阅读说明：本技术 包含环烯烃共聚物的聚乙烯组合物 (Polyethylene composition comprising cycloolefin copolymer ) 是由 Y·杨 A·I·诺曼 A·H·周 K·T·M·斯劳特 B·M·维尔克 D·R·苏纳格图利纳 于 2018-04-27 设计创作，主要内容包括：一种复合物,包含聚乙烯和基于组合物的重量计在1wt％至25wt％的范围内的至少一种环烯烃共聚物,其中所述聚乙烯可以具有至少0.90g/cm<Sup>3</Sup>的密度,并且其中所述环烯烃共聚物具有至少30℃的玻璃化转变温度(Tg)。还公开了使所述复合物取向以形成的取向制品的特征,其中所述制品包括具有至少1μm的平均长度,以及至少5nm的平均直径的棒。(A composite comprising a polyethylene and in the range of from 1 wt% to 25 wt% of at least one cyclic olefin copolymer, based on the weight of the composition, wherein the polyethylene may have at least 0.90g/cm 3 And wherein the cyclic olefin copolymer has a glass transition temperature (Tg) of at least 30 ℃. Also disclosed are features of an oriented article formed by orienting the composite, wherein the article comprises rods having an average length of at least 1 μm, and an average diameter of at least 5 nm.)

1. A composite comprising polyethylene and in the range of from 1 wt% to 25 wt% based on the weight of the composition of at least one cyclic olefin copolymer, wherein the cyclic olefin copolymer has a glass transition temperature (Tg) of at least 30 ℃.

2. The composite of claim 1, wherein the cyclic olefin copolymer comprises at least 50 wt% cyclic olefin derived units based on the weight of the copolymer.

3. The composite of claim 1 or 2, wherein the cyclic olefin copolymer has a Tg value in the range of 30 ℃ to 180 ℃.

4. The composite of any preceding claim, wherein the polyethylene has a branching index (g' vis) of less than 0.8 and the composite has a melt strength (σ z) in the range of 300kPa to 600 kPa.

5. The composite of any preceding claim, wherein the polyethylene has a g' vis of greater than 0.95, and the composite has a melt strength (σ z) in the range of 100kPa to 1000 kPa.

6. The composite of any preceding claim, wherein the polyethylene has a g' vis in the range of 0.95 to 0.8, and the composite has a melt strength (σ z) of greater than 800 kPa.

7. The process of any of the preceding claimsThe composite, wherein the polyethylene has a molecular weight of at 0.90g/cm³To 0.94g/cm³A density within the range of (1).

8. The composite of any one of the preceding claims, having a crystallization temperature (Tc) of at least 100 ℃.

9. The composite of any of the preceding claims, having a heat of fusion (Δ H) of less than 120J/g.

10. The composite of any of the preceding claims, wherein no inorganic filler and/or fiber is present.

11. The composite of any of the preceding claims, wherein no polymeric compatibilizer is present.

12. The complex of any preceding claim, comprising rods having an average length of at least 4 μm, and an average diameter of at least 5 nm.

13. An oriented article comprising the composite of any of the preceding claims.

14. A method for forming the composite of any of the preceding claims 1 to 12, comprising combining polyethylene and at least one cyclic olefin copolymer in a range of from 1 wt% to 25 wt%, based on the weight of the composition; and orienting the composite.

15. The method of claim 14, wherein the orienting step comprises melt blending, film forming, thermoforming, rotomolding, blow molding, injection molding, extrusion coating, and/or foaming.

Technical Field

The present invention relates to blends of polyethylene and cyclic olefin copolymers that form composites having improved stiffness and melt strength relative to polyethylene alone.

Background

Cyclic Olefin Copolymers (COC) can be broadly defined as polyolefins incorporating cyclic comonomers, an example of which is ethylene-norbornene copolymer. Many commercial COCs are amorphous materials with high glass transition temperatures (above 50 ℃), with norbornene contents of 40 mol% and above. Generally, COCs have high use temperatures, good optical properties, high stiffness and strength, are excellent moisture barriers, and have good resistance to polar chemicals. However, conventional COCs have poor toughness, insufficient oxygen barrier properties, poor oil resistance, and pure resin processing difficulties. The poor miscibility of amorphous COCs with semi-crystalline polyolefins also limits their application and realization of value localization in blends and composites.

It is desirable to form blends or composites of COC with other polymers and fillers. A "composite" is a material made of two or more different materials (which when combined result in a material having different properties than the individual components) having significantly different physical and/or chemical properties.

To improve the properties of COCs, such as their toughness, fillers and reinforcing agents are often used. Typical reinforcing agents for organic polymers are inorganic materials such as glass and carbon fibers. Due to the large difference between organic and inorganic materials, sizing or compatibilizers are often required to provide good chemical or physical attachment of the inorganic fibers to the organic polymer matrix for improved overall composite performance. It would be desirable to have a method of reinforcing polyolefins such as polyethylene without the need for inorganic fillers, fibers, and/or other inorganic additives.

Interesting disclosures include U.S. patent nos. 7,727,620; 7,179,521, respectively; 6,872,462, respectively; U.S. patent publication nos. 2015/0010741; 2014/0353197, respectively; 2011/0256373, respectively; 2007/00098933, respectively; 2006/0159878, respectively; and PCT publication No. wo 2014/141820. Other interesting disclosures include:

randy Jester, "Heat Seal Characteristics of Cyclic-olyfin Copolymer/Polyethylene Blends," TAPPI 2002PLACE CONFERENCE, Boston, Mass. (2002);

david R.constant, "Cyclic organic polymers as Non-Migratingpolymeric Slip Additives in LDPE Cast Films," ANTEC2002CONFERENCE, san Francisco, California (2002);

ronald R.Lamonte, "Stiffer, Thinner, Packaging Films with improved sealing Using Cyclic-olexin Copolymers," FLEXPAC CONFERENCE, Amsterdam, the Netherlands (11 months 2003);

randy Jester, "High Aroma Barrier composites with Low Extractables," 2005PLACE CONFERENCE, Las Vegas, Nevada (9 months and 27 days 2005);

randy Jester, "Cyclic-Olefin Copolymer-A High Performance modified for computational polymers," SPA POLYOLEFEINS CONFERENCE, Houston, Texas (2.25.2007);

paul D.Tatarka, "Improved Properties and Cost Efficiencies of cyclic-olymin Enhanced formulation Films," SPE ANNUAL TECHNICAL CONFERENCE (5/7 days 2007);

paul D.Tatarka, "polyofin Film Enhancement Using Cyclic-oleosin polymers for Retort Applications," SPE POLYOLEFIN & FLEXPACK CONFERENCE, 25.2 months (2008);

paul D.Tatarka, "thermo engineering With Cyclic-oleosinpolymers," SPE INTERNATIONAL POLYOLEFINS CONFERENCE, Houston, Texas (2.22.2009);

norman Aube & Timothy Kneale, "Blending of Cyclic Olefins in Single LLDPE (sLLDPE) for Improved Bubble Stability and Output Rates on Blow FilmExclusion Process," SPE INTERNATIONAL POLYOLEFINS CONFERENCE, Houston, Texas (2.22 days 2.2009); and

randy Jester, "COC Enhanced polyofin Films for Shrink sheets and LABELs," AWA INTERNATIONAL SLEEVE & LABEL CONFERENCE, Chicago, Illinois (2010).

SUMMARY

Disclosed herein is a composite comprising (or consisting of, or consisting essentially of) a polyethylene, and in the range of from 1 or 3 wt% to 7, or 8, or 10, or 15, or 20 or 25 wt%, based on the weight of the composition, of at least one cyclic olefin copolymer, wherein the cyclic olefin copolymer has a glass transition temperature (Tg) of at least 30, or 40, or 50, or 60, or 65, or 70 ℃.

Also disclosed is a method of forming a composite comprising (or consisting of, or consisting essentially of) combining a polyethylene and in the range of from 1 or 3 wt% to 7, or 8, or 10, or 15, or 20 or 25 wt%, based on the weight of the composition, of at least one cyclic olefin copolymer, wherein the cyclic olefin copolymer has a Tg of at least 30, or 40, or 50, or 60, or 65, or 70 ℃; and orienting the composite to form an article comprising a composite having an average length of at least 1, or 2, or 4, or 5 μ ι η, and an average diameter of at least 5, or 10, or 20, or 30 nm; or a mean length in the range of 1, or 2, or 4, or 5 μm to 8, or 10, or 20, or 50 μm, and a mean diameter in the range of 5, or 10, or 20, or 30nm to 60, or 80, or 100, or 120 nm.

Brief description of the drawings

FIG. 1 shows a block diagram comprising 10 wt% of a cycloolefin copolymer (1) and an excepted^TM1018 images of inventive composites of LLDPE using Atomic Force Microscopy (AFM).

FIG. 2 shows a block diagram comprising 10 wt% of a cycloolefin copolymer (2) and an excepted^TM1018 images obtained using AFM of inventive composites of LLDPE.

FIG. 3 shows a block diagram comprising 10 wt% of a cycloolefin copolymer (1) and an excepted^TMImages obtained using AFM of 1018LLDPE of the inventive composite, which had been oriented in the direction of travel of the dark structures (from top to bottom in the micrograph).

FIG. 4 shows a block diagram containing 10 wt% of a cycloolefin copolymer (2) and an excepted^TMImages obtained using AFM of 1018LLDPE of the inventive composite, which had been oriented in the direction of travel of the dark structures (from top to bottom in the micrograph).

Detailed description of the invention

The inventors have found that COC can be used as a method to reinforce polyolefins such as polyethylene without the need for inorganic fillers, fibers, and/or other inorganic additives. Thus, in the present disclosure, the immiscibility and compatibility between COC and Polyethylene (PE), as demonstrated by Atomic Force Microscopy (AFM) and other tools described herein, is exploited to form improved compositions that can be oriented by standard methods, such as by forming a film or thermoforming an article. In this way, in-situ generated COC "rods" are formed during normal manufacturing processes with strongly oriented flow components. COC rods sit well between oriented fibrous PE sheets, with smooth interfaces and dangling COC chains diffusing inside the amorphous domains of PE, forming all organic polymer nanocomposites with good entanglement. An example of a benefit is a sharp melt strength enhancement as described herein. For uses such as extrusion coating, the melt strength enhancement can potentially help LLDPE to replace LDPE or polypropylene (PP). The COC-PE compounds are expected to give improved and balanced mechanical properties, synergistic excellent stiffness from COC and toughness from LLDPE.

As used herein, a "cyclic olefin copolymer" (COC) is a copolymer comprising 50 wt% or more cyclic olefins or derived units thereof, the remainder being ethylene and optionally α -olefin, the cyclic olefin derived units being selected from C5 to C8, or C12, or C16, or C20 olefins comprising at least one C5 to C8 cyclic structure, for example bicyclic compounds such as bicyclo- (2,3,1) -heptene-2, preferably the cyclic olefin derived units are selected from C5, or C6 to C8, or C10, or C12, or C20 cyclic olefin derived units, and more preferably the bicyclic olefin derived units are cyclic olefins comprising a bridging hydrocarbon moiety forming two rings in the overall structure (e.g. bicyclo- (2,3,1) -heptene-2 (norbornene).

The cyclic olefin copolymer may be prepared by any suitable polymerization means. In any embodiment, the cyclic olefin monomer combined with the ethylene monomer in the polymerization process is selected from C5 to C8, or C12, or C16, or C20 olefins comprising at least one C5 to C8 cyclic structure, e.g., bicyclic compounds, such as bicyclo- (2,3,1) -heptene-2. Preferably, the cycloalkene is selected from C5, or C6 to C8, or C10, or C12, or C20 cycloalkenes, and more preferably, a bicycloalkene, which is a cycloalkene comprising a bridging hydrocarbon moiety forming two rings in the overall structure, e.g., bicyclo- (2,3,1) -heptene-2 (norbornene). Most preferably, the cyclic olefin used to prepare the COC is selected from norbornene, tetracyclododecene and substituted forms thereof. To carry out the polymerization process when combined and when combined at the desired temperature, it is preferred to combine the components at a pressure in the range of at least 0.8, or 1, or 2, or 3MPa, or 0.8, or 1, or 2, or 3MPa to 4, or 6, or 8, or 10 MPa. This pressure may come from the addition of ethylene and/or other gases in the polymerization reactor and is of course influenced by the reactor temperature. The levels of ethylene and cyclic olefin are adjusted to obtain the desired catalytic activity and the desired level of cyclic olefin comonomer incorporated into the polyethylene described herein. In any embodiment, the combining of the monomer and catalyst may be carried out at a reaction temperature in the range of 80, or 85, or 90, or 100 ℃ to 120, or 130, or 140, or 150 ℃, which is the average temperature within the vessel or reactor used to combine the components to carry out the polymerization.

Thus, in any embodiment is a composite comprising (or consisting of, or consisting essentially of) a polyethylene and in the range of from 1, or 3 wt% to 7, or 8, or 10, or 15, or 20, or 25 wt%, based on the weight of the composition, of at least one cyclic olefin copolymer, wherein the cyclic olefin copolymer has a Tg value of at least 30, or 40, or 50, or 60, or 65, or 70 ℃. In any embodiment, the cyclic olefin copolymer comprises at least 50, or 60, or 65, or 70, or 75 wt% cyclic olefin derived units, based on the weight of the copolymer. In any embodiment, the cyclic olefin copolymer has a Tg value in the range of 30, or 40, or 50, or 60, or 65, or 70, or 75, or 80, or 90, or 100 ℃ to 145, or 155, or 160, or 170, or 180 ℃. Finally, the composites described herein can have a heat of fusion (Δ H) of less than 120, or 115J/g, or in the range of 80, or 85, or 90, or 95, or 100, or 105J/g to 115, or 120J/g.

Cyclic olefin copolymers can also be described by several other properties. In any embodiment, the cyclic olefin copolymer has a melt index (MI (190 ℃/2.16kg)) in the range of 0.05, 0.10g/10min to 1, or 2, or 3, or 4g/10 min. In any embodiment, the cyclic olefin copolymer useful in the complexes described herein has a molecular weight at 0.96 or 0.98g/cm³To 1, or 1.05 or 1.1g/cm³A density within the range of (1). Finally, in any embodiment, the cyclic olefin copolymer has a branching index (g' vis) greater than 0.95, or 0.96, or 0.97, or in the range of 0.95, or 0.96, or 0.97 to 1, or 1.1.

As used herein, "polyethylene" refers to a polymer comprising at least 60, or 70, or 80, or 90 wt% ethylene-derived units, based on the weight of the polymer, with the remainder comprising C3 to C12 α -olefin (especially 1-butene, 1-hexene, and/or 1-octene) derived unitsLinear Low Density Polyethylene (LLDPE). High Density Polyethylene (HDPE) may also be used in the invention described herein. In any embodiment, the polyethylene has a molecular weight in the range of 0.90, or 0.91, or 0.915, or 0.92 to 0.925, or 0.93 or 0.935, or 0.94g/cm³A density within the range of (1). In any embodiment, a blend of LLDPE, LDPE and/or HDPE may be used alone or together as "polyethylene". For example, "polyethylene" may be a blend of HDPE and LDPE, or two different LLDPEs, etc. In any embodiment, the polyethylene is LLDPE, or LDPE, or a blend of the two.

In any embodiment, the MI (190 ℃/21.6kg) of the polyethylene is greater than 10, or 12, or 14, or 15g/10min, and preferably in the range of 10, or 12, or 14, or 15, or 20, or 28g/10min to 34, or 36, or 38, or 40, or 44, or 48, or 50g/10 min.

The properties of the composite may vary depending on the nature of the cycloolefin copolymer and the polyethylene. For example, in any embodiment, the polyethylene has a branching index (g' vis) of less than 0.8 (highly branched), and the composite has a melt strength (σ z) in a range of 300kPa to 500, or 600 kPa. In any embodiment, the polyethylene has a branching index (g' vis) greater than 0.95 (highly linear) and the composite has a melt strength (σ z) in a range from 100kPa to 500kPa, or 900, or 1000 kPa. Further, in any embodiment, the polyethylene has a branching index (g' vis) in the range of 0.95 to 0.8 (moderate branching) and the composite has a melt strength (σ z) of greater than 800, or 1000, or 1200, or 1400 kPa.

Composites include intimate blends of cyclic olefin copolymer and polyethylene, such as melt blends of the two components that have been coextruded by single or twin screw extruders or Brabender-type blenders. The blend may have rods as described below, but preferably the oriented article comprises a plurality of such rods. In any case, the composite has a crystallization temperature (Tc) in any embodiment of at least 100, or 102 ℃, or in the range of 100, or 102 ℃ to 106, or 110 ℃. Further, in any embodiment, the composite has a melt strength (σ z) greater than 500, or 600, or 800, or 1000, or 1200, or 1400kPa, or in the range of 500, or 600, or 800, or 1000, or 1200, or 1400kPa to 2000, or 2400, or 2600, or 3000, or 3400, or 3600, or 4000, or 4400, or 4600, or 5000 kPa. Finally, in any embodiment, the complex has a pull-off force (F) of at least 8, or 10, or 12, or 14cN, or in the range of 8, or 10, or 12, or 14cN to 20cN or 30, or 40 cN.

The use of reinforcing additives is generally not required in view of the properties of the composite and its final properties, particularly the properties of the oriented articles made therefrom. For example, in any embodiment, no inorganic filler and/or fibers are present. Such fillers would include talc, calcium carbonate, mica, glass fibers, and other inorganic compounds known in the art. Further, in any embodiment, no polymeric compatibilizer and/or sizing agent is present.

As used herein, a polymeric "compatibilizer" is generally a block or graft copolymer, preferably of low molecular weight (e.g., Mw less than 50,000g/mol), that improves the immiscibility of two or more polymers in a blend by breaking up the large domains of the polymers into smaller domains. In general, the different blocks of the copolymer resemble the chemical structure of the individual components of the blend. Various portions of the copolymer are capable of interacting with the phases of the blend to make the phase morphology more stable. This helps the immiscible domains within the continuous phase of the blend break up into smaller particles in the melt phase. One example is an ethylene-propylene block copolymer used to compatibilize blends of polyethylene and polypropylene. Small molecule compatibilizers, which may also be referred to as "coupling agents," may react with components of the blend to form copolymers or block copolymers in situ, which in turn act as polymeric compatibilizers.

Finally, in any embodiment, there is also no compound known as a "sizing agent". As used herein, a "sizing agent" is a chemical used to treat an inorganic filler, typically by chemically reacting with or otherwise combining with moieties on a solid surface to improve its compatibility with an organic polymer matrix. Sizing agents are amphiphilic molecules in which the hydrophilic end is physically or chemically linked to the inorganic filler and the hydrophobic end forms a "film" that is compatible with the organic polymer matrix. Examples include silanes and imides, compounds that can react with hydroxyl groups on the surface of the solid support.

In any embodiment, the composites described herein can be formed into oriented articles. The "orientation" process may include any number of processes that impart a directional shear stress on the melt of the composite, such as melt blending processes in single or twin screw extruders, melt blending processes in Brabender-type equipment, or forming a film from the composite or a composition comprising the composite, thermoforming, rotomolding, blow molding, injection molding, extrusion coating, and/or foaming of the composite or composition comprising the composite. Most preferably, the orientation process comprises forming a film from the composite or composition comprising the composite, which is thermoformed, blow molded, injection molded, extrusion coated and/or foamed. Thus, in any embodiment, the composite, but most preferably an oriented article made therefrom, comprises a composite having an average length of at least 1, or 2, or 4, or 5 μm, and an average diameter of at least 5, or 10, or 20, or 30 nm; or a mean length in the range of 1, or 2, or 4, or 5 μm to 8, or 10, or 20, or 50 μm, and a mean diameter in the range of 5, or 10, or 20, or 30 to 60, or 80, or 100, or 120 nm.

Accordingly, also disclosed is a method of forming a composite comprising (or consisting of, or consisting essentially of) combining a polyethylene and in the range of from 1 or 3 wt% to 7, or 8, or 10, or 15, or 20 or 25 wt%, based on the weight of the composition, of at least one cyclic olefin copolymer, wherein the cyclic olefin copolymer has a Tg value of at least 30, or 40, or 50, or 60, or 65, or 70 ℃; and orienting the composite to form an article, wherein the article comprises a composite having an average length of at least 1, or 2, or 4, or 5 μ ι η, and an average diameter of at least 5, or 10, or 20, or 30 nm; or a mean length in the range of 1, or 2, or 4, or 5 μm to 8, or 10, or 20, or 50 μm, and a mean diameter in the range of 10, or 20, or 30, or 40nm to 60, or 80, or 100, or 120 nm. The oriented article is then formed by an orientation step (e.g., film forming, thermoforming, etc.).

The composite so produced can be formed into useful articles by methods that orient the material to facilitate formation of the rod. For example, in any embodiment, a foamed article may be formed from a composite or a composite blended with another polymer and/or additives (e.g., fillers, antioxidants, etc.). Blowing agents useful in forming the foamed articles described herein can generally be compounds or elements or mixtures thereof that are generally in a gaseous, liquid, or solid state. These blowing agents may be characterized as physically expanding or chemically decomposing. In physically expanding blowing agents, the term "generally gaseous" means that the expansion medium used is a gas at the temperatures and pressures encountered during the preparation of the foamable compound, and that the medium can be introduced in gaseous or liquid form, for convenience. Such agents may be added to the composite by blending the dried polymer with a blowing agent, followed by melt extrusion, or by blending the agents in the polymer melt during extrusion. The blowing agent (particularly the gaseous agent) may be blended with the polymer melt as it exits the melt extruder or die used to form the foamed article.

Exemplary normally gaseous and liquid blowing agents include halogen derivatives of methane and ethane, such as fluoromethane, methyl chloride, difluoromethane, dichloromethane, perfluoromethane, trichloromethane, difluoromethyl chloride, dichlorofluoromethane, dichlorodifluoromethane, trifluoromethyl chloride, trichloromonofluoromethane, fluoroethane, ethyl chloride, 2,2, 2-trifluoro-1, 1-dichloroethane, 1,1, 1-trichloroethane, difluoro-tetrachloroethane, 1, 1-dichloro-1-fluoroethane, 1, 1-difluoro-1-chloroethane, dichloro-tetrafluoroethane, chlorotrifluoroethane, trichlorotrifluoroethane, 1-chloro-1, 2,2, 2-tetrafluoroethane, 1, 1-difluoroethane, 1,1, 1-trifluoroethane, 1,1,1, 2-tetrafluoroethane, perfluoroethane, pentafluoroethane, 2, 2-difluoropropane, 1,1, 1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, chloroheptafluoropropane, dichlorohexafluoropropane, perfluorobutane, perfluorocyclobutane, sulfur hexafluoride and mixtures thereof. Other normally gaseous and liquid blowing agents which may be used are hydrocarbons and other organic compounds such as acetylene, ammonia, butadiene, butane, butene, isobutane, isobutene, dimethylamine, propane, dimethylpropane, ethane, ethylamine, methane, monomethylamine, trimethylamine, pentane, cyclopentane, hexane, propane, propylene, alcohols, ethers, ketones and the like. Inert gases and compounds, such as nitrogen, argon, neon or helium, may also be used as blowing agents.

Solid, chemically decomposable blowing agents that decompose at elevated temperatures to form a gas may be used to expand the composite. Typically, a decomposable blowing agent will have a decomposition temperature (with the release of gaseous material) of 130 ℃ to 200, or 250, or 300 or 350 ℃. Exemplary chemical blowing agents include azodicarbonamide, p, p' -oxybis (benzene) sulfonyl hydrazide, p-toluenesulfonyl semicarbazide, 5-phenyltetrazole, ethyl-5-phenyltetrazole, dinitrosopentamethylenetetramine and other azo, N-nitroso, carbonate and sulfonyl hydrazide compounds as well as various acid/bicarbonate compounds that decompose upon heating. Representative volatile liquid blowing agents include isobutane, difluoroethane or mixtures of the two. For decomposable solid blowing agents azodicarbonamide is preferred, while for inert gases carbon dioxide is preferred.

Techniques for producing foam structures are known, particularly for styrenic compositions. The foamed articles of the present invention may take any physical configuration known in the art, such as sheets, slabs, other regular or irregular extruded profiles, and regular or irregular molded gum blocks (buns). Other useful examples of forms of foamed or foamable objects known in the art include expandable or foamable particles, moldable foam particles or beads, and articles formed by the expansion and/or consolidation and fusion of such particles. In any embodiment, the foamable article or composite can be crosslinked prior to expansion, such as a free radical initiated chemical crosslinking or ionizing radiation process, or crosslinked after expansion. If desired, crosslinking after swelling can be carried out by exposure to chemical crosslinking agents or radiation or, when silane-grafted polymers are used, optionally with exposure to moisture with a suitable silanolysis catalyst.

Exemplary, but non-limiting methods of combining the various components of the foamable composite include melt blending, diffusion limited imbibition, liquid mixing, and the like, optionally preceded by pulverization or other reduction of particle size of any or all of the components. Melt blending can be achieved in a batch or continuous process, and it is preferably conducted under temperature control. In addition, many suitable devices for melt blending are known in the art, including those having single and multiple archimedes screw conveyor barrels, high shear "Banbury" type mixers and other internal mixers. The purpose of such blending or mixing, by means and conditions appropriate to the physical processing characteristics of the components, is to provide a homogeneous mixture therein. The one or more components may be introduced in a stepwise manner after an existing mixing operation, during a subsequent mixing operation, or in the case of an extruder, at one or more downstream locations in the barrel.

An expandable or foamable composite will have incorporated therein a blowing agent, such as a decomposable or physically expandable chemical blowing agent, for expansion in a mold upon exposure of the composition to appropriate heat, and optionally sudden release of pressure. The composites have many uses as foamed articles, including automotive parts, insulation and other building parts, food containers, sports equipment and other household and commercial uses.

The composites can also be thermoformed to produce useful thermoformed articles. Thermoforming is a manufacturing process in which a composite sheet is heated to a pliable forming temperature, formed into a particular shape in a mold, and trimmed to produce a usable product. When thinner gauge (gauge) and certain material types are involved, the sheet or "film" is heated in an oven to a sufficiently high temperature that it can be stretched in or on a mold and cooled to its final shape. Its simplified form is vacuum forming. The composites described herein may desirably be formed into films or sheets suitable for thermoforming processes.

In any embodiment, a small bench-top or laboratory-sized machine may be used to heat the small cut portions of the composite sheet and draw them on the mold using a vacuum. This method is commonly used for sample and prototype parts. In complex and high volume applications, very large production machines may be used to heat and shape the composite sheet and trim the parts formed from the sheet in a continuous high speed process, and thousands of finished parts may be produced per hour, depending on the size of the machine and die and the size of the parts formed. The composites described herein are suitable for both types of thermoforming.

One desired type of thermoforming is thin thickness thermoforming. Thin thickness thermoforming the manufacture of mainly disposable cups, containers, lids, trays, blisters, clamshells and other products used in the food, medical and general retail industries. Heavy gauge thermoforming includes a variety of parts such as vehicle doors and dashboards, refrigerator liners, utility lathes, and plastic pallets. Thick thickness forming uses the same basic method as continuous thin thickness sheet forming, typically with a heated plastic sheet draped over a mold. Many thick gauge molding applications use vacuum only during the molding process, although some use two halves of a mating molding tool and include air pressure to assist in molding.

In any embodiment, the sheet comprising (or consisting essentially of) the composite is fed from a roll or extruder into a set of guide (index) chains incorporating pins or spikes that pierce the sheet and transport it through an oven heated to a forming temperature. The heated sheet is then directed to a forming station (station) where the mating mold and pressure box are closed on the sheet, and then a vacuum is applied to remove trapped air and push the material into or onto the mold along with pressurized air, thereby forming the plastic of the detailed shape of the mold. In the case of higher, deeper drawn, formed parts, plunger-assisted pressing is often used in addition to vacuum to provide the desired material distribution and thickness in the finished part. In any event, after a short molding cycle, when the molding tool is opened, a burst of reverse air pressure, commonly referred to as an air jet, is triggered from the vacuum side of the mold to break the vacuum and assist in releasing the molded part, or ejecting the mold. A stripper plate may also be used on the mold when the mold is opened to strip finer parts or those with negative patterns, undercut areas. The composite sheet containing the shaped parts is then directed to a finishing station on the same machine where the die cuts the parts from the remaining web of sheet (web) or to a separate finishing press where the shaped parts are finished. The web of sheet material remaining after trimming the formed part is typically wound onto a take-up reel or fed to an in-line (inline) pelletizer for recycling.

In general, the composites of the present invention can be used to make a variety of thermoformed articles, such as automotive parts, building parts, electronic devices, medical devices, sports devices, food containers, appliances, and other household and commercial uses. Similarly, the compounds can be used for thermoformed articles made by injection molding, blow molding, and rotational molding processes.

The various descriptive elements and numerical ranges of the COC/PE complexes of the invention and methods of forming the same disclosed herein may be combined with other descriptive elements and numerical ranges to describe the invention(s); furthermore, for a given element, any numerical upper limit described herein can be combined with any numerical lower limit, including embodiments in jurisdictions that permit such combinations. The features of the present invention are illustrated in the following non-limiting examples.

Examples

A method. Extracting Topas^TM5013COC (Topas Advanced polymers) (norbornene: 78 wt% or 51 mol%, Density: 1.02 g/cm)³MI less than 0.1g/10min at 190 ℃ and 2.16kg load, Tg: 134 deg.C) ("COC 1") was added to the exceted at a level of 3, 5, 10%, respectively^TM1018LLDPE (ExxonMobil chemical company). The mixture was melt blended and pelletized in an 18mm twin screw extruder. The compounded blend was subjected to a Rheotester 1000 capillary rheometer as described below with Rheotens 71.97

The combination of (a) and (b) is subjected to melt strength measurement. In the test, the sample was oriented by pulling down the roller. Application ofThe pull down onto the wire is considered an orientation, triggering the formation of COC rods, as demonstrated in AFM measurements.

In the same manner, Topas was administered^TM9506 ("COC 2") (norbornene: 62 wt%, 33 mol%; density: 1.01 g/cm)³MI at 190 ℃ under a 2.16kg load is 1g/10min, Tg: 65 ℃ C.) with other LLDPE and LD. These materials are summarized in table 1. These COCs are also linked to Enable^TM2010(ExxonMobil Chemical Company) and low density LD165BW (ExxonMobil Chemical Company). The melt strength values are summarized in tables 2 and 3. Samples of the blends and LLDPE and LD alone were further characterized and are summarized in tables 4, 5 and 6.

Excepted containing 5 wt% COC^TM1018LLDPE blends exhibit purer Exceed^TM1018LLDPE has a melt strength increase of over 25 times that of LDPE (which has the highest melt strength in PE due to long chain branching) which is typically 1.5 times that of LDPE.

AFM images were taken at the beginning (no orientation) and at the end (strong orientation) of the rhetens line with the LL3 mixture of COC1 and COC 2. Without orientation, the separate COC domains are spherical (FIG. 1: COC1/LL3 blend, FIG. 2: COC2/LL3 blend), while in MD orientation they elongate and form fibers (FIG. 3: COC1/LL3 blend, FIG. 4: COC2/LL3 blend). COC1 can form long fibers better, thereby enhancing the polyethylene matrix better, which can explain why COC1 in LLDPE blend films shows much better performance.

Melt index. ASTM D1238, 2.16kg, and 190 ℃.

Differential scanning calorimetry. The crystallinity of the polyolefin is obtained by dividing its heat of fusion as measured by DSC by the heat of fusion of a 100% crystalline polyethylene having a value of 293J/g (B.Wunderlich, Thermal Analysis, 417-. DSC procedure can be used to determine the glass transition temperature (T) of COC_g) And for determining the heat of fusion (Δ H), melting point temperature (T) of the composites described herein_m) And crystallization temperature (T)_c). Specifically, about 6mg of untreated (unannealed) material was placed on a microliter aluminum sampleIn the disc. The sample was placed in a differential scanning calorimeter (Perkin Elmer or TA instrument thermal analysis system) and heated from ambient temperature to 210 ℃ at 10 ℃/min and held at 210 ℃ for 5 minutes. Thereafter, the sample was cooled to-90 ℃ at 10 ℃/min. The sample was held at-90 ℃ for 5 minutes and then heated at 10 ℃/minute from-90 ℃ to 210 ℃ for a second heating cycle. T is determined after the second heating cycle_gAnd T_mBut the sample was not annealed in other ways. Determination of the melting temperature T in the second heating cycle in TA Universal Analysis_m，T_gAnd heat of fusion (Δ H). Calculation of T in DSC Using the "glass transition" menu item on the TA Universal Analysis device_gStart point, end point, inflection point, and signal transition. The program can determine a starting point, i.e., the intersection of the first and second tangents, where the inflection point is the portion of the curve between the first and third tangents where the slope is greatest and the ending point is the intersection of the second and third tangents.

Sentmanat extensional rheology. Tensile rheological tests were performed on Anton-Paar MCR 501 or TA Instruments DHR-3 using the SER Universal testing platform (XPansion Instruments, LLC) model SER2-P or SER 3-G. The ser (sentmanat extension rheometer) test platform is described in U.S. patent No.6,578,413 and U.S. patent No.6,691,569. General descriptions of transient uniaxial extensional viscosity measurements are described, for example, in "stress concentration of polymeric in uniaxial elastic flow," 47(3) The Society of Rheology, Inc., J.Rheol., 619-; and "Measuring The transient extended morphology of polyethylene substrates using The SER undivided simulation," 49(3) The Society of Rheology, Inc., J.Rheol.,585-606 (2005). Strain hardening occurs when the polymer is uniaxially stretched and the transient elongational viscosity increases beyond the value predicted by linear viscoelasticity theory. In the transient elongational viscosity versus time diagram, strain hardening is observed with a sudden increase in elongational viscosity. Strain Hardening Rate (SHR) is used to characterize the rise in elongational viscosity and is defined as the ratio of the maximum transient elongational viscosity to three times the transient zero shear rate viscosity value at the same strain. When the ratio is greater than 1, the material is presentAnd hardening under strain. The SER instrument consists of a main winding (windup) drum and a secondary winding drum mounted in pairs on bearings in a chassis and mechanically coupled by intermeshing gears. Rotation of the drive shaft causes rotation of the fixed primary drum and equal but opposite rotation of the secondary drum, which causes the end of the polymer sample to wind onto the drum, causing the sample to stretch. In most cases, the samples were mounted on the drum by a retaining clip. In addition to the tensile test, the samples were also tested using transient steady state shear conditions and matched to the tensile data using a correlation factor of 3. This provides a Linear Viscoelastic Envelope (LVE). A rectangular sample specimen measuring approximately 18.0mm long by 12.70mm wide was mounted on the SER fixture. The samples were typically tested at three Hencky strain rates: 0.01s^-1，0.1s^-1And 1s^-1. The test temperature was 150 ℃. Polymer samples were prepared as follows: the sample specimens were hot pressed at 190 ℃, mounted on a jig, and equilibrated at 150 ℃.

Rheotens. Using a Rheotest 1000 capillary rheometer with Rheotens 71.97

The total amount of material present in the Rheotester barrel was extruded through the die and picked up by the Rheotens rolls.

Density. The density of the polymer was determined according to ASTM D1505-10. Compression molded samples for density measurement were prepared according to ASTM D4703-10 a. Prior to density measurement, the samples (typically made from pellet samples) were conditioned by density conditioning the samples at 23 ℃ for 40 hours.

Atomic force microscopy. Atomic Force Microscopy (AFM) is a type of microscope performed using an Asylum Research Cypher atomic force microscopeAnd (3) a phase imaging technology. Prior to scanning, the samples were cryomicrotomed to form a smooth surface at-120 ℃. After microtomy, samples were dried in a desiccator at N prior to evaluation₂And (5) performing lower purging. Imaging was performed according to the following: the instrument was tuned to the fundamental (first) mode of the cantilever, setting the amplitude to 1.0V and the drive frequency to be about 5% below the free air resonant frequency of the cantilever. If operating in a multi-frequency mode, the higher mode (second, third or fourth depending on the cantilever and the support) is selected, setting the amplitude to 100mV and the drive frequency to resonance. The set point was set to 640mV, the scan rate was set to 1Hz, and the scan angle was set to 90 deg.. AFM SQC and X, Y and Z corrections an Asylum Research reference standard (10 micron x10 micron pitch grating x200nm deep pits) was used. The instrument has been calibrated to be accurate to within 2% or better of the true X-Y value and within 5% or better of the true Z value. A representative scan size is 500x500 nm.

The branching index. The branching index was determined by using high temperature GPC (Agilent PL-220) equipped with three in-line detectors, i.e., a differential refractive index detector ("DRI"), a light scattering ("LS") detector, and a viscometer. Detector calibration is described in the paper and references in T.Sun, P.Brant, R.R.Chance and W.W.Graessley, 34(19) MACROMOLECULES, 6812-. GPC measurements herein were performed using three Agilent PLGel 10 μm mix-B LS columns. The nominal flow rate was 0.5mL/min and the nominal injection volume was 300. mu.L. The various transmission lines, columns, viscometer and differential refractometer (DRI detector) were contained in an oven maintained at 145 ℃. The solvents used for the experiments were prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2, 4-trichlorobenzene ("TCB"). The TCB mixture was then filtered through a 0.1 μm Teflon filter. The TCB was then degassed using an in-line degasser prior to entering the GPC. The polymer solution was prepared by placing the dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160 ℃ and shaking continuously for about 2 hours. All quantities were measured gravimetrically. The TCB density, which is used to express the polymer concentration in units of mass/volume, is 1.463g/ml at 23 ℃ and 1.284g/ml at 145 ℃.The injection concentration is 0.5 to 2.0mg/ml, with lower concentrations being used for higher molecular weight samples. Before running each sample, the DRI detector and viscometer were purged. The flow rate in the column was then increased to 0.5ml/min and the DRI was allowed to stabilize for 8 hours before injecting the first sample. The LS laser was turned on at least 1 to 1.5 hours before running the sample. The concentration c at each point in the chromatogram is determined by the baseline-subtracted DRI signal I_DRICalculated using the following equation:

c＝K_DRII_DRI/(dn/dc),

wherein K_DRIIs a constant determined by correcting for DRI and (dn/dc) is the incremental refractive index of the system. The refractive index n of TCB at 145 ℃ and a lambda of 690nm is 1.500. The molecular weight units are expressed in kg/mol or g/mol and the intrinsic viscosity is expressed in dL/g.

The LS detector is Wyatt Technology High Temperature Dawn Heleos. The molecular weight M at each point in the chromatogram was determined by analyzing the LS output using a Zimm model for static Light Scattering (W.Burchard & W.Ritchering, "Dynamic Light Scattering from Polymer Solutions," 80Progress in Colloid & Polymer Science, 151-:

here, Δ R (θ) is the measured excess Rayleigh scattering intensity at the scattering angle θ, "c" is the polymer concentration determined from the DRI analysis, A₂Is the second dimensional coefficient, P (θ) is the shape factor for a monodisperse random coil, K_oIs the optical constant of the system, as shown by the following equation:

wherein N is_AIs the afugard constant, and (dn/dc) is the incremental refractive index of the system, which takes the same value as obtained by the DRI method, and the value of "n" is as described above. The value of Mn is. + -.50 g/mol and the value of Mw is. + -.100 g/mol.

A high temperature Viscotek Corporation viscometer (with four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors) is used to determine specific viscosity and branching one sensor measures the total pressure drop across the detector and the other sensor, located between the two sides of the bridge, measures the differential pressure_S) Intrinsic viscosity at each point in the chromatogram [ η]Calculated according to the following equation:

ηs＝c[η]+0.3(c[η])²，

where "c" is the concentration and is determined from the DRI output the average intrinsic viscosity of the sample [ η]_avgCalculated using the following equation:

where the sum is taken from all chromatographic sections i between the integral limits. For data processing, the Mark-Houwink constants used were K-0.000579 and a-0.695.

The branching index (g 'vis or simply g') is defined as the ratio of the intrinsic viscosity of a branched polymer to the intrinsic viscosity of a linear polymer of the same molecular weight and the same composition. The branching index g' is mathematically defined as:

for purposes of this invention and its claims, for linear polyethylene homopolymers α ═ 0.695 and k ═ 0.000579 linear polyethylene homopolymers are used for the calculation of g', regardless of comonomer content_vIs the viscosity average molecular weight based on the molecular weight determined by LS analysis.

TABLE 1 materials used in the examples

Table 2 melt Strength (Rheotens) of COC/LLDPE blends (COC 1 ═ 78 wt% norbornene

Table 3 melt Strength (Rheotens) of COC/LLDPE blends (COC 2 ═ 62% by weight of norbornene

TABLE 4 characterization of COC/LLDPE blends

TABLE 5 characterization of COC/LLDPE blends

TABLE 6 Properties of the comparative polyethylenes

As used herein, "consisting essentially of means that the claimed article or composite includes only the referenced components and does not contain any additional components that would alter its measured properties by more than 20, or 15, or 10%, and most preferably means that the" additive "is present in an amount less than 5, or 4, or 3, or 2 wt% of the weight of the composition. Such additional additives may include, for example, fillers, nucleating or clarifying agents, colorants, blowing agents, antioxidants, alkyl radical scavengers (preferably vitamin E, or other tocopherols and/or tocotrienols), UV inhibitors, acid scavengers, curing agents and crosslinking agents, aliphatic and/or cyclic containing oligomers or polymers (commonly referred to as hydrocarbon resins), and other additives generally known in the art. The phrase "consisting essentially of when referring to a process means that no other process features can alter the properties of the claimed polymers, polymer blends or articles produced therefrom by any more than 10, 15 or 20%, but in addition to that there may be process features not mentioned.

For all jurisdictions in which the teachings of "incorporated by reference" are applicable, all test methods, patent publications, patents, and reference articles are incorporated by reference herein in their entirety or in relevant portions thereof.