Zeolite-containing polyolefin film

Abstract

A method for producing a zeolite embedded polyolefin film for packaging polyurethane foam in which the zeolite is also entrapped.

Description

[Technical Field]

[0001] This disclosure relates to the use of high silica zeolites in foam packaging. More specifically, this disclosure relates to the production and use of zeolite-containing polyolefin film compositions used to package polyurethane (PUR) foams that also contain zeolite. [Background technology]

[0002] Introduction Polyurethane materials can be produced in a wide range of densities (6-1220 kg / m³) and rigidities (soft elastomers to rigid, hard plastics). These materials are widely used in many high-performance applications. One advantage of polyurethanes is that the final product is typically formed from polymers during a polymerization reaction, allowing for fine tuning of processing conditions to control the properties of the final product. This final product, a polyurethane polymer, is formed between an isocyanate and a polyol.

[0003] Major polyurethane markets, such as flexible foams, have stringent mechanical performance targets, such as load-bearing capacity and resilience. Additionally, comfort, tactility, and a degree of protection are equally important to end users. Another key attribute that has long been sought is low odor and low volatile chemical content. Because the emission of volatile molecules in the final product can have both regulatory and quality considerations, polyurethane products with minimal volatile content (VOC) are highly desirable.

[0004] Volatility and odor-causing molecules in polyurethane systems can be attributed to unreacted monomers or by-product molecules formed from the alkoxylation reaction used to produce polyols. Typically, these undesirable volatiles are removed after alkoxylation by time-consuming and wasteful stripping methods. However, current stripping methods are unable to cost-effectively remove residual volatile molecules. Summary of the Invention

[0005] The objective of this disclosure is to provide a composition for producing zeolite in plastic films used to package polyurethane (PU) foam. Zeolite embedded in polyolefin films can adsorb and remove odor-causing volatile compounds (VOCs) emitted from packaged PU foam, resulting in a low- or odorless composition. This packaging approach can be applied during shipping to consumers or during storage of foam products in warehouses. Because this approach removes odorous volatiles after production, PU foam can be produced without any modifications to the foam formulation.

[0006] Surprisingly, high-silica zeolites with low affinity for HO molecules have been found to have very high selectivity for non-polar and polar organic molecules. These zeolites are capable of physically adsorbing small organic molecules in the presence of HO. Under normal operating conditions, the hydrophobic nature of these high-silica zeolites prevents the displacement of adsorbed odor-causing VOC molecules by HO molecules. Compared to other commercially available zeolites, these high-silica substitutes demonstrate significant reductions in odor-causing VOC molecules at relatively low loading levels.

[0007] Another object of the present disclosure is to provide compositions for producing polyisocyanurate (PIR) and polyurethane (PUR) foams, processes for preparing PUR foams, and novel high silica zeolite additives for preparing PUR foams, and foams made therewith.

[0008] The incorporation of such zeolites into PU foams results in compositions with low or no odor. In one embodiment, the flexible polyurethane foam produced has a greater than 80% (less than 10 ppm) reduction in total aldehyde content compared to foams produced by currently known methods. Another embodiment achieves a greater than 50% reduction in total odor-causing VOC content compared to conventional production methods, in addition to or instead of the reduction in aldehyde content. None of these embodiments alters the mechanical and physical properties of the resulting foam compared to conventional production methods. Zeolites can be used to reduce odor-causing VOC molecules in both open-cell and closed-cell foams, and similar results in reducing odor-causing VOCs have been observed when zeolites are used in polyolefin packaging films for PU foams.

[0009] Additionally, the inert nature of these zeolites, when incorporated during production, has minimal effect on the mechanical and physical properties of the resulting foams and / or films, enabling the production and packaging of flexible, low-odor foams for use in automotive applications, mattresses, pillows, furniture, and other consumer comfort applications.

[0010] Zeolite may be added to the polyol component, the foaming formulation, and / or the polyolefin film in which the formed PU foam is stored. The use of zeolite in this manner can substantially eliminate detectable odors emitted by the PU foam.

[0011] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. DETAILED DESCRIPTION OF THE INVENTION

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Additionally, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference. As disclosed herein, the terms "composition," "formulation," or "mixture" refer to a physical blend of different components obtained by simply mixing the different components by physical means. As disclosed herein, "and / or" means "and, or alternatively." All ranges include endpoints unless otherwise indicated.

[0013] I. Polyolefin film In various embodiments, disclosed herein are polyolefin films, which may be described as shrink films, including monolayer films or multilayer films having at least one layer comprising a blended resin, the blended resin comprising: (i) low-density polyethylene (LDPE), the LDPE having a density of 0.915 g / cc to 0.925 g / cc and a melt index I2 of 0.1 g / 10 min to 1 g / 10 min; or (ii) linear low-density polyethylene (LLDPE), the LLDPE having a density of 0.915 g / cc to 0.945 g / cc and a melt index I2 of 0.1 g / 10 min to 1 g / 10 min; or (iii) a combination of (i) and (ii), and a high-silica zeolite having a Si / Al molar ratio greater than 35.

[0014] Also disclosed herein is a method for making a shrink film, the method including providing a blended resin and forming a monolayer or multilayer film from the blended resin.

[0015] Also disclosed herein is a multilayer shrink film. The multilayer shrink film includes a core layer and two skin layers, the skin layers including high optical properties skin layers, the core layer including a blended resin. The blended resin includes: (i) low density polyethylene (LDPE), the LDPE having a density of 0.915 g / cc to 0.925 g / cc and a melt index I2 of 0.1 g / 10 min to 1 g / 10 min; or (ii) linear low density polyethylene (LLDPE), the LLDPE having a density of 0.915 g / cc to 0.945 g / cc and a melt index I2 of 0.1 g / 10 min to 1 g / 10 min; or (iii) a combination of (i) and (ii), and a high silica zeolite having a Si / Al molar ratio greater than 35.

[0016] As used herein, the terms "polyethylene" or "ethylene-based polymer" are intended to mean a polymer containing greater than 50 mole percent units derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).

[0017] The term "LDPE," sometimes also referred to as "high pressure ethylene polymer" or "highly branched polyethylene," is defined to mean that the polymer is partially or fully homopolymerized or copolymerized in an autoclave or tubular reactor at pressures greater than 14,500 psi (100 MPa) using a free radical initiator such as peroxide (see, e.g., U.S. Pat. No. 4,599,392). LDPE resins typically have densities in the range of 0.915 to 0.935 g / cm.

[0018] The term "LLDPE" includes resins made using Ziegler-Natta catalyst systems, as well as resins made using single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as "m-LLDPE") and constrained geometry catalysts, and resins made using post-metallocene, molecular catalysts. LLDPE includes linear, substantially linear, or heterogeneous polyethylene copolymers or homopolymers. LLDPE contains less long chain branching than LDPE and includes substantially linear ethylene polymers as further defined in U.S. Patent Nos. 5,272,236, 5,278,272, 5,582,923, and 5,733,155, homogeneously branched linear ethylene polymer compositions such as those in U.S. Patent No. 3,645,992, heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698, and blends thereof (such as those disclosed in U.S. Patent No. 3,914,342 or 5,854,045). LLDPE resins may be made via gas phase, solution phase, or slurry polymerization, or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0019] The term "MDPE" refers to polyethylene having a density of 0.926 to 0.945 g / cc. "MDPE" is typically made using chromium or Ziegler-Natta catalysts, or using single-site catalysts, including but not limited to bis-metallocene catalysts and constrained geometry catalysts.

[0020] The term "HDPE" refers to polyethylene having a density greater than 0.945 g / cc, which is generally prepared using a Ziegler-Natta catalyst, a chromium catalyst, or a single-site catalyst, including, but not limited to, bis-metallocene catalysts and constrained geometry catalysts.

[0021] As used herein, the term "post-consumer recycled resin" (or "PCR resin"), as defined by ISO-14021, refers to a polymeric material containing a blend of polymers recovered from materials previously used in consumer or industrial applications. Thus, the general term "post-consumer recycled resin" includes blends of polymers recovered from materials generated by households or commercial, industrial, and business facilities in their role as end users of materials that can no longer be used for their intended purposes. The general term "post-consumer recycled resin" also includes blends of polymers recovered from the return of materials from the distribution chain. PCR resins are often collected from reclamation programs and recycling plants. PCR resins may contain one or more of the following: polyethylene, polypropylene, polyester, poly(vinyl chloride), polystyrene, acrylonitrile butadiene styrene, polyamide, ethylene vinyl alcohol, ethylene vinyl acetate, or polyvinyl chloride. PCR may contain one or more contaminants. Contaminants may be the result of the use of the polymeric material before it is modified for reuse. For example, contaminants may include paper, ink, food residue, or other recycled materials in addition to polymers that may result from the recycling process.

[0022] PCR differs from virgin polymeric materials. Virgin polymeric materials do not include materials previously used in consumer or industrial applications. Virgin polymeric materials have not been subjected to heating or molding processes other than the polymer synthesis process or pelletization, as typical PCR resins have, or have not been otherwise subjected to such processes. The physical, chemical, and flow properties of PCR resins are different compared to virgin polymeric resins, which can present challenges for incorporating PCR resins into formulations for commercial use.

[0023] PCR resins are typically polyolefins, particularly polyethylene. PCR can include HDPE packaging such as bottles (milk jugs, juice bottles) and LDPE / LLDPE packaging such as films. PCR also contains residues from its original use, such as paper, adhesives, inks, nylon, ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), and other odor-causing agents. Sources of PCR resins can include, for example, bottle caps and closures, milk, water, or orange juice containers, detergent bottles, office automation equipment (e.g., printers, computers, copiers), white goods (e.g., refrigerators, washing machines), household appliances (e.g., televisions, video cassette recorders, stereos), automobile shredder residue (the mixed material remaining after most of the metals have been separated from shredded automobiles and other metal-rich products "shredded" by metal recyclers), packaging waste, household waste, rotomolded parts (e.g., kayaks / coolers), construction waste, and industrial molding and extrusion scrap.

[0024] In embodiments, the polyolefin in the PCR resin can be any polyolefin found in recycle streams, such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), MDPE, ULDPE, polypropylene (PP), functionalized polyolefins, and combinations of two or more of the foregoing polymers.

[0025] In embodiments, PCR resin further contains residues from its original use, such as paper, adhesives, inks, nylon, ethylene vinyl alcohol (EVOH), polyamide (PA), polyethylene terephthalate (PET), and other odor-causing agents.

[0026] In embodiments, the PCR resin comprises at least 50 weight percent (wt%), or at least 60 wt%, or at least 70 wt%, or at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt%, or at least 95 wt% polyolefin, based on the total weight of the post-consumer recycled resin. In embodiments, the PCR resin may comprise up to 99.9 wt%, or up to 99.5 wt%, or up to 99 wt%, or up to 98 wt%, or up to 97 wt%, or up to 96 wt%, or up to 95 wt%, or up to 90 wt% polyolefin, based on the total weight of the post-consumer recycled resin.

[0027] The term "odor-active zeolite" refers to a zeolite that is an odor control agent, for example, due to its ability to absorb and / or adsorb odorous liquids and gases, thereby neutralizing odor. A description of such zeolites can be found below under the heading Zeolites in this disclosure.

[0028] As used throughout this specification, the following abbreviations have the following meanings, unless the context clearly dictates otherwise: "=" means "equal to", "@" means "at", "<" means "less than", ">" means "greater than", "I2" means "melt index" measured at 2.16 kg and 190°C, g = grams, mg = milligrams, pts = parts by weight, kg = kilogram, "kg / hr" = kilograms per hour, g / cc = grams per cubic centimeter, kg / m 3 = kilograms per cubic meter, g / mol = grams per mole, L = liter, mL = milliliter, g / L = grams per liter, Mw = weight average molecular weight, Mn = number average molecular weight, Mz = z average molecular weight, m ​​= meter, μm = micrometer, mm = millimeter, cm = centimeter, min = minute, s = second, mm / s 2 = millimeters per second squared, mm / s = millimeters per second, ms = milliseconds, hr = hours, mm / min = millimeters per minute, m / s = meters per second, °C = degrees Celsius, °C / min = degrees Celsius per minute, mPa.s = millipascal-seconds, MPa = megapascals, kPa = kilopascals, Pa.s / m 2 = Pascal-seconds per square meter, N = Newton, cN = centinewton, rpm = revolutions per minute, mm 2 = square millimeters, g / 10min = grams per 10 minutes, J = joules, J / g = joules per gram, % = percent, eq% = equivalent percent, vol% = volume percent, and wt% = weight percent.

[0029] Unless otherwise specified, all percentages, parts, ratios, and other amounts are defined by weight. For example, all percentages set forth herein are weight percentages (wt %) unless otherwise indicated. Temperatures are in degrees Celsius (°C), and "ambient temperature" means 20°C to 25°C unless otherwise indicated.

[0030] In one or more embodiments, the present invention relates to a shrink film having at least one layer comprising a blended resin. In embodiments herein, the at least one layer may comprise at least 50%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97%, at least 99%, or 100% by weight of the blended resin. The shrink film may be a completely recyclable, mono-material PE structure without any additional barrier layers added to the film PE product structure.

[0031] As previously described herein, the compounded resin comprises at least (i) low-density polyethylene (LDPE), or (ii) linear low-density polyethylene (LLDPE), or (iii) a combination of (i) and (ii), and a zeolite additive. In one or more embodiments herein, the compounded resin comprises 20 to 100 weight percent post-consumer recycled resin (alternatively, from a lower limit of 30, 35, 40, 50, or 60 weight percent to an upper limit of 100, 90, 80, or 75 weight percent). In some embodiments, the compounded resin comprises 30 to 100 weight percent, 35 to 100 weight percent, 35 to 90 weight percent, or 40 to 80 weight percent post-consumer recycled resin. In addition to the amount of post-consumer recycled resin in the compounded resin, in one or more embodiments herein, the compounded resin concentration of component (i) is 0 weight percent to 60 weight percent, or alternatively, 5 weight percent to 60 weight percent, 5 weight percent to 50 weight percent, 5 weight percent to 40 weight percent, 5 weight percent to 30 weight percent, or 10 weight percent to 30 weight percent. In addition to the amount of post-consumer recycled resin and component (i) in the compounded resin, in one or more embodiments herein, the compounded resin concentration of component (ii) is 0 weight percent to 60 weight percent, or alternatively, 10 weight percent to 60 weight percent, 25 weight percent to 60 weight percent, 30 weight percent to 60 weight percent, 30 weight percent to 50 weight percent, or 35 weight percent to 50 weight percent. In some embodiments, the compounded resin includes the aforementioned amounts of LDPE. In other embodiments, the compounded resin includes the aforementioned amounts of LLDPE. In further embodiments, the compounded resin includes the aforementioned amounts of LDPE and LLDPE.

[0032] Examples of suitable LDPE include commercially available resins such as LDPE150E available from The Dow Chemical Company or LDPE310E available from The Dow Chemical Company.

[0033] In embodiments herein, the LLDPE has a density from 0.915 g / cc to 0.945 g / cc and a melt index I2 from 0.1 g / 10 min to 1 g / 10 min, all individual values ​​and subranges being included and disclosed herein. For example, in some embodiments, the LLDPE has a density from 0.915 g / cc to 0.945 g / cc (alternatively, from 0.915 g / cc to 0.940 g / cc, from 0.915 g / cc to 0.938 g / cc, or from 0.917 g / cc to 0.938 g / cc) and a melt index, I2, from 0.1 g / 10 min to 1 g / 10 min (alternatively, from 0.1 g / 10 min to 1.0 g / 10 min, from 0.1 g / 10 min to 0.8 g / 10 min, from 0.1 g / 10 min to 0.6 g / 10 min, from 0.1 g / 10 min to 0.5 g / 10 min, or from 0.1 g / 10 min to 0.4 g / 10 min).

[0034] Examples of suitable LLDPEs include commercially available compounds such as TUFLIN™, DOWLEX™, DOWLEX™ NG, and ELITE™ resins (all available from The Dow Chemical Company) and mixtures thereof; ENABLE™ and EXCEED™ resins (both available from ExxonMobil) and mixtures thereof; LUMICENE™ and SUPERTOUGH™ resins (both available from Total) and mixtures thereof; and two or more of the foregoing resins in blends. Specific examples of suitable LLDPEs include DOWLEX™ 2045G resin, DOWLEX™ 2049G resin, DOWLEX™ 2098P resin, DOWLEX™ 2038.68G resin, DOWLEX™ 2645G resin, and DOWLEX™ NG5045P resin (all available from The Dow Chemical Company) and mixtures thereof.

[0035] In embodiments described herein, the compounded resin may have a density of from 0.925 g / cc to 0.960 g / cc. All individual values ​​and subranges from at least 0.925 g / cc to 0.960 g / cc are included and disclosed herein. For example, in some embodiments, the compounded resin may have a density of from 0.925 g / cc to 0.960 g / cc. 3 ~0.955g / cm 3 , 0.930g / cm 3 ~0.955g / cm 3 , or 0.935 g / cm 3 ~0.955g / cm 3 , or 0.935 g / cm 3 ~0.950g / cm 3 The density can be measured according to ASTM D792.

[0036] In addition to density, the compounded resin may have a molecular weight distribution (Mw / Mn) of 2.0 to 10.0. All individual values ​​and subranges from 2.0 to 10.0 are included and disclosed herein. For example, in some embodiments, the compounded resin may have a Mw / Mn ratio from a lower limit of 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, or 6.0 to an upper limit of 10.0, 9.5, 9.0, 8.5, or 8.0. In other embodiments, the compounded resin may have a Mw / Mn ratio of 5.0 to 10.0. In further embodiments, the compounded resin may have a Mw / Mn ratio of 6.0 to 9.0. In further embodiments, the compounded resin may have a Mw / Mn ratio of 6.0 to 8.5. The molecular weight distribution may be determined by the weight average molecular weight (M w ) number average molecular weight (M n ) to (i.e., M w / M n ) and can be measured by gel permeation chromatography techniques.

[0037] In addition to density and molecular weight distribution, the compounded resin may have a melt index I2 from 0.1 g / 10 min to 1.0 g / 10 min. All individual values ​​and subranges from 0.1 g / 10 min to 1.0 g / 10 min are included and disclosed herein. For example, in some embodiments, the polyethylene composition may have a melt index I2 from 0.1 g / 10 min to 0.8 g / 10 min, from 0.1 g / 10 min to 0.6 g / 10 min, from 0.1 g / 10 min to 0.5 g / 10 min, or from 0.1 g / 10 min to 0.4 g / 10 min. Melt index I2 may be measured according to ASTM D1238 (190°C and 2.16 kg).

[0038] In addition to density, molecular weight distribution, and melt index I2, the compounded resin may have a melt flow ratio I10 / I2 of 10.0 to 25.0. All individual values ​​and subranges from 10.0 to 25.0 are included and disclosed herein. For example, in some embodiments, the compounded resin may have a melt flow ratio I10 / I2 ranging from a lower limit of 10.0, 12.0, or 14.0 to an upper limit of 25.0, 23.0, or 22.0. In one or more embodiments, the compounded resin may have a melt flow ratio I10 / I2 of 12.0 to 25.0, 14.0 to 23.0, or 14.0 to 22.0. Melt index I10 can be measured according to ASTM D1238 (190°C and 10.0 kg).

[0039] In addition to the density, molecular weight distribution, melt index I2, and melt flow ratio I10 / I2, the compounded resin may have a melt flow ratio I21 / I2 of 25 to 200. All individual values ​​and subranges from 25 to 200 are included and disclosed herein. For example, in some embodiments, the compounded resin may have a melt flow ratio I21 / I2 ranging from a lower limit of 25, 30, 40, or 50 to an upper limit of 200, 175, 150, 125, 110, or 90. In one or more embodiments, the compounded resin may have a melt flow ratio I21 / I2 of 40 to 150, 40 to 125, or 50 to 110. Melt index I21 can be measured according to ASTM D1238 (190°C and 21.6 kg).

[0040] In addition to density, molecular weight distribution, melt index I2, melt flow ratios I10 / I2, and I21 / I2, the compounded resin can have a number average molecular weight Mn (g / mol) of 10,000 to 50,000 g / mol. All individual values ​​and subranges from 10,000 g / mol to 50,000 g / mol are included and disclosed herein. For example, the compounded resin can have an Mn of 12,000 to 50,000 g / mol, 12,000 to 45,000 g / mol, 12,000 to 30,000 g / mol, or 12,000 to 27,000 g / mol.

[0041] In addition to density, molecular weight distribution, melt index I2, melt flow ratios I10 / I2, I21 / I2, and number average molecular weight, the compounded resin can have a weight average molecular weight Mw (g / mol) of 80,000 to 200,000 g / mol. All individual values ​​and subranges between 80,000 and 200,000 g / mol are included and disclosed herein. For example, the compounded resin can have a Mw of 95,000 to 185,000 g / mol, 100,000 to 175,000 g / mol, or 110,000 to 170,000 g / mol.

[0042] In addition to density, molecular weight distribution, melt index I2, melt flow ratios I10 / I2, I21 / I2, number average molecular weight, and weight average molecular weight, the compounded resin can have a z-average molecular weight Mz (g / mol) of 300,000 to 1,000,000 g / mol. All individual values ​​and subranges from 300,000 g / mol to 1,000,000 g / mol are included and disclosed herein. For example, the compounded resin can have an Mz of 350,000 to 950,000, 400,000 to 900,000 g / mol, or 500,000 to 900,000 g / mol.

[0043] In addition to density, molecular weight distribution, melt index I2, melt flow ratios I10 / I2, I21 / I2, number average molecular weight, weight average molecular weight, and z-average molecular weight, the compounded resin may have an Mz / Mw ratio of 3 to 10. All individual values ​​and subranges between 3 and 10 are included and disclosed herein. For example, in some embodiments, the compounded resin may have an Mz / Mw ratio from a lower limit of 3, 3.0, 3.5, or 4.0 to an upper limit of 10, 10.0, 9.0, 8.5, 8.0, 7.5, 7.0, or 6.5. In other embodiments, the compounded resin may have an Mz / Mw ratio of 3.0 to 9.0, 3.0 to 8.0, 3.0 to 7.5, or 3.5 to 6.5. Mz can be measured by gel permeation chromatography techniques.

[0044] In addition to density, molecular weight distribution, melt index I2, melt flow ratios I10 / I2, I21 / I2, number average molecular weight, weight average molecular weight, z-average molecular weight, and Mz / Mw, the compounded resin can have a melt strength of 0.03 to 0.25 N. All individual values ​​and subranges from 0.03 to 0.25 N are included and disclosed herein. For example, in some embodiments, the compounded resin can have a melt strength of 0.05 to 0.20 N or 0.06 to 0.17 N.

[0045] In embodiments herein, the compounded resin may include one or more additives. The additives combined with the composition of the present invention may be blended to enable performance of a specified function while maintaining the excellent benefits / properties of the compounded resin. For example, the following additives that may be blended with the compounded resin include zeolites (see the Zeolites section below for more details), antioxidants, pigments, colorants, UV stabilizers, UV absorbers, processing aids, fillers, slip agents, antiblocking agents, etc., and mixtures thereof.

[0046] When used in a formulated resin, additives may generally be present in an amount ranging from 0% to 10% by weight in one embodiment, from about 0.001% to 5% by weight in another embodiment, and from 0.001% to 3% by weight in yet another embodiment. In other embodiments, optional additives may be added to a formulated resin in an amount of less than 5% by weight in one typical embodiment, less than 3% by weight in another embodiment, and less than 1% by weight in yet another embodiment.

[0047] The shrink film may be a monolayer film or a multilayer film. In one or more embodiments herein, the multilayer film has at least one layer comprising the blended resin. In other embodiments, the multilayer film has at least three layers, with at least one layer comprising the blended resin. In further embodiments, the multilayer film comprises a core layer and two skin layers, one skin layer on each side of the core layer, and the core layer comprises the blended resin. The core layer may comprise at least 50%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97%, at least 99%, or 100% by weight of the blended resin.

[0048] The process for making the compounded resin includes, for example, mixing together the above components (a), (b), and (c) and any desired optional additives. The mixing can be accomplished using a dry blending process or a melt blending process, both of which are well known to those skilled in the mixing art. In some embodiments, the compounded resin is a melt blended compounded resin.

[0049] In one or more embodiments, the shrink monolayer or multilayer film can have any desired length and width and thickness, for example, from 30 micrometers to 120 micrometers. All individual values ​​and subranges between 30 micrometers and 120 micrometers are included and disclosed herein. For example, in some embodiments, the shrink monolayer or multilayer film can have a thickness of 30 micrometers to 100 micrometers, 30 micrometers to 90 micrometers, or 30 micrometers to 80 micrometers.

[0050] Also disclosed herein is a method for producing a shrink film. The method includes providing a blended resin as described in one or more embodiments herein and forming a monolayer or multilayer film from the blended resin. Any conventional film-forming process can be used to form the monolayer or multilayer film. Examples include blown film lines (e.g., blown lines manufactured by Battenfeld Gloucester) using typical fabrication parameters that are readily determined by one skilled in the art of producing blown films.

[0051] In some embodiments, shrink films can be prepared that may be multilayer shrink films having an A / B / A film structure, where A is a skin layer of the same material and B is a core layer disposed between skin layers A, or an A / B / C film structure, where A and C are skin layers having different material compositions and B is a core layer disposed between skin layers A and C. In both embodiments, the B core layer comprises a blended resin as described herein. The shrink film may have a 1:2:1 ratio of skin layers to core layers, respectively. Each skin layer used in the films of the present invention may independently have a thickness of 8 μm to 30 μm in one embodiment, 10 μm to 25 μm in another embodiment, or 12 μm to 20 μm in yet another embodiment. The core layer used in the films of the present invention may have a thickness of, for example, 20 μm to 60 μm in one embodiment, 25 μm to 55 μm in another embodiment, or 30 μm to 50 μm in yet another embodiment. The present invention is not limited to three layers and may include more than three layers, so long as at least one core or inner layer of the multilayer shrink film comprises a blended resin and still allows for an appropriate balance of properties such as stiffness, toughness, and shrinkage.

[0052] Each skin layer of the multilayer shrink film comprises one or more ethylene-based polymer materials, including, for example, HDPE, LDPE, MDPE, LLDPE, and mixtures thereof. In one or more embodiments, the skin layers useful in the present invention may independently comprise HDPE, LDPE, LLDPE, and mixtures thereof. In some embodiments, each skin layer independently comprises LDPE, LLDPE, and HDPE, where the LDPE has a density of 0.915 g / cc to 0.925 g / cc and a melt index I2 of 0.2 g / 10 min to 2.0 g / 10 min, the LLDPE has a density of 0.915 g / cc to 0.940 g / cc and a melt index I2 of 0.2 g / 10 min to 2.0 g / 10 min, and the HDPE has a density of 0.945 g / cc to 0.965 g / cc and a melt index I2 of 0.04 g / 10 min to 1.0 g / 10 min. In another embodiment, each skin layer independently comprises LDPE and LLDPE, wherein the LDPE has a density of 0.915 g / cc to 0.925 g / cc and a melt index I2 of 0.1 g / 10 min to 2.0 g / 10 min, and the LLDPE has a density of 0.915 g / cc to 0.940 g / cc and a melt index I2 of 0.2 g / 10 min to 2.0 g / 10 min.

[0053] In one or more embodiments herein, the shrink film may exhibit one or more of the following properties: a tensile strength of 20 MPa to 40 MPa as measured by ASTM D882; an MD shrinkage of 40 percent to 70 percent (alternatively, 45 percent to 70 percent, or 50 percent to 70 percent) and a TD shrinkage of 10 percent to 50 percent (alternatively, 12 percent to 50 percent, or 15 percent to 50 percent) as measured by ASTM D2732-03 at 130°C and 20 seconds; a haze of 5 percent to 50 percent (alternatively, 5 percent to 30 percent, or 5 percent to 20 percent) as measured by ASTM D1003. In addition to the tensile strength, shrinkage, and haze properties, the shrink films described herein may also exhibit improved toughness, quantified in one embodiment as greater than 70 g Dart Impact (A) (60 micrometer film), in another embodiment greater than 75 g Dart Impact (A) (60 micrometer film), and in yet another embodiment greater than 80 g Dart Impact (A) (60 micrometer film).

[0054] The monolayer or multilayer shrink films described herein can be used, for example, in packaging applications. In one or more embodiments, an article is packaged using the monolayer or multilayer shrink films described herein.

[0055] II. Polyurethane Foam Formulations In various embodiments, compositions for producing flexible polyurethane (PUR) foams are provided, including an isocyanate, an isocyanate-reactive component including one or more polyols capable of reacting with isocyanate groups, a blowing agent, and at least one zeolite additive. An amine and an organometallic catalyst may also be included. Without being bound by theory, the isocyanate component and the isocyanate-reactive component are generally stored in separate containers until they are blended together and undergo a polymerization reaction between the isocyanate groups and the hydroxyl groups to form polyisocyanurate and polyurethane. Polyurethane refers to a polymer containing a backbone formed by repeating units (—NH—C(O)—O—) resulting from the reaction between isocyanate groups and hydroxyl groups.

[0056] As used herein, the terms "polyisocyanurate and polyurethane," "polyisocyanurate or polyurethane," "PIR and PUR," "PIR or PUR," and "PIR / PUR" are used interchangeably and refer to polymer systems containing both polyurethane chains and polyisocyanurate groups, the relative proportions of which essentially depend on the stoichiometric ratio of polyisocyanurate compounds to polyol compounds contained in the raw materials. Furthermore, ingredients such as catalysts and other additives, as well as processing conditions such as temperature and reaction time, can also slightly affect the relative amounts of PUR and PIR in the final foam product. Therefore, polyisocyanurate and polyurethane foams (PIR / PUR foams) mentioned in the context of this disclosure refer to foams obtained as the product of the reaction between the above-mentioned polyisocyanates and compounds, particularly polyols, having isocyanate-reactive groups. Furthermore, additional functional groups, such as allophanates, biurets, or ureas, may be formed during the reaction. PIR / PUR foams may be rigid or flexible. The compositions of the present disclosure may further include catalysts, blowing agents, and other additives.

[0057] According to one broad embodiment of the present disclosure, a foam-forming composition and a method for making rigid polyurethane foams for the foam-forming composition include three components: an isocyanate component including at least one polyisocyanate compound, an isocyanate-reactive component including at least one or more polyols, and a high-silica-containing zeolite.

[0058] High-silica zeolites can be introduced into foam formulations (and resulting foams) in a number of ways. These include blending the zeolite into the polyol component of the foam formulation immediately prior to the foaming process. Zeolite may also be added directly to the foam formulation as a powder. The powder addition mode can be used in blended polyol systems for pillows and car seats (which require premixing of the blended polyol and is standard practice in discontinuous processes). The powder addition mode can also be used in box former formulations (which require premixing with the polyol). While the above powder addition mode relies on stable powdered zeolites, unstable powdered zeolites may also be used. These unstable powdered zeolites require mixing before or after addition to the polyol. Powdered zeolites may also be added to polyols for use as a component in flex slab continuous machine production, where premixing is not possible.

[0059] The zeolite may also be added by any other functionally possible method that allows the zeolite to be embedded on and / or in the foaming formulation or formed foam. For example, liquid and / or powdered zeolite may be provided as separate streams in the forming formulation as the components are mixed (e.g., streams of polyhydric alcohol, iscocyante, and zeolite mixed simultaneously). The zeolite may also be placed (poured, sprinkled, etc.) on the substrate, or the foaming formulation may be poured onto the zeolite without or in addition to mixing. The zeolite may also be poured, sprinkled, or otherwise applied to the foaming formulation (or rising foam) after the formulation has been mixed and poured onto the substrate.

[0060] Additionally, other optional adjunct ingredients such as surfactants, catalysts, additional blowing agents, flame retardant additives, etc. may be premixed with the isocyanate-reactive or isocyanate component and then mixed with the other ingredients to produce the PU foam, or may be incorporated into the foam-forming composition as a separate stream to produce the foam. Not all of these optional adjunct ingredients are required to produce the foam, and they should not be read as limiting the scope of the present disclosure in any way.

[0061] Various embodiments of the disclosed compositions may vary in the amount, content, or concentration of the isocyanate-reactive component and the isocyanate component, which in these embodiments is calculated based on the total weight of the foam-forming composition, i.e., the combined weight of the isocyanate-reactive component, the isocyanate component, the zeolite, and any optional adjunct components, if not already incorporated into another component.

[0062] Isocyanate component In various embodiments, for example, the isocyanate component of the foam-forming compositions of the present invention can include one or more isocyanate compounds, including, for example, polyisocyanates. As used herein, "polyisocyanate" refers to molecules having an average of greater than 1.0 isocyanate (NCO) groups / molecule, e.g., an average NCO functionality greater than 1.0.

[0063] The isocyanate compounds useful in the present invention can be aliphatic polyisocyanates, cycloaliphatic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, or combinations thereof. Examples of isocyanates useful in the present invention include polymethylene polyphenylisocyanate, toluene 2,4- / 2,6-diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), polymeric MDI, triisocyanatononane (TIN), naphthyl diisocyanate (NDI), 4,4'-diisocyanatodicyclohexyl-methane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate IPDI), tetramethylene diisocyanate, hexamethylene diisocyanate, among others. diisocyanate (HDI), 2-methyl-pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 4,4'-diisocyanato-3,3'-dimethyl-dicyclohexylmethane, 4,4'-diisocyanato-2,2-dicyclohexylpropane, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI), 1,3-diisooctylcyanato-4-methylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, and combinations thereof. In addition to the isocyanates mentioned above, partially modified polyisocyanates containing uretdione, isocyanurate, carbodiimide, uretonimine, allophanate, or biuret structures, among others, and combinations thereof, may be utilized in the present invention.

[0064] The isocyanate compound may be polymeric. As used herein, "polymeric" refers to higher molecular weight homologs and / or isomers in describing an isocyanate. For example, polymeric methylene diphenyl isocyanate refers to higher molecular weight homologs and / or isomers of methylene diphenyl isocyanate.

[0065] The isocyanate compounds useful in the present invention may be modified polyfunctional isocyanates, i.e., products obtained by chemical reaction of isocyanate compounds. Exemplary are polyisocyanates containing esters, ureas, biurets, allophanates, and carbodiimides and / or uretonamines. Liquid polyisocyanates containing carbodiimide groups, uretonamine groups, and / or isocyanurate rings and having an isocyanate group (NCO) content of 10 to 35 weight percent, 10 to 32 weight percent, 10 to 30 weight percent, 15 to 30 weight percent, or 15 to 28 weight percent may also be used. These include, for example, polyisocyanates based on 4,4'-, 2,4'-, and / or 2,2'-diphenylmethane diisocyanate and the corresponding isomer mixtures, 2,4- and / or 2,6-toluene diisocyanate and the corresponding isomer mixtures; mixtures of diphenylmethane diisocyanate and PMDI; and mixtures of toluene diisocyanate with PMDI and / or diphenylmethane diisocyanate.

[0066] Alternatively, or additionally, the isocyanate component may also include an isocyanate prepolymer, which is known in the art and is generally prepared by reacting (1) at least one isocyanate compound with (2) at least one polyol compound. Isocyanate prepolymers can be obtained by reacting the above-mentioned monomeric isocyanate compounds or polymeric isocyanates with one or more isocyanate-reactive compounds, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, bis(hydroxymethyl)cyclohexane, such as 1,4-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1,3-diol, methylpentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, and polybutylene glycol.

[0067] Prepolymers suitable for use as the polyisocyanate component are those having an NCO group content of 5 to 30 weight percent, or preferably 10 to 30 weight percent. These prepolymers can be prepared by reacting di- and / or polyisocyanates with materials including lower molecular weight diols and triols. Specific examples are aromatic polyisocyanates containing urethane groups having an NCO content of 5 to 30 weight percent (e.g., 10 to 30 or 15 to 30 weight percent), preferably obtained by reacting diisocyanates and / or polyisocyanates with low molecular weight diols, triols, oxyalkylene glycols, dioxyalkylene glycols, or polyoxyalkylene glycols, e.g., having a molecular weight of up to about 1000. These polyols can be used individually or in mixtures, as can the di- and / or polyoxyalkylene glycols. For example, diethylene glycol, dipropylene glycol, polyoxyethylene glycol, ethylene glycol, propylene glycol, butylene glycol, polyoxypropylene glycol, and polyoxypropylene polyoxyethylene glycol can be used. Polyester polyols and alkyl diols such as butanediol can also be used. Other useful diols include bishydroxyethyl- or bishydroxypropyl-bisphenol A, cyclohexanedimethanol, and bishydroxyethylhydroquinone. In a preferred embodiment, a combination of PMDI / TDI can be used as the isocyanate component.

[0068] As previously mentioned, the isocyanate can have an average functionality of greater than 1.0 isocyanate groups / molecule. For example, the isocyanate can have an average functionality of 1.75 to 3.50. All individual values ​​and subranges between 1.75 and 3.50 are included, for example, the isocyanate can have an average functionality of a lower limit of 1.5, 1.75, 1.85, or 1.95 to an upper limit of 3.5, 3.4, 3.3, 3.2, 3.1, or 3.

[0069] The isocyanate may have an isocyanate equivalent weight of 80 g / eq to 300 g / eq, including all individual values ​​and subranges between 80 g / eq and 300 g / eq, for example, the isocyanate may have an isocyanate equivalent weight of a lower limit of 80 g / eq, 90 g / eq, or 100 g / eq to an upper limit of 300 g / eq, 290 g / eq, or 280 g / eq.

[0070] The isocyanates used in the present invention can be prepared by known processes, for example, polyisocyanates can be prepared by phosgenation of the corresponding polyamine with the formation of a polycarbamoyl chloride and its thermal decomposition to provide a polyisocyanate and hydrogen chloride, or in another embodiment, polyisocyanates can be prepared by a phosgene-free process, for example, by reacting the corresponding polyamine with urea and an alcohol to obtain a polycarbamate and its thermal decomposition to yield, for example, a polyisocyanate and an alcohol.

[0071] The isocyanates used in the present invention can be commercially available. Examples of commercially available isocyanates useful in the present invention include, but are not limited to, polyisocyanates under the trade names VORANATE™, PAPI™, and ISONATE™, such as VORANATE™ M220 and PAPI™ 27, among other commercially available isocyanates such as VORANATE™ T-80, PAPI™ 94, or PAPI™ 23, all of which are available from Dow, Inc.

[0072] Generally, the amount of isocyanate component can vary based on the end use of the rigid PU foam. For example, in one exemplary embodiment, the concentration of the isocyanate component can be about 20% to about 80% by weight, or about 25% to about 80% by weight, or about 30% to about 75% by weight, based on the total weight of all components in the foam-forming composition for preparing the PU foam. In one embodiment, the stoichiometric ratio of isocyanate groups in the isocyanate component to hydroxyl groups in the isocyanate-reactive component is about 1.0 to 6, such that the polyurethane and polyisocyanurate foams formed have an isocyanate index of 70 to 600. The isocyanate index can have lower limits of 70, 80, 90, 100, 105, 110, 115, 120, 125, 150, 175, and 180, to upper limits of 600, 575, 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, and 300.

[0073] In other embodiments, there are other types of isocyanates that can be used to form softer foams, for example, memory foam made with PMDI has an Isocyanate Index of <100 (approximately 75).

[0074] Isocyanate-reactive component In various embodiments of the present disclosure, the isocyanate-reactive component comprises one or more isocyanate-reactive compounds, such as polyols selected from the group consisting of aliphatic polyhydric alcohols containing at least two hydroxyl groups, cycloaliphatic or aromatic polyhydric alcohols containing at least two hydroxyl groups, araliphatic polyhydric alcohols containing at least two hydroxyl groups, polyether polyols, polycarbonate polyols, polyester polyols, polyester ether polyols, and mixtures thereof. In one example, the polyol is selected from the group consisting of C2-C16 aliphatic polyhydric alcohols containing at least two hydroxyl groups, C6-C15 cycloaliphatic or aromatic polyhydric alcohols containing at least two hydroxyl groups, C7-C15 araliphatic polyhydric alcohols containing at least two hydroxyl groups, and combinations thereof. The polyester polyols generally have an average molecular weight of 200 to 5,000. The polyether polyols have an average molecular weight of 100 to 5,000.

[0075] In one embodiment, the isocyanate-reactive component comprises a mixture of two or more different polyols, such as a mixture of two or more polyether polyols, a mixture of two or more polyester polyols, or a mixture of at least one polyether polyol with at least one polyester polyol. The isocyanate-reactive component has a functionality (average number of isocyanate-reactive groups, particularly the average number of hydroxyl groups, in the polyol molecule) of at least 1.8 and an OH number of 80 to 2,000 mg KOH / g. The OH number of the isocyanate-reactive component is preferably 100 to 1,500 mg KOH / g, more preferably 120 to 1,000 mg KOH / g, even more preferably 150 to 750 mg KOH / g, still more preferably 150 to 750 mg KOH / g, and even still more preferably 150 to 500 mg KOH / g.

[0076] Generally, the average hydroxyl functionality of the polyol compounds useful in the present invention, as described above, can range from as low as less than 1.8 to as high as 7.5. For example, aromatic polyester polyols can have an average hydroxyl functionality of 1.8 to 3.0, and sucrose / glycerin-initiated polyether polyols can have an average hydroxyl functionality of 3.0 to 7.5. Thus, the average hydroxyl functionality of the polyol compounds used in the present invention can range from 1.8 to 7.5. All individual values ​​and subranges between 1.8 and 7.5 are included. For example, the polyol compounds can have an average hydroxyl functionality ranging from a lower limit of 1.8, 2.0, 2.2, 2.5, 2.7, 3.0, or 3.5 to an upper limit of 7.5, 7.0, 6.5, 6.0, 5.7, 5.5, 5.2, 5.0, 4.8, 4.5, 4.2, or 4.0.

[0077] Generally, the polyol compound can have an average hydroxyl number in the range of 75 mg KOH / g to 650 mg KOH / g, including all individual values ​​and subranges therebetween, for example, the polyol compound can have an average hydroxyl number from a lower limit of 75 mg KOH / g, 80 mg KOH / g, 100 mg KOH / g, 125 mg KOH / g, 150 mg KOH / g, or 175 mg KOH / g to an upper limit of 650 mg KOH / g, 600 mg KOH / g, 550 mg KOH / g, 500 mg KOH / g, 450 mg KOH / g, or 400 mg KOH / g.

[0078] Generally, the polyol compound can have a number average molecular weight of 100 g / mol to 1,500 g / mol, including all individual values ​​and subranges therebetween, for example, from a lower limit of 100 g / mol, 150 g / mol, 175 g / mol, or 200 g / mol to an upper limit of 1,500 g / mol, 1250 g / mol, 1,000 g / mol, or 900 g / mol.

[0079] Generally, the polyol compound can have a hydroxyl equivalent molecular weight of from 50 g / eq to 750 g / eq, including all individual values ​​and subranges between 50 g / eq and 750 g / eq, for example, the polyol compound can have a hydroxyl equivalent molecular weight of from a lower limit of 50 g / eq, 90 g / eq, 100 g / eq, or 110 g / eq to an upper limit of 350 g / eq, 300 g / eq, 275 g / eq, or 250 g / eq.

[0080] Polyester polyols are typically obtained by condensation of polyhydric alcohols with polyfunctional carboxylic acids having 2 to 12 carbon atoms (e.g., 2 to 6 carbon atoms). Typical polyhydric alcohols for preparing polyester polyols are diols or triols, such as ethylene glycol, diethylene glycol, polyethylene glycols such as PEG200, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, pentylene glycol, or hexylene glycol, polyether polyols, and glycerol. Typical polyfunctional carboxylic acids are selected from the group consisting of succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, and phthalic acid, isophthalic acid, terephthalic acid, isomeric naphthalenedicarboxylic acids, and combinations thereof. The average OH functionality of the polyester polyol is preferably at least 1.8, and even more preferably at least 2.0. Aromatic polyester polyols are one common type of polyester polyol used in rigid polyurethane foams.

[0081] As used herein, "aromatic polyester polyol" refers to a polyester polyol containing an aromatic ring. For example, the aromatic polyester polyol may be a phthalic anhydride diethylene glycol polyester or may be prepared using an aromatic dicarboxylic acid together with a glycol. The aromatic polyester polyol may be, for example, a hybrid polyester-polyether polyol, such as those discussed in WO 2013 / 053555.

[0082] Aromatic polyester polyols can be prepared using known equipment and reaction conditions. In another embodiment, aromatic polyester polyols can be commercially available. Examples of commercially available aromatic polyester polyols include, but are not limited to, several polyols sold under the trade name STEPANPOL (trademark), such as STEPANPOL (trademark) PS-2352, available from Stepan Company.

[0083] Polyether polyols usually have 2 to 8, especially 2 to 6, hydroxyl functional groups and are generally prepared by polymerizing one or more alkylene oxides selected from propylene oxide (PO), ethylene oxide (EO), butylene oxide, tetrahydrofuran, and mixtures thereof, with a suitable starter molecule or a mixture of starter molecules in the presence of a catalyst. Typical starter molecules include compounds having at least two hydroxyl groups or at least one primary amine group in the molecule. Suitable starter molecules may be ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, sugar compounds such as glucose, sorbitol, mannitol and sucrose, aliphatic and aromatic amines, polyhydric phenols, resols such as oligomeric condensation products of phenol with formaldehyde and Mannich condensation products of phenols, formaldehyde and dialkanolamines, and also melamine.

[0084] Examples of starter molecules having at least two (e.g., 2 to 8) hydroxyl groups per molecule include, but are not limited to, trimethylolpropane, glycerol, pentaerythritol, castor oil, sugar compounds such as glucose, sorbitol, mannitol, and sucrose, polyhydric phenols, resols such as oligomeric condensation products of phenols with formaldehyde, and Mannich condensation products of phenols, formaldehyde, and dialkanolamines, as well as melamine. Catalysts for preparing polyether polyols can include alkaline catalysts such as potassium hydroxide for anionic polymerization, or Lewis acid catalysts such as boron trifluoride for cationic polymerization. Suitable polymerization catalysts include potassium hydroxide, cesium hydroxide, boron trifluoride, or double cyanide complex (DMC) catalysts such as zinc hexacyanocobaltate or tetraphosphazenium compounds. In one embodiment of the present disclosure, the polyether polyol has a number average molecular weight in the range of 100 to 2,000 g / mol, for example, in the range of 125 to 1,500 g / mol, 150 to 1,250 g / mol, 150 to 1,000 g / mol, or 200 to 1,000 g / mol.

[0085] Polyether polyols suitable for use in embodiments may have an average hydroxyl functionality of 2.0 and are commonly referred to as diols. Diols may be ethylene glycol, propylene glycol, ethoxylates of ethylene glycol or propylene glycol, propyloxylates of ethylene glycol or propylene glycol, and the like. Examples of commercially available diols include, but are not limited to, many polyols sold under the trade name VORANOL™, such as VORANOL™ 2110-TB, available from The Dow Chemical Company. Other polyols that may be used include, but are not limited to, VORANOL™ 8136, VORANOL™ 3943A, VORALUX™ HL 431, VORALUX™ HN 395, VORANOL™ WK 3140, VORANOL™ 8150, VORANOL™ 4053, and VORANOL™ 1447.

[0086] Polyether polyols suitable for use in embodiments may have an average hydroxyl functionality of 3.0 and are commonly referred to as triols. Triols may be glycerol, trimethylolpropane, ethoxylates or propyloxylates of glycerol or trimethylolpropane, or the like. Triols may be prepared using known equipment and reaction conditions. Examples of commercially available triols include, but are not limited to, several polyols sold under the trade name VORATEC™, such as VORATEC™ SD 301, available from The Dow Chemical Company, among others.

[0087] Polyether polyols suitable for use in the present invention may include sucrose / glycerin-initiated polyether polyols. The sucrose / glycerin-initiated polyether polyols may include structural units derived from other alkylene oxides, such as ethylene oxide or propylene oxide. The sucrose / glycerin-initiated polyether polyols may include structural units derived from styrene-acrylonitrile, polyisocyanates, and / or polyureas. The sucrose / glycerin-initiated polyether polyols may be prepared using known equipment and reaction conditions. For example, the sucrose / glycerin-initiated polyether polyol may be formed from a reaction mixture containing sucrose, propylene oxide, and glycerin. One or more embodiments provide that the sucrose / glycerin-initiated polyether polyol is formed via the reaction of sucrose with propylene oxide. In another embodiment, the sucrose / glycerin-initiated polyether polyol may be commercially available. Examples of commercially available sucrose / glycerin-initiated polyether polyols include, but are not limited to, several polyols sold under the VORANOL™ trade name, such as VORANOL™ 360, VORANOL™ 490, and VORANOL™ 280, available from The Dow Chemical Company (Dow, Inc.), among others.

[0088] Polyether polyols suitable for use in the present invention may include sorbitol-initiated polyether polyols. Sorbitol-initiated polyether polyols can be prepared using known equipment and reaction conditions. For example, sorbitol-initiated polyether polyols can be formed from a reaction mixture containing sorbitol and an alkylene oxide, such as ethylene oxide, propylene oxide, and / or butylene oxide. Sorbitol-initiated polyether polyols can be capped, for example, by adding alkylene oxides to preferentially place or cap specific alkylene oxides at desired positions in the polyol. Sorbitol-initiated polyether polyols can be commercially available. Examples of commercially available sorbitol-initiated polyether polyols include, but are not limited to, several polyols sold under the trade name VORANOL™, available from The Dow Chemical Company, such as VORANOL™ RN 482.

[0089] Polyether polyols suitable for use in the present invention may include polyol compounds, including amine-initiated polyols. The amine-initiated polyols may be initiated with aromatic or aliphatic amines. For example, the amine-initiated polyol may be, among others, orthotoluenediamine (o-TDA)-initiated polyols, ethylenediamine-initiated polyols, diethylenetriamine, triisopropanolamine-initiated polyols, or combinations thereof. The amine-initiated polyols may be prepared using known equipment and reaction conditions. For example, the amine-initiated polyol may be formed from a reaction mixture containing an aromatic or aliphatic amine and an alkylene oxide, among others, such as ethylene oxide and / or butylene oxide. The alkylene oxide may be added to the alkoxylation reactor in one step or sequentially through several steps, with each step using a single alkylene oxide or a mixture of alkylene oxides.

[0090] Polyols can be prepared using the following catalysts, non-limiting examples: KOH, T121 (tert-amylperoxy-2-ethylhexanoate), or Lewis acid polymerization catalysts. Polyols may also contain volatile molecules, including, but not limited to, low molecular weight aldehydes, ketones, aromatics (e.g., styrene, benzene derivatives), nitriles, dioxolanes, dioxanes, amines, thiols, and mixtures thereof.

[0091] The Lewis acid catalyst may have the general formula M(R1)1(R2)1(R3)1(R4)0 or 1, where M is boron, aluminum, indium, bismuth, or erbium; R1, R2, R3, and R4 are each independently; R1 comprises a first fluoroalkyl-substituted phenyl group; R2 comprises a second fluoroalkyl-substituted phenyl group or a first fluoro / chloro-substituted phenyl group; R3 comprises a third fluoroalkyl-substituted phenyl group or a second fluoro / chloro-substituted phenyl group; optional R4 comprises a functional group or a functional polymer group; and R1 is different from at least one of R2 and R3. The method further includes forming a polyether polyol having a number average molecular weight greater than the number average molecular weight of the low molecular weight initiator in the presence of the Lewis acid catalyst.

[0092] Generally, the amount of polyol used herein can range from about 10% to about 80% by weight, or from about 12% to 70% by weight, or from about 15% to 60% by weight, or from about 15% to about 55% by weight, or from about 15% to about 50% by weight, based on the total weight of all components in the foam-forming composition for preparing PUR / PIR foam.

[0093] Optional Adjunct Ingredients In addition to the at least one isocyanate-reactive component, at least one isocyanate component, and at least one zeolite additive described above present in the foam-forming composition for producing polyurethane / polyisocyanurate foams, the foam-forming compositions of the present invention may also include other additional optional adjunct components, compounds, agents, or additives. Such optional components may be added to the reactive mixture with any of the other components in the foam-forming composition (e.g., isocyanate component, isocyanate-reactive component, zeolite additive), or may be added as a separate stream during foam production.

[0094] The optional auxiliary components, compounds, agents, or additives that can be used in the present invention can include one or more optional compounds known in the art for their use or function. For example, optional components can include methylene chloride, acetone, water, chain extenders, crosslinkers, expandable graphite, additional physical or chemical blowing agents that may be the same as or different from the aforementioned blowing agents, blowing catalysts, flame retardants, emulsifiers, antioxidants, surfactants, compatibilizers, chain extenders, other liquid nucleating agents, solid nucleating agents, Ostwald ripening inhibitor additives, pigments, fillers; solvents, including those selected from the group consisting of ethyl acetate, methyl ether ketone, toluene, and mixtures of two or more thereof; and mixtures of two or more of the above optional additives.

[0095] The amount of optional auxiliary compound used to add to the foam-forming composition of the present invention can be, for example, in one embodiment, 0 pts to 50 pts, in another embodiment, 0.1 to 40 pts, and in yet another embodiment, 1 pt to 35 pts, based on 100 pts of the total polyol amount in the isocyanate-reactive component. For example, in one embodiment, the amount of additional physical blowing agent used, if used, can be 1 pt to 40 pts, based on 100 pts of the total polyol amount in the isocyanate-reactive component. In another embodiment, the amount of additional chemical blowing agent used, if used, can be 0.1 pt to 10 pts, based on 100 pts of the total polyol amount in the isocyanate-reactive component. In yet another embodiment, the amount of flame retardant additive used, if used, can be 1 pt to 25 pts, based on 100 pts of the total polyol amount in the isocyanate-reactive component. In yet another embodiment, the amount of surfactant used, if used, is typically 0.1 pt to 10 pts, based on 100 pts of the total polyol amount in the isocyanate-reactive component. In yet another embodiment, the amount of foaming catalyst used, if used, is 0.05 pts to 5 pts based on 100 pts of the total polyol amount in the isocyanate-reactive component. Also, in a typical embodiment, the amount of other additives used, if used, can be 0.1 pts to 10 pts based on 100 pts of the total polyol amount in the isocyanate-reactive component.

[0096] catalyst Catalysts may include urethane reaction catalysts and isocyanate trimerization reaction catalysts. The trimerization catalyst may be any trimerization catalyst known in the art for catalyzing the trimerization of organic isocyanate compounds. The trimerization of isocyanates may produce polyisocyanurate compounds within the polyurethane foam. Without being limited by theory, the polyisocyanurate compounds may make the polyurethane foam more rigid and provide improved fire response. Trimerization catalysts may include, for example, glycine salts, tertiary amine trimerization catalysts, alkali metal carboxylate salts, and mixtures thereof. In some embodiments, sodium N-2-hydroxy-5-nonylphenyl-methyl-N-methylglycinate may be used. When used, the trimerization catalyst may be present in an amount of 0.05 to 5 pts (e.g., 0.1 to 3.5 pts, or 0.2 to 2.5 pts, or 0.5 to 2.5 pts) based on 100 pts of the total polyol in the isocyanate-reactive component.

[0097] Tertiary amine catalysts include organic compounds that contain at least one tertiary nitrogen atom and are capable of catalyzing the hydroxyl / isocyanate reaction between an isocyanate component and an isocyanate-reactive component. Tertiary amine catalysts, by way of example and not limitation, can include triethylenediamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, N-ethylmorpholine, 2-methylpropanediamine, methyltriethylenediamine, 2,4,6-tridimethylamino-methyl)phenol, N,N',N"-tris(dimethylamino-propyl)sym-hexahydrotriazine, and mixtures thereof. If used, the tertiary amine catalyst can be present in an amount of 0.05 to 5 pts (e.g., 0.1 to 3.5 pts, or 0.2 to 2.5 pts, or 0.5 to 2.5 pts) based on 100 pts of the total polyol amount in the isocyanate-reactive component.

[0098] The compositions of the present disclosure may be used with the following catalysts: tertiary phosphines, e.g., trialkylphosphines and alkylbenzylphosphines; chelates of various metals, such as those obtainable from metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, and Ni, and acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, and the like; acidic metal salts of strong acids, such as ferric chloride and stannic chloride; and various metals, such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni, and Cu. Organic tin compounds such as tin(II) salts of organic carboxylic acids, e.g., tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, e.g., dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate; bismuth salts of organic carboxylic acids, e.g., bismuth octoate; organometallic derivatives of trivalent and pentavalent As, Sb, and Bi, and metal carbonyls of iron and cobalt. The total amount of catalyst components used herein can generally range from about 0.01 pts to about 10 pts, and from 0.05 pts to about 5 pts in one embodiment, based on 100 pts of the total polyol amount in the isocyanate-reactive component.

[0099] surfactants The foam-forming composition of the present invention may contain a surfactant. For example, the surfactant may be added to any one of the components in the foam-forming composition or may be added as a separate stream during foam production. The surfactant may be a cell-stabilizing surfactant. Examples of surfactants useful in the present invention include silicon-based compounds such as organosilicone-polyether copolymers, e.g., polydimethylsiloxane-polyoxyalkylene block copolymers, e.g., polyether-modified polydimethylsiloxane, and combinations thereof. Surfactants are commercially available, including those available under trade names such as NIAXT™ (e.g., NIAX™ L 6988) and TEGOSTAB™ (e.g., TEGOSTAB™ B 8462). Examples of surfactants also include non-silicone organic surfactants such as VORASURF™ 504 and VORASURF™ DC 5043, available from The Dow Chemical Company.

[0100] Other surfactants that may be useful herein include polyethylene glycol ethers of long-chain alcohols, tertiary amine or alkanolamine salts of long-chain aryl acid sulfates, alkyl sulfonates, alkylaryl sulfonic acids, and combinations thereof. Such surfactants are used in amounts sufficient to stabilize the foaming reaction against collapse and the formation of large, non-uniform cells. When used, the amount of surfactant may range from 0.1 pts to 10.0 pts, based on 100 pts of total polyol present in the isocyanate-reactive component. All individual values ​​and subranges between 0.1 pts and 10.0 pts are included. For example, the surfactant may range from a lower limit of 0.1 pts, 0.2 pts, or 0.3 pts to an upper limit of 10.0 pts, 9.0 pts, 7.5 pts, or 6 pts, based on 100 pts of total polyol present in the isocyanate-reactive component.

[0101] foaming agent A variety of conventional blowing agents can be used, for example, the blowing agent can be one or more of water, various hydrocarbons, various hydrofluorocarbons, various hydrofluoroolefins, formic acid, noble gases, various chemical blowing agents that generate nitrogen or carbon dioxide under the conditions of the foam-forming reaction, and the like, and mixtures thereof.

[0102] The blowing agent used in the present invention should have a boiling point at atmospheric pressure of about -30°C to about 100°C, preferably about -20°C to about 80°C, more preferably about 0°C to about 80°C, even more preferably about 5°C to about 75°C, and most preferably about 10°C to about 70°C. Illustrative examples of blowing agents that can be used in the present invention include low-boiling hydrocarbons such as heptane, hexane, n- and iso-pentane, technical-grade mixtures of n- and iso-pentane, n- and iso-butane, and propane, cycloalkanes such as cyclopentane and / or cyclohexane, low-boiling ethers such as furan, dimethyl ether, and diethyl ether, low-boiling ketones such as acetone and methyl ethyl ketone, alkyl carboxylates such as methyl formate, dimethyl oxalate, and ethylene lactate, various hydrochlorofluorocarbons (HCFCs), and the like. ), hydrofluorocarbons (HFCs), and hydrofluoroolefins (HFOs), such as 1,1-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane, pentafluoropropane, heptafluoropropane, hexafluorobutene, (E,Z)1,1,1,4,4,4-hexafluoro-2-butene, and trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoroprop-1-ene, 1,3,3,3-tetrafluoropropene, and the like. Among these blowing agents are commercially available materials known as Solstice® LBA, Solstice® GBA, Opteon™ 1100, Opteon™ 1150, and the like. Mixtures of these low-boiling liquids with each other and / or with other substituted or unsubstituted hydrocarbons can also be used.

[0103] In one embodiment, the at least one blowing agent of the present invention is selected from the group consisting of aliphatic hydrocarbons having 3 to 7 carbon atoms, cycloaliphatic hydrocarbons having 3 to 7 carbon atoms, and hydrofluoroolefins, or mixtures thereof.

[0104] In various embodiments, the blowing agent may be selected based at least in part on the desired density of the final foam. The blowing agent may be added to the polyol side before the isocyanate-reactive component is combined with the isocyanate component or added as a separate stream. The amount of blowing agent is from about 0.1 pts to about 40 pts (e.g., from about 0.5 pts to about 35 pts, from 1 pts to 30 pts, or from 5 pts to 25 pts) based on 100 pts of total polyol in the foam-forming composition.

[0105] In various embodiments, the foam-forming compositions of the present invention may include an additional blowing agent, which may be the same as or different from component (C). The additional blowing agent may be incorporated into either one of the two components (A) and (B) prior to foam production, or may be added as a separate stream and on-site mixed with components (A), (B), (C), and (D) during foam production. The additional blowing agent may be selected based at least in part on the desired density of the final foam.

[0106] Various conventional blowing agents can be used. For example, the blowing agent can be one or more of water, various hydrocarbons, various hydrofluorocarbons, various hydrofluoroolefins, formic acid, noble gases, various chemical blowing agents that produce nitrogen or carbon dioxide under the conditions of the foaming reaction, and the like, and mixtures thereof. Methylene chloride or acetone may also be used.

[0107] Chemical blowing agents such as water may be used alone or in combination with other chemical and / or physical blowing agents. Also suitable as chemical blowing agents are organic carboxylic acids such as formic acid, acetic acid, oxalic acid, and carboxyl-containing compounds.

[0108] Physical blowing agents such as low-boiling hydrocarbons can be used. Examples of such liquids include alkanes such as heptane, hexane, n- and iso-pentane, technical-grade mixtures of n- and iso-pentane with n- and iso-butane and propane, cycloalkanes such as cyclopentane and / or cyclohexane, ethers such as furan, dimethyl ether, and diethyl ether, ketones such as acetone and methyl ethyl ketone, alkyl carboxylates such as methyl formate, dimethyl oxalate, and ethylene lactate, and halogenated hydrocarbons such as methylene chloride, dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethane, 1,1- Dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane, hexafluorobutene, various hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), and hydrofluoroolefins (HFOs), such as 1,1-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane, pentafluoropropane, heptafluoropropane, hexafluorobutene, (E,Z)1,1,1,4,4,4-hexafluoro-2-butene, and trans-1 chloro-,3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoroprop-1-ene, 1,3,3,3-tetrafluoropropene, and the like. Some of these blowing agents are commercially available materials known as Solstice® LBA, Solstice® GBA, Opteon™ 1100, Opteon™ 1150, etc. Mixtures of these low boiling liquids with each other and / or with other substituted or unsubstituted hydrocarbons may also be used.

[0109] In various embodiments, the amount of additional blowing agent is from about 0.1 pts to about 40 pts (e.g., from about 0.5 pts to about 35 pts, from 1 pts to 30 pts, or from 5 pts to 25 pts) based on 100 pts of the total polyol amount in the isocyanate-reactive component.

[0110] Other optional / auxiliary additives Other optional / auxiliary compounds or additives that can be used in the foam-forming compositions of the present embodiments to produce polyurethane foams can include, for example, other cocatalysts, cosurfactants, toughening agents, flow modifiers, adhesion promoters, diluents, stabilizers, plasticizers, dispersants, flame retardant (FR) additives, and mixtures thereof.

[0111] In various embodiments, fire performance can be enhanced by including one or more flame retardants. Flame retardants can be halogenated or non-halogenated, and examples include, but are not limited to, tris(1,3-dichloro-2-propyl)phosphate, tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, triethylphosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, alumina trihydrate, and combinations thereof. When used, the flame retardant can be present in an amount of 0.1 pts to about 30 pts, or about 1 pts to about 25 pts, or about 2 pts to about 25 pts, or about 5 pts to about 25 pts, based on 100 pts of total polyol in the isocyanate-reactive component.

[0112] Other additives can be included for the production of PIR / PUR foams, such as fillers and pigments, which, in non-limiting embodiments, can include barium sulfate, calcium carbonate, graphite, carbon black, titanium dioxide, iron oxide, microspheres, alumina trihydrate, wollastonite, glass fibers, polyester fibers, other polymer fibers, combinations thereof, and the like.

[0113] III. Zeolite As used herein, the term "zeolite" refers to a microporous crystalline material with a well-defined structure of discretely sized voids and channels, composed primarily of aluminum, silicon, and oxygen (i.e., aluminosilicates) in an ordered framework. Zeolites may additionally contain various cations. Zeolites can be used as adsorbents and catalysts. Zeolites occur naturally but can also be produced industrially on a large scale. Zeolites have a highly ordered crystalline pore structure with molecular-scale dimensions. Due to their porosity, zeolites have molecular sieve properties, allowing them to separate molecules primarily based on a size exclusion process. As used herein, the term "odor-active zeolite" refers to a zeolite that is an odor control agent due to its ability to absorb and / or adsorb odorous liquids and gases, thereby neutralizing odors, for example.

[0114] Different zeolite species have different crystalline structures that determine the distribution, shape, and size of the pores in the zeolite. Natural zeolites can be crystallized by a variety of natural processes, while artificial zeolites can be crystallized, for example, from silica-alumina gel in the presence of a template and alkali. There are over 200 known types of zeolite crystalline structures. The MFI crystalline structure, sometimes referred to as the silicate-1 crystalline structure, contains multiple pentasil units linked by oxygen bridges to form pentasil chains and has the following chemical formula: Na n Al n Si 96-n O 192 16H2O, where n is greater than 0 and less than 27. Faujasite (FAU) crystal structure, sometimes referred to as the Y-type crystal structure or IZA crystal structure, is a zeolite crystal structure consisting of sodalite cages tetrahedrally connected via hexagonal prisms and having pores formed by 12-membered rings. In an embodiment, the composition comprises a zeolite having a mixture of crystal structures including the MFI crystal structure and the FAU crystal structure.

[0115] Zeolites can be classified by the molar ratio of silicon to aluminum ("Si / Al molar ratio") within the zeolite. In embodiments, the composition comprises a zeolite having a Si / Al molar ratio of 1 to 1000. All individual values ​​and subranges of the molar ratio from 1 to 1000 are disclosed and included herein, including 1 to 100, 1 to 200, 1 to 300, 1 to 400, 1 to 500, 1 to 600, 1 to 700, 1 to 800, 1 to 900, 100 to 1000, 200 to 1000, 300 to 1000, 400 to 1000, 500 to 1000, 600 to 1000, 700 to 1000, 800 to 1000, or 900 to 1000. Still other embodiments may feature Si / Al molar ratios ranging from 35 to 700, 150 to 650, etc.

[0116] Zeolites can be further classified by their particle size. Zeolite particle size refers to the size of individual zeolite crystals. In embodiments, a composition can include a zeolite having a particle size of 250 nm to 2000 nm. All individual values ​​and subranges between 250 nm and 2000 nm are disclosed and included herein. For example, a zeolite can have a particle size of 250 nm to 2000 nm, 250 nm to 1000 nm, 250 nm to 750 nm, 250 nm to 500 nm, 500 nm to 2000 nm, 750 nm to 2000 nm, or 1000 nm to 2000 nm.

[0117] It is contemplated that various commercial embodiments of the odor-activated zeolite are possible. For example, suitable commercial embodiments of at least one odor-activated zeolite are Abscents 2000 (ABS 2000) and Abscents 3000 (ABS 3000), both of which are commercially available from UOP.

[0118] [Table 1]

[0119] IV. Method of Foam Preparation Compounding: Samples were compounded in an 11 barrel (44 L / D) Coperion ZSK-26 twin screw extruder. Extrusion was performed at a screw speed of 200 rpm, a throughput of 20 lb / h, and barrel and die temperature set points of 220°C.

[0120] The film was prepared using a heated hydraulic press manufactured by Reliable Rubber and Plastics Machinery Company. The heated platen was 14 inches by 14 inches. First, a 14 x 14 inch chrome-plated backing plate was placed on the benchtop. This was covered with a piece of Teflon-coated cloth. Approximately 12 grams of polymer was then placed on the Teflon and spread. Another piece of Teflon-coated cloth was then placed on top of the assembly, followed by another chrome-plated backing plate. The entire assembly was then placed between heated platens. The temperature used was 350°F. The platens were then closed without any pressure for 15 seconds. The platens were then pressurized to 6500 psi for an additional 15 seconds. The pressure was then released, and the assembly was removed from the press and placed on a cold benchtop. After cooling, the film was removed from the cavity and the edges were trimmed. This procedure produced a 10 x 10 inch film approximately 0.5 mm thick.

[0121] V. Methods of Foam Preparation In various embodiments, PU foams are prepared by mixing all of the individual components, including at least one isocyanate-reactive component with at least one high-silica zeolite, at least one isocyanate component, and any optional auxiliary additives, such as catalysts, surfactants, additional blowing agents, and any other additives, at room temperature or at elevated temperatures between 25 and 200°C (e.g., 30 and 90°C or 40 and 70°C) for 1 to 20 seconds, followed by immediate pouring, spraying, injection, or laying down the resulting mixture into a mold cavity or foam-forming substrate. In some embodiments, optional auxiliary additives, such as catalysts, flame retardants, additional blowing agents, and surfactants, may be added to the isocyanate-reactive component or the isocyanate component prior to mixing with the other components, or may be combined with the other components on-the-fly as a separate stream.

[0122] In a preferred embodiment, the zeolite was added to the polyol blend and premixed, then the isocyanate was added and a final mix was performed to ensure a uniform reaction.

[0123] Mixing can be performed in a spray device, a mix head, or a container. Immediately after mixing, the foaming mixture can be sprayed or otherwise deposited, injected, or poured onto a substrate or into a mold. Regardless of any particular method of foam production, the amount of foaming mixture introduced into the mold or onto the substrate is sufficient to completely fill the mold or assume the shape of a panel or any other functional shape as the foam expands and hardens. A degree of overpack can be introduced by using an amount of reactant mixture that is slightly in excess of the minimum required amount. For example, a cavity can be overfilled by 5 to 35 percent, i.e., 5 to 35% by weight of the reactant system, beyond the minimum required to fill the cavity when the reactant mixture is fully expanded at a given production condition. The cavity can optionally be maintained at atmospheric pressure or partially evacuated to a subatmospheric pressure.

[0124] Upon reaction, the foaming mixture may take the shape of a mold or adhere to a substrate to produce a PU foam, which may then be partially or fully cured. The foam may be allowed to rise freely at room temperature. Suitable conditions for accelerating the curing of the PU polymer include temperatures of about 20°C to about 150°C. In some embodiments, curing is carried out at a temperature of about 30°C to about 75°C. In other embodiments, curing is carried out at a temperature of about 35°C to about 65°C. In various embodiments, the temperature for curing can be selected based, at least in part, on the duration required for the PU polymer to gel and / or cure at that particular temperature. The curing time will also depend on other factors, including, for example, the amount of specific components used (e.g., type and amount of catalyst) and the size and shape of the article being produced. Different articles produced can include, but are not limited to, consumer comfort articles such as furniture, pillows, and mattresses, as well as automotive applications (headliners, car seats, etc.) and any other application in which a low-odor PU foam may be desirable.

[0125] Zeolite Measurement X-ray powder diffraction patterns (XRD) were obtained on powdered samples using a Bruker D4 diffractometer operating at 40 KV and 40 mA with the divergence slit set at 0.20 mm and the anti-scatter slit set at 0.25 mm. X-ray diffraction was used to determine the crystalline structure of the zeolite by comparing the diffraction patterns with a publicly available X-ray zeolite database (IZA Zeolite Structure Database).

[0126] The Si / Al molar ratio was analyzed using wavelength dispersive X-ray fluorescence under helium using semiquantitative omnium analysis to calculate the elemental composition. The particle size of the zeolite was determined by measuring the size distribution of the particles present using a scanning electron microscope (SEM).

[0127] The surface area and pore volume of the ABSCENTS materials were measured by nitrogen adsorption at 77.4 K using conventional techniques on a Micromeritics ASAP 2420 instrument. Prior to the adsorption measurements, the samples were degassed at 300 °C for at least 3 hours in high vacuum. Pore volumes were determined from the adsorption and desorption branches of the isotherms using the Barret-Joyner-Halenda (BJH) procedure. Surface areas were calculated using the BET method. Abscents 2000 zeolite has a Si / Al molar ratio of 6 and a BET (Brunauer-Emmett-Teller) surface area of ​​455 m 2 / g, pore volume 0.29 cm 3 / g, a mixture of FAU and MFI crystalline structures, and a particle size of about 250 nm to 2 μm. In some embodiments, useful zeolites have pore sizes of less than 10 Å.

[0128] Abscents 3000 zeolite has a Si / Al molar ratio of 650 and a BET (Brunauer-Emmett-Teller) surface area of ​​344 m 2 / g, pore volume 0.18 cm 3 / g, MFI crystalline structure, and particle size of approximately 250 nm to 2 μm. [Example]

[0129] I. Zeolite film + zeolite foam test material In a separate test from the three tests above, silica zeolites were used to evaluate the absorption and removal of residual VOC molecules from the formed foam. The zeolites were used as received from the supplier without any additional treatment. Tables 15, 16, and 17 below list the zeolites, polymers, and PU foams tested.

[0130] Polyolefin films were prepared using a heated hydraulic press manufactured by Reliable Rubber and Plastics Machinery Company. The heated platen was 14 inches by 14 inches. First, a 14 by 14 inch chrome-plated backing plate was placed on a benchtop. This was covered with a piece of Teflon-coated cloth. Approximately 12 grams of polymer was then placed on the Teflon and spread out. Zeolite was added during the compounding stage using a twin-screw extruder. Compounded pellets containing zeolite, PCR, and Dowlex 2045G virgin resin were then compression molded into these films.

[0131] Next, another piece of Teflon-coated cloth was placed on top of the assembly, followed by another chrome-plated backing plate. The entire assembly was then placed between heated platens. The temperature used was 350°F. The platens were then closed without any pressure for 15 seconds. The platens were then pressurized to 6500 psi for an additional 15 seconds. The pressure was then released and the assembly was removed from the press and placed on a cold benchtop. After cooling, the film was removed from the cavity and the edges were trimmed. This procedure produced a 10 x 10 inch film approximately 0.5 mm thick.

[0132] To test the above films, polyurethane foams were made, the weights of the various components used in the foaming formulation from which the foams were made are listed below.

[0133] [Table 2]

[0134] Notes: Polyol 1 is a glycerin-initiated polyol containing PO and EO (approximately 14% EO content) with an EW of 2040. Polyol CPP is a grafted polyether polyol containing copolymerized styrene and acrylonitrile with a solids content of 43% and an EW of 1861. Polyol 2 is a sucrose-glycerin-initiated polyol containing PO and EO (approximately 75% EO content) with an EW of 1795. DABCO 33LV is a catalyst solution of 33% triethylenediamine in 67% dipropylene glycol. TDI is an 80-20 mixture of the 2,4 and 2,6 isomers of toluene diisocyanate.

[0135] Foams may be prepared by any means known in the art, including a standard box-forming process used to produce free-rising foams at room temperature. The first step was to premix the reactive mixture containing all of the polyol, additives, water, silica zeolite, etc., into a pouring cup. The appropriate amount of TDI was then added to reach a target isocyanate index (108), followed by a final intensive mix using a high-shear pin mixer to incorporate the TDI. The reaction mixture was then poured into a 15" x 15" x 10" wooden box, where the polyurethane foam was grown and allowed to cure overnight before being sectioned for testing its mechanical properties according to ASTM D 3574.

[0136] Common Protocols For the HS-GC experiments, the calculated amount of zeolite was melt-blended into a blend of PCR (rLDPE NC+505010) and Dowlex 2045G resin at 200 °C in a 50 / 50 blend ratio as shown in the table. 20 mil (~0.5 mm) thick films were produced from the zeolite-containing PCR / Dowlex 2045G resin by compression molding (molding conditions were as described above). 10.6 g of the compression-molded film with and without zeolite and 20 g of PU foam with and without zeolite were placed together in a 32 oz glass jar. The film was used to loosely wrap the PU foam. The film + foam was allowed to stand at room temperature for 3 months before analysis. Headspace gas samples from the jar were analyzed for propanal by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry.

[0137] [Table 3]

[0138] As shown, the presence of the zeolite-embedded PE film significantly reduces the amount of volatile compounds (e.g., propanal) present in the gas headspace, significantly reducing the foam odor. Additionally, the zeolite-containing film / zeolite-containing foam sample exhibited 26.7% fewer odor molecules in the headspace compared to the zeolite foam alone. The zeolite-containing film / zeolite-containing foam sample also showed an improvement over the zeolite film alone, demonstrating a synergistic effect. The present application provides, for example, the following inventions. [1] A product, (1) A film, The present invention also includes a monolayer film or a multilayer film having at least one layer comprising a blended resin, the blended resin comprising: a low density polyethylene (LDPE), the LDPE having a density of 0.915 g / cc to 0.925 g / cc and a melt index I2 of 0.1 g / 10 min to 1 g / 10 min; or Linear low density polyethylene (LLDPE), wherein the LLDPE has a density of 0.915 g / cc to 0.945 g / cc and a melt index I2 of 0.1 g / 10 min to 1 g / 10 min; and a film comprising at least a first silica-containing zeolite having a Si / Al molar ratio greater than 35 and a particle size from 250 nm to 2000 nm; (2) A flexible polyurethane foam that is the reaction product of an isocyanate component and an isocyanate-reactive component, said flexible polyurethane foam comprising at least a second silica-containing zeolite, said silica-containing zeolite having a Si / Al molar ratio greater than 35 and a particle size of 250 nm to 2000 nm. [2] The product of [1] above, wherein the blended resin comprises 30% to 70% by weight of post-consumer recycled polymer. [3] The product of [1] above, wherein the at least one silica-containing zeolite has a Si / Al molar ratio greater than 500 and less than 700. [4] The product of [1] above, wherein the second silica-containing zeolite is present in an amount ranging from 0.1% to 20% by weight of the total isocyanate-reactive composition. [5] The product of [1] above, wherein at least one silica-zeolite additive has a pore size of less than 10 Å. [6] The product of [1] above, wherein at least one silica-zeolite additive has a Na wt% of less than 2. [7] The product described in [1] above, wherein the polyurethane foam is wrapped in the film. [8] The polyurethane foam has a strength of about 35 kg / cm 3 The product according to [1] above, having a density of [9] A method for packaging polyurethane foam, comprising: and disposing a polyolefin film within the polyurethane foam packaging, the polyolefin film comprising: The present invention also includes a monolayer film or a multilayer film having at least one layer comprising a blended resin, the blended resin comprising: Low density polyethylene (LDPE), wherein the LDPE has a density of 0.915 g / cc to 0.925 g / cc and a melt index I of 0.1 g / 10 min to 1 g / 10 min. 2 low density polyethylene (LDPE), or Linear low density polyethylene (LLDPE), wherein the LLDPE has a density of 0.915 g / cc to 0.945 g / cc and a melt index I of 0.1 g / 10 min to 1 g / 10 min. 2 Linear low density polyethylene (LLDPE) having At least a first silica-containing zeolite having a Si / Al molar ratio greater than 35 and a particle size ranging from 250 nm to 2000 nm, wherein the polyurethane foam is at least one isocyanate-reactive component, and 10. A method comprising: at least a second silica-containing zeolite, said silica-containing zeolite having a Si / Al molar ratio greater than 35 and a particle size between 250 nm and 2000 nm.

[10] The method according to [9] above, wherein the blended resin comprises 30% to 70% by weight of post-consumer recycled polymer.

[11] The method according to [9] above, wherein the at least one silica-containing zeolite has a Si / Al molar ratio greater than 500 and less than 700.

[12] The method of [9] above, wherein the second silica-zeolite additive is present in an amount ranging from 0.1% to 20% by weight of the total isocyanate-reactive composition.

[13] The method according to [9] above, wherein at least one zeolite additive has a pore size of less than 10 Å.

[14] The method of [9] above, wherein the at least one silica-containing zeolite has a Na wt% of less than 2.

[15] The method according to [9] above, wherein the polyurethane foam is wrapped in the film.

Claims

1. A product, (1) A film, The present invention also includes a monolayer film or a multilayer film having at least one layer comprising a blended resin, the blended resin comprising: a low density polyethylene (LDPE), the LDPE having a density of 0.915 g / cc to 0.925 g / cc and a melt index I2 of 0.1 g / 10 min to 1 g / 10 min; or a linear low density polyethylene (LLDPE), the LLDPE having a density of 0.915 g / cc to 0.945 g / cc and a melt index I2 of 0.1 g / 10 min to 1 g / 10 min; and a film comprising at least a first silica-containing zeolite having a Si / Al molar ratio greater than 35 and a particle size from a particle size of 250 nm to 2000 nm; (2) a flexible polyurethane foam that is the reaction product of an isocyanate component and an isocyanate-reactive component, the flexible polyurethane foam comprising at least a second silica-containing zeolite, the silica-containing zeolite having a Si / Al molar ratio greater than 35 and a particle size between 250 nm and 2000 nm; A product wherein the flexible polyurethane foam is encased in the film.

2. 10. The article of manufacture of claim 1, wherein the compounded resin comprises 30% to 70% by weight of post-consumer recycled polymer.

3. 10. The article of claim 1, wherein the at least one silica-containing zeolite has a Si / Al molar ratio greater than 500 and less than 700.

4. 10. The article of claim 1, wherein the at least one silica-containing zeolite has a pore size of less than 10 Å.

5. 10. The product of claim 1, wherein the at least one silica-containing zeolite has a Na wt% of less than 2.

6. The polyurethane foam has a strength of about 35 kg / cm ３ 10. The article of claim 1 having a density of

7. 1. A method for packaging polyurethane foam, comprising: and wrapping the polyurethane foam in a polyolefin film, the polyolefin film comprising: The present invention also includes a monolayer film or a multilayer film having at least one layer comprising a blended resin, the blended resin comprising: Low density polyethylene (LDPE), wherein the LDPE has a density of 0.915 g / cc to 0.925 g / cc and a melt index I of 0.1 g / 10 min to 1 g / 10 min. ２ low density polyethylene (LDPE), or A linear low density polyethylene (LLDPE), wherein the LLDPE has a density of 0.915 g / cc to 0.945 g / cc and a melt index I of 0.1 g / 10 min to 1 g / 10 min. ２ Linear low density polyethylene (LLDPE) having at least a first silica-containing zeolite having a Si / Al molar ratio greater than 35 and a particle size from 250 nm to 2000 nm, and the polyurethane foam at least one isocyanate-reactive component, and The method comprises at least a second silica-containing zeolite, said silica-containing zeolite having a Si / Al molar ratio greater than 35 and a particle size between 250 nm and 2000 nm.

8. The method of claim 7, wherein the formulated resin comprises 30% to 70% by weight of post-consumer recycled polymer.

9. 8. The method of claim 7, wherein the at least one silica-containing zeolite has a Si / Al molar ratio greater than 500 and less than 700.

10. 8. The method of claim 7, wherein the at least one silica-containing zeolite has a pore size of less than 10 Å.

11. 8. The method of claim 7, wherein the at least one silica-containing zeolite has a Na wt% of less than 2.

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