# Patent

## Title
Cellular polymeric material

## Abstract

A formulation includes a polymeric material and can be used to form an insulated container.

## Background
PRIORITY CLAIM
This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Ser. No. 61/737,342, filed Dec. 14, 2012, which is expressly incorporated by reference herein.


BACKGROUND
The present disclosure relates to polymeric materials that can be formed to produce a container, in particular polymeric materials that insulate. More particular, the present disclosure relates to morphology and crystalline structure of cellular polymeric material that can be transformed into usable articles, such as insulated containers.
SUMMARY
An insulated container in accordance with the present disclosure is manufactured from a sheet extrudate or tubular extrudate produced in an extrusion process. In illustrative embodiments, the extrudate is a cellular polymeric material and the insulated container is later formed to provide a drink cup, a food-storage, cup, or a container.
In illustrative embodiments, an insulative container in accordance with the present disclosure is manufactured from a tubular extrudate produced in an extrusion process. In illustrative embodiments, the extrudate in an insulative cellular polypropylene-based material configured to provide resistance to creasing and/or wrinkling during cup convolution or shaping.
In illustrative embodiments, an extruded tube of insulative cellular polypropylene-based material has an inside-of-extruded-tube (InET) surface/layer and an outside-of-extruded-tube (OET) surface/layer that can be sliced to provide a strip of insulative cellular polypropylene-based material. An extruded tube of insulative cellular polypropylene-based material in accordance with the present disclosure has a surface morphology that includes a beta-crystalline polypropylene phase identified by X-ray wide angle diffraction analysis, which phase is not observable by differential scanning calorimetry (DSC).
In illustrative embodiments, the surface morphology of an extruded tube of insulative cellular polypropylene-based material in accordance with the present disclosure has a profound effect on the quality of an article, such as an insulative cup, formed therewith. In particular, the specific crystalline structure of the extruded tube surface/layer (InET or OET) facing inside of the insulative cup is directly related to a reduction in, if not an elimination of, visible deep creases and/or wrinkles inside the formed insulative cup.
In illustrative embodiments, a surface quality exists for a sheet of insulative cellular polypropylene-based material in accordance with the present disclosure that leads to a noticeable crease-free surface in an insulative cup prepared at a specified formulation, and under specified processing and forming conditions. In particular, such surface quality is determined by the properties of the crystalline phases of the polypropylene-based material. More particularly, such surface quality is determined by the relative size and the relative amounts of both the alpha- and beta-crystalline phases present in the polypropylene-based material.
In illustrative embodiments, a cup-forming process in accordance with the present disclosure provides an insulative cup. The cup-forming process also minimizes wrinkling and/or creasing includes the step of arranging in a cross-web direction (CD) the shape to be cut from an extruded tube of insulative cellular polypropylene-based mate with the OET surface/layer facing the inside of the cup.
In illustrative embodiments, creasing and/or wrinkling of insulative cellular polypropylene-based material having a fixed chemical composition, and made under controlled extrusion process conditions with controlled processing parameters, can essentially be eliminated if die cut parts are oriented in a CD direction. As a result, a cell aspect ratio close to 1 and a coefficient of anisotropy close to 1 is provided. In illustrative embodiments, performance of an extruded sheet of insulative cellular polypropylene-based material in accordance with the present disclosure can be a function of alpha and beta crystal domain size and relative content of beta phase as determined by K-value.
Additional features of the present disclosure will become apparent to those skilled in the art upon consideration of illustrative embodiments exemplifying the best mode of carrying out the disclosure as presently perceived.



BRIEF DESCRIPTION OF THE DRAWINGS
The detailed description particularly refers to the accompanying figures in which:
FIG. 1 illustrates sampling for microscopy and X-Ray analysis for which samples were cut from the side of an insulative cup side wall and analyzed in two perpendicular directions: View A from top to bottom of the cup and view B looking sideways;
FIG. 2 shows a View A microscopy image of the insulative cup side wall from the cup of Example 5 (with printed film laminated to the foam), where OET is outside of the insulative cup, illustrating that the insulative cup side wall collapsed in compression during cup formation leading to crease formation with crease depth of 0.23 mm;
FIG. 3 shows a View A microscopy image of the insulative cup side wall from the insulative cup of Example 1 (without laminated printed film and with black marker used to eliminate light reflection for clearer image), where OET is outside of the insulative cup, again illustrating that creasing/deep wrinkles formed on the inside of the insulative cup in the same way as in FIG. 2/Example 5;
FIG. 4 shows a differential scanning calorimetry (DSC) graph in which a beta-crystalline phase (i.e., beta-crystallinity) is not detected during a 2nd heat scan for an insulative cellular polypropylene-based material of the present disclosure;
FIG. 5A shows the wide angle X-ray diffraction (WAXD) pattern for an OET surface sample from the sheet of insulative cellular polypropylene-based material used in Examples 1-5 having a crystalline size of 99 Å and percent crystallinity of 57.8%;
FIG. 5B shows a comparison of the WAXD patterns for the InET and OET surfaces of the sheet of insulative cellular polypropylene-based material used in Examples 1-5 illustrating the OET with a smaller crystal domain size than the InET and with beta-crystalline phase present; and
FIG. 6 shows the phase identification for three samples: Top trace—WAXD pattern for Extra talc Sample #1, InET surface showing presence of beta-crystalline phase peak at 16.1°; Middle trace—WAXD pattern for Extra talc Sample #2, InET surface showing presence of beta-crystalline phase peak at 16.1°; Bottom trace—WAXD pattern for Sample B=conventional cellular polypropylene material with no beta-crystalline phase peak present at 16.1°.



DETAILED DESCRIPTION
An insulated container in accordance with the present disclosure is manufactured from a sheet of insulative cellular non-aromatic polymeric material produced in an extrusion process. The sheet of insulative cellular non-aromatic polymeric material is then formed to provide an insulative cup or container which may be used as a drink cup or a food-storage cup as suggested in FIG. 1. The insulative cellular non-aromatic polymeric material of the present disclosure is an insulative cellular polypropylene-based material that is configured to provide resistance to creasing and/or wrinkling during cup convolution, shaping, or forming. FIGS. 2-6 are a series of views showing support for various theories explaining how material of the present disclosure is able to resist creasing and/or wrinkling during cup convoluting, shaping, and forming.
In exemplary embodiments, a tube of extruded insulative cellular polypropylene-based material in accordance with the present disclosure has two surfaces that are formed under different cooling conditions when the material is extruded. One surface, referred to herein as the outside-of-extruded-tube (OET) surface, is in contact with air, and does not have physical barriers restricting expansion. The OET surface is cooled by blowing compressed air at cooling rate equal or higher than 12° F. per second. The surface on the opposite side of an extruded tube of insulative cellular polypropylene-based material is referred to herein as the inside-of-extruded-tube (InET) surface. The InET surface is formed when the extruded tube is drawn in the web or machine direction on a metal cooling surface of a torpedo mandrel that is physically restricting the inside of the extruded tube and is cooled by combination of water and compressed air at a cooling rate below 10° F. per second. In exemplary embodiments, the cooling water temperature is about 135° F. (57.22° C.). In other exemplary embodiments, the cooling air temperature is about 85° F. (29.44° C.). As a result of different cooling mechanisms and/or rates, the OET and InET surfaces have different surface characteristics. Cooling rate and method affects the crystallization process of polypropylene thereby altering its morphology (size of crystal domains) and topography (surface profile).
An unexpected feature of exemplary embodiments of an extruded sheet of insulative cellular polypropylene-based material as described herein is the ability of the sheet to form a noticeably crease-free and wrinkle-free surface when curved to form a round article, such as an insulative cup. The surface is wrinkle-free even inside the cup, where compression forces typically cause material to crush and/or crease easily, especially for low density material with large cell size. In exemplary embodiments, the surface profile of an extruded sheet of insulative cellular polypropylene-based material as detected by microscopy is such that the depth of the indentations (i.e., creases and/or wrinkles) naturally occurring in the outside and inside of the cup surface when it is subject to extension and compression forces during cup forming may be less than about 100 microns. In one exemplary embodiment, the surface profile may be less than about 50 microns. In one exemplary embodiment, the surface profile may be about 5 microns or less. At a depth of about 10 microns and less, the micro-wrinkles on a cup surface are ordinarily not visible to the naked eye.
In one exemplary embodiment, an insulative cup formed from a sheet comprising a skin and a strip of insulative cellular polypropylene-based material had typical creases (i.e., deep wrinkles) about 200 microns deep extending from a top of the cup to a bottom of the cup. In one exemplary embodiment, an insulative cup formed from a sheet comprising a strip of insulative cellular polypropylene-based material only (without a skin) had typical creases about 200 microns deep extending from a top of the cup to a bottom of the cup. Such creases with depths from about 100 microns to about 500 microns are typically formed when InET is facing inside of the cup in a compression mode. Creases and deep wrinkles may present a problem of unsatisfactory surface quality making final cups unusable or undesirable. Creases may form in instances where sheets include a skin or exclude a skin.
In exemplary embodiments, the insulative cellular polypropylene-based material may be extruded as strip. However microscopy images show that two distinct layers exist within the extruded strip, namely, a dull OET layer and shiny InET layer. The difference between the two layers is in reflectance of the surface due to the difference in crystal domain size. If a black marker is used to color the surface examined by microscopy, reflectance is eliminated and the difference between the two surfaces may be minimal or undetectable. In one exemplary embodiment, a sample strip of insulative cellular polypropylene-based material was prepared without any skin Black marker was used to eliminate any difference in reflectance between the layers. Images showed that the cell size and cell distribution was the same throughout the strip thickness.
Differential scanning calorimetry (DSC) analysis conducted on a TA Instruments DSC 2910 in nitrogen atmosphere showed that with an increase in cooling rate, the crystallization temperature and crystallinity degree decreased for the insulative cellular polypropylene-based polymer matrix of the strip, as shown below in Table 1.







TABLE 1







Crystallization of polymer matrix








Crystallization temp, in ° C.
Crystallinity degree, in %












Slower

Faster
Slower

Faster


cooling
10° C./
cooling
cooling
10° C./
cooling


5° C./min
min
15° C./min
5° C./min
min
15° C./min





135.3
131.5
129.0
49.2
48.2
47.4










Melting (2nd heat) of polymer matrix (heating rate 10° C./min)


after crystallization








Melting temp, ° C.
Crystallinity degree, %












Slower

Faster
Slower

Faster


cooling
10° C./
cooling
cooling
10° C./
cooling


5° C./min
min
15° C./min
5° C./min
min
15° C./min





162.3
162.1
161.8
48.7
47.2
46.9









Differential scanning calorimetry data thus demonstrates the dependence of crystallization temperature, subsequent 2nd heat melting temperature, and percent crystallinity on the rate of cooling during crystallization. Exemplary embodiments of a strip of insulative cellular polypropylene-based material may have a melting temperature between about 160° C. (320° F.) and about 172° C. (341.6° F.), a crystallization temperature between about 108° C. (226.4° F.) and about 135° C. (275° F.), and a percent crystallinity between about 42% and about 62%.
In an illustrative embodiment, a method of producing a wrinkle-resistant polymeric container includes cutting a shape in a cross-web direction (CD) from the extruded tube, wherein an outside-of-extruded-tube (OET) surface or layer faces the inside of the container. In an embodiment, a method of producing a wrinkle-resistant polymeric container includes providing an extruded tube of a resin mixture comprising a primary polypropylene resin and cutting a shape in a cross-web direction (CD) from the extruded tube, wherein an outside-of-extruded-tube (OET) surface or layer faces the inside of the container. In an embodiment, a crystal domain size of alpha-phase polypropylene as determined by wide angle X-Ray diffraction is below 100 Å. In an embodiment, a crystal domain size of beta-phase polypropylene as determined by wide angle X-Ray diffraction is above 190 Å.
In exemplary embodiments, an extruded sheet of insulative cellular polypropylene-based material had a melting temperature of about 162° C. (323.6° F.), a crystallization temperature of about 131° C. (267.8° F.) and a crystallinity degree of about 46% as determined by differential scanning calorimetry at 10° C. per minute heating and cooling rate.
Differential scanning calorimetry (DSC) also unexpectedly revealed that, for all exemplary cup formulations described herein (Cups 1-6), beta-crystallinity is absent from the DSC 2nd heat curve (FIG. 4), but could be identified via wide angle X-ray diffraction (FIGS. 5-6). For conventional polypropylene-based foams known to those skilled in the art, beta-crystallinity identified by X-ray wide angle diffraction would lead to an expectation of beta-crystallinity also being identified by differential scanning calorimetry. Thus, a feature of an insulative cellular polypropylene-based material in accordance with the present disclosure is beta-crystallinity that is identifiable by wide angle X-ray diffraction, but not by differential scanning calorimetry.
Furthermore, conventional polypropylene-based foam might be expected to contain alpha- and beta-crystalline phases detectable by wide angle X-ray diffraction. However, the extra peak present at 16.1° in the wide angle X-ray diffraction patterns for all exemplary insulative cellular polypropylene materials described herein (see, FIGS. 5-6), which peak may be attributed to the presence of the beta-crystalline phase of polypropylene, i.e., the beta-polymorph, or more specifically, to the diffraction of crystal reflections from the β(300) plane, is noticeably absent in the wide angle X-ray diffraction pattern of a sample of conventional polypropylene-based foam (Sample B in FIG. 6). Thus, whereas conventional polypropylene-based foam appears to include pure alpha-crystalline phase, the insulative cellular polypropylene-based material of the present disclosure includes a mixture of alpha- and beta-crystalline phases.
It was found unexpectedly that the OET surface works favorably in a compression mode without causing appreciable creasing, and therefore that an insulative cup (or other structure) may be made with the OET surface facing inside of the insulative cup. In an exemplary embodiment, a crease of about 200 microns deep was seen as a fold where the cell wall collapsed under the compression forces when the InET surface faces inside of the insulative cup (see FIG. 2 and FIG. 3). The difference in the resistance of the InET layer and the OET layer to compression force may be due to difference in the morphology of the layers because they were crystallized at different cooling rates. Interestingly, however, microscopy revealed that cell size appearance in layers close to the surface appears to be the same for InET and OET, nor is there any difference detected between InET and OET by differential scanning calorimetry.
In exemplary embodiments of formation of an extruded sheet of insulative cellular polypropylene-based material, the InET surface may be cooled by a combination of water cooling and compressed air. The OET surface may be cooled by compressed air by using a torpedo with circulating water and air outlet. Faster cooling may result in the formation of smaller size crystals. Typically, the higher the cooling rate, the greater the relative amount of smaller crystals that are formed. X-Ray diffraction analysis of an exemplary extruded sheet of insulative cellular polypropylene-based material was conducted on Panalytical X'pert MPD Pro diffractometer using Cu radiation at 45 KV/40 mA. It was confirmed that, while the degree of crystallinity is the same for InET and OET, the OET surface had smallest alpha-domain size of about 99 Å, highest beta-domain size (231 Å) and K-value of 28, while the InET surface compared to OET surface had a larger alpha-domain size of about 121 Å, smaller beta-domain size of 183 Å and higher content of beta-domain as seen from the K-value of 37. (see, Table 3 from Examples 1-5). Without wishing to be bound by theory, it is believed that a higher cooling rate for the OET surface influenced a crystal domain size therein, which, as a result enables the OET surface due to its unique morphology to better withstand a compression force without irreversible deformation.
The most direct evidence of partially crystalline structure of polymers is provided by X-ray diffraction studies. There is a close relation between regularity of molecular structure and ability of polymer to crystallize. The term lamellae refers to a structure described as single polymer crystal. Lamellae of different polymers have the same general appearance, being composed of thin, flat platelets about 100 Å thick and often many microns in lateral dimensions. The thickness of the lamellae depends on crystallization temperature and any subsequent annealing treatment. Since the molecules comprising the polymers are at least 1000 Å long and the lamellae are only about 100 Å thick, the only plausible explanation is that the polymer chains are folded. Fringed micelle models or fringe crystalline models of the structures of polymer crystals formed from melts states that polymer chains are precisely aligned over distances corresponding to dimensions of the crystallites, but indicate more disordered segments of amorphous regions around them.
The defect structure of highly crystalline polymers is another theory used to describe X-ray diffraction patterns from polymer crystals. Defect-crystal concept accounts for X-ray diffraction pattern broadening due to (1) point defects, such as vacant sites and polymer chain ends, (2) dislocations of polymer edges, (3) two-dimensional imperfections in fold surfaces, (4) chain-disorder defects, and (5) amorphous defects. While all listed factors contribute in part to X-ray line broadening, it is not known exactly how large such an impact is for every specific polymer. For all practical purposes of comparing and ranking one polymer structure versus another in terms of larger or smaller crystal domain size, wide-angle X-ray diffraction is commonly used. In wide-angle X-Ray diffraction, the final crystal domain size is obtained in units of Angstrom (Å).
For all practical purposes of ranking, measuring, and describing aspects of the present disclosure in terms of crystal domain size, wide angle X-ray scattering was used as the test method. In the present disclosure, the term crystal domain size means lamellae thickness, and the term X-Ray refers to wide-angle X-Ray diffraction.
In exemplary embodiments, an extruded strip of insulative cellular polypropylene-based material may have an alpha-domain size below about 200 Å, beta-domain size above 200 Å and K-value of 18 to 30. In exemplary embodiments, an extruded strip of insulative cellular polypropylene-based material may have an alpha-domain size preferably below about 115 Å, beta-domain size above 220 and K-values 25 to 28. In exemplary embodiments, an extruded strip of insulative cellular polypropylene-based material may have a K-values of less than 30.
The present disclosure provides material characterized by the crystalline structure of the polypropylene foam to control morphology and the crease-resistant properties.
An insulative cellular polypropylene-based material of the present disclosure satisfies a need for a material that can be formed into an article, such as an insulative cup, that includes the features of wrinkle-resistance and crease-resistance as described herein, as well as many, if not all, of the features of insulative performance, recyclability, puncture resistance, frangibility resistance, and microwaveability, which features are described in U.S. patent application Ser. Nos. 13/491,007 and 13/491,327 both of which are incorporated herein by reference in their entirety. Such polymeric material has an alpha phase and beta phase detectable by X-ray analysis, but with only alpha-phase identifiable by DSC.
In exemplary embodiments, a formulation includes at least two polymeric materials. In one exemplary embodiment, a primary or base polymer comprises a high melt strength polypropylene that has long chain branching. In one exemplary embodiment, the polymeric material also has non-uniform dispersity. Long chain branching occurs by the replacement of a substituent, e.g., a hydrogen atom, on a monomer subunit, by another covalently bonded chain of that polymer, or, in the case of a graft copolymer, by a chain of another type. For example, chain transfer reactions during polymerization could cause branching of the polymer. Long chain branching is branching with side polymer chain lengths longer than the average critical entanglement distance of a linear polymer chain. Long chain branching is generally understood to include polymer chains with at least 20 carbon atoms depending on specific monomer structure used for polymerization. Another example of branching is by crosslinking of the polymer after polymerization is complete. Some long chain branch polymers are formed without crosslinking. Polymer chain branching can have a significant impact on material properties.
In illustrative embodiments, a polymeric material includes a primary base resin. In illustrative embodiments, a base resin may polypropylene. In illustrative embodiments, an insulative cellular non-aromatic polymeric material comprises a polypropylene base resin having a high melt strength, a polypropylene copolymer or homopolymer (or both). In an embodiment, a formulation of the polymeric material comprises about 50 to about 100 wt % of the primary base resin. Suitably, a formulation comprises about 70 to about 100 wt % of a primary base resin. Suitably, a formulation comprises about 50 to about 99 wt % of a primary base resin. Suitably, a formulation comprises about 50 to about 95 wt % of a primary base resin. Suitably, a formulation comprises about 50 to about 85 wt % of a primary base resin. Suitably, a formulation comprises about 55 to about 85 wt % of the primary base resin. As defined hereinbefore, any suitable primary base resin may be used. One illustrative example of a suitable polypropylene base resin is DAPLOYTM WB140 homopolymer (available from Borealis A/S), a high melt strength structural isomeric modified polypropylene homopolymer (melt strength=36, as tested per ISO 16790 which is incorporated by reference herein, melting temperature=325.4° F. (163° C.) using ISO 11357
In illustrative embodiments, a polymeric material includes a polypropylene copolymer or homopolymer (or both). In another embodiment, a polymeric material comprises about 0 to about 50 wt % of a secondary resin. In an embodiment, a polymeric material comprises about 0 to about 50 wt % of a secondary resin. In an embodiment, a polymeric material comprises about 0 to about 50 wt % of a secondary resin. In an embodiment, a polymeric material does not have a secondary resin. In a particular embodiment, a secondary resin can be a high crystalline polypropylene homopolymer, such as F020HC (available from Braskem), and PP 527K (available from Sabic).
In exemplary embodiments, a secondary resin may be or may include polyethylene. In exemplary embodiments, a secondary resin may include low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymers, ethylene-ethylacrylate copolymers, ethylene-acrylic acid copolymers, polymethylmethacrylate mixtures of at least two of the foregoing and the like.
The polymer resins may be blended with any additional desired components and melted to form a resin formulation.
In one aspect of the present disclosure, at least one slip agent may be incorporated into a formulation of the polymeric material to aid in increasing production rates. A slip agent (also known as a process aid) is a term used to describe a general class of materials which are added to a resin mixture and provide surface lubrication to the polymer during and after conversion. Slip agents may also reduce or eliminate die drool. Representative examples of slip agent materials include amides of fats or fatty acids, such as, but not limited to, erucamide and oleamide. In one exemplary aspect, amides from oleyl (single unsaturated C18) through erucyl (C22 single unsaturated) may be used. Other representative examples of slip agent materials include low molecular weight amides and fluoroelastomers. Combinations of two or more slip agents can be used. Slip agents may be provided in a master batch pellet form and blended with the resin formulation.
In another embodiment, a formulation comprises about 0 to about 10 wt % of a slip agent. In an embodiment, a formulation comprises about 0 to about 5 wt % of a slip agent. In a further embodiment, a formulation comprises about 0 to about 3 wt % of a slip agent. Any suitable slip agent may be used. In a particular embodiment, a slip agent is the linear low-density polyethylene, AmpacetTM 102823.
In another embodiment, a formulation comprises about 0 to about 10 wt % of a colorant. In an embodiment, a formulation comprises about 0 to about 5 wt % of a colorant. In a further embodiment, a formulation comprises about 0 to about 3 wt % of a colorant. In another embodiment, a formulation comprises about 0.5 to about 1.5 wt % of a colorant. Any suitable colorant may be used. In a particular embodiment, a colorant is TiO2.
One or more nucleating agents are used to provide and control nucleation sites to promote formation of cells, bubbles, or voids in the molten resin during the extrusion process. A nucleating agent refers to a chemical or physical material that provides sites for cells to form in a molten resin mixture. Nucleating agents may be physical agents or chemical agents. Suitable physical nucleating agents have desirable particle size, aspect ratio, and top-cut properties, shape, and surface compatibility. Examples include, but are not limited to, talc, CaCO3, mica, kaolin clay, chitin, aluminosilicates, graphite, cellulose, and mixtures of at least two of the foregoing. A nucleating agent may be blended with the polymer resin formulation that is introduced into the hopper. Alternatively, a nucleating agent may be added to a molten resin mixture in an extruder. When the chemical reaction temperature is reached the nucleating agent acts to enable formation of bubbles that create cells in the molten resin. An illustrative example of a chemical blowing agent is citric acid or a citric acid-based material. After decomposition, a chemical blowing agent forms small gas cells which further serve as nucleation sites for larger cell growth from physical blowing agents or other types thereof. One representative example is HydrocerolTM CF-40ETM (available from Clariant Corporation), which contains citric acid and a crystal nucleating agent. Another representative example is HydrocerolTM CF-05ETM (available from Clariant Corporation), which contains citric acid and a crystal nucleating agent. In illustrative embodiments one or more catalysts or other reactants may be added to accelerate or facilitate the formation of cells.
In certain exemplary embodiments, one or more blowing agents may be incorporated. Blowing agent means a physical or a chemical material (or combination of materials) that acts to expand nucleation sites. Nucleating agents and blowing agents may work together. A blowing agent acts to reduce density by forming cells in the molten resin. A blowing agent may be added to the molten resin mixture in the extruder. Representative examples of physical blowing agents include, but are not limited to, carbon dioxide, nitrogen, helium, argon, air, water vapor, pentane, butane, or other alkane mixtures of the foregoing and the like. In certain exemplary embodiments, a processing aid may be employed that enhances the solubility of the physical blowing agent. Alternatively, a physical blowing agent may be a hydrofluorocarbon, such as 1,1,1,2-tetrafluoroethane, also known as R134a, a hydrofluoroolefin, such as, but not limited to, 1,3,3,3-tetrafluoropropene, also known as HFO-1234ze, or other haloalkane or haloalkane refrigerant. Selection of a blowing agent may be made to take environmental impact into consideration.
In exemplary embodiments, physical blowing agents are typically gases that are introduced as liquids under pressure into a molten resin via a port in an extruder. As the molten resin passes through the extruder and the die head, the pressure drops causing the physical blowing agent to change phase from a liquid to a gas, thereby creating cells in the extruded resin. Excess gas blows off after extrusion with the remaining gas being trapped in the cells in the extrudate.
Chemical blowing agents are materials that degrade or react to produce a gas. Chemical blowing agents may be endothermic or exothermic. Chemical blowing agents typically degrade at a certain temperature to decompose and release gas. In one aspect a chemical blowing agent may be one or more materials selected from the group consisting of azodicarbonamide; azodiisobutyro-nitrile; benzenesulfonhydrazide; 4,4-oxybenzene sulfonylsemicarbazide; p-toluene sulfonyl semi-carbazide; barium azodicarboxylate; N,N′-dimethyl-N,N′-dinitrosoterephthalamide; trihydrazino triazine; methane; ethane; propane; n-butane; isobutane; n-pentane; isopentane; neopentane; methyl fluoride; perfluoromethane; ethyl fluoride; 1,1-difluoroethane; 1,1,1-trifluoroethane; 1,1,1,2-tetrafluoro-ethane; pentafluoroethane; perfluoroethane; 2,2-difluoropropane; 1,1,1-trifluoropropane; perfluoropropane; perfluorobutane; perfluorocyclobutane; methyl chloride; methylene chloride; ethyl chloride; 1,1,1-trichloroethane; 1,1-dichloro-1-fluoroethane; 1-chloro-1,1-difluoroethane; 1,1-dichloro-2,2,2-trifluoroethane; 1-chloro-1,2,2,2-tetrafluoroethane; trichloromonofluoromethane; dichlorodifluoromethane; trichlorotrifluoroethane; dichlorotetrafluoroethane; chloroheptafluoropropane; dichlorohexafluoropropane; methanol; ethanol; n-propanol; isopropanol; sodium bicarbonate; sodium carbonate; ammonium bicarbonate; ammonium carbonate; ammonium nitrite; N,N′-dimethyl-N,N′-dinitrosoterephthalamide; N,N′-dinitrosopentamethylene tetramine; azodicarbonamide; azobisisobutylonitrile; azocyclohexylnitrile; azodiaminobenzene; bariumazodicarboxylate; benzene sulfonyl hydrazide; toluene sulfonyl hydrazide; p,p′-oxybis(benzene sulfonyl hydrazide); diphenyl sulfone-3,3′-disulfonyl hydrazide; calcium azide; 4,4′-diphenyl disulfonyl azide; and p-toluene sulfonyl azide.
In one aspect of the present disclosure, where a chemical blowing agent is used, a chemical blowing agent may be introduced into a resin formulation that is added to a hopper.
In one aspect of the present disclosure, a blowing agent may be a decomposable material that forms a gas upon decomposition. A representative example of such a material is citric acid or a citric-acid based material. In one exemplary aspect of the present disclosure it may be possible to use a mixture of physical and chemical blowing agents.
In another embodiment, a formulation comprises about 0 to about 20 wt % of a nucleating agent. In an embodiment, a formulation comprises about 0 to about 10 wt % of a nucleating agent. In another embodiment, a formulation comprises about 0 to about 5 wt % of a nucleating agent. In another embodiment, a formulation comprises about 0.1 to about 2.5 wt % of a nucleating agent. In an embodiment, a formulation comprises about 0.35 to about 1.5 wt % of a nucleating agent. Any suitable nucleating agent or nucleating agents may be used. In a particular embodiment, the nucleating agent is selected from the group consisting of HydrocerolTM CF-40ETM (available from Clariant Corporation), HPR-803i fibers (available from Milliken), talc, and mixtures thereof.
In another embodiment, a nucleating agent comprises a primary nucleating agent and a secondary nucleating agent. In an embodiment, a formulation comprises about 0.01 to about 10 wt % of a primary nucleating agent. In an embodiment, a formulation comprises about 0.01 to about 5 wt % of a primary nucleating agent. In an embodiment, a formulation comprises about 0.01 to about 0.15 wt % of a primary nucleating agent. In an embodiment, a formulation comprises about 0.02 to about 0.1 wt % of a primary nucleating agent. In an embodiment, a formulation comprises about 0.03 to about 0.7 wt % of a primary nucleating agent. Any suitable primary nucleating agent may be used. A primary nucleating agent may be defined as a chemical blowing agent or chemical foaming agent, itself comprising a nucleating agent. In a particular embodiment, a primary nucleating agent is HydrocerolTM CF-40ETM (available from Clariant Corporation).
In an embodiment, a formulation comprises about 0.01 to about 10 wt % of a secondary nucleating agent. In an embodiment, a formulation comprises about 0.01 to about 5 wt % of the secondary nucleating agent. In an embodiment, a formulation comprises about 0.1 to about 2.2 wt % of a secondary nucleating agent. In an embodiment, a formulation comprises about 0.3 to about 1.7 wt % of a secondary nucleating agent. In an embodiment, a formulation comprises about 0.4 to about 1.5 wt % of a secondary nucleating agent. In an embodiment, a formulation comprises about 0.45 to about 1.25 wt % of a secondary nucleating agent. Any suitable secondary nucleating agent may be used. In a particular embodiment, a secondary nucleating agent is from HPR-803i fibers (available from Milliken) or talc.
Formulations described herein can be used to form insulative, polymeric containers. In an embodiment, a container can be a cup. In an embodiment, a container can be a microwaveable tray.
EXAMPLES
The following examples are set forth for purposes of illustration only. Parts and percentages appearing in such examples are by weight unless otherwise stipulated.
Example 1: Sample Cup Formulation and Extrusion
An exemplary formulation used to illustrate the present disclosure is presented below and is described in U.S. patent application Ser. No. 13/491,327, filed Jun. 7, 2012 and entitled POLYMERIC MATERIAL FOR AN INSULATED CONTAINER, the disclosure of which is hereby incorporated herein by reference in its entirety:
DAPLOYTM WB140 high melt strength polypropylene homopolymer (available from Borealis A/S) was used as the primary base resin. F020HC, available from Braskem, a polypropylene homopolymer resin, was used as the secondary resin. The two resins were blended with: HydrocerolTM CF-40ETM as a primary nucleation agent, talc as a secondary nucleation agent, CO2 as a blowing agent, a slip agent, and titanium dioxide as a colorant. Formulation 1 was the following:













80.7%
Primary resin: high melt strength polypropylene Borealis



WB140 HMS


15.0%
Secondary resin: F020HC (Braskem)


0.05%
Chemical blowing agent Clariant Hydrocerol TM CF-40E TM


0.25%
Nucleating agent: Talc


 2.0%
Colorant: TiO2 PE (alternatively, PP can be used)


 2.0%
Slip agent: Ampacet TM 102823 LLDPE (linear low-density



polyethylene), available from Ampacet Corporation









The formulation described above was added to an extruder hopper. The extruder heated the formulation to form a molten resin mixture. To this mixture was added 3.4 lbs/hr CO2, which was injected into the resin blend to expand the resin and reduce density. The mixture thus formed was extruded through a die head into a sheet. The sheet was then die-cut and formed into a cup as described in U.S. patent application Ser. No. 13/491,007, filed Jun. 7, 2012 and entitled INSULATED CONTAINER, the disclosure of which is hereby incorporated herein by reference in its entirety.
Example 2: Sample Cup Preparations
Cup 1
Insulative cellular polypropylene-based material was extruded with the formulation described above. Die-cut article shapes were oriented in the MD (machine direction) with the longer side of the article oriented along the web direction. Insulated cups were formed with OET facing outside of the insulated cup resulting in multiple creases and wrinkles, some deeper than 5 mm. FIG. 3 shows a microscopy image of the foam cell wall collapsed forming a crease during article formation. The insulated cups were not usable.
Cup 2
The same insulative cellular polypropylene-based material as in Cup 1 was used to make die cut shapes in MD direction, but articles were formed with OET facing inside the insulative cup. Unexpectedly, the insulative cup surface was free of creases and the insulative cups were acceptable for use.
Cup 3
The same insulative cellular polypropylene-based material as in Cup 1 was used to make die cut shapes in CD (cross-web direction), with the longer side of the article oriented across the web. Insulative cups were formed with OET facing outside of the insulative cup. Appearance further improved compared to Cup 2. The insulative cups were usable.
Cup 4
The same insulative cellular polypropylene-based material as in Cup 1 was used to make die cut shapes in CD, with the longer side of the article oriented across the web. Insulative cups were formed with OET tube facing inside of the insulative cup. Appearance further improved compared to Example 2. The insulative cups were usable and had no creases.
Cup 5
Printed polypropylene (PP) film was laminated to the OET layer of the insulative cellular polypropylene-based material of Example 1, the article shape was die cut in MD, and insulated cups were formed with printed layer facing outside of the insulated cup. Appearance was the worst, with creases exceeding 5 mm depth.
Cup 6
Printed polypropylene (PP) film was laminated to the OET layer of the insulative cellular polypropylene-based material of Example 1, the article shape was die cut in CD, and insulated cups were formed with printed layer facing outside of the insulated cup. Appearance improved compared to Example 5, but did not compare favorably with Cups 2, 3, and 4.







TABLE 2







Test Results for Sample Cups 1-6












Direction






the
Outside of extruded tube

Appearance



shape
(OET) surface location on

scale (1—bad,


Sample ID
was cut
the formed cup
Visual appearance
5—excellent)





Cup 1 (insulative
MD
OET - OUTSIDE the cup
Multiple bad creases
2


cellular polypropylene-


based material only)


Cup 2 (insulative
MD
OET - INSIDE the cup
No creases
4


cellular polypropylene-


based material only)


Cup 3 (insulative
CD
OET - OUTSIDE the cup
No creases
4


cellular polypropylene-


based material only)


Cup 4 (insulative
CD
OET - INSIDE the cup
Smooth inside surface, no
5


cellular polypropylene-


creases


based material only)


Cup 5 (with printed PP
MD
Printed PP film on OET - 
Deep creases from top to
1


film on OET side)

OUTSIDE the cup
bottom of the cup


Cup 6 (with printed PP
CD
Printed PP film on OET - 
Two creases: one along the
3


film on OET side)

OUTSIDE the cup
seam, another opposite to





the seam









The cup-forming process that best minimized wrinkling and/or creasing (Cup 4) included a step of cutting the shape in a cross-web direction (CD) from an extruded tube of insulative cellular polypropylene-based material with the OET surface/layer facing the inside of the cup. When (a) the cup shape was cut out in the CD and (b) the cup was obtained from laminating a printed polypropylene film to OET surface/layer facing the outside of the cup as in Cup 6, there was significant improvement in visual appearance. When (a) the shape was cut in the CD and (b) the printed polypropylene film was laminated to InET surface/layer, the appearance and rim shape further improved compared to Cup 6.
As evident from microscopy images (FIG. 2 and FIG. 3), the cup is folded under a compressive force when the InET is the inside of a cup, resulting in wrinkles and creases. Unexpectedly, the OET as the inside of a cup does not fold. The OET can withstand a compressive force, despite the fact that there is no difference detected between InET and OET by differential scanning calorimetry. Further, cell size in layers close to the surface appears to be the same for InET and OET as confirmed by microscopy.
The difference between InET and OET was investigated by wide angle X-Ray diffraction (WAXD) analysis. WAXD analysis was conducted as follows: A sample section with a size of 1′′×1′′ fixed in a standard sample holder was placed into a Panalytical X'pert MPD Pro diffractometer using Cu radiation at 45 KV/40 mA. Scans were run over the range of 5°-50° with a step size of 0.0157° and a counting time of 50 seconds per step. The diffraction patterns for the InET and OET surfaces of the sample were determined. The WAXD patterns of polypropylene exhibited five major peaks located at 14.2°, 16.1°, 17.1°, and 18.6°, corresponding to the diffraction of crystal reflections from the α(110), β(300), α(040), α(130), and γ(117) planes, respectively. The α(110) peak was used to calculate the crystal domain size as shown at FIG. 5A.
The K-value was calculated using RIR method (Reference Intensity Ratio) to characterize the relative content of the beta-phase in the material in accordance to the following formula:

K value=(Aβ/(Aα+Aβ)×100,

where

the K value is the content of beta domain expressed as a percent (%);
Aα is total area of the alpha-domain peak on WAXD pattern graph corresponding to the diffraction of crystal reflections from the α(110) plane;
Aβ is the total area of the beta-domain peak on WAXD pattern graph corresponding to the diffraction of crystal reflections from the β(300) plane.
Although the degree (percent) of crystallinity was the same for InET and OET, the size of the crystalline domains was different (Table 3). This size difference may have been due to a differential rate of cooling which afforded a crystalline structure in the OET better able to withstand a compressive force without irreversible deformation. Without being bound by theory, the difference in the surface morphology and crystalline structure between the OET and InET may have be an important factor in the occurrence of creasing and/or wrinkling







TABLE 3







X-Ray Data Summary for Sample Cups 1-6












Percent





Crystallinity, %



Domain Size, Å
(Determined
% β-Phase =











Sample ID
α-Phase
β-Phase
by X-Ray)
K-value * 100














Cups 1-5 InET
121
183
61
37


Cups 1-5 OET
99
231
58
28


Extra talc1 - Inner
158
156
59
76


Extra talc - Outer
164
169
57
77


Sample B2 - Inner
145
Not
61
Not Applicable




Present


Sample B - Outer
152
Not
59
Not Applicable




Present





1Extra talc = Cup of formula 5


2Sample B = Commercially available polypropylene cup






Crystalline domain size was sensitive to material formulation. As shown in Table 3, the alpha-phase crystal domain size for a sample with extra talc (2% talc) that exhibited creasing came out to be very large, i.e., 158 Å for InET and 164 Å for OET, compared to the smaller alpha-phase crystal domain size for OET of Cups 1-5, which was measured at 99 Å. The InET surface of Cups 1-5 had an alpha-phase crystal domain size of 121 Å. Cell size, polypropylene melting point, crystallization temperature, and degree of crystallinity (measured by differential scanning calorimetry and X-Ray analysis) of InET and OET foam surface were similar.
The OET surface of Cups 1-4 had the optimal cup appearance when OET was facing inside of the cup and had the best resistance to compression forces during cup formation. These cups also had the following unique combination of features:

    
    
        smallest alpha-phase crystal domain size;
        largest beta-phase crystal domain size; and
        K-value below 30 (Table 3).
    
    


Differential scanning calorimetry (DSC) analysis was conducted on a TA Instruments DSC 2910 using heat-cool-heat, 10° C./min, under a nitrogen atmosphere. Differential scanning calorimetry unexpectedly revealed that, for all examples of cup formation described above, beta-crystallinity was absent from the DSC 2nd heat curve (FIG. 4), but could be identified via X-ray wide angle diffraction. For known conventional polypropylene-based foams, beta-crystallinity identified by X-ray wide angle diffraction would lead to an expectation of beta-crystallinity also being identified by differential scanning calorimetry. Thus, a feature of an insulative cellular polypropylene-based material in accordance with the present disclosure includes beta-crystallinity that is identifiable by wide angle X-ray diffraction but not by differential scanning calorimetry.
The beta-phase content (231 Å) was highest for the material that resulted in best performance (Table 3). Further study was conducted on the samples with comparable alpha domain size and comparable beta-phase domain size (all above 200 Å) and variable content of beta-phase as described by K-values. Unexpectedly, the relationship between the K-value and the ability to form a high surface quality cup without wrinkles was not proportional. There was a region of optimal K-values that resulted in excellent PP foam surface. The best cup appearance corresponded to the K-values ranging from 18 to 30, more preferably from 22 to 28.












TABLE 4








Crystal



Appearance



Domain Size,

K

scale



Å

Value,

(1 - bad,













Formulation
α-Phase
β-Phase
Crystallinity, %
ratio
Visual appearance
5 - excellent)
















2
152
207
62
9
Deep creases, cup
1







is not usable



3
138
235
57
11
Rough surface, cup
1







is not usable



4
142
205
56
15
Rough surface, cup
1







is not usable



2
130
236
59
17
Creases, cup is not
2







usable



2
149
230
58
25
Good quality cup,
3-4







smooth surface



2
150
245
57
23
Best quality cup,
4-5







smooth surface



1
99
231
58
28
Good cup quality,
4







smooth surface



1
121
183
61
37
Creases, cup is not
2







usable



5
158
156
59
77
Creases, cup is not
1







usable



5
164
169
57
77
Creases, cup is not
1







usable









Formulation 2:













81.45% 
Primary resin: high melt strength polypropylene Borealis



WB140 HMS


15.0% 
Secondary resin: F020HC (Braskem)


0.05% 
Chemical blowing agent Clariant Hydrocerol TM CF-40E TM


0.5%
Nucleating agent: Talc


1.0%
Colorant: Colortech 11933-19 TiO2-PP


2.0%
Slip agent: Ampacet TM 102823






















81.45% 
Primary resin: high melt strength polypropylene Borealis



WB140 HMS


15.0%
Secondary resin: F020HC (Braskem)


0.05%
Chemical blowing agent Clariant 



Hydrocerol TM CF-40E TM


 0.5%
Nucleating agent: Techmer PPM 16464 Silica


 1.0%
Colorant: Colortech 11933-19 TiO2-PP


 2.0%
Slip agent: Ampacet TM 102823






















81.45%  
Primary resin: high melt strength polypropylene Borealis



WB140 HMS


15.0% 
Secondary resin: F020HC (Braskem)


0.05%
Chemical blowing agent Clariant 



Hydrocerol TM CF-40E TM


0.5%
Nucleating agent: Talc


1.0%
Colorant: Colortech 11933-19 TiO2-PP


2.0%
Slip agent: Ampacet TM 102823






















78.96% 
Primary resin: high melt strength polypropylene Borealis



WB140 HMS


14.99% 
Secondary resin: F020HC (Braskem)


0.05% 
Chemical blowing agent Clariant Hydrocerol TM CF-40E TM


2.0%
Nucleating agent: Talc


1.0%
Colorant: Colortech 11933-19 TiO2-PP


3.0%
Slip agent: Ampacet TM 102823









Crystal domain size of alpha-phase and beta-phase varied for the samples in Table 4, however there was an optimal K-values range of from about 20 to about 30 which corresponded to a best cup surface quality.
Example 3: Cell Density and Dimension Morphology
A study of foam cell morphology provided insight into the ability to form wrinkle- and crease-resistant insulative cellular polypropylene-based material. Wrinkle- and crease-resistance refers to lack of wrinkle formation and/or creasing during cup convolution or shaping of a sheet of insulative cellular polypropylene-based material.
Cell length and cell height were measured by scanning electron microscopy (SEM) for an extruded sheet of insulative cellular polypropylene-based material of the present disclosure (Sample A, using the formulation described above) and for a sheet of conventional polypropylene foam (Sample B). The microscopy image was evaluated visually, and representative cells were chosen for measurement of cell length and cell width. Such a method of cell size determination, based on measurements made at 3-10 points, was well known and is mostly used as a quality control tool in foam manufacturing. The purpose of the measurement was to find typical or average/representative cell size, not to provide cell size distribution. The aspect ratio was calculated by dividing cell length by cell width for the same specified direction (MD or CD).
Sample B (conventional foam) had a much higher MD cell aspect ratio than Sample A foam, i.e., the cells of Sample B were long and narrow (Table 4). Sample B foam also possessed an aspect ratio below 2.0 in the CD direction, which was consistent with the cells of Sample B foam being long and narrow. In contrast, cells of Sample A foam had a much lower MD cell aspect ratio than cells of Sample B foam and an aspect ratio below 2.0 in the CD direction, thus indicative of cells with a more round shape.







TABLE 5







Cell Aspect Ratios











Cell dimensions, mm
Sample B
Sample A
















MD
Cell length
1.19
0.92




Cell width
0.12
0.26




MD Cell Aspect Ratio
9.92
3.54



CD
Cell length
0.30
0.52




Cell width
0.20
0.27




CD Cell Aspect Ratio
1.50
1.93










A coefficient of anisotropy was calculated as a ratio of cell width (or height) in MD to the same parameter in opposite direction (CD). As shown in Table 5, Sample B foam was highly anisotropic. In contrast, Sample A was not much different in MD vs. CD, and therefore has low coefficient of anisotropy.







TABLE 6







Coefficients of Anisotropy











Anisotropy Coefficient
Sample B
Sample A







MD cell length/CD cell length
4.0
1.8



MD cell width/CD cell width
0.6
1.0










Wrinkling of a cellular material with a fixed chemical composition, made in the identical extrusion process with the same processing parameters, was eliminated when die cut parts were oriented in CD direction providing a cell aspect ratio close to 1 and a coefficient of anisotropy close to 1.

## Claims

1. An insulative container of cellular polymeric material comprising
an extruded sheet having an inside extrusion tube surface, an outside extrusion tube surface and an elongated shape die-cut in a cross direction and formed into a tubular container wall with the outside extrusion surface facing the inside of the tubular container wall, the cellular polymeric material comprising
a primary polypropylene resin, wherein beta-phase crystallinity is identifiable by wide angle X-ray diffraction and is not identifiable by differential scanning calorimetry.

2. The insulative cellular polymeric material of claim 1, further comprising a polypropylene secondary resin.

3. The insulative cellular polymeric material of claim 1, further comprising a slip agent.

4. The insulative cellular polymeric material of claim 1, further comprising at least one nucleating agent.

5. The insulative cellular polymeric material of claim 1, wherein a beta-phase crystallinity peak is present in the diffraction pattern from diffraction of crystal reflections from a β(300)plane.

6. An insulative container of cellular polymeric material comprising
an extruded sheet having an inside extrusion tube surface, an outside extrusion tube surface and an elongated die-cut shape formed into a tubular container wall with the outside extrusion surface facing the inside of the tubular container wall, the cellular polymeric material comprising
a primary polypropylene resin, wherein beta-phase crystallinity is identifiable by wide angle X-ray diffraction and is not identifiable by differential scanning calorimetry.

7. An insulative container of cellular polymeric material comprising
an extruded sheet having an inside extrusion tube surface, an outside extrusion tube surface and wherein the extruded sheet is formed into a tubular container wall with the outside extrusion surface facing the inside of the tubular container wall, the cellular polymeric material comprising
a primary polypropylene resin, wherein beta-phase crystallinity is identifiable by wide angle X-ray diffraction and is not identifiable by differential scanning calorimetry.