonate", as used herein is defined as any polycarbonate which does not contain aromatic rings.

The term "polyolefm", as used herein, is defined as any polymer produced from a simple olefin as a monomer having the general formula C_nI¾n.

The term "paper", as used herein, is defined as any thin packaging material formed by pressing moist fiber together. Although the fibers are typically formed of cellulose, any fibrous material may be used.

The term "paperboard", as used herein, is defined as any paper having a thickness of at least about 0.25 mm (0.01 inches).

The term "laminate", as used herein, is defined as any composite material constructed of two or more layers of materials. The layers may be held together by any method known in the art, including, but not limited to, use of a tie layer between the layers, use of an adhesive between the layers, and extrusion coating of one layer directly onto another layer.

The term "extrusion coating", as used herein, is defined as a process of coating a substrate layer with a polymer in the form of a molten plastic, in contrast to the process of "solvent casting", whereby the coating is formed upon evaporation of solvent from solution, in that the coated polymer layer is melt-extruded onto the substrate layer, which may be metal, paperboard, or another polymer layer.

The term "tie layer", as used herein, is defined as any layer used for the purpose of providing adhesion between two layers in a laminate that would otherwise either insufficiently adhere or not adhere at all to each other.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows an extrusion coating apparatus in an embodiment of the present invention. Fig. 2 shows an extrusion coating apparatus in another embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

A paper or paperboard laminate packaging material includes at least one extrusion- coated layer including at least one aliphatic polycarbonate (APC). In some embodiments, the extrusion-coated layer substantially includes only an aliphatic polycarbonate. In some embodiments, the extrusion-coated layer includes a polymer blend of an aliphatic polycarbonate and at least one other polymer, which may also be an aliphatic

polycarbonate. In some embodiments, the extrusion-coated layer is applied without a tie layer. In some embodiments, the aliphatic polycarbonate is poly(ethylene carbonate). In some embodiments, the aliphatic polycarbonate is poly(propylene carbonate). In other embodiments, the aliphatic polycarbonate is not poly(propylene carbonate). In some embodiments, the aliphatic polycarbonate is poly(propylene carbonate)-co-poly(ethylene carbonate). In some embodiments, the aliphatic polycarbonate is poly(cyclohexene carbonate). In some embodiments, the aliphatic polycarbonate is poly(propylene carbonate)-co-poly(cyclohexene carbonate). In some embodiments, the aliphatic polycarbonate is poly(ethylene carbonate)-co-poly(cyclohexene carbonate).

An extrusion-coated layer of APC is preferably about 0.2 mil (0.005 mm) to about 10 mil (0.25 mm) thick, more preferably about 0.5 mil (0.013 mm) to about 5 mil (0.13 mm) thick, and most preferably about 0.5 mil (0.013 mm) to about 2 mil (0.05 mm) thick.

Fig. 1 shows an apparatus for extrusion-coating a substrate with a film containing an APC. The APC 10 is extruded from the head 12 of an extruder as a sheet. The extruded molten polymer film 10 is laid down on a substrate 14 and then the laminate passes into the nip between the rolls below the die. The extruded sheet of APC 10 is coated onto the substrate 14 and the two layers pass between a substrate roller 16 and a laminate roller 18 with the extrusion-coated product 20 exiting the opposite side of the rollers 16, 18. In some embodiments, the substrate 14 is paper, and more preferably, paperboard. The rollers 16, 18 turn in the directions indicated by the arrows during the extrusion coating process. Fig. 2 shows an apparatus for extrusion-coating a film containing an APC between two substrates. The APC 10 is extruded from the head 12 of an extruder as a sheet. The extruded sheet of APC 10 is coated onto a first substrate 14 and a second substrate 22, and the three layers pass between a first substrate roller 26 and a laminate roller 28 with the extrusion-coated product 30 exiting the opposite side of the rollers 26, 28. The second substrate 22 is fed by a second substrate roller 24. In some embodiments, however, the second substrate may be fed without a second substrate roller. In some embodiments, the second substrate may be fed by an extruder head in a manner similar to the feeding of the APC layer of Fig. 2. In some embodiments, the first substrate 14 is paper, and more preferably, paperboard. The rollers 24, 26, 28 turn in the directions indicated by the arrows during the extrusion coating process.

In other embodiments, more than three layers are included in the laminate. In some embodiments, the laminate includes four layers. In other embodiments, the laminate includes five layers. In yet other embodiments, the laminate includes six layers. In other embodiments, the laminate includes seven layers. In some embodiments, one or more layers provide oxygen barrier functionality to the laminate. In some embodiments, one or more layers provide water vapor barrier functionality to the laminate. In some

embodiments, one or more layers provide heat-sealability to the laminate. Each additional layer may be fed using an additional roller for feeding the layer or without using an additional roller. Each additional layer that is substantially a polymer layer may be formed and supplied by an extruder in a manner similar to the manner in which the APC layer 10 is formed and supplied in the embodiments of Figs. 1 and 2.

In some embodiments, one of the layers includes a metal foil, such as disclosed in U.S. Patent No. 3,972,467, which may be applied in a separate step of metallization as one of the outer layers or alternatively co-extruded as one of the layers that make up the laminate. In some embodiments, one of the layers includes a liquid coated film, such as disclosed in U.S. Patent Application Publication No. 2011/0132975.

In some embodiments, the APC layer is located directly on the paperboard with one or more other layers on top of it. In some of these embodiments, the laminate includes another APC layer in addition to the layer directly on the paperboard. Whether the APC layer flanks a paper layer, a paperboard layer, a polymer layer, or a foil layer, the APC layer is preferably of a composition that may adhere to the neighboring layers either with or without a tie-layer being used.

In some embodiments, the order of the layers is varied. In some of these embodiments, the laminate includes at least one layer on each side of the paper or paperboard substrate. In embodiments with double-sided coating of substrates, the substrates are coated with polymer on both sides, and the polymer may be the same one or different polymers on the two sides.

If all of the non-substrate layers are being melt-extruded and extrusion-coated, all layers are preferably formed and applied simultaneously. In some embodiments, however, some layers may be applied by solution coating, as a chemical vapor deposition (CVD)- deposited inorganic barrier layer, or as a foil layer, in separate steps from the extrusion- coated layers.

Poly(propylene carbonate) (PPC) In some embodiments, the extrusion-coated APC is a poly(propylene carbonate)

(PPC). In some embodiments, the PPC is of a composition as described below. The following description is adapted from a co-owned PCT publication WO/2010/060038, the entirety of which is incorporated herein by reference.

In some embodiments, the APC is a PPC composition with advantageous properties made with careful control of reaction parameters. For example, such control of certain reaction parameters leads to PPC that is more structurally precise than previous PPC compositions. Unexpectedly, this structurally precise PPC has improved processing characteristics that allow use of the material in numerous applications where PPC has performed poorly in the past. In certain embodiments, extrusion coatings for laminates are formed from structurally precise PPC wherein the PPC has a high head-to-tail ratio, a low ether linkage content, a narrow polydispersity, and a low cyclic carbonate content. PPC compositions from which these articles are made have physical characteristics that differentiate them from prior PPC compositions typically formed by the polymerization of propylene oxide and carbon dioxide in the presence of heterogeneous zinc catalyst systems.

In some embodiments, the PPC possesses improved processing and performance characteristics relative to less structurally-precise poly(propylene carbonate) compositions from the prior art. These prior art materials contain a larger percentage of ether linkages, a lower head-to-tail ratio, a broader molecular weight distribution, a higher cyclic carbonate content, or combinations of any two or more of these. In some embodiments, the PPC is able to be processed by means including, but not limited to: injection molding; extrusion, melt processing, blowing, thermoforming, foaming, and casting under conditions where prior art poly(propylene carbonate) compositions degrade or otherwise perform poorly.

In some embodiments, the resulting poly(propylene carbonate)-containing extrusion coatings for laminates thereby produced possess unexpectedly improved physical characteristics including, but not limited to: higher strength, less tendency toward thermal deformation, improved gas barrier properties, higher glass transition temperatures, and combinations of two or more of these.

It will be understood that in the present disclosure for providing laminates, the terms "structurally precise poly(propylene carbonate)" and "poly(propylene carbonate)", unless otherwise noted, are used interchangeably.

In certain embodiments, the PPC is characterized in that it has a high head-to-tail ratio. In some embodiments, the PPC is characterized in that it has a high percentage of carbonate linkages. In some embodiments, the PPC is characterized in that it has a narrow polydispersity index. In certain embodiments, the PPC is characterized in that it contains very low levels of cyclic carbonate.

In those embodiments where the structurally precise poly(propylene carbonate) is characterized by a high head-to-tail ratio, polymers have on average greater than about

80% of adjacent monomer units oriented head-to-tail. In certain embodiments, on average in provided laminates including PPC, greater than about 85% of adjacent monomer units in the PPC are oriented head-to-tail. In some embodiments, on average in provided laminates including PPC, greater than about 90% of adjacent monomer units in the PPC are oriented head-to-tail. In some embodiments, on average in provided laminates including PPC, greater than about 95% of adjacent monomer units in the PPC are oriented head-to-tail. In some embodiments, on average in provided laminates including PPC, essentially all adjacent monomer units in the PPC are oriented head-to-tail.

In those embodiments where the structurally precise poly(propylene carbonate) is characterized by a high percentage of carbonate linkages, polymers have on average greater than about 90% of adjacent monomer units connected via carbonate linkages and less than about 10% ether linkages. In certain embodiments, on average in provided laminates including PPC, greater than about 95% of adjacent monomer units in the PPC connected via carbonate linkages. In some embodiments, on average in provided laminates including PPC, greater than about 97% of adjacent monomer units in the PPC are connected via carbonate linkages. In some embodiments, on average in provided laminates including PPC, greater than about 99% of adjacent monomer units in the PPC are connected via carbonate linkages. In some embodiments, on average in provided laminates including PPC, essentially all adjacent monomer units in the PPC are connected via carbonate linkages. In certain embodiments, laminates may contain polyether portions formed in a separate process from the carbonate chains, and in such cases the ether linkages of the polyether portions are to be understood to be distinct from the ether linkages described above which typically arise from imperfect copolymerization of C0₂ and propylene oxide.

In those embodiments where the structurally precise poly(propylene carbonate) is characterized by a narrow polydispersity index (PDI), the PPC has a PDI less than about 2. In certain embodiments, the PPC has a PDI less than about 1.8. In some embodiments, the PPC has a PDI less than about 1.5. In some embodiments, the PPC has a PDI less than about 1.4, less than about 1.2 or less than about 1.1. In certain embodiments, the PPC has a PDI between about 1.0 and about 1.2.

In those embodiments where the structurally precise poly(propylene carbonate) is characterized by a low cyclic carbonate content, the PPC has a cyclic carbonate content less than about 5%. In certain embodiments, the PPC contains less than 5% propylene carbonate. In some embodiments, the PPC contains less than 3% propylene carbonate. In some embodiments, the PPC contains less than 1% propylene carbonate. In certain embodiments, the PPC contains essentially no propylene carbonate.

In some embodiments, structurally the precise poly(propylene carbonate) is characterized in that it possesses a combination of two or more characteristics selected from the group consisting of a high head-to-tail ratio, a high percentage of carbonate linkages, a narrow polydispersity index, and a low cyclic carbonate content. In some embodiments, the poly(propylene carbonate) is characterized in that it has a combination of a high head-to-tail ratio and a high percentage of carbonate linkages. In some embodiments, the poly(propylene carbonate) is characterized in that it has a combination of a high head-to-tail ratio and a narrow polydispersity index. In some embodiments, the poly(propylene carbonate) is characterized in that it has a combination of a high head-to- tail ratio and a low cyclic carbonate content. In some embodiments, the poly(propylene carbonate) is characterized in that it has a combination of a narrow polydispersity index and high percentage of carbonate linkages. In some embodiments, the poly(propylene carbonate) is characterized in that it has a combination of a high head-to-tail ratio, a high percentage of carbonate linkages, and a narrow polydispersity index.

The structurally precise poly(propylene carbonate) may have a range of molecular weights in the laminates. For specific applications it may be desirable to use a higher or lower molecular weight material to obtain the optimum combination of performance and processing characteristics. Such selection processes are well known to the skilled artisan.

The molecular weight of the polymer can be represented by the number average molecular weight (M_N). High molecular weight PPC as described herein generally has an M greater than about 5 x 10⁴ g/mol. Low molecular weight PPC as described herein has an M_N between about 1 x 10³ and about 5 x 10⁴ g/mol. In certain embodiments, the poly(propylene carbonate) is a thermoplastic having a relatively high M_N. In certain embodiments, the structurally precise thermoplastic poly(propylene carbonate) has an M_N above about 5 x 10⁴ g/mol. In certain embodiments, the poly(propylene carbonate) has an M_N above about 1 x 10⁵ g/mol. In certain

embodiments, the poly(propylene carbonate) has an M_N between about 5 x 10⁴ g/mol and about 2 x 10⁷ g/mol. In certain embodiments, laminates include structurally precise poly(propylene carbonate) having a molecular weight between about 40,000 and about 400,000 g/mol. In certain embodiments, laminates include structurally precise poly(propylene carbonate) having a molecular weight between about 50,000 and about 350,000 g/mol. In certain embodiments, laminates include structurally precise poly(propylene carbonate) having a molecular weight between about 100,000 and about 300,000 g/mol. In certain

embodiments, the M_N is in the range of about 150,000 and about 250,000 g/mol. In some embodiments, the structurally precise poly(propylene carbonate) has an M_N between about 160,000 and about 240,000 g/mol. In certain embodiments, the poly(propylene carbonate) has an M between about 180,000 and about 220,000 g/mol. In certain embodiments, the poly(propylene carbonate) has an M_N of about 180,000 g/mol.

In certain embodiments, the structurally precise poly(propylene carbonate) has the following combination of properties: an M in the range of about 60,000 to about 400,000 g/mol; a carbonate linkage content above 95%, a head-to-tail ratio greater than about 85%, a polydispersity index less than about 1.5, and a cyclic carbonate content below about 5%.

In some embodiments, the structurally precise poly(propylene carbonate) has the following combination of properties: an M in the range of about 60,000 to about 100,000 g/mol; a carbonate linkage content above 95%, a head-to-tail ratio greater than about 85%, a polydispersity index less than about 1.5, and a cyclic carbonate content below about 5%. In certain embodiments, the structurally precise poly(propylene carbonate) has the following combination of properties: an M_N of about 80,000 g/mol, a carbonate linkage content above 98%>, a head-to-tail ratio greater than about 85%, a polydispersity index less than about 1.2, and a cyclic carbonate content below about 2%.

In some embodiments, the structurally precise poly(propylene carbonate) has the following combination of properties: an M_N in the range of about 120,000 to about

250,000 g/mol, a carbonate linkage content above 95%, a head-to-tail ratio greater than about 85%o, a polydispersity index less than about 1.5, and a cyclic carbonate content below about 5%. In certain embodiments, the structurally precise poly(propylene carbonate) has the following combination of properties: an M of about 180,000 g/mol, a carbonate linkage content above 98%, a head-to-tail ratio greater than about 85%, a polydispersity index less than about 1.2, and a cyclic carbonate content below about 2%. In some embodiments, the structurally precise poly(propylene carbonate) possesses some degree of stereoregularity. In some embodiments, the PPC is at least partially isotactic. In some embodiments, the PPC is at least partially syndiotactic. In certain embodiments, the PPC is substantially isotactic. In some embodiments, the PPC is a blend of atactic PPC with isotactic or syndiotactic PPC. In certain embodiments, the structurally precise PPC includes a blend of two or more PPC compositions characterized in that each PPC composition in the blend has a different average molecular weight. In certain embodiments, the polycarbonate component includes a blend of high molecular weight PPC having an M_N between about 150,000 and about 400,000 g/mol with a lower molecular weight PPC having an M below about 100,000 g/mol. In certain embodiments, the polycarbonate component includes a blend of high molecular weight PPC having an M_N between about 150,000 and about 250,000 g/mol with a lower molecular weight PPC having an M between about 30,000 g/mol and about 80,000 g/mol. In certain embodiments, each component of such blends has a narrow polydispersity. In certain embodiments, the PDI of the high molecular weight and low molecular weight components of a blend are each less than 1.2 when measured

independently. In certain embodiments, such blends are produced by mixing discrete samples of PPC polymer having low and high molecular weights.

In certain embodiments, the structurally precise poly(propylene carbonate) has a glass transition temperature (T_g) above 40 °C. In certain embodiments, the structurally precise poly(propylene carbonate) has a glass transition temperature (T_g) above 41 °C. In certain embodiments, the structurally precise poly(propylene carbonate) has a glass transition temperature (T_g) above 42 °C. In certain embodiments, the structurally precise poly(propylene carbonate) has a glass transition temperature (T_g) above 43 °C. In certain embodiments, the structurally precise poly(propylene carbonate) has a glass transition temperature (T_g) above 44 °C. In certain embodiments, the structurally precise

poly(propylene carbonate) has a glass transition temperature (T_g) above 45 °C.

In certain embodiments, the structurally precise poly(propylene carbonate) is formed using catalysts other than zinc-containing catalysts. In certain embodiments, the structurally precise poly(propylene carbonate) contains no detectable zinc residue.

In some embodiments, the aliphatic polycarbonates are obtained by

copolymerization of epoxides and carbon dioxide in the presence of transition metal catalysts. In certain embodiments, the structurally precise poly(propylene carbonate) is formed using metal salen catalysts. In certain embodiments, the structurally precise poly(propylene carbonate) is formed using cobalt salen catalysts. Suitable catalysts and methods include those described in US Patent No. 7,304,172 and in published PCT Application No. WO/2010/022388 A2 the entire content of each of which is incorporated herein by reference.

In some embodiments, the structurally precise poly(propylene carbonate) includes polymer chains having a structure represented by formula I:

where X is a moiety corresponding to the bound form of any nucleophile that can ring- open an epoxide and n is an integer from about 10 to about 40,000. In certain embodiments, X in structure I is selected from the group consisting of halide, azide, or an optionally substituted group consisting from the group of carboxylate, sulfonate, phenol, and alkoxide. In some embodiments, n is from about 50 to about 3,000.

In certain embodiments, the structurally precise poly(propylene carbonate) polymers are present as a mixture of two or more different polymer chain types, where the different chain types are distinguished by the presence of two or more different chain terminating groups and/or the presence, absence, or differences in small molecule polymer initiation molecules embedded within the polymer chain. In certain embodiments, the structurally precise poly(propylene carbonate) is characterized in that it includes two polymer chain types, A and B, where the types differ in their terminating groups. In certain embodiments, the polymer chain types A and B have the following formulae:

where n is as defined above, -X and -Y each represent a nucleophile that can ring-open an epoxide, and where -X and -Y are different.

In certain embodiments, X and Y are independently selected from the group consisting of halide, azide, or an optionally substituted group selected from the group consisting of carboxylate, sulfonate, phenol, and alkoxide. In certain embodiments, X is a halide and Y is an optionally substituted group selected from the group consisting of carboxylate, sulfonate, phenol, and alkoxide. In certain embodiments, X is a halide and Y is a carboxylate. In certain embodiments, X is chloride and Y is a carboxylate. In certain embodiments, X is chloride and Y is selected from the group consisting of: formate, acetate, benzoate, trifluoroacetate, and pentafluorobenzoate. In certain embodiments, X is chloride and Y is trifluoroacetate (shown below as structures A² and B²).

where n is as defined above.

In certain embodiments, the ratio between chain types A and B ranges from about 1 :3 to about 3 : 1. In certain embodiments, the ratio between chain types A and B ranges from about 1 :2 to about 2: 1. In certain embodiments, the structurally precise

poly(propylene carbonate) includes an approximately equimolar mixture of chain types A and B. In certain embodiments, the structurally precise poly(propylene carbonate) includes an approximately equimolar mixture of chain types A² and B². In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type C:

where each n is independently as defined above. In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type C in combination with chains of types A or A and B. In certain embodiments, the ratio of chains of type C to chains of types A or A and B ranges (e.g. the ratios C:A or C:[A+B]) from about 0.1 : 1 to about 100: 1. In certain embodiments, this ratio is between about 1 : 1 and about 10: 1. In certain embodiments, this ratio is between about 2: 1 and about 5: 1.

In some embodiments, the structurally precise poly(propylene carbonate) includes chains of type D which have a polymer initiation moiety embedded within them. In certain embodiments, an embedded polymer initiation moiety is located approximately in the center of the polycarbonate chains (in other words, the moiety is linked to two or more poly(propylene carbonate) chains where statistically each chain is of approximately equal length). In certain embodiments, chains of type D are linear polymer chains with two polycarbonate chains linked to an embedded polymer initiation moiety. In certain embodiments, chains of type D are star polymers with three or more polycarbonate chains linked to an embedded polymer initiation moiety. In certain embodiments, chains of type D have a formula D¹:

where each n is independently as defined above, y is an integer from 1 to 5 indicating how many additional individual polycarbonate chains are linked to the embedded polymer initiation moiety (e.g. the total number of poly(propylene carbonate) chains linked to the embedded polymer initiation moiety ranges from 2 to 6); and where Z is any polyfunctional molecule that can react with carbon dioxide at two or more sites to initiate a polymer chain (e.g. to form a carbonate, carbamate, thiocarbonate, or ester from an oxygen, nitrogen, sulfur, or carbon nucleophile respectively). In certain embodiments, the value of y for polymers of type D¹ is 1. In certain embodiments, the value of y for polymers of type D¹ is 2. In certain embodiments, the value of y for polymers of type D¹ is 3.

In some embodiments, chains of type D have a formula D²:

where each n is independently as defined above, y is an integer from 1 to 5 indicating how many additional individual polycarbonate chains are linked to the embedded polymer initiation moiety (e.g. the total number of poly(propylene carbonate) chains linked to the embedded polymer initiation moiety ranges from 2 to 6); and where Z is any polyfunctional molecule that can react at two or more sites with an epoxide to initiate formation of a polycarbonate chain (e.g. by an oxygen, nitrogen, sulfur, or carbon nucleophile respectively to form an ether, amine, thioether, or carbon-carbon bond, respectively). In certain embodiments, the value of y for polymers of type D² is 1. In certain embodiments, the value of y for polymers of type D² is 2. In certain embodiments, the value of y for polymers of type D² is 3.

In some embodiments, chains of type D have a formula D³:

where each n is independently as defined above, y and y ' are each independently an integer from 0 to 6 and the sum of y and y ' is at least 2; and where Z is any polyfunctional molecule that can react at two or more sites with carbon dioxide or an epoxide to initiate formation of polycarbonate chains as described above for structures D¹ and D², respectively. In certain embodiments, the value of y ' for polymers of type D³ is 2. In certain embodiments, the value of y for polymers of type D³ is 2. In certain embodiments, for polymers of type D³ the value of one of y or y ' is 2 and the value of the other is 0. In some embodiments, the sum of y and y ' is greater than 2.

In certain embodiments, the structurally precise poly(propylene carbonate) contains chains of formula A and chains of formula D³ in a ratio from about 1 :50 to about 50: 1. In certain embodiments the ratio of chains of formula A to chains of formula D³ ranges from 1 :50 to 1 : 1. In certain embodiments the ratio of chains of formula A to chains of formula D³ ranges from 1 : 10 to 10: 1. In certain embodiments the ratio of chains of formula A to chains of formula D³ ranges from 1 :2 to 2: 1.

In certain embodiments, the structurally precise poly(propylene carbonate) contains at least 0.1% of chains D³ where the sum of y and y' is greater than 2. In certain embodiments, the structurally precise poly(propylene carbonate) contains at least 0.5% and 20% of chains D³ where the sum of y and y' is greater than 2.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D along with chains of type A. In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D along with a mixture of chains of types A and B. In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D along with chains of type C, and optionally also containing chains of types A or a mixture of types A and B.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D¹ wherein the embedded chain transfer moiety is a bound form of ethylene glycol (e.g. where Z is -OCH₂CH₂O-) and the resulting polymer chains have the formula D⁴:

D⁴ where each n is independently as defined above.

In certain embodiments, the structurally precise poly(propylene carbonate) has approximately 10 to 90% of the chains with structure D⁴ with the balance made up of chains of structures A, B, or C or mixtures of two or more of these.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D¹ wherein the embedded chain transfer moiety is a bound form of dipropylene glycol (which may be a mixture of isomers) and the resulting polymer chains have the formula D⁵:

where each n is independently as defined above, one of Ri and R₂ is methyl and the other is hydrogen and one of R₃ and R4 is methyl and the other is hydrogen (e.g. Z in formula D¹ has one of the following structures:

In certain embodiments, the structurally precise poly(propylene carbonate) has approximately 10 to 90% of the chains with structure D⁵ with the balance made up of chains of structures A, B, or C or mixtures of two or more of these.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D¹ wherein the embedded chain transfer moiety is a bound form of 1,3 propane diol (e.g. where Z is -OCH₂CH₂CH₂0-) and the resulting polymer chains have the formula D⁶:

where each n is independently as defined above.

In certain embodiments, the structurally precise poly(propylene carbonate) has approximately 10 to 90% of the chains with structure D⁶ with the balance made up of chains of structures A, B, or C or mixtures of two or more of these.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D³ wherein the embedded chain transfer moiety is a bound form of glycolic acid and the resulting polymer chains have the formula D⁷:

D'

In certain embodiments, the structurally precise poly(propylene carbonate) has approximately 10 to 90% of the chains with structure D⁷ with the balance made up of chains of structures A, B, or C or mixtures of two or more of these.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D³ wherein the embedded chain transfer moiety is a bound form of propoxylated glycerol and the resulting polymer chains have the formula D⁸:

where each n is independently as defined above.

In certain embodiments, the structurally precise poly(propylene carbonate) has approximately 10 to 90% of the chains with structure D⁹ with the balance made up of chains of structures A, B, or C or mixtures of two or more of these.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D³ wherein the embedded chain transfer moiety is a bound form of propoxylated pentaerythritol and the resulting polymer chains have the formula D⁹:

where each n is independently as defined above.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D³ wherein the embedded chain transfer moiety is a bound form of polyethylene glycol or polypropylene glycol and the resulting polymer chains have the formula D¹⁰:

_Dio where each n is independently as defined above, p is an integer from 2 to 200 inclusive, and R¹ is optionally present, and if present is methyl. In certain embodiments, the structurally precise poly(propylene carbonate) has approximately 10 to 90% of the chains with structure D¹⁰ with the balance made up of chains of structures A, B, or C or mixtures of two or more of these.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type D³ wherein the embedded chain transfer moiety is a bound form of an optionally unsubstituted diacid. In certain embodiments the diacid is a straight chain saturated diacid and the resulting polymer chains have the formula D¹¹:

where each n is independently as defined above, and q is an integer from 0 to 32 inclusive. In certain embodiments, the structurally precise poly(propylene carbonate) has approximately 10 to 90% of the chains with structure D¹¹ with the balance made up of chains of structures A, B, or C or mixtures of two or more of these.

In certain embodiments, the structurally precise poly(propylene carbonate) includes two or more varieties of chains of type D differentiated from each other by the identity of the embedded chain transfer moiety. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type D⁴ along with one or more additional different chain D types. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type D⁵ along with one or more additional different chain D types. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type D⁶ along with one or more additional different chain D types. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type D⁷ along with one or more additional different chain D types. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type D⁸ along with one or more additional different chain D types. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type D along with one or more additional different chain D types.

In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type C along with chains of type D. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type C along with chains of type D⁴. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type C along with chains of type D⁵. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type C along with chains of type D⁶. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type C along with chains of type D⁷. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type C along with chains of type D⁸. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type C along with chains of type D⁹. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type A along with chains of types C and D. In certain embodiments, the structurally precise poly(propylene carbonate) includes polymer chains of type A and B along with chains of types C and D.

In certain embodiments, the structurally precise poly(propylene carbonate) includes chains of type C along with chain types A or A and B. In certain embodiments, the structurally precise poly(propylene carbonate) includes predominantly chains of type C along with lesser amounts of chain types A or A and B. In certain embodiments, the structurally precise poly(propylene carbonate) includes a majority (e.g. > 50%, > 60%>, > 70%o, > 80%), or >90%>) of chains of type C along with lesser amounts of chains of type A. In certain embodiments, the structurally precise poly(propylene carbonate) includes a majority (e.g. > 50%, > 60%, > 70%, > 80%, or >90%) of chains of type C along with lesser amounts of a mixture of chains of types A and B. In certain embodiments, the structurally precise poly(propylene carbonate) includes a majority (e.g. > 50%>, > 60%>, > 70%o, > 80%o, or >90%>) of chains of types C and D along with lesser amounts of a mixture of chains of types A and B. In some embodiments, the structurally precise poly(propylene carbonate) includes about 30 to 80% of polymer chains selected from chains of structure C and D or a mixture of C and D, and 20 to 70% of chains selected from structures A, B, or a mixture of A and B. In certain embodiments, the PPC has equal proportions of A² and B² (e.g. a 1 : 1 ratio between A² chains and B² chains) along with any proportion of one or more chain types C and/or D. In certain embodiments, the PPC contains about equal proportions of four chain types having structures A², B², C, and D⁴. In certain embodiments, the PPC has approximately equal proportions of A² B² and D⁴ (e.g. approximately a 1 : 1 : 1 ratio between A² chains B² chains and D⁴ chains) along with any proportion of chains type C. In certain embodiments, the PPC contains approximately 10 to 90% of each of chain types A², B², C and D⁴.

In certain embodiments, the PPC has approximately equal proportions of A², B² and D⁵ (e.g. approximately a 1 : 1 : 1 ratio between A² chains B² chains and D⁵ chains) along with any proportion of chains type C. In certain embodiments, the PPC contains approximately 10 to 90% of each of chain types A², B², C and D⁵.

In certain embodiments, the PPC has approximately equal proportions of A², B²

6 2 2 6

and D (e.g. approximately a 1 : 1 : 1 ratio between A chains B chains and D chains) along with any proportion of chains type C. In certain embodiments, the PPC contains approximately 10 to 90% of each of chain types A², B², C and D⁶.

In certain embodiments, the PPC has approximately equal proportions of A², B² and D⁷ (e.g. approximately a 1 : 1 : 1 ratio between A² chains B² chains and D⁷ chains) along with any proportion of chains type C. In certain embodiments, the PPC contains approximately 10 to 90% of each of chain types A², B², C and D⁷. In certain embodiments, the PPC has approximately equal proportions of A², B² and D⁸ (e.g. approximately a 1 : 1 : 1 ratio between A² chains B² chains and D⁸ chains) along with any proportion of chains type C. In certain embodiments, the PPC contains approximately 10 to 90% of each of chain types A², B², C and D⁸. In certain embodiments, the PPC has approximately equal proportions of A², B² and D⁹ (e.g. approximately a 1 : 1 : 1 ratio between A² chains B² chains and D⁹ chains) along with any proportion of chains type C. In certain embodiments, the PPC contains approximately 10 to 90% of each of chain types A², B², C and D⁹.

In certain embodiments, the PPC has approximately equal proportions of A², B²

10 2 2 10

and D (e.g. approximately a 1 : 1 : 1 ratio between A chains B chains and D chains) along with any proportion of chains type C. In certain embodiments, the PPC contains approximately 10 to 90% of each of chain types A², B², C and D¹⁰.

In certain embodiments, the PPC has approximately equal proportions of A², B² and D¹¹ (e.g. approximately a 1 : 1 : 1 ratio between A² chains B² chains and D¹¹ chains) along with any proportion of chains type C. In certain embodiments, the PPC contains approximately 10 to 90% of each of chain types A², B², C and D¹¹.

In certain embodiments, where the structurally precise PPC includes two or more chain types (e.g. any of structures A through D¹¹), the value of n at each occurrence is approximately the same.

In certain embodiments, any of the structures A through D¹¹ described above may be modified. In certain embodiments, this may be done by performing chemistry post- polymerization on the terminal hydroxyl group(s). In certain embodiments, the structurally precise poly(propylene carbonate) may contain chains of type A through D¹¹, where the terminating groups are esters, ethers, carbamates, sulfonates, or carbonates. In certain embodiments, these derivatives may be formed by reaction with acylating agents to provide groups such as acetate, trifluoroacetate, benzoate or pentafluorobenzoate. In some embodiments, hydroxyl groups may be reacted with isocyanates to form carbamates, with silyl halides or silyl sulfonates to form silyl ethers, with alkyl halides or alkyl sulfonates to form ethers, or with sulfonyl halides or anhydrides to form sulfonates.

Methods Al through A4 describe methods of making structurally precise PPC. By using different chain transfer agents and controlling the amount of water present in the reactions, the identity and relative ratios of chain types in the samples are changed.

Method Al: synthesis of PPC including chains of B² and C. A 1 -liter Parr reactor was charged with 200 grams propylene oxide containing 33 ppm water, 123 mg of racemic N,N'-Bis(3,5-di-tert-butylsalicylidene)-l ,2- cyclohexanediamino cobalt(III) trifluoroacetate (salcyCoTFA) catalyst and 1 12 mg bis(triphenylphosphine)iminium trifluoroacetate (PPN-TFA) co-catalyst. The reactor was sealed, pressurized to 100 psi with C0₂, and agitated at 250 rpm while the temperature was maintained at 35 °C. After 23 hours, the polymerization was quenched with 2.1 equivalents of methane sulfonic acid (MSA) in 200 g acetone. The reaction mixture was distilled to remove unreacted propylene oxide and the sample was then precipitated in 50/50 MeOH/H₂0 to isolate the solid polymer. The recovered polymer was dried in a vacuum oven, then redissolved at 20 wt% into acetone, and precipitated a second time.

Recovered polymer was dried in 75 °C vacuum oven for 8 hours. GPC analysis revealed the PPC sample resulting from Method 1 has a bimodal molecular weight distribution and contains approximately equal populations of chains with M of 230.8 kg/mol and 1 10 kg/mol, corresponding to chains of types C and B² respectively. Method la: synthesis of PPC including chains of A², B², and C.

The PPC of this method is produced under conditions identical to Method 1 , except 104 mg of bis(triphenylphosphine)iminium chloride (PPN-C1) was substituted for the PPN-TFA). The presence and relative abundances of chains of types A² and B² can be detected by analytical methods to detect chlorine and fluorine. Suitable methods are known in the art and include mass spectroscopy and fluorine NMR among others.

Method 2: synthesis of PPC including chains of B², C, and D⁵.

A 1 -liter Parr reactor was charged with 200 grams propylene oxide containing 33 ppm water, 58 mg of dipropylene glycol, 123 mg of salcyCoTFA catalyst and 1 12 mg PPN-TFA co-catalyst. The reactor was sealed, pressurized to 100 psi with C0₂, and agitated at 250 rpm while the temperature was maintained at 35 °C. After 23 hours, the polymerization was quenched with 2.1 equivalents of methane sulfonic acid (MSA) in 200 g acetone. The reaction mixture was distilled to remove unreacted propylene oxide and the sample was then precipitated in 50/50 MeOH/H₂0 to isolate the solid polymer. The recovered polymer was dried in a vacuum oven, then redissolved at 20wt% into acetone, and precipitated a second time. Recovered polymer was dried in 75 °C vacuum oven for 8 hours.

Method 3: synthesis of PPC including chains of B², C, and D⁸.

This material was produced under conditions identical to those described in Method 2 except 76 mg glycerol propoxylate was substituted for the dipropylene glycol.

Method 4: synthesis of PPC including chains of B², C, and D⁹.

This material was produced under conditions identical to those described in Method 2 except 92 mg pentaerythritol propoxylate was substituted for the dipropylene glycol. Gel permeation chromatography (GPC) was performed on the polymers from

Methods 2 through 4. The polymer resulting from Method 2 has a bimodal molecular weight distribution and contains predominantly chains with M_w of approximately 120 kg/mol (a mixture of chains of type D⁵ and C) with a smaller population of chains with M of approximately 60 kg/mol, corresponding to a mixture of chains of type B². For the polymer from Method 2, the M_N was about 92 kg/mol, the M_w was about 118 kg/mol, and the PDI was about 1.29. The samples from Methods 3 and 4 each show a characteristic trimodal molecular weight distribution in the GPC. The three components correspond to chains of type B² (the low molecular weight population), a middle population containing chains of type C and a high M_w population corresponding to chains of type D⁸ (Method 3) or D⁹ (Method 4). For the polymer from Method 3, the M_N was about 90 kg/mol, the M_w was about 127 kg/mol, and the PDI was about 1.42. For the polymer from Method 4, the M_N was about 115 kg/mol, the M_w was about 185 kg/mol, and the PDI was about 1.61.

The ratio of these chain types can be manipulated using the methods disclosed in the preceding methods or by physical blending of samples having different chain types to provide PPC compositions with varying melt flow indices (MFIs). In certain applications having a higher MFI can be advantageous for injection molding and extrusion operations to make plastic articles of the present invention. The PPC of Method 2 was found to have an MFI of 2.56 g/10 min when measured at 170 °C at 2.16 kg. Under the same conditions, the PPC of Method 3 was found to have an MFI of 2.35 g/10 min while that of Method 4 was found to be 0.79 g/10 min. It will be appreciated that the skilled artisan can use these trends to formulate PPC compositions with a range of melt flow properties.

PPC was passed through an extruder at 170 °C and injection molded to make tensile bars and extruded into films of various thicknesses. Attempts were made to treat prior art PPC available commercially under the trade name QAPC, but the prior art material was either unable to be processed under these conditions or yielded films and tensile bars with that were extremely soft and lacked the structural integrity exhibited by the samples of the inventive PPC. Without being bound by any theory or thereby limiting the scope of the claimed invention, it is believed this may be due to thermal degradation of the commercial PPC during the extrusion process at these temperatures.

In certain embodiments, the PPC has a polydispersity index (PDI) of less than about 1.7. In some embodiments, the PPC has a PDI of between about 1.0 and about 1.5. In some embodiments, the PPC has a PDI of between about 1.2 and about 1.4. In some embodiments, the PPC has a PDI of less than about 1.2. In some embodiments, the PPC has a PDI of about 1.1.

In certain embodiments, the PPC has a head to tail ratio (H:T) greater than about 4: 1. In certain embodiments, the PPC has a head to tail ratio (H:T) greater than about 5: 1. In certain embodiments, the PPC has a head to tail ratio (H:T) greater than about 10:1. In certain embodiments, the PPC has a head to tail ratio (H:T) greater than about 100:1. In certain embodiments, the PPC is characterized in that, on average the percentage of carbonate linkages is 85% or greater. In certain embodiments, the PPC is characterized in that, on average in the composition, the percentage of carbonate linkages is 90% or greater. In certain embodiments, the poly(propylene carbonate) composition is

characterized in that, on average in the composition, the percentage of carbonate linkages is 91% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that, on average in the composition, the percentage of carbonate linkages is 92% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that, on average in the composition, the percentage of carbonate linkages is 93% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that, on average in the composition, the percentage of carbonate linkages is 94% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that, on average in the composition, the percentage of carbonate linkages is 95% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that, on average in the composition, the percentage of carbonate linkages is 96% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that, on average in the composition, the percentage of carbonate linkages is 97% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that, on average in the composition, the percentage of carbonate linkages is 98% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that, on average in the composition, the percentage of carbonate linkages is 99% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that, on average in the composition, the percentage of carbonate linkages is 99.5% or greater. In certain embodiments, the poly(propylene carbonate) composition is characterized in that ether linkages are not detectable by 1H or ¹³C NMR. It will be appreciated that where the present disclosure describes one characteristic of provided compositions, the disclosure encompasses compositions having such individual characteristics alone and in combination with one or more other characteristics as described herein. In certain embodiments, the PPC has a head-to-tail ratio of at least 4: 1, a PDI less than 1.5, an ether content of less than 10%, and a number-average molecular weight (M_N) between 75,000 g/mol and 350,000 g/mol. In certain embodiments, the PPC has a head-to-tail ratio of at least 9: 1, a PDI less than 1.5, an ether content of less than 10%), and a M_N between 75,000 g/mol and 350,000 g/mol. In certain embodiments, the PPC has a head-to-tail ratio of at least 6: 1, a PDI less than 1.4, an ether content of less than 10%), and a M_N between 75,000 g/mol and 350,000 g/mol. In certain embodiments, the PPC has a head-to-tail ratio of at least 4: 1 , a PDI less than 1.4, an ether content of less than 10%), and a M_N between 75,000 g/mol and 350,000 g/mol. In certain embodiments, the PPC has a head-to-tail ratio of at least 4: 1, a PDI less than 1.5, an ether content of less than 5%o, and a M_N between 75,000 g/mol and 350,000 g/mol. In certain embodiments, the PPC has a head-to-tail ratio of at least 20:1, a PDI less than 1.3, an ether content of less than 2%, and a M_N between 75,000 g/mol and 350,000 g/mol.

Poly(ethylene carbonate) (PEC) In other embodiments, the extrusion-coated APC is a poly(ethylene carbonate) (PEC). In some embodiments, the PEC has greater than about 90% carbonate linkages. In some embodiments, the PEC is of a composition as described below.

In certain embodiments, the PEC is characterized in that it has a high percentage of carbonate linkages. In some embodiments, the PEC is characterized in that it has a narrow polydispersity index. In certain embodiments, the PEC is characterized in that it contains very low levels of cyclic carbonate.

In those embodiments where the structurally precise poly(ethylene carbonate) is characterized by a high percentage of carbonate linkages, polymers have on average greater than about 90% of adjacent monomer units connected via carbonate linkages and less than about 10% ether linkages. In certain embodiments, on average in provided laminates including PEC, greater than about 95% of adjacent monomer units in the PEC connected via carbonate linkages. In some embodiments, on average in provided laminates including PEC, greater than about 97% of adjacent monomer units in the PEC are connected via carbonate linkages. In some embodiments, on average in provided laminates including PEC, greater than about 99% of adjacent monomer units in the PEC are connected via carbonate linkages. In some embodiments, on average in provided laminates including PEC, essentially all adjacent monomer units in the PEC are connected via carbonate linkages. In certain embodiments, laminates including PEC may contain polyether portions formed in a separate process from the carbonate chains, and in such cases the ether linkages of the polyether portions are to be understood to be distinct from the ether linkages described above which typically arise from imperfect copolymerization of C0₂ and propylene oxide.

In those embodiments where the poly(ethylene carbonate) is characterized by a narrow polydispersity index (PDI), the PEC has a PDI less than about 2. In certain embodiments, the PEC has a PDI less than about 1.8. In some embodiments, the PEC has a PDI less than about 1.5. In some embodiments, the PEC has a PDI less than about 1.4, less than about 1.2 or less than about 1.1. In certain embodiments, the PEC has a PDI between about 1.0 and about 1.2. In those embodiments where the poly(ethylene carbonate) is characterized by a low cyclic carbonate content, the PEC has a cyclic carbonate content less than about 5%. In certain embodiments, the PEC contains less than 5% ethylene carbonate. In some embodiments, the PEC contains less than 3% ethylene carbonate. In some embodiments, the PEC contains less than 1 % ethylene carbonate. In certain embodiments, the PEC contains essentially no ethylene carbonate.

In some embodiments, structurally the precise poly(ethylene carbonate) is characterized in that it possesses a combination of two or more characteristics selected from the group consisting of a high percentage of carbonate linkages, a narrow

polydispersity index, and a low cyclic carbonate content. In some embodiments, the poly(ethylene carbonate) is characterized in that it has a combination of a narrow polydispersity index and high percentage of carbonate linkages. In some embodiments, the poly(ethylene carbonate) is characterized in that it has a combination of a high percentage of carbonate linkages, and a low cyclic content. In some embodiments, the poly(ethylene carbonate) is characterized in that it has a combination of a narrow polydispersity index, and a low cyclic content.

The poly(ethylene carbonate) may have a range of molecular weights in the laminate. For specific applications it may be desirable to use a higher or lower molecular weight material to obtain the optimum combination of performance and processing characteristics. Such selection processes are well known to the skilled artisan. The molecular weight of the polymer can be represented by the number average molecular weight (M_N). High molecular weight PEC as described herein generally has an M greater than about 5 x 10⁴ g/mol. Low molecular weight PEC as described herein has an M_N between about 1 x 10³ and about 5 x 10⁴ g/mol. In certain embodiments, the poly(ethylene carbonate) is a thermoplastic having a relatively high M_N. In certain embodiments, the thermoplastic poly(ethylene carbonate) has an M_N above about 5 x 10⁴ g/mol. In certain embodiments, the poly(ethylene carbonate) has an M_N above about 1 x 10⁵ g/mol. In certain embodiments, the

poly(ethylene carbonate) has an M_N between about 5 x 10⁴ g/mol and about 2 x 10⁷ g/mol. In certain embodiments, laminates include poly(ethylene carbonate) having a molecular weight between about 40,000 and about 400,000 g/mol. In certain

embodiments, laminates include poly(ethylene carbonate) having a molecular weight between about 50,000 and about 350,000 g/mol. In certain embodiments, laminates include poly(ethylene carbonate) having a molecular weight between about 100,000 and about 300,000 g/mol. In certain embodiments, the M is in the range of about 150,000 and about 250,000 g/mol. In some embodiments, the poly(ethylene carbonate) has an M between about 160,000 and about 240,000 g/mol. In certain embodiments, the

poly(ethylene carbonate) has an M_N between about 180,000 and about 220,000 g/mol. In certain embodiments, the poly(ethylene carbonate) has an M_N of about 180,000 g/mol.

In certain embodiments, the poly(ethylene carbonate) has the following combination of properties: an M_N in the range of about 60,000 to about 400,000 g/mol; a carbonate linkage content above 95%, a polydispersity index less than about 1.5, and a cyclic carbonate content below about 5%.

In some embodiments, the poly(ethylene carbonate) has the following combination of properties: an M_N in the range of about 60,000 to about 100,000 g/mol; a carbonate linkage content above 95%, a polydispersity index less than about 1.5, and a cyclic carbonate content below about 5%.

In certain embodiments, the poly(ethylene carbonate) has the following combination of properties: an M_N of about 80,000 g/mol, a carbonate linkage content above 98%>, a polydispersity index less than about 1.2, and a cyclic carbonate content below about 2%>.

In some embodiments, the poly(ethylene carbonate) has the following combination of properties: an M_N in the range of about 120,000 to about 250,000 g/mol, a carbonate linkage content above 95%>, a polydispersity index less than about 1.5, and a cyclic carbonate content below about 5%.

In certain embodiments, the poly(ethylene carbonate) has the following combination of properties: an M_N of about 180,000 g/mol, a carbonate linkage content above 98%, a polydispersity index less than about 1.2, and a cyclic carbonate content below about 2%.

In certain embodiments, the PEC includes a blend of two or more PEC

compositions characterized in that each PEC composition in the blend has a different average molecular weight. In certain embodiments, the polycarbonate component includes a blend of high molecular weight PEC having an M between about 150,000 and about 400,000 g/mol with a lower molecular weight PEC having an M_N below about 100,000 g/mol. In certain embodiments, the polycarbonate component includes a blend of high molecular weight PEC having an M_N between about 150,000 and about 250,000 g/mol with a lower molecular weight PEC having an M between about 30,000 g/mol and about 80,000 g/mol. In certain embodiments, each component of such blends has a narrow polydispersity. In certain embodiments, the PDI of the high molecular weight and low molecular weight components of a blend are each less than 1.2 when measured independently. In certain embodiments, such blends are produced by mixing discrete samples of PEC polymer having low and high molecular weights.

In certain embodiments, the poly(ethylene carbonate) has a glass transition temperature (T_g) above 40 °C. In certain embodiments, the poly(ethylene carbonate) has a glass transition temperature (T_g) above 41 °C. In certain embodiments, the poly(ethylene carbonate) has a glass transition temperature (T_g) above 42 °C. In certain embodiments, the poly(ethylene carbonate) has a glass transition temperature (T_g) above 43 °C. In certain embodiments, the poly(ethylene carbonate) has a glass transition temperature (T_g) above 44 °C. In certain embodiments, the poly(ethylene carbonate) has a glass transition temperature (T_g) above 45 °C.

In certain embodiments, the poly(ethylene carbonate) is formed using catalysts other than zinc-containing catalysts. In certain embodiments, the poly(ethylene carbonate) contains no detectable zinc residue.

In some embodiments, the aliphatic polycarbonates are obtained by

copolymerization of epoxides and carbon dioxide in the presence of transition metal catalysts. In certain embodiments, the poly(ethylene carbonate) is formed using metal salen catalysts. In certain embodiments, the poly(ethylene carbonate) is formed using cobalt salen catalysts. Suitable catalysts and methods include those described in US Patent No. 7,304,172 and in PCT Publication No. WO/2010/022388 A2 the entire content of each of which is incorporated herein by reference.

In some embodiments, the poly(ethylene carbonate) includes polymer chains having a structure represented by formula 1 :

where X is a moiety corresponding to the bound form of any nucleophile that can ring- open an epoxide and n is an integer from about 10 to about 40,000. In certain embodiments, X in structure 1 is selected from the group consisting of halide, azide, or an optionally substituted group consisting from the group of carboxylate, sulfonate, phenol, and alkoxide. In some embodiments, n is from about 50 to about 3,000.

In certain embodiments, the poly(ethylene carbonate) polymers are present as a mixture of two or more different polymer chain types, where the different chain types are distinguished by the presence of two or more different chain terminating groups and/or the presence, absence, or differences in small molecule polymer initiation molecules embedded within the polymer chain.

In certain embodiments, the poly(ethylene carbonate) is characterized in that it includes two polymer chain types, 1A and IB, where the types differ in their terminating groups. In certain embodiments, the polymer chain types 1A and IB have the following formulae:

where n is as defined above, -X and -Y each represent a nucleophile that can ring-open an epoxide, and where -X and -Y are different. In certain embodiments, X and Y are independently selected from the group consisting of halide, azide, or an optionally substituted group selected from the group consisting of carboxylate, sulfonate, phenol, and alkoxide. In certain embodiments, X is a halide and Y is an optionally substituted group selected from the group consisting of carboxylate, sulfonate, phenol, and alkoxide. In certain embodiments, X is a halide and Y is a carboxylate. In certain embodiments, X is chloride and Y is a carboxylate. In certain embodiments, X is chloride and Y is selected from the group consisting of: formate, acetate, benzoate, trifluoroacetate, and pentafluorobenzoate. In certain embodiments, X is chloride and Y is trifluoroacetate (shown below as structures 1A² and IB²).

where n is as defined above.

In certain embodiments, the ratio between chain types 1A and IB ranges from about 1 :3 to about 3 : 1. In certain embodiments, the ratio between chain types 1 A and IB ranges from about 1 :2 to about 2: 1. In certain embodiments, the poly(ethylene carbonate) includes an approximately equimolar mixture of chain types 1A and IB. In certain embodiments, the poly(ethylene carbonate) includes an approximately equimolar mixture of chain types 1A² and IB².

In certain embodiments, the poly(ethylene carbonate) includes chains of type 1C:

where each n is independently as defined above.

In certain embodiments, the poly(ethylene carbonate) includes chains of type 1C in combination with chains of types 1A or 1A and IB. In certain embodiments, the ratio of chains of type 1C to chains of types 1A or 1A and IB ranges (e.g. the ratios 1C: 1A or 1C:[1A+1B]) from about 0.1 : 1 to about 100: 1. In certain embodiments, this ratio is between about 1 : 1 and about 10: 1. In certain embodiments, this ratio is between about 2:1 and about 5: 1.

In some embodiments, the poly(ethylene carbonate) includes chains of type ID which have a polymer initiation moiety embedded within them. In certain embodiments, an embedded polymer initiation moiety is located approximately in the center of the polycarbonate chains (in other words, the moiety is linked to two or more poly(ethylene carbonate) chains where statistically each chain is of approximately equal length). In certain embodiments, chains of type ID are linear polymer chains with two polycarbonate chains linked to an embedded polymer initiation moiety. In certain embodiments, chains of type ID are star polymers with three or more polycarbonate chains linked to an embedded polymer initiation moiety.

In certain embodiments, chains of type ID have a formula ID¹:

where each n is independently as defined above, y is an integer from 1 to 5 indicating how many additional individual polycarbonate chains are linked to the embedded polymer initiation moiety (e.g. the total number of poly(ethylene carbonate) chains linked to the embedded polymer initiation moiety ranges from 2 to 6); and where Z is any polyfunctional molecule that can react with carbon dioxide at two or more sites to initiate a polymer chain (e.g. to form a carbonate, carbamate, thiocarbonate, or ester from an oxygen, nitrogen, sulfur, or carbon nucleophile respectively). In certain embodiments, the value of y for polymers of type ID¹ is 1. In certain embodiments, the value of y for polymers of type ID¹ is 2. In certain embodiments, the value of y for polymers of type ID¹ is 3. In some embodiments, chains of type ID have a formula ID²:

where each n is independently as defined above, y is an integer from 1 to 5 indicating how many additional individual polycarbonate chains are linked to the embedded polymer initiation moiety (e.g. the total number of poly(ethylene carbonate) chains linked to the embedded polymer initiation moiety ranges from 2 to 6); and where Z is any polyfunctional molecule that can react at two or more sites with an epoxide to initiate formation of a polycarbonate chain (e.g. by an oxygen, nitrogen, sulfur, or carbon nucleophile respectively to form an ether, amine, thioether, or carbon- carbon bond, respectively). In certain embodiments, the value of y for polymers of type ID² is 1. In certain embodiments, the value of y for polymers of type ID² is 2. In certain embodiments, the value of y for polymers of type ID² is 3.

In some embodiments, chains of type ID have a formula ID³:

where each n is independently as defined above, y and y ' are each independently an

integer from 0 to 6 and the sum of y and y ' is at least 2; and where Z is any polyfunctional molecule that can react at two or more sites with carbon dioxide or an epoxide to initiate formation of polycarbonate chains as described above for structures ID¹ and ID², respectively. In certain embodiments, the value of y ' for polymers of type ID³ is 2. In certain embodiments, the value of y for polymers of type ID³ is 2. In certain embodiments, for polymers of type ID³ the value of one of y or y ' is 2 and the value of the other is 0. In some embodiments, the sum of y and y ' is greater than 2.

In certain embodiments, the poly(ethylene carbonate) contains chains of formula 1A and chains of formula ID³ in a ratio from about 1 :50 to about 50: 1. In certain embodiments the ratio of chains of formula 1A to chains of formula ID³ ranges from 1 :50 to 1 : 1. In certain embodiments the ratio of chains of formula 1 A to chains of formula ID³ ranges from 1 : 10 to 10: 1. In certain embodiments the ratio of chains of formula 1A to chains of formula ID³ ranges from 1 :2 to 2: 1.

In certain embodiments, the poly(ethylene carbonate) contains at least 0.1% of chains ID³ where the sum of y and y' is greater than 2. In certain embodiments, the poly(ethylene carbonate) contains at least 0.5% and 20% of chains ID³ where the sum of y and y' is greater than 2.

In certain embodiments, the poly(ethylene carbonate) includes chains of type ID along with chains of type 1A. In certain embodiments, the poly(ethylene carbonate) includes chains of type ID along with a mixture of chains of types 1A and IB. In certain embodiments, the poly(ethylene carbonate) includes chains of type D along with chains of type C, and optionally also containing chains of types 1A or a mixture of types 1A and IB.

In certain embodiments, the poly(ethylene carbonate) includes chains of type ID¹ wherein the embedded chain transfer moiety is a bound form of ethylene glycol (e.g.

where Z is -OCH₂CH₂0-) and the resulting polymer chains have the formula ID⁴:

where each n is independently as defined above.

In certain embodiments, the poly(ethylene carbonate) has approximately 10 to 90% of the chains with structure ID⁴ with the balance made up of chains of structures 1A, IB, or C or mixtures of two or more of these.

In certain embodiments, the poly(ethylene carbonate) includes chains of type ID¹ wherein the embedded chain transfer moiety is a bound form of dipropylene glycol (which may be a mixture of isomers) and the resulting polymer chains have the formula ID⁵:

In certain embodiments, the poly(ethylene carbonate) has approximately 10 to 90% of the chains with structure ID⁵ with the balance made up of chains of structures 1A, IB, or 1C or mixtures of two or more of these.

In certain embodiments, the poly(ethylene carbonate) includes chains of type ID¹ wherein the embedded chain transfer moiety is a bound form of 1,3 propane diol (e.g. where Z is -OCH₂CH₂CH₂0-) and the resulting polymer chains have the formula ID⁶:

where each n is independently as defined above.

In certain embodiments, the poly(ethylene carbonate) has approximately 10 to 90% of the chains with structure ID⁶ with the balance made up of chains of structures 1A, IB, or 1C or mixtures of two or more of these.

In certain embodiments, the poly(ethylene carbonate) includes chains of type ID³ wherein the embedded chain transfer moiety is a bound form of glycolic acid and the resulting polymer chains have the formula ID⁷:

In certain embodiments, the poly(ethylene carbonate) has approximately 10 to 90% of the chains with structure ID⁷ with the balance made up of chains of structures 1A, IB, or 1C or mixtures of two or more of these.

In certain embodiments, the poly(ethylene carbonate) includes chains of type ID³ wherein the embedded chain transfer moiety is a bound form of propoxylated glycerol and the resulting polymer chains have the formula ID⁸:

where each n is independently as defined above.

In certain embodiments, the poly(ethylene carbonate) has approximately 10 to 90% of the chains with structure ID⁹ with the balance made up of chains of structures 1A, IB, or C or mixtures of two or more of these.

In certain embodiments, the poly(ethylene carbonate) includes chains of type ID³ wherein the embedded chain transfer moiety is a bound form of propoxylated

pentaerythritol and the resulting polymer chains have the formula ID⁹:

where each n is independently as defined above.

In certain embodiments, the poly(ethylene carbonate) includes chains of type ID³ wherein the embedded chain transfer moiety is a bound form of polyethylene glycol or polypropylene glycol and the resulting polymer chains have the formula ID¹⁰:

ID¹⁰ where each n is independently as defined above, p is an integer from 2 to 200 inclusive, and R¹ is optionally present, and if present is methyl.

In certain embodiments, the poly(ethylene carbonate) has approximately 10 to 90% of the chains with structure ID¹⁰ with the balance made up of chains of structures 1A, IB, or 1C or mixtures of two or more of these.

In certain embodiments, the poly(ethylene carbonate) includes chains of type ID³ wherein the embedded chain transfer moiety is a bound form of an optionally

unsubstituted diacid. In certain embodiments the diacid is a straight chain saturated diacid and the resulting polymer chains have the formula ID¹¹:

ID¹¹ where each n is independently as defined above, and q is an integer from 0 to 32 inclusive. In certain embodiments, the poly(ethylene carbonate) has approximately 10 to 90% of the chains with structure ID¹¹ with the balance made up of chains of structures 1A, IB, or 1C or mixtures of two or more of these.

In certain embodiments, the poly(ethylene carbonate) includes two or more varieties of chains of type ID differentiated from each other by the identity of the embedded chain transfer moiety. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type ID⁴ along with one or more additional different chain ID types. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type ID⁵ along with one or more additional different chain ID types. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type ID⁶ along with one or more additional different chain ID types. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type ID⁷ along with one or more additional different chain ID types. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type ID⁸ along with one or more additional different chain ID types. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type ID⁹ along with one or more additional different chain ID types.

In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type 1C along with chains of type ID. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type 1C along with chains of type ID⁴. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type 1C along with chains of type ID⁵. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type 1C along with chains of type ID⁶. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type 1C along with chains of type ID⁷. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type 1C along with chains of type ID⁸. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type 1C along with chains of type ID⁹. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type 1A along with chains of types 1C and ID. In certain embodiments, the poly(ethylene carbonate) includes polymer chains of type 1A and IB along with chains of types 1C and ID. In certain embodiments, the poly(ethylene carbonate) includes chains of type 1C along with chain types 1A or 1A and IB. In certain embodiments, the poly(ethylene carbonate) includes predominantly chains of type 1C along with lesser amounts of chain types 1A or 1A and IB. In certain embodiments, the poly(ethylene carbonate) includes a majority (e.g. > 50%, > 60%, > 70%, > 80%, or >90%) of chains of type 1C along with lesser amounts of chains of type A. In certain embodiments, the poly(ethylene carbonate) includes a majority (e.g. > 50%, > 60%, > 70%, > 80%, or >90%) of chains of type 1C along with lesser amounts of a mixture of chains of types 1A and IB. In certain embodiments, the poly(ethylene carbonate) includes a majority (e.g. > 50%>, > 60%>, > 70%), > 80%), or >90%) of chains of types 1C and ID along with lesser amounts of a mixture of chains of types 1A and IB.

In some embodiments, the poly(ethylene carbonate) includes about 30 to 80%> of polymer chains selected from chains of structure 1C and ID or a mixture of 1C and ID, and 20 to 70% of chains selected from structures 1A, IB, or a mixture of 1A and IB.

In certain embodiments, the PEC has equal proportions of 1A² and IB² (e.g. a 1 : 1 ratio between 1A² chains and IB² chains) along with any proportion of one or more chain types 1C and/or ID. In certain embodiments, the PEC contains about equal proportions of four chain types having structures 1A², IB², C, and D⁴. In certain embodiments, the PEC has approximately equal proportions of 1A² IB² and D⁴ (e.g. approximately a 1 : 1 : 1 ratio between 1A² chains IB² chains and ID⁴ chains) along with any proportion of chains type 1C. In certain embodiments, the PEC contains approximately 10 to 90% of each of chain types 1A², IB², 1C and ID⁴.

In certain embodiments, the PEC has approximately equal proportions of 1A², IB² and ID⁵ (e.g. approximately a 1 : 1 : 1 ratio between 1 A² chains IB² chains and ID⁵ chains) along with any proportion of chains type 1C. In certain embodiments, the PEC contains approximately 10 to 90% of each of chain types 1A², IB², 1C and ID⁵.

In certain embodiments, the PEC has approximately equal proportions of 1A², IB²

6 2 2 6 and ID (e.g. approximately a 1 : 1 : 1 ratio between 1 A chains IB chains and ID chains) along with any proportion of chains type 1C. In certain embodiments, the PEC contains approximately 10 to 90% of each of chain types 1A², IB², 1C and ID⁶. In certain embodiments, the PEC has approximately equal proportions of 1A², IB² and ID⁷ (e.g. approximately a 1 : 1 : 1 ratio between 1 A² chains IB² chains and ID⁷ chains) along with any proportion of chains type C. In certain embodiments, the PEC contains approximately 10 to 90% of each of chain types 1A², IB², 1C and ID⁷.

In certain embodiments, the PEC has approximately equal proportions of 1A², IB² and ID⁸ (e.g. approximately a 1 : 1 : 1 ratio between 1 A² chains IB² chains and ID⁸ chains) along with any proportion of chains type 1C. In certain embodiments, the PEC contains approximately 10 to 90% of each of chain types 1A², IB², 1C and ID⁸.

In certain embodiments, the PEC has approximately equal proportions of 1A², IB² and ID⁹ (e.g. approximately a 1 : 1 : 1 ratio between 1 A² chains IB² chains and ID⁹ chains) along with any proportion of chains type C. In certain embodiments, the PEC contains approximately 10 to 90% of each of chain types 1A², IB², 1C and ID⁹.

10 2 2 10 and ID (e.g. approximately a 1 : 1 : 1 ratio between 1A chains IB chains and ID

chains) along with any proportion of chains type 1C. In certain embodiments, the PEC contains approximately 10 to 90% of each of chain types 1A², IB², 1C and ID¹⁰.

In certain embodiments, the PEC has approximately equal proportions of 1A², IB² and ID¹¹ (e.g. approximately a 1 : 1 : 1 ratio between 1A² chains IB² chains and ID¹¹ chains) along with any proportion of chains type C. In certain embodiments, the PEC contains approximately 10 to 90% of each of chain types 1A², IB², 1C and ID¹¹.

In certain embodiments, where the PEC includes two or more chain types (e.g. any of structures 1A through ID¹¹), the value of n at each occurrence is approximately the same.

In certain embodiments, any of the structures 1A through ID¹¹ described above may be modified. In certain embodiments, this may be done by performing chemistry post-polymerization on the terminal hydroxyl group(s). In certain embodiments, the poly(ethylene carbonate) may contain chains of type 1A through ID¹¹, where the terminating groups are esters, ethers, carbamates, sulfonates, or carbonates. In certain embodiments, these derivatives may be formed by reaction with acylating agents to provide groups such as acetate, trifluoroacetate, benzoate or pentafluorobenzoate. In some embodiments, hydroxyl groups may be reacted with isocyanates to form carbamates, with silyl halides or silyl sulfonates to form silyl ethers, with alkyl halides or alkyl sulfonates to form ethers, or with sulfonyl halides or anhydrides to form sulfonates. Copolymers of PPC and PEC

In yet other embodiments, the extrusion-coated APC is a poly(propylene carbonate)-co-poly(ethylene carbonate). In some embodiments the poly(propylene carbonate)-co-poly(ethylene carbonate) is a random copolymer. In other embodiments, the poly(propylene carbonate)-co-poly(ethylene carbonate) is a tapered copolymer. In yet other embodiments, the poly(propylene carbonate)-co-poly(ethylene carbonate) is a block copolymer. The poly(propylene carbonate)-co-poly(ethylene carbonate) compositions may contain ratios of EO to PO ranging from about 0.5% to about 99.5%. In other aspects, the poly(propylene carbonate)-co-poly(ethylene carbonate) compositions have characteristics similar to those described above for the pure polycarbonates. Other Aliphatic Polycarbonates (APCs)

In other embodiments, the extrusion-coated APC includes an APC other than PPC or PEC. In some embodiments, the APC is of a composition as described below.

In certain embodiments, the laminate includes a terpolymer of poly(propylene carbonate) and poly(ethylene carbonate), or poly(propylene carbonate)-co- poly(ethylene carbonate) terpolymer, where the polymer include both ethylene carbonate and propylene carbonate repeat units throughout the chain.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 1 :

where:

R^a is hydrogen, halogen, -L-0R², or an optionally substituted moiety selected from the group consisting of Ci_₃o aliphatic; 3- to 14-membered carbocycle; 6- to 14- membered aryl; 5- to 14-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 3- to 12- membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; or R^a is a Ci_g saturated or unsaturated, straight or branched, hydrocarbon chain, where one or more methylene units are optionally and independently replaced by -NR-, - N(R)C(0)-, -C(0)N(R)-, -N(R)S0₂-, -S0₂N(R)-, -0-, -C(O)-, -OC(O)-, -

OC(0)0-, -C(0)0-, -OC(0)N(R)-, -S-, -SO-, -S0₂-, -C(=S)-, or -C(=NR)- and where one or more hydrogen atoms is optionally replaced with -OR^z;

L is a Ci_8 saturated or unsaturated, straight or branched, hydrocarbon chain, each R is independently hydrogen, optionally substituted Ci_₆ aliphatic, or: two R on the same nitrogen atom are taken together with the nitrogen atom to form a 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from nitrogen, oxygen, or sulfur;

R^z is selected from the group consisting of hydrogen, a silyl group, a hydroxyl protecting group, or an optionally substituted group selected from the group consisting of Ci_₂o acyl; Ci_₂o aliphatic; 3- to 14-membered carbocycle; 6- to

14-membered aryl; 5- to 14-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 3- to 12- membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; each of R^b, R^c, and R^d is independently hydrogen, halogen, or an optionally

substituted group selected from the group consisting of Ci_i₂ aliphatic; Ci_i₂ heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 3- to 14-membered carbocycle; 6- to 14-membered aryl; 5- to 14-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 3- to 12- membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; where any of (R^a and R^c), (R^c and R^d), and (R^a and R^b) can be taken together with intervening atoms to form one or more optionally substituted rings selected from the group consisting of: 3- to 14-membered carbocycle; and 3- to 12-membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;

E is any group that can ring-open an epoxide;

G is selected from the group consisting of hydrogen, a Ci_₂o acyl group, a silyl group, an optionally substituted Ci_₂o aliphatic group, an optionally substituted 6- to 14- membered aryl group, a carbamoyl group, and a hydroxyl protecting group; j is an integer from about 50 to about 15,000; k is an integer from about 0 to about 2,500; and m is the sum of j and k, where m is an integer from about 50 to about 17,500.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula la:

la where E, G, R^a, R^b, R^c, and R^d are as defined above, and m is an integer between about 20 and about 2,000.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 2:

where E, G, R^a,y, k, and m are as defined above.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 2 where R^a is selected from the group consisting of -H, methyl, ethyl, propyl, butyl, higher saturated aliphatic, chloromethyl, trifluoromethyl, pentafluoroethyl, higher fluoroalkyl, vinyl, allyl, phenyl, benzyl, higher unsaturated aliphatic, and CH₂OR^z, where R^z is as defined above. In certain embodiments, the polycarbonate is part of a random-, tapered-, or block-copolymer including monomer units incorporating any two or more of these R^a groups.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 2 where R^a is selected from the group consisting of -H, methyl, ethyl, propyl, butyl, C₅_3o alkyl, chloromethyl, trifluoromethyl, pentafluoroethyl, vinyl, allyl, phenyl, benzyl, CH₂OAc, CH₂OC(0)CF₃, CH₂OC(0)Et, CH₂OBz, CH₂OMe, CH₂OEt, CH₂OPr, CH₂OBu, CH₂OPh, CH₂OBn, CH₂0 Allyl, and CH₂OCF₃. In certain embodiments, the polycarbonate is part of a random-, tapered-, or block-copolymer including monomer units incorporating any two or more of these R^a groups.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 3:

where E, G,j, k, and m are as defined above.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 3a:

3a where E and G are as defined above and m is an integer between about 20 and about

2,000.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 4:

where E, G,j, k, and m are as defined above.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 5:

where E, G, R^a,y, k, and m are as defined above, each R is independently an optionally substituted C_1-10 aliphatic group, and x is an integer between 0 and 5 inclusive.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 6:

where E, G,j, k, and m are as defined above.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 7:

where E, G,j, k, and m are as defined above.

In some embodiments, R^a is -L-0R². In some embodiments, L is a bivalent Ci_8 saturated or unsaturated, straight or branched, hydrocarbon chain. In some embodiments, one or more methylene units of L are optionally and independently replaced by -NR-, - N(R)C(0)-, -C(0)N(R)-, -N(R)S0₂-, -S0₂N(R)-, -0-, -C(O)-, -OC(O)-, -C(0)0-, -S-, - SO-, -S0₂-, -C(=S)-, or -C(=NR)-. In some embodiments, L is a bivalent Ci_g saturated hydrocarbon chain, where one or two methylene units of L are optionally and

independently replaced by -0-. In certain embodiments, L is -CH₂-.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 8:

where R^z, E, G,j, k, and m are as defined above.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 9:

where E, G,j, k, and m are as defined above.

In certain embodiments, the laminate includes a polycarbonate having the structure of formula 10 or formula 11:

where E, G,j, k, and m are as defined above, each x is independently an integer between 0 and 4 inclusive, and each x' is independently an integer between 0 and 8 inclusive.

In certain embodiments, the polycarbonate may be characterized by the percentage of carbonate and ether linkages in the polymer chains. This characteristic may also be expressed as the ratio of j:k as shown in formulae 1 through 11. In certain embodiments, the laminate includes a polycarbonate having the structure of any of formulae 1 through 11, where the value of j is greater than the value of k. In certain embodiments, the value of j is at least about 10 times greater than the value of k. In other embodiments, the value of j is at least about 20 times greater than the value of k. In certain embodiments, the value of j is at least about 50 times greater than the value of k. In other embodiments, the value of j is at least about 100 times greater than the value of k. In certain embodiments, the value of k is 0. In some embodiments, the polycarbonate composition is essentially free of k repeating units (ether linkages). In certain embodiments, the laminate includes a polycarbonate having the structure of any of formulae 1 through 11, where the number average molecular weight (M_N) of the APC is in the range from about 1 x 10⁴ g/mol to about 2 x 10⁶ g/mol. In certain embodiments, M_N ranges from about 20,000 g/mol to about 400,000 g/mol. In certain embodiments, M_N ranges from about 80,000 g/mol to about 300,000 g/mol. In certain embodiments, M_N ranges from about 100,000 g/mol to about 300,000 g/mol. In certain embodiments, M_N ranges from about 150,000 g/mol to about 250,000 g/mol.

In certain embodiments, the APC is characterized in that it has a high head-to-tail ratio. In some embodiments, the APC is characterized in that it has a high percentage of carbonate linkages. In some embodiments, the APC is characterized in that it has a narrow polydispersity index. In certain embodiments, the APC is characterized in that it contains very low levels of cyclic carbonate.

In those embodiments where the aliphatic polycarbonate is characterized by a narrow polydispersity index (PDI), the APC has a PDI less than about 2. In certain embodiments, the APC has a PDI less than about 1.8. In some embodiments, the APC has a PDI less than about 1.5. In some embodiments, the APC has a PDI less than about 1.4, less than about 1.2 or less than about 1.1. In certain embodiments, the APC has a PDI between about 1.0 and about 1.2.

In those embodiments where the aliphatic polycarbonate is characterized by a low cyclic carbonate content, the APC has a cyclic carbonate content less than about 5%. In some embodiments, the APC has a cyclic carbonate content less than about 3%. In some embodiments, the APC has a cyclic carbonate content less than about 1%. In certain embodiments, the APC contains essentially no cyclic carbonate.

In those embodiments where the APC is characterized by a high head-to-tail ratio, polymers have on average greater than about 80% of adjacent monomer units oriented head-to-tail. In certain embodiments, on average in provided laminates including APC, greater than about 85% of adjacent monomer units in the APC are oriented head-to-tail. In some embodiments, on average in provided laminates including APC, greater than about 90% of adjacent monomer units in the APC are oriented head-to-tail. In some

embodiments, on average in provided laminates including APC, greater than about 95% of adjacent monomer units in the APC are oriented head-to-tail. In some embodiments, on average in provided laminates including APC, essentially all adjacent monomer units in the APC are oriented head-to-tail.

In certain embodiments, the laminate includes a random, block, or tapered copolymer of two or more of 1 through 11. In some embodiments of the present invention, PPC (No vomer, Inc., Waltham,

MA, US) was extrusion-coated onto a paperboard substrate. The PPC had a weight- average molecular weight (M_w) of 184,970 and a number-average molecular weight (M_N) of 159,294, as determined by gel permeation chromatography (GPC) calibrated to polystyrene standards, for a calculated polydispersity index of about 1.16. The PPC had a mid-point glass transition temperature (T_g) of 41.7 °C as determined by differential scanning calorimetry (DSC).

In these embodiments, the substrate was paperboard of 345 g/m² with a thickness of 20 point (0.51 mm) and 7 inches wide on a 3-inch internal diameter core (RockTenn Company, Norcross, GA). In these embodiments, PPC was dried at 35 °C (95 °F) for 48 hours prior to the extrusion. The PPC was fed via a feed hopper to a single-screw Haake extruder with a 6" die (Thermo Fisher Scientific, Inc., Waltham, MA, US). The PPC film was then extrusion- coated onto the paperboard substrate and collected on a 2-roll system like the system shown in Fig. 1, with the PPC film being pressed onto the substrate in the nip of the rolls. The extruder barrel temperatures were maintained between 160 °C and 180 °C during the experiment. The roll temperature was varied during the experiments within the range of 10 °C to 45 °C. Either a steel or rubber roll was used as the lower roll in different

experiments during different extrusion coatings to vary the pressure in the nip between the rolls. The paperboard with the coated PPC film on it was taken up on the take-up roll at a speed in the range of 1 foot per minute to 10 feet per minute with the speed of the take-up roll determining the thickness of the film coated onto the paperboard. Varying the take-up speed varied the resulting thickness of the PPC film in the range of 0.8 mil (0.02 mm) to 8 mil (0.2 mm). The deposited PPC layer was determined to be amorphous.

The take-up roll speed is preferably equal to or faster than the extrusion film speed, with the take-up speed preferably being adjusted only to thin the gauge of the film down. The thickness of the die lip gap sets the approximate maximum width for the laminate, not accounting for a phenomenon of die-swell, whereby the polymer film coming out of the constricted die may actually swell a little bit.

In these embodiments, no tie-layer was used between the paperboard and the PPC in the above-described embodiments. In some embodiments, the extrusion coating was applied to the paperboard as received, and the PPC film was extrusion-coated directly onto the paperboard. In other embodiments, the surface of the paperboard substrate was treated by a corona discharge treatment before coating the PPC onto the paperboard substrate, and the PPC film was extrusion-coated directly onto the corona discharge treated paperboard substrate. Adhesion was observed usually to be better on the corona discharge-treated paperboard. In fact, even with film-on- film multiple layer laminates, surface treatment of the substrate film using corona or plasma treatment is common and may be used to help layer adhesion. Flame treatment of paperboard is also known to the art of extrusion coating paperboard substrates. Both flame treatment and corona treatment are known to promote adhesion to the paperboard.

Although in the above embodiments, only a single layer of PPC was extrusion coated onto paperboard, in other embodiments multiple layers of polymer, including at least one APC, are co-extruded to make multi-layer paperboard-based laminates. In some embodiments, the additional layers may be formed from any material, including, but not limited to, PPC, PEC, another APC, EVOH, LDPE, LLDPE, HDPE, polypropylene, polyesters, or foil. In some embodiments, these additional layers provide one or more additional functionalities, including, but not limited to, an oxygen barrier and a water vapor barrier, or other beneficial properties necessary for the use of the product as a useful packaging material.

In some embodiments, adhesive tie-layers are used between the different layers to enhance adhesion between the layers. Adhesive tie-layers may be of any material, including, but not limited to, ethylene acrylic acid polymers, other functionalized polyethylenes, ethylene methyl acrylate copolymers, ethylene/vinyl acetate copolymers, and ethylene grafted with an anhydride or other functionality, including, but not limited to, Bynel® and Elvaloy® grades (E. I. du Pont de Nemours and Company, Wilmington, DE, US), Admer® grades (Mitsui Chemicals, Inc., Tokyo, JP), Plexar® grades

(LyondellBasell Industries, Rotterdam, NL), or Amplify™ resins (Dow Chemical

Company, Midland, MI, US). In some embodiments, an adhesive tie-layer is located between the paperboard and the APC layer to enhance adhesion.

In some embodiments, the APC is combined with one or more additives normally added to elastomers and thermoplastics (see, for example Encyclopedia of Polymer Science and Engineering, 2nd Ed., vol. 14, p. 327-410), including, but not limited to, a filler, a nano-filler, a clay, a processing aid, an anti-oxidant, a plasticizer, a nanomaterial, a nanoparticle and a chain extender. Fillers may be reinforcing, non-reinforcing, or conductive, including, but not limited to, carbon black, glass fiber, organic materials such as starch and wood flour, minerals such as clay, mica, and talc, glass spheres, barium sulfate, zinc oxide, carbon fiber, and aramid fiber or fibrids. Antioxidants, antiozonants, pigments, dyes, delusterants, or compounds to promote crosslinking may also be added. Plasticizers such as various hydrocarbon oils may also be used. In some embodiments, the laminate may contain nanoparticles or nanomaterials. Nanomaterials such as carbon nano- tubes, Fullerenes, graphene, buckyballs, quantum dots, colloidal metals such as colloidal silver, gold, platinum, or iron, other metal nanoparticles, or other non-carbon nanoparticles may also be incorporated into the laminate. A chain extender may be used to build up melt strength stability, to build molecular weight, or to improve one or more mechanical properties of the polymer. In some embodiments, the APC is combined with one or more other polymers to form a blend before being extrusion-coated as a film as part of the laminate with paper or paperboard as the substrate. In these embodiments, the other polymers may include, but are not limited to, polyolefins, polyesters, thermoplastic starches, aromatic polycarbonates, other aliphatic polycarbonates, polyamides, fluorinated polymers, other halogenated polymers, (meth)acrylic polymers, olefin copolymers, aromatic polyesters, liquid crystalline polymers, and polyethers. In these embodiments, polyolefins may include, but are not limited to, polyethylene, polypropylene, polyvinyl alcohol, polystyrene, and copolymers thereof. In these embodiments, polyesters may include, but are not limited to, poly(lactic acid) (PLA), poly(caprolactone) (PCL), poly(3-hydroxybutyrate) (P3HB), poly(4-hydroxybutyrate) (P4HB), poly(hydroxy valerate) (PHV), poly(3 -hydroxy propionate) (P3HP), polyhydroxyoctanoate (PHO), poly(ethylene terephthalate), poly(butylene terephthalate), aliphatic polyesters, including, but not limited to,

polybutylene succinate and poly(ethylene adipate), and aromatic-aliphatic copolyesters, including, but not limited to, copolymers based on butanediol, adipic acid, or terephthalic acid, such as Ecoflex® biodegradable plastic (BASF Corporation, Florham Park, NJ). In these embodiments, other aliphatic polycarbonates may include, but are not limited to, poly(ethylene carbonate), poly(butylene carbonate), poly(cyclohexane carbonate), poly(limonene carbonate) and terpolymers of C0₂ and any two or more epoxides. In these embodiments, polyamides may include, but are not limited to, nylon-6, nylon-6,6, nylon- 12, nylon- 12, 12, nylon- 11, and a copolymer of hexamethylene diamine, adipic acid, and terephthalic acid. In these embodiments, fluorinated polymers may include, but are not limited to, copolymers of ethylene and vinylidene fluoride, copolymers of

tetrafluoroethylene and hexafluoropropylene, and copolymers of tetrafluoroethylene and a perfluoro(alkyl vinyl ether) such as perfluoro(propyl vinyl ether), and poly(vinyl fluoride). In these embodiments, other halogenated polymers may include, but are not limited to, poly( vinyl chloride) and poly(vinylidene chloride) and its copolymers. In these

embodiments, (meth)acrylic polymers may include, but are not limited to, poly(methyl methacrylate) and copolymers thereof. In these embodiments, olefin copolymers may include, but are not limited to, ethylene with various (meth) acrylic monomers such as alkyl acrylates, (meth)acrylic acid and ionomers thereof, and glycidyl (meth)acrylate. In these embodiments, aromatic polyesters may include, but are not limited to, the copolymer of Bisphenol A and terephthalic and/or isophthalic acid. In these embodiments, liquid crystalline polymers may include, but are not limited to, aromatic polyesters or aromatic poly(ester-amides). In these embodiments, polyethers may include, but are not limited to, polyethylene glycol, polypropylene glycol, polyether ether ketone, poly(tetramethylene ether) glycol, polyphenyl ether, and polyoxymethylene.

In some embodiments, a compatibilizer is combined with the APC and other polymer to enable enhanced dispersion of the two or more polymers.

Suitable thermosets for blending with the APCs described herein include, but are not limited to, epoxy resins, phenol-formaldehyde resins, melamine resins, and unsaturated polyester resins (sometimes called thermoset polyesters). In some

embodiments, blending with thermoset polymers will be done using standard techniques before the thermoset is crosslinked.

In some embodiments, the APCs described herein are blended with uncrosslinked polymers which are not usually considered thermoplastics for various reasons, such as excessive viscosity and/or a melting point so high the polymer decomposes below the melting temperature. Such polymers include, but are not limited to,

poly(tetrafluoroethylene) (PTFE), aramids, such as poly(p-phenylene terephthalate) and poly(m-phenylene isophthalate), liquid crystalline polymers, such as poly(benzoxazoles), and non-melt processible polyimides, such as aromatic polyimides. All references mentioned herein are hereby incorporated by reference herein.

It is to be understood that the embodiments of the invention herein described are merely illustrative of the application of the principles of the invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features regarded as essential to the invention.

Claims

What is claimed is:

1. A laminate comprising: a substrate; and at least one laminate layer applied to at least one side of the substrate comprising at least one extrusion-coated layer comprising at least one aliphatic polycarbonate; wherein the aliphatic polycarbonate is not poly(propylene carbonate).

2. The laminate of claim 1, wherein the aliphatic polycarbonate comprises a copolymer of carbon dioxide and one or more epoxides.

3. The laminate of claim 1 or 2, wherein the aliphatic polycarbonate is selected from the group consisting of poly(ethylene carbonate), poly(propylene carbonate)-co- poly(ethylene carbonate), poly(cyclohexene carbonate), poly (propylene carbonate)-co-poly(cyclohexene carbonate), poly(ethylene carbonate)-co- poly(cyclohexene carbonate), a poly(propylene carbonate) co-polymer with one or more additional aliphatic polycarbonates, a poly(ethylene carbonate) co-polymer with one or more additional aliphatic polycarbonates, a physical blend of any two or more of the above, and a copolymer comprising any of the above.

4. The laminate of any of claims 1-3, wherein the aliphatic polycarbonate comprises

poly(ethylene carbonate).

5. The laminate of any of claims 1-4, wherein the extrusion-coated layer consists

essentially of the aliphatic polycarbonate.

6. The laminate of any of claims 1-4, wherein the extrusion-coated layer further comprises at least one additional component.

7. The laminate of claim 6, wherein the at least one additional component comprises at least one polymer blended and co-extruded with the aliphatic polycarbonate.

8. The laminate of claim 7, wherein the polymer is selected from the group consisting of:

LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), poly(caprolactone) (PCL), thermoplastic starches, poly(3-hydroxylbutyrate), poly(3-hydroxyvalerate), poly(3-hydroxylbutyrate-co-3-hydroxyvalerate), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), polyether ether ketone (PEEK), biodegradable polyesters, poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co-butylene succinate), aliphatic polyesters, aromatic polyesters, aromatic-aliphatic polyesters, poly(vinyl alcohol), poly( vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol) dimethacrylates, polyesteramide, polyolefms, aromatic polycarbonates, aliphatic polycarbonates, polyamides, fluorinated polymers, halogenated polymers, acrylic polymers, methacrylic polymers, olefin copolymers, liquid crystalline polymers, polyethers, and any combination of the above.

9. The laminate of claim 7, wherein the polymer is selected from the group consisting of:

LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), poly(caprolactone) (PCL), thermoplastic starches, poly(3-hydroxylbutyrate), poly(3-hydroxyvalerate), poly(3-hydroxylbutyrate-co-3-hydroxyvalerate), biodegradable polyesters, poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co-butylene succinate), aliphatic polyesters, aromatic polyesters, aromatic-aliphatic polyesters, poly(vinyl alcohol), poly(vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol) dimethacrylates, polyesteramide, polyolefms, aromatic polycarbonates, aliphatic polycarbonates, fluorinated polymers, halogenated polymers, acrylic polymers, liquid crystalline polymers, and any combination of the above.

10. The laminate of any of claims 7-9, wherein the extrusion-coated layer further

comprises at least one compatibilizer.

11. The laminate any of claims 1-10 further comprising at least one additive.

12. The laminate of any of claims 1-11, wherein the substrate comprises a material

selected from the group consisting of paper and paperboard.

13. The laminate of any of claims 1-12, wherein the substrate comprises paperboard.

14. The laminate of any of claims 1-13, wherein no tie layer contacts the extrusion-coated layer in the laminate.

15. The laminate of any of claims 1-14, wherein the extrusion-coated layer is non- crystalline.

16. The laminate of any of claims 1-15, wherein the laminate is used as a packaging

material.

17. The laminate of any of claims 1-16, wherein the at least one laminate layer further comprises at least one additional laminate layer comprising a polymer selected from the group consisting of: LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), thermoplastic starches, poly(3- hydroxylbutyrate), poly(3 -hydroxyvalerate), poly(3 -hydroxylbutyrate-co-3 - hydroxyvalerate), poly(ethylene terephthalate) (PET), biodegradable polyesters, poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co- butylene succinate), aliphatic polyesters, aromatic polyesters, aromatic-aliphatic polyesters, poly(vinyl alcohol), poly( vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol) dimethacrylates,

polyesteramide, polyolefms, aromatic polycarbonates, polyamides, fluorinated polymers, halogenated polymers, acrylic polymers, methacrylic polymers, olefin copolymers, liquid crystalline polymers, polyethers, and any combination of the above.

18. The laminate of any of claims 1-17, wherein the extrusion-coated layer has a thickness in the range of about 0.2 mil (0.005 mm) to about 10 mil (0.25 mm).

19. The laminate of any of claims 1-18, wherein the extrusion-coated layer has a thickness in the range of about 0.5 mil (0.013 mm) to about 5 mil (0.13 mm).

20. The laminate of any of claims 1-19, wherein the extrusion-coated layer has a thickness in the range of about 0.5 mil (0.013 mm) to about 2 mil (0.05 mm).

21. The laminate of any of claims 1-20, wherein the aliphatic polycarbonate has a polydispersity index of less than about 1.5.

22. The laminate of any of claims 1-20, wherein the aliphatic polycarbonate has a

polydispersity index of less than about 1.2.

23. The laminate of any of claims 1-22, wherein the aliphatic polycarbonate has a head to tail ratio of at least about 17:3.

24. The laminate of any of claims 1-23, wherein the aliphatic polycarbonate has a

carbonate linkage content of at least about 95%.

25. The laminate of any of claims 1-24, wherein the aliphatic polycarbonate has a cyclic carbon content of less than about 5%.

26. A method of producing a laminate comprising the steps of: extruding an extruded layer comprising at least one aliphatic polycarbonate; and depositing the extruded layer as an extrusion-coated layer on a side of a substrate to form the laminate; wherein the aliphatic polycarbonate is not poly(propylene carbonate).

27. The method of claim 26, wherein the aliphatic polycarbonate comprises a copolymer of carbon dioxide and one or more epoxides.

28. The method of claim 26 or 27, wherein the aliphatic polycarbonate is selected from the group consisting of poly(ethylene carbonate), poly(propylene carbonate)-co- poly(ethylene carbonate), poly(cyclohexene carbonate), poly(propylene carbonate)-co-poly(cyclohexene carbonate), poly (ethylene carbonate)-co- poly(cyclohexene carbonate), a poly(propylene carbonate) co-polymer with one or more additional aliphatic polycarbonates, a poly(ethylene carbonate) co-polymer with one or more additional aliphatic polycarbonates, a physical blend of any two or more of the above, and a copolymer comprising any of the above.

29. The method of any of claims 26-28, wherein the aliphatic polycarbonate comprises poly(ethylene carbonate).

30. The method of any of claims 26-29, wherein the extrusion-coated layer consists

essentially of the aliphatic polycarbonate.

31. The method of any of claims 26-29, wherein the extrusion-coated layer further

comprises at least one additional component.

32. The method of claim 31, wherein the at least one additional component comprises at least one polymer blended and co-extruded with the aliphatic polycarbonate.

33. The method of claim 32, wherein the polymer is selected from the group consisting of:

LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), thermoplastic starches, poly(3-hydroxylbutyrate), poly(3-hydroxyvalerate), poly(3 -hydroxylbutyrate-co-3 -hydroxyvalerate), poly(ethylene terephthalate) (PET), biodegradable polyesters, poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co-butylene succinate), aliphatic polyesters, aromatic polyesters, aromatic-aliphatic polyesters, poly(vinyl alcohol), poly( vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol) dimethacrylates, polyesteramide, polyolefms, aromatic polycarbonates, aliphatic polycarbonates, polyamides, fluorinated polymers, halogenated polymers, acrylic polymers, methacrylic polymers, olefin copolymers, liquid crystalline polymers, poly ethers, and any combination of the above.

34. The method of claim 32, wherein the polymer is selected from the group consisting of:

35. The method of any of claims 32-34, wherein the extrusion-coated layer further

comprises at least one compatibilizer.

36. The method of any of claims 26-35 further comprising at least one additive.

37. The method of any of claims 26-36, wherein the substrate comprises paperboard.

38. The method of any of claims 26-37, wherein the laminate includes no tie layer

contacting the extrusion-coated layer in the laminate.

39. The method of any of claims 26-38, wherein the aliphatic polycarbonate in the

extrusion-coated layer is amorphous.

40. The method of any of claims 26-39 further comprising the sub-step of depositing at least one other layer comprising a polymer selected from the group consisting of: LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), thermoplastic starches, poly(3-hydroxylbutyrate), poly(3-hydroxyvalerate), poly(3 -hydroxylbutyrate-co-3 -hydroxyvalerate), poly(ethylene terephthalate) (PET), biodegradable polyesters, poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co-butylene succinate), aliphatic polyesters, aromatic polyesters, aromatic-aliphatic polyesters, poly(vinyl alcohol), poly(vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol) dimethacrylates, polyesteramide, polyolefms, aromatic polycarbonates, polyamides, fluorinated polymers, halogenated polymers, acrylic polymers, methacrylic polymers, olefin copolymers, liquid crystalline polymers, polyethers, and any combination of the above.

41. The method of any of claims 26-40, wherein the extrusion-coated layer is deposited with a take-up roller speed of at least about 1 foot per minute.

42. The method of any of claims 26-40, wherein the extrusion-coated layer is deposited with a take-up roller speed of less than about 10 feet per minute.

43. The method of any of claims 26-42, wherein the extrusion-coated layer is deposited with a thickness in the range of about 0.2 mil (0.005 mm) to about 10 mil (0.25 mm).

44. The method of any of claims 26-42, wherein the extrusion-coated layer is deposited with a thickness in the range of about 0.5 mil (0.013 mm) to about 5 mil (0.13 mm).

45. The method of any of claims 26-42, wherein the extrusion-coated layer is deposited with a thickness in the range of about 0.5 mil (0.013 mm) to about 2 mil (0.05 mm).

46. The method of any of claims 26-45 further comprising the step of corona discharge- treating the substrate prior to the step of depositing the extruded layer on the substrate.

47. The method of any of claims 26-45 further comprising the step of plasma-treating the substrate prior to the step of depositing the extruded layer on the substrate.

48. The method of any of claims 26-45 further comprising the step of flame-treating the substrate prior to the step of depositing the extruded layer on the substrate.

49. A laminate comprising: a substrate; and at least one laminate layer applied to at least one side of the substrate comprising at least one extrusion-coated layer comprising poly(propylene carbonate); wherein the poly(propylene carbonate) has at least one characteristic selected from the group consisting of: a polydispersity index of less than about 1.2; a head to tail ratio of at least about 17:3; a carbonate linkage content of at least about 95%; and a cyclic carbon content of less than about 5%.

50. The laminate of claim 49, wherein the extrusion-coated layer consists essentially of poly(propylene carbonate).

51. The laminate of claim 49, wherein the extrusion-coated layer further comprises at least one additional component.

52. The laminate of claim 51, wherein the at least one additional component comprises at least one polymer blended and co-extruded with the poly(propylene carbonate).

53. The laminate of claim 52, wherein the polymer is selected from the group consisting of: LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), poly(caprolactone) (PCL), thermoplastic starches, poly(3- hydroxylbutyrate), poly(3 -hydroxyvalerate), poly(3 -hydroxylbutyrate-co-3 - hydroxyvalerate), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), polyether ether ketone (PEEK), biodegradable polyesters, poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co-butylene succinate), aliphatic polyesters, aromatic polyesters, aromatic-aliphatic polyesters, poly( vinyl alcohol), poly( vinyl acetate), ethylene vinyl alcohol polymer (EVOH),

poly(caprolactone), poly(ethylene glycol) dimethacrylates, polyesteramide, polyolefms, aromatic polycarbonates, aliphatic polycarbonates, polyamides, fluorinated polymers, halogenated polymers, acrylic polymers, methacrylic polymers, olefin copolymers, liquid crystalline polymers, polyethers, and any combination of the above.

54. The laminate of claim 52, wherein the polymer is selected from the group consisting of: LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), poly(caprolactone) (PCL), thermoplastic starches, poly(3- hydroxylbutyrate), poly(3 -hydroxyvalerate), poly(3 -hydroxylbutyrate-co-3 - hydroxyvalerate), biodegradable polyesters, poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co-butylene succinate), aliphatic polyesters, aromatic polyesters, aromatic-aliphatic polyesters, poly( vinyl alcohol), poly(vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone),

poly(ethylene glycol) dimethacrylates, polyesteramide, polyolefms, aromatic polycarbonates, aliphatic polycarbonates, fluorinated polymers, halogenated polymers, acrylic polymers, liquid crystalline polymers, and any combination of the above.

55. The laminate of any of claims 52-54, wherein the extrusion-coated layer further

comprises at least one compatibilizer.

56. The laminate any of claims 49-55 further comprising at least one additive.

57. The laminate of any of claims 49-56, wherein the substrate comprises a material

selected from the group consisting of paper and paperboard.

58. The laminate of any of claims 49-57, wherein the substrate comprises paperboard.

59. The laminate of any of claims 49-58, wherein no tie layer contacts the extrusion- coated layer in the laminate.

60. The laminate of any of claims 49-59, wherein the extrusion-coated layer is noncrystalline.

61. The laminate of any of claims 49-60, wherein the laminate is used as a packaging material.

62. The laminate of any of claims 49-61, wherein the at least one laminate layer further comprises at least one additional laminate layer comprising a polymer selected from the group consisting of: LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), thermoplastic starches, poly(3- hydroxylbutyrate), poly(3 -hydroxyvalerate), poly(3 -hydroxylbutyrate-co-3 - hydroxyvalerate), poly(ethylene terephthalate) (PET), biodegradable polyesters, poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co- butylene succinate), aliphatic polyesters, aromatic polyesters, aromatic-aliphatic polyesters, poly(vinyl alcohol), poly( vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol) dimethacrylates, polyesteramide, polyolefms, aromatic polycarbonates, polyamides, fluorinated polymers, halogenated polymers, acrylic polymers, methacrylic polymers, olefin copolymers, liquid crystalline polymers, polyethers, and any combination of the above.

63. The laminate of any of claims 49-62, wherein the extrusion-coated layer has a

thickness in the range of about 0.2 mil (0.005 mm) to about 10 mil (0.25 mm).

64. The laminate of any of claims 49-62, wherein the extrusion-coated layer has a

thickness in the range of about 0.5 mil (0.013 mm) to about 5 mil (0.13 mm).

65. The laminate of any of claims 49-62, wherein the extrusion-coated layer has a

thickness in the range of about 0.5 mil (0.013 mm) to about 2 mil (0.05 mm).

66. The laminate of any of claims 49-65, wherein the poly(propylene carbonate) has a polydispersity index of less than about 1.1.

67. A method of producing a laminate comprising the steps of: extruding an extruded layer comprising poly(propylene carbonate), wherein the poly(propylene carbonate) has at least one characteristic selected from the group consisting of: a polydispersity index of less than about 1.2; a head to tail ratio of at least about 17:3; a carbonate linkage content of at least about 95%; and a cyclic carbon content of less than about 5%; and depositing the extruded layer as an extrusion-coated layer on a side of a substrate to form the laminate.

68. The method of claim 67, wherein the extrusion-coated layer consists essentially of poly(propylene carbonate).

69. The method of claim 67, wherein the extrusion-coated layer further comprises at least one additional component.

70. The method of claim 69, wherein the at least one additional component comprises at least one polymer blended and co-extruded with the aliphatic polycarbonate.

71. The method of claim 70, wherein the polymer is selected from the group consisting of:

72. The method of claim 70, wherein the polymer is selected from the group consisting of:

73. The method of any of claims 70-72, wherein the extrusion-coated layer further comprises at least one compatibilizer.

74. The method of any of claims 67-73 further comprising at least one additive.

75. The method of any of claims 67-74, wherein the substrate comprises paperboard.

76. The method of any of claims 67-75, wherein the laminate includes no tie layer

contacting the extrusion-coated layer in the laminate.

77. The method of any of claims 67-76, wherein the aliphatic polycarbonate in the

extrusion-coated layer is amorphous.

78. The method of any of claims 67-77 further comprising the sub-step of depositing at least one other layer comprising a polymer selected from the group consisting of:

LDPE, LLDPE, HDPE, polypropylene, polystyrene, polyvinyl chloride, poly(lactic acid), thermoplastic starches, poly(3-hydroxylbutyrate), poly(3-hydroxyvalerate), poly(3 -hydroxylbutyrate-co-3 -hydroxyvalerate), poly(ethylene terephthalate) (PET), biodegradable polyesters, poly(butylene adipate), poly(butylene succinate), poly(butylene adipate-co-butylene succinate), aliphatic polyesters, aromatic polyesters, aromatic-aliphatic polyesters, poly(vinyl alcohol), poly( vinyl acetate), ethylene vinyl alcohol polymer (EVOH), poly(caprolactone), poly(ethylene glycol) dimethacrylates, polyesteramide, polyolefms, aromatic polycarbonates, polyamides, fluorinated polymers, halogenated polymers, acrylic polymers, methacrylic polymers, olefin copolymers, liquid crystalline polymers, polyethers, and any combination of the above.

79. The method of any of claims 67-78, wherein the extrusion-coated layer is deposited with a take-up roller speed of at least about 1 foot per minute.

80. The method of any of claims 67-78, wherein the extrusion-coated layer is deposited with a take-up roller speed of less than about 10 feet per minute.

81. The method of any of claims 67-80, wherein the extrusion-coated layer is deposited with a thickness in the range of about 0.2 mil (0.005 mm) to about 10 mil (0.25 mm).

82. The method of any of claims 67-80, wherein the extrusion-coated layer is deposited with a thickness in the range of about 0.5 mil (0.013 mm) to about 5 mil (0.13 mm).

83. The method of any of claims 67-80, wherein the extrusion-coated layer is deposited with a thickness in the range of about 0.5 mil (0.013 mm) to about 2 mil (0.05 mm).

84. The method of any of claims 67-83 further comprising the step of corona discharge- treating the substrate prior to the step of depositing the extruded layer on the substrate.

85. The method of any of claims 67-83 further comprising the step of plasma-treating the substrate prior to the step of depositing the extruded layer on the substrate.

86. The method of any of claims 67-83 further comprising the step of flame-treating the substrate prior to the step of depositing the extruded layer on the substrate.