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    • 专利摘要:
    MULTI-LAYER FORMULATION AND STRUCTURE The invention provides flexible polyolefin-based formulations with halogen-free flame retardant.
    公开号:BR112014019935B1
    申请号:R112014019935-3
    申请日:2013-03-04
    公开日:2021-03-09
    发明作者:Stefan Ultsch
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Technical field
    [0001] The present invention relates to formulations of a polyolefin-based composition that is filled with halogen-free flame retardants. Prior art
    [0002] Thermoplastic polyolefin (TPO) formulations of elastomeric mixtures based on polypropylene / propylene are commonly used in TPO for the extrusion of roofing and waterproof membranes. In general, they are filled with 30 to 45% by weight of halogen-free flame retardants such as aluminum trihydrate (ATH) or magnesium hydroxide [Mg (OH) 2], and have a flexural modulus in the range of 80 to 100 MPa . They meet the standard requirements for flame resistance, such as Euroclass D and E according to EN 119256-2, as well as the ASTM and EN-system tests, such as ENV 1187 t1 to t4. TPO formulations are in use for thicker membranes as a single layer roof covering, when installed on substrates, or when reduced flame resistance requirements apply. Until now, Euroclass A2 flame resistance levels, according to EN 11925-2, or the similar and demanding vertical flame tests may not be compatible with halogen-free olefinic formulations. Table 1 provides an overview of European fire regulations.

    [0003] Coated fabrics for applications such as architectural textile materials, banners, tarpaulins or artificial leather may require higher loads of flame retardants to meet strict test requirements such as EN 11925-2 (small burner test) according to Euroclass B or BS7837. EN 13823 (isolated object test in combustion) must pass a classification of B-S1- dO.
    [0004] Flexible coated fabrics for applications that require flame resistance at Euroclass B level are generally prepared with polymers with intrinsic fire resistance, such as polyvinyl chloride, polyurethanes, fluoroelastomers or silicones.
    [0005] At the same time, compounds for such applications must demonstrate processability in the extrusion coating, and good penetration and adhesion on fabric. In the final application, they generally need to meet various properties such as flexibility (the common goal is a flexibility module of less than <30 MPa), weldability, abrasion resistance, mechanical resistance, printability, weathering and UV resistance, and fire resistance . To meet these combinations of demanding requirements, polyvinyl chloride, fluoropolymers or even silicones, are commonly used today. TPOs were not employed because they do not meet the demanding ownership requirements. In particular, they lack flexibility in combination with sufficient flame resistance.
    [0006] WO 2005/090427 describes a multiblock copolymer comprising, in polymerized form, ethylene and one or more copolymerizable comonomers, said copolymer containing two or more segments or blocks that differ in comonomer content, crystallinity, density, melting point or glass transition temperature.
    [0007] WO 2006/101924 describes mixtures of at least two polyolefins with ethylene / α-olefin (multiblock) interpolymers with improved compatibility.
    [0008] WO 2006/101932 describes compositions comprising ethylene / α-olefin (multiblock) interpolymers and fillers.
    [0009] WO / 2011/008336 describes a multilayer structure comprising an upper skin layer comprising a propylene / alpha-olefin copolymer mixed with at least one other component; an intermediate foam layer comprising a propylene / alpha-olefin copolymer; and a lower layer of fabric comprising a nonwoven, polymeric or spunbond material. Summary of the Invention
    [0010] The invention provides a formulation comprising (A) olefinic block copolymer, (B) propylene / α-olefin interpolymer, and (C) halogen-free flame retardant. Brief Description of Drawings
    [0011] Figure 1 shows examples of non-woven fabrics (canvas);
    [0012] Figure 2 shows the preparation of the sample for welding test;
    [0013] Figure 3 shows the appropriate pattern for cutting strips for welding test;
    [0014] Figure 4 shows the weld quality test: tear with pliers until the sample fails;
    [0015] Figure 5 shows sample failure inside the weld joint (“joint delamination”); and
    [0016] Figure 6 shows a schematic example of a multilayer structure. Detailed Description
    [0017] The present invention provides polyolefin-based formulations comprising olefinic block copolymers (OBC) and propylene-α-olefin interpolymers incorporating halogen-free flame retardants in amounts greater than 60% by weight, while maintaining good processability , mechanical properties, thermal weldability and excellent fire resistance. In addition, such non-thermoset and halogen-free compounds show excellent recyclability. The formulations are an ecological, halogen-free, economical and high-performance alternative to PVC, polyurethanes, fluoropolymers, silicones and the like.
    [0018] Such formulations can be applied to various substrates using different conventional methods. These conventional methods include, but are not limited to, calendering, lamination, extrusion, direct extrusion, cast plate, or combinations thereof.
    [0019] The invention provides OBC / propylene-α-olefin interpolymer formulations that have low modulus in the range of 50 MPa, even when filled with flame retardants. Its high flexibility / low modulus facilitates its handling during manufacture, installation and welding. The OBC / propylene-α-olefin interpolymer formulations exhibit excellent fill / fill and melt absorption properties, with a low oligomer content, which generates good processing and good welding performance.
    [0020] The mixtures of the present invention weld as well as the more rigid and PP-based TPOs (modulus> 80 MPa), such as those commonly used for standard single-layer roof membranes. This property allows thermal welding of rigid products with soft products, such as soft profiles, such as vertical joints in the single layer of TPO, or welding of sealing edges in PP profiles. Common thermal welding devices and processes can be used. An additional advantage of OBC / propylene-α-olefin interpolymer blends is their relatively high softening / melting point which provides a high level of heat resistance.
    [0021] The formulation may also comprise one or more thermoplastic polymers which include, but are not restricted to polypropylene, random propylene copolymer and homogeneously branched ethylene / α-olefin copolymer.
    [0022] In addition, pre-mixes of polyolefinic dispersions with flame retardants, dyes and stabilizers can be used for coating fabrics using methods such as blade, upper contact roller, size press, curtain or spray. Definitions
    [0023] "Polymer" means a compound prepared by polymerizing monomers, whether they are of the same or different type. The generic term polymer then encompasses the term homopolymer, generally used to refer to polymers prepared with only one type of monomer and the term interpolymer, as defined below.
    [0024] "Interpolymer" and similar terms means a polymer prepared by polymerizing at least two different types of monomers. Interpolymer refers to both polymers prepared with two different types of monomers, and polymers prepared with more than two different types of monomers, for example, copolymers, terpolymers, tetrapolymers, etc.
    [0025] "Layer" and similar terms mean a simple thickness or coating of a compound, polymer or composition spread or covering a surface.
    [0026] "Multilayer structure" and similar terms mean a structure that comprises two or more layers. The multilayer structures of the present invention comprise a lower layer of fabric and at least an upper layer of lining.
    [0027] "Calendering / calendering" and similar terms mean, in the context of the present invention, a mechanical process in which a molten polymer is converted into sheet by passing the molten polymer through a series of cylinders / rollers to coalesce, flatten and smooth the polymer, transforming it into sheet or film.
    [0028] "Lamination / laminar" and similar terms mean a process in which a film, typically of plastic or similar material, is applied to a substrate that can be another film. The film can be applied to the substrate with or without adhesive. If it is adhesive-free, the film and / or substrate can be heated to perform heat or fusion lamination. Laminations are products of a laminating process, these products being presented in multilayer, that is, they comprise at least two layers, a film layer in contact with a base layer or substrate.
    [0029] "Non-woven" and similar terms mean a fabric or similar material prepared with long fibers, joined by chemical, mechanical, thermal or solvent treatment. The term is used to designate fabrics such as felt, which are neither woven nor worked in knit stitch.
    [0030] "Continuous spinning fabric" and similar terms mean a fabric or similar material prepared by depositing extruded and spun filaments on a collecting belt in a uniform and random manner, followed by the union of these fibers.
    [0031] "Spun Fabrics" or knitted fabrics are commonly used for flexible membranes. See illustrative examples in Figure 1.
    [0032] The term "polypropylene" includes propylene homopolymers, such as isotactic polypropylene, syndiotactic polypropylene and propylene copolymers and one or more C2,4,8 α-olefins in which propylene comprises at least 50 mole percent.
    [0033] The term "crystalline" refers to a polymer or polymer block that has a first order transition or crystalline melting point (Tm), as determined by differential scanning calorimetry (DSC) or equivalent technique. The term can be used concurrently with the term "semi-crystalline". Block Olefin Copolymer (OBC)
    [0034] The term "block olefinic copolymer" or "OBC" means a multiblock ethylene / α-olefin copolymer and includes ethylene and one or more copolymerizable α-olefin comonomers in polymerized form, characterized by blocks or multiple segments of two or more units of polymerized monomer differing in chemical or physical properties. The terms "interpolymer" and "copolymer" are used concurrently in the present invention. In some embodiments, the multiblock copolymer can be represented by the following formula: (AB) n
    [0035] where n is at least 1, preferably an integer greater than 1, such as 2,3,4,5,10,15,20,30,40,50,60,70,80,90,100 or greater. "A" represents a hard block or segment and "B" represents a soft block or segment. Preferably, As and Bs are connected in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped shape. In other embodiments, blocks A and blocks B are randomly distributed along the polymeric chain. In other words, block copolymers generally do not have a structure as follows: AAA-AA-BBB-BB
    [0036] In yet other embodiments, block copolymers generally do not have a third type of block, which comprises different comonomer (s). In yet other embodiments, each block A and block B have monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor block B comprises two or more subsegments (or sub-blocks) of different composition, such as a terminal segment, which has a composition substantially different from that of the rest of the block.
    [0037] Preferably, ethylene comprises the majority of the molar fraction of the total block copolymer, i.e., ethylene comprises at least 50 mole percent of the total polymer. More preferably, ethylene comprises at least 60 mole percent, at least 70 mole percent, or at least 80 mole percent, with the substantial remainder of the total polymer comprising at least another comonomer which is preferably an α-olefin containing 3 or more carbon atoms. For many ethylene / octene block copolymers, the preferred composition comprises an ethylene content greater than 80 mole percent of the total polymer and an octene content of 10 to 15, preferably 15 to 20 mole percent of the total polymer.
    [0038] The olefinic block copolymer includes various amounts of "hard" and "soft" segments. "Hard" segments refer to blocks of polymerized units in which ethylene is present in an amount greater than 95 percent by weight or greater than 98 percent by weight, based on the weight of the polymer. In other words, the comonomer content (monomer content other than ethylene) in the hard segments is less than 5 percent by weight or less than 2 percent by weight, based on the weight of the polymer. In some embodiments, the hard segments comprise all or substantially all units derived from ethylene. "Soft" segments are blocks of polymerized units in which the comonomer content (monomer content other than ethylene) is greater than about 5 percent by weight or greater than 8 percent by weight, greater than 10 percent by weight or greater than 15 weight percent, based on the weight of the polymer. In some embodiments, the comonomer content in the soft segments can be greater than 20 percent by weight, greater than 25 percent by weight, greater than 30 percent by weight, greater than 35 percent by weight, greater than 40 percent by weight, greater than 45 weight percent, greater than 50 weight percent, or greater than 60 weight percent.
    [0039] The soft segments may be present in OBC from 1 weight percent to 99 weight percent of the total weight of the OBC, or from 5 weight percent to 95 weight percent, from 10 weight percent to 90 percent by weight, 15 percent by weight to 85 percent by weight, 20 percent by weight to 80 percent by weight, 25 percent by weight to 75 percent by weight, 30 percent by weight to 70 percent by weight, from 35 percent by weight to 65 percent by weight, from 40 percent by weight to 60 percent by weight, or from 45 percent by weight to 55 percent by weight of the total weight of the CBO. The hard segments, on the contrary, can be present in similar bands. The percentage by weight of the soft segment and the percentage by weight of the hard segment can be calculated based on the data obtained from DSC or NMR. Such methods and calculations are described, for example, in US patent application No. 7,608,668, entitled "Ethylene / α-Olefin Block Interpolymers", filed on March 15, 2006, in the name of Colin LPShan, Lonnie Hazlitt, et.al. and assigned to Dow Global Technologies, Inc., the description of which has been incorporated herein by reference in its entirety. In particular, the hard and soft segment weight percentages and the comonomer content can be determined as described in Column 57 to Column 63 of U.S. Patent 7,608,668.
    [0040] The olefinic block copolymer is a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") preferably joined in a linear fashion, that is, a polymer comprising chemically differentiated units, which are joined end to end with with respect to polymerized ethylene functionality, rather than in pending or grafted form. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated in it, density, amount of crystallinity, size of the crystallite attributable to a polymer of such composition, type or degree of tacticity (isotactic or syndiotactic), regioregularity or regioiregularity, amount of branching (including long chain branching or hyper-branching), homogeneity or any other chemical or physical property. In comparison with the state-of-the-art block interpolymers, including interpolymers produced through sequential addition of monomer, flux catalysts, or anionic polymerization techniques, the OBC of the present invention is defined by unusual distributions of both polymer polydispersity (PDI or Mw / Mn or MWD), block extension distribution, and / or block number distribution, due, in one embodiment, to the effect of the transfer agent (s), in combination with multiple catalysts used in its preparation.
    [0041] In one embodiment, the OBC is produced in a continuous process and has a polydispersity index, PDI, of 1.7 to 3.5, or 1.8 to 3, or 1.8 to 2.5 , or 1.8 to 2.2. When produced in a batch or semi-batch process, the OBC has a PDI of about 1.0 to 3.5, or 1.3 to 3, or from 1.4 to 2.5, or from 1.4 to 2.
    [0042] In addition, the block olefinic copolymer has a PDI that fits a Schultz-Flory distribution instead of a Poisson distribution. The OBC of the present invention has both a polydispersed distribution of blocks, as well as a polydispersed distribution of block sizes. This results in the formation of polymeric products with improved and distinguishable physical properties. The theoretical benefits of a polydispersed block distribution were previously modeled and discussed in Potemkin, Physical Review E (1998) 57 (6), p. 6902-6912 and Dobrynin, J. Chem.Phys. (1997) 107 (21), p. 9234-9238.
    [0043] In one embodiment, the block olefinic copolymer of the present invention has a more likely distribution of block lengths. In one embodiment, the block olefinic copolymer is defined as having: a) Mw / Mn of 1.7 to 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams / cubic centimeter, where the numerical values of Tm and d correspond to the relationship: Tm> - 2002.9 + 4538.5 (d) - 2422.2 (d) 2, and / or b) Mw / Mn from 1.7 to 3 , 5, being defined by a heat of fusion, ΔH in J / g and a delta amount, ΔT, in degrees Celsius defined as the temperature difference between the highest DSC peak and the fractionation peak by crystallization analysis ("CRYSTAF" ) higher, where the numerical values of ΔT and ΔH have the following relationships: ΔT> -0.1299 (ΔH) + 62.81 for ΔH greater (>) than zero and up to 130 J / g, ΔT> 48oC for ΔH greater than 130 J / g, where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature will be 30oC; and / or c) Elastic recovery, Re, in percentage, at 300 percent deformation and 1 cycle measured with a film molded by compression of the ethylene / α-olefin interpolymer, having a density, d, in grams / cubic centimeter, where the numerical values of Re ed satisfy the following relationship when the ethylene / α-olefin interpolymer is substantially free of cross-linked phase: Re> 1481 - 1629 (d); and / or d) It has a molecular weight fraction that elutes between 40oC and 130oC when fractionated using TREF, defined by the fact that the fraction has a molar comonomer content equal to or greater than the amount (-0,2013) T + 20, 07, more preferably equal to or greater than the quantity (-0,2013) T + 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction, measured in ° C; and / or, e)) has a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° C, G' (100 ° C), where the ratio of G '( 25 ° C) for G '(100 ° C) is in the range of 1: 1 to 9: 1. The multiblock olefinic copolymer may also have: f) a molecular fraction that elutes between 40 ° C and 130 ° C when fractioned using TREF, the fraction having a block index of at least 0.5 and up to 1 and a molecular weight distribution, Mw / Mn, greater than 1.3; and / or g) an average block index greater than zero and up to 1.0 and a molecular weight distribution, Mw / Mn, greater than 1.3. It is understood that the block olefinic copolymer may have any, some, all or any combination of properties (A) - (G). The block index can be determined as described in detail in U.S. Patent No. 7,608,668, incorporated herein by reference for that purpose. Analytical methods for determining the properties of (A) to (G) are described, for example, in U.S. Patent 7,608,668, column 31, row 26 to column 35, row 44, incorporated herein by reference for that purpose.
    [0044] Monomers suitable for use in the preparation of the OBC of the present invention include ethylene and one or more addition-curable monomers other than ethylene. Examples of suitable comonomers include 3 to 30 straight or branched chain α-olefins, preferably 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene , 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cycloolefins from 3 to 30, preferably from 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethane- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene; di and polyolefins, such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenonorbornene, norbornene vinyl, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene -8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decathriene; and 3-phenylpropene, 4-phenylpropene, 1,2-difluoroethylene, tetrafluoroethylene, and 3,3,3-trifluoro-1-propene.
    [0045] The olefinic block copolymer has a density of 0.850 g / cc to 0.925 g / cc or 0.860 g / cc to 0.88 g / cc or 0.860 g / cc to 0.879 g / cc. The OBC has a Shore A value of 40 to 70, preferably 45 to 65 and more preferably 50 to 65. In one embodiment, the block olefinic copolymer has a melt index (MI) of 0.1 g / 10 min at 30 g / 10, or from 0.1 g / 10 min to 20 g / 10 min, or from 0.1 g / 10 min to 15 g / 10 min, as measured using ASTM D 1238 (190 ° C / 2.16 kg) . The olefinic block copolymer is present in an amount of 5 wt% to 45 wt%, preferably 10 wt% to 30 wt%, more preferably 10 wt% to 25 wt%. The composition may comprise more than an olefinic block copolymer.
    [0046] The olefinic block copolymers are produced through a chain transfer process, such as those described in U.S. Patent No. 7,858,706, incorporated herein by reference. In particular, appropriate chain transfer agents and related information are listed in column 16, line 39 to column 19, line 44. Suitable catalysts are described in column 19, line 45 to column 46, line 19 and suitable cocatalysts in column 46, line 20 to column 51, line 28. The process is described throughout the document, but particularly in column 51, line 29 to column 54, line 56. The process is also described, for example, in the following US patents Nos. 7,608,668; 7,893,166; and 7,947,793. Propylene-α-Olefin Interpolymer
    [0047] The propylene-alpha-olefin interpolymer is defined by having substantially isotactic propylene sequences. Propylene-alpha-olefin interpolymers include propylene-based elastomers (PBE). “Substantially isotactic propylene sequences” means that the sequences have an isotactic triad (mm) measured by 13C NMR greater than 0.85; alternatively, greater than 0.90; alternatively, greater than 0.92; and alternatively, greater than 0.93. Isotactic triads are well known in the state of the art, and described, for example, in U.S. Patent No. 5,504,172 and international publication No. WO 00/01745, which refer to the isotactic sequence in terms of a triadic unit in the molecular chain of copolymer determined through 13C NMR spectra.
    [0048] The propylene / alpha-olefin interpolymer can have a melt flow rate in the range of 0.1 to 500g / 10 minutes (g / 10 min), measured according to ASTM D-1238 (at 230oC / 2 , 16 kg). All values and individual sub-ranges from 0.1 to 500g / 10 minutes are included and described here; for example, the melt flow rate can vary from a minimum limit of 0.1g / 10 minutes, 0.2g / 10 minutes or 0.5g / 10 minutes to a maximum limit of 500g / 10 minutes, 200g / 10 minutes , 100g / 10 minutes or 25g / 10 minutes. For example, the propylene / alpha-olefin copolymer can have a melt flow rate in the range of 0.1 to 200g / 10 minutes; or alternatively, the propylene / alpha-olefin copolymer can have a melt flow rate in the range of 0.2 to 100g / 10 minutes; or alternatively, the propylene / alpha-olefin copolymer can have a melt flow rate in the range of 0.2 to 50g / 10 minutes; or alternatively, the propylene / alpha-olefin copolymer can have a melt flow rate in the range of 0.5 to 50g / 10 minutes; or alternatively, the propylene / alpha-olefin copolymer can have a melt flow rate in the range of 1 to 50g / 10 minutes; or alternatively, the propylene / alpha-olefin copolymer can have a melt flow rate in the range of 1 to 40g / 10 minutes; or alternatively, the propylene / alpha-olefin interpolymer may have a melt flow rate in the range of 1 to 30 g / 10 minutes.
    [0049] The propylene / alpha-olefin interpolymer has a crystallinity in the range of at least 1 weight percent (a heat of fusion (Hf) of at least 2 Joules / gram) to 30 weight percent (a lower Hf than 50 Joules / gram). All values and individual sub-ranges from 1 weight percent (one Hf less than 2 Joules / gram) to 30 weight percent (one Hf less than 50 Joules / gram) are included and described here; for example, crystallinity can range from a minimum limit of 1 percent by weight (an Hf of at least 2 Joules / gram), 2.5 percent (an Hf of at least 4 Joules / gram) or 3 percent ( one Hf of at least 5 Joules / gram) up to a maximum limit of 30 percent by weight (one Hf less than 50 Joules / gram), 24 percent by weight (one Hf less than 40 Joules / gram), 15 percent by weight (one Hf less than 24.8 Joules / gram) or 7 percent by weight (one Hf less than 11 Joules / gram). For example, the propylene / alpha-olefin copolymer can have a crystallinity in the range of at least 1 weight percent (a melting heat of at least 2 Joules / gram) to 24 weight percent (a melting heat of less than 40 Joules / gram); or alternatively, the propylene / alpha-olefin copolymer can have a crystallinity in the range of at least 1 weight percent (a melting heat of at least 2 Joules / gram to 15 weight percent (a melting heat of less than 24.8 Joules / gram), or alternatively, the propylene / alpha-olefin copolymer may have a crystallinity in the range of at least 1 weight percent (a heat of fusion of at least 2 Joules / gram) at 7 percent weight percent (a heat of fusion less than 11 Joules / gram), or alternatively, the propylene / alpha-olefin copolymer may have a crystallinity in the Hf range of less than 8.3 J / g). Crystallinity is measured by differential scanning calorimetry (DSC), as described in patent SP 7,199,203. The propylene / alpha-olefin copolymer comprises units derived from propylene and polymer units derived from one or more alpha-olefin comonomers. Representative comonomers used in the manufacture of the propylene / alpha-olefin copolymer are alpha-olefins C2, and C4 to C10; for example, C2, C4, C6 and C8 alpha olefins.
    [0050] The propylene / alpha-olefin interpolymer comprises from 1 to 40 weight percent of one or more alpha-olefin comonomers. All individual values and sub-ranges from 1 to 40 weight percent are included and described here; for example, the comonomer content can vary from a minimum limit of 1 percent by weight, 3 percent by weight, 4 percent by weight, 5 percent by weight, 7 percent by weight, or 9 percent by weight , up to a maximum of 40 per cent by weight, 35 per cent by weight, 30 per cent by weight, 27 per cent by weight, 20 per cent by weight, 15 per cent by weight, 12 per cent by weight, or 9 percent by weight. For example, the propylene / alpha-olefin copolymer comprises from 1 to 35 weight percent of one or more alpha-olefin comonomers; or alternatively, the propylene / alpha-olefin copolymer comprises from 1 to 30 weight percent of one or more alpha-olefin comonomers; or alternatively, the propylene / alpha-olefin copolymer comprises from 3 to 27 weight percent of one or more alpha-olefin comonomers; or alternatively, the propylene / alpha-olefin copolymer comprises from 3 to 20 weight percent of one or more alpha-olefin comonomers; or alternatively, the propylene / alpha-olefin copolymer comprises from 3 to 15 weight percent of one or more alpha-olefin comonomers.
    [0051] The propylene / alpha-olefin interpolymer has a density typically less than 0.895 g / cm3; or alternatively less than 0.890 g / cm3; or alternatively, less than 0.880 g / cm3; or alternatively, less than 0.870 g / cm3. The propylene / alpha-olefin interpolymer has a density typically greater than 0.855 g / cm3; or alternatively, greater than 0.860 g / cm3; or alternatively, greater than 0.865 g / cm3.
    [0052] The propylene / alpha-olefin interpolymer has a melting temperature (Tm) typically less than 120 ° C; or alternatively, <100 ° C; or alternatively, <90 ° C; or alternatively, <80 ° C; or alternatively, <70 ° C; and a heat of fusion (Hf) typically less than 70 Joules per gram (J / g) measured by differential scanning calorimetry (DSC) as described in USP 7,199,203.
    [0053] The propylene / alpha-olefin interpolymer has a molecular weight distribution (MWD), defined as the average molecular weight by weight divided by the numerical average molecular weight (Mw / Mn) of 3.5 or less; or 3.0 or less; or 1.8 to 3.0.
    [0054] Such propylene / alpha-olefin interpolymers are also described in detail in U.S. Patent Nos. 6,960,635 and 6,525,157. Such propylene / alpha-olefin interpolymers are available on the market, supplied by The Dow Chemical Company under the trade name VERSIFYTM or by ExxonMobil Chemical Company under the trade name VISTAMAXXTM.
    [0055] In one embodiment, the propylene / alpha-olefin interpolymers are further characterized as comprising: (A) between 60 and less than 100, preferably between 80 and 99 and more preferably between 85 and 99 weight percent of derivative units propylene, and (B) between more than zero and 40, preferably between 1 and 20, more preferably between 4 and 16, and even more preferably between 4 and 15 weight percent of units derived from at least one of ethylene and / or a C4-10 α-olefin; and containing an average of at least 0.001, preferably an average of at least 0.005 and more preferably an average of at least 0.01 long chain branches / 1000 total carbons. The maximum number of long chain branches in the propylene / alpha-olefin copolymer is not critical, although it typically does not exceed 3 long chain branches / 1000 total carbons. The term long chain branching, as used herein in relation to propylene / alpha-olefin copolymers, refers to a chain extension of at least one (1) carbon more than a short chain branching, and branching of short chain, as used herein in connection with propylene / alpha-olefin copolymers refers to a two (2) carbon chain length less than the number of carbons in the comonomer. For example, a propylene / 1-octene interpolymer has main chains with long chain branches with at least seven (7) extension carbons, although these main chains also have short chain branches with only six (6) extension carbons. Such propylene / alpha-olefin copolymers are also described in detail in U.S. Patent Publication No. 2010-0285253 and International Patent Publication No. WO 2009/067337. Random Polypropylene Copolymer
    [0056] Random propylene polymers typically comprise 90 or more mole percent units derived from propylene. The remainder of the units in the propylene copolymer are derived from units of at least one α-olefin. In the context of the present invention, random polypropylene copolymers are not propylene / alpha-olefin interpolymers.
    The alpha-olefin component of the propylene copolymer is preferably ethylene (considered an α-olefin for the purposes of the present invention) or a linear, branched or cyclic α-olefin C4-20. Examples of C4-20 α-olefins include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. Α-olefins can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. Although not α-olefins in the classic sense of the term, for purposes of the present invention, certain cyclic olefins, such as norbornene and related olefins, particularly 5-ethylene-2-norbornene, are α-olefins and can be used in place of some or all of the α-olefins described above. Similarly, styrene and its related olefins (e.g., α-methylstyrene, etc.) are α-olefins for purposes of the invention. Illustrative random propylene copolymers include, but are not limited to, propylene / ethylene, propylene / 1-butene, propylene / 1-hexene, propylene / 1-octene and the like. Illustrative terpolymers include ethylene / propylene / 1-octene monomer, ethylene / propylene / 1-butene and ethylene / propylene / diene (EPDM).
    [0058] In one embodiment, the random polypropylene copolymer has a melting temperature (Tm) determined by differential scanning calorimetry (DSC) that is greater than the Tm of the propylene / alpha-olefin copolymer. An acceptable DSC procedure for determining the melting temperature of the random polypropylene copolymer and the propylene / alpha-olefin copolymer is described in USP 7,199,203. In one embodiment, the random polypropylene copolymer has a Tm greater than 120 ° C, and / or a heat of fusion greater than 70 J / g (both measured by DSC) and preferably, but not necessarily, prepared through Ziegler catalysis -Natta. Polypropylene homopolymer
    [0059] The polymer component of polypropylene can be homopolymer of propylene. There is no specific restriction on the method for preparing the propylene polymer. However, in general, the polymer is obtained through the homopolymerization of propylene in a single-stage or multi-stage reactor. Polymerization methods include high pressure, paste, gas, in bulk or in solution, or a combination of these, using a traditional Ziegler-Natta catalyst or a single-site or metallocene catalyst system. The catalyst used is preferably one that has high isospecificity. Polymerization can be conducted through a continuous or batch process and may include the use of chain transfer agents, sweepers / scavengers, or other additives as deemed applicable. Homogeneously Branched Ethylene / Alpha-olefin Copolymer
    [0060] The homogeneously branched ethylene / alpha-olefin copolymers useful in the practice of the present invention can be prepared with a single site catalyst, such as the metallocene catalyst or constricted geometry catalyst and typically have a melting point less than 105, preferably less than 90, more preferably less than 85, even more preferably less than 80, and even more preferably less than 75 ° C. The melting point is measured using differential scanning calorimetry (DSC) as described, for example, in USP 5,783,638. Such low-melting ethylene / α-olefin copolymers often exhibit desirable flexibility and thermoplastic properties useful in the manufacture of the multilayer structures of the present invention.
    [0061] α-olefin is preferably a linear, branched or cyclic α-olefin C3-20. Examples of C3-20 α-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1- octadecene. Α-olefins can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. Although not α-olefins in the classic sense of the term, for the purposes of the present invention, certain cyclic olefins, such as norbornene and related olefins, are α-olefins and can be used in place of some or all of the α-olefins described above. . Similarly, styrene and its related olefins (e.g., α-methylstyrene, etc.) are α-olefins for purposes of the invention. Illustrative homogeneously branched ethylene / alpha-olefin copolymers include ethylene / propylene, ethylene / butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / styrene, and the like. Illustrative terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene and ethylene / butene / styrene. Copolymers can be random or block.
    [0062] More specific examples of homogeneously branched ethylene / alpha-olefin interpolymers useful in the present invention include homogeneously branched linear ethylene / α-olefin copolymers (eg TAFMER® from Mitsui Petrochemicals Company Limited and EXACT® from Exxon Chemical Company) and homogenously branched, substantially linear ethylene / α-olefin polymers (eg AFFINITY® polyethylene and ENGAGE® from The Dow Chemical Company). Substantially linear ethylene copolymers are especially preferred and more widely described in U.S. Patent Nos. 5,272,236, 5,278,272 and 5,986,028. Mixtures of any of these interpolymers can also be used in the practice of the present invention. In the context of the present invention, homogeneously branched ethylene / alpha-olefin interpolymers are not block olefinic copolymers. Halogen-Free Flame Retardant / Fill-Filler
    [0063] A halogen-free flame retardant is used in the formulations to impart flame-resistant properties. By "halogen-free" is meant that the flame retardant molecules do not contain halogen atoms, as is generally understood in the state of the art. The flame retardant-loaded polymer formulations provided herein are capable of maintaining desirable manufacturing characteristics with high fill / fill levels. Obtaining filler loads of approximately 50 percent by volume and greater, while at the same time maintaining adequate mechanical properties, is favorable to the formulation of economical compositions. In addition, the compositions provided herein, in certain embodiments, can maintain desirable mechanical properties, over a wide range of fill / fill levels.
    [0064] Useful charges in the compositions include, but are not limited to, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, polyphosphates, hindered amines, glass fibers, nano-clay, zinc oxide, aluminum silicate, calcium silicate , titanium dioxide, titanates, glass and chalk microspheres. Particularly preferred compounds are aluminum trihydrate or magnesium hydroxide. In certain embodiments, the filler is selected from calcium carbonate and barium sulfate. Combustion-resistant fillers that can be used in the compositions include antimony oxide, aluminum trihydrate, magnesium hydroxide and borates. The amount of the charge depends on its density; the greater the density of the filler, the greater the amount to be added to the formulation without appreciably affecting the volumetric fraction of that filler. The level of charge in a mixing composition can be described by weight or volume. The volumetric percentage of the load can be estimated by the equation:% vol F = [(% weight F / pF) x100%] / [% weight F / pF) + ∑ (% weight i / pi)
    [0065] where% vol F is equal to the volumetric percentage of the charge in the final composition,% weight F is equal to 5 percent by weight of the charge; pF is the density of the charge measured in grams per cubic centimeter (g / cm3); Weight% i is the percentage by weight of the ith component; pi is the density of the ith component in grams per cubic centimeter (g / cm3).
    [0066] Consequently, the level of charge is discussed here in terms of percentage by weight of charge, based on the total weight of the composition. The particle size of the charge has some effect on the amount of charge used in the compositions. Loads with fine particle size generally tend to result in higher mixing viscosities, while providing improved physical strength. They are also more expensive. The use of fine filler, especially at high fill / fill load, results in a smoother extrudate surface when the molten mixture is extruded through a die orifice. The current benefits of using fine particle size fillers in charged polymeric compositions are described in U.S. Patent No. 4,263,196, the description of which is incorporated herein by reference in its entirety. In the representative compositions provided herein, the magnesium hydroxide used has a particle size between about 0.65 micron and 0.95 micron.
    [0067] In certain embodiments, the use of many types of fillers or their combinations is possible without changing the properties of the charged polymeric compositions. For example, the inclusion of aluminum trihydrate (ATH, Al2O3.3H2O) or magnesium hydroxide (Mg (OH) 2) is highly desirable when flame retardant or low smoke emission compositions are desired. Finally, loads with varying aspect ratios, such as talc, mica, from highly acicular (wolastonite, for example) to round (glass beads, for example) can also be used to alter ratios, such as tensile strength or elongation. The filler is present in an amount ranging from 30% to 95% by total weight of the loaded polymeric compositions provided herein. In certain embodiments, the filler is present in an amount ranging from 40% to 90%, from 45% to 85%, from 50% to 85%, from 60% to 81% in total weight of the composition. Additions
    [0068] A variety of additional additives can be used in the formulations of the present invention. Additives include, but are not restricted to, antioxidants; surfactant modifiers; anti-blocking agents; plasticizers; processing oils, crosslinking agents, dispersants, blowing agents, UV stabilizers, antimicrobial agents, such as organometallic, isothiazolones, organo-sulfur and mercaptans; antioxidants, such as phenolics, secondary amines, phosphites and thioesters; antistatic agents, such as quaternary ammonium compounds, amines and ethoxylated, propoxylated or glycerol compounds; hydrolytic stabilizers; lubricants, such as fatty acids, fatty alcohols, esters, fatty amides, metal stearates, paraffinic and microcrystalline waxes, silicones and orthophosphoric acid esters; acid neutralizers or halogen scavengers, such as zinc oxide; release agents, such as fine particulate or powder solids, soaps, waxes, silicones, polyglycols and complex esters, such as trimethylol propane tristearate or pentaerythritol tetra stearate; pigments, dyes and dyes; heat stabilizers, such as organo-tin mercaptides, an octyl ester of thioglycolic acid and a barium or cadmium carboxylate; ultraviolet light stabilizers, such as hindered amine, an o-hydroxy-phenylbenzotriazole, a 2-hydroxy-4-alkoxybenzophenone, a salicylate, a cyanoacrylate, a nickel chelate and a benzylidene and oxalanilide malonate; acid scavengers; and zeolites, molecular sieves and other known deodorants.
    [0069] Other additives include additives to improve scratch / scratch resistance, such as polydimethyl siloxane (PDMS), or functionalized polydimethyl siloxane, or IRGASURF®SR 100 (from Ciba Specialty Chemicals) or formulations to improve scratch / scratch resistance containing erucamide. Functionalized polydimethyl siloxanes include, but are not limited to, hydroxyl-functionalized polydimethyl siloxane, amine-functionalized polydimethyl siloxane, vinyl-functionalized polydimethyl siloxane, alkyl-functionalized polydimethyl siloxane, alkyl-functionalized polydimethyl siloxane, polydimethyl siloxane functionalized mercaptan, and derivatives thereof. One skilled in the art can readily determine the quantities of additives needed, based on the application involved.
    [0070] Antioxidant and antiozonizing additives for use in the invention include hindered phenols, bisphenols and thiobisphenols; substituted hydroquinones; tris (alkylphenyl) phosphites; dialkylthiodipropionates; phenylnaphthylamines; substituted diphenylamines; p-phenylenediamines substituted with dialkyl, alkyl aryl and diaryl; monomeric and polymeric dihydroquinolines; 2- (4-hydroxy-3,5-t-butylaniline) -4,6-bis (octylthio) 1,3,5-triazine, hexahydro-1,3,5-tris-β- (3,5-di -t- butyl-4-hydroxyphenyl) propionyl-s-triazine, 2,4,6-tris (n-1,4-dimethylpentylphenylene-diamino) -1,3,5-triazine, tris- (3,5-di - t-butyl-4-hydroxybenzyl) isocyanurate, nickel dibutyldithiocarbamate, 2-mercaptotolylimidazole and its zinc salt waxes, petroleum and the like.
    [0071] Additives can be used in amounts of 0.01% by weight or less to 10% by weight or more based on the weight of the composition.
    [0072] The formulation may further comprise one or more thermoplastic polymers including, although not restricted to functional degrees of polyolefins, either grafted or copolymers, with portions such as esters of maleic acid, esters of acrylic and methacrylic acid, vinyl acetate, or as ionomers. Functional groups tend to increase load acceptance and can also increase fire resistance.
    [0073] To feed highly concentrated additives in the final composition, some additives can be pre-combined with a polyolefin matrix in the form of a binder. For certain examples, additional TiO2 is added to the existing compounds via a standard batch of 50% by weight in a low viscosity PP carrier at 40% by weight.
    [0074] Formulations can have a specific Organic / Inorganic Ratio. This is defined as: polymer (s) + organic additives (A / O, UV, etc.) divided by TiO2 + inorganic filler, all in percentage by weight. The terms "organic" and "inorganic" have meanings as understood in the prior art. TiO2 does not perform as a flame retardant (does not release water), but it also does not contribute to the fuel load of the formulations, and can therefore make a difference in fire resistance. The organic / inorganic ratio is preferably less than 0.35 and can also be 0.200 to 0.340, 0.220 to 0.330 or 0.230 to 0.320.
    [0075] Formulations can also have a Polymer / Flame Retardant Ratio. This is defined as polymer (s) + organic additives (A / O, UV, etc.) divided by the inorganic charge (not including TiO2, all in weight percent). The halogen-free flame retardant does not contribute to fuel load and releases water above its decomposition point (270 ° C for Mg (OH) 2). The polymer / flame retardant ratio is preferably less than 0.35 and can also be from 0.20 to 0.34, 0.22 to 0.33, or from 0.23 to 0.32. Dispersal
    [0076] An alternative method for preparing a fire resistant coating on a non-woven or fabric substrate is to use a polyolefin dispersion as the polymeric matrix. Polyolefin dispersions can be prepared by melting the product of one or more thermoplastic polymers and one or more stabilizing agents in the presence of water and one or more neutralizing agents, the aqueous dispersion having an average volumetric size of particle in the range of 0.05 to 5μ m, a pH in the range of 8 to 11, a total solids content in the range of 35 to 65 weight percent of one or more thermoplastic polymers and one or more stabilizing agents, and / or 35 to 65 weight percent water, based on the weight of the aqueous dispersion. The method for producing the aqueous dispersion comprises the steps of (1) melting one or more thermoplastic polymers and one or more stabilizing agents in the presence of water and one or more neutralizing agents to form an emulsified mixture; (2) diluting said emulsified mixture with additional water, while optionally removing heat from said emulsified mixture; (3) thus forming solid polymeric particles dispersed in water, (4) thereby producing said aqueous dispersion. The initial water content to form the emulsified mixture is typically less than 5 percent; for example, from 1 to 3 weight percent water based on the weight of the emulsified mixture. The additional dilution step increases the water content of the dispersion to a range of 35 to 65 weight percent water based on the weight of the dispersion. The polymers described in the present patent application can be converted into stable water-based dispersions using the mechanical dispersion processes described in US7803865, US7763676 and US7935755, insofar as they describe the process for such dispersions. They are typically manufactured with solids in the 40 to 60% range with a pH in the 8 to 11 range. They can be used with a wide range of additives used to formulate liquid coatings. These ingredients include, but are not limited to, thickeners, dispersants, wetting agents, solvents, fillers, pigments, dyes, UV stabilizers, defoamers, and flame retardant additives, such as magnesium hydroxide. The formulated coating, including polymeric dispersion and flame retardant, can be applied to a nonwoven or fabric using coating methods, including blade, upper contact roller, size press, curtain or spray. The excess water is then removed in a drying process (air heated by convection and / or combined with infrared heaters) and the coated item is recovered. The coated item can also be treated to increase performance and adapt the final item for different applications (primer for printability, for example). In general, the required drying temperatures are slightly above the melting point of the polymer used in the polyolefin dispersion. This allows the use of fibers in the non-woven or fabric that has less thermal resistance. Thus, polypropylene fibers can be used with water-based coatings of polyolefinic dispersions, whereas polyester fibers are preferred for systems where the coating is applied by melt extrusion or calendering. Fabric Layer (Substrate)
    [0077] The formulation can be used on a substrate of a fabric layer comprising a polymeric material which can be spun, non-woven, knitted, filamented, continuous spinning, etc., and can comprise natural and / or synthetic fiber. In one embodiment, the fabric layer is a non-woven, polymeric, continuously spinning material weighing 50-500, more typically 150-400 and even more typically 200-350 grams per square meter (g / m2 ). Fabrics that can be used in the practice of the present invention include, but are not limited to cotton, silk, and various polyolefin-based synthetics (eg, polyethylene, polypropylene, etc.), polyamide, polyester, polyurethane (eg, spandex material), glass fibers, aramides or carbon fibers, metallic fibers, and the like. In one embodiment, the preferred fabric is prepared with polyester, polyethylene or polypropylene. The fabric can be subjected to a pre-lamination treatment, for example, surface treatment by corona effect, impregnation, etc., or not, and the foam or top layer of skin is finally hot-rolled over it.
    [0078] "Calendering" and similar terms mean, in the context of the present invention, a mechanical process in which a molten polymer is converted to sheet, the molten polymer being passed through a series of cylinders to coalesce, flatten and smooth the polymer, turning it into sheet or film. “Lamination / laminar” and similar terms mean a process in which a film, typically made of plastic or similar material, is applied to a substrate that may be another film. The film can be applied to the substrate with or without adhesive. If it is adhesive-free, the film and / or substrate can be heated to perform heat or fusion lamination. Laminations are products of a laminating process, these products being presented in multilayer, that is, they comprise at least two layers, a film layer in contact with a base layer or substrate.
    [0079] Multilayer structures comprising the formulation can be manufactured, for example, using the same conventional calendering and lamination processes used for PVC-based artificial leather. Propylene-ethylene-based resins can be easily used in this process because their stickiness to the cylinder surface is small compared to other ethylene / propylene-based copolymers. The glass transition temperature of the propylene-ethylene copolymer is relatively higher than that of the ethylene / alpha-olefin copolymer which has a high elastic modulus and tackiness.
    [0080] One of the important factors in the calendering process is to optimize the condition of lateral roll inclination ("roll banking"), a condition well known in the state of the art. This indicates good mixing under melting of the resins. Generally, a high melt tension requires high molecular weight resin, although high molecular weight resins are not easily melted in the cylinder mixture. For good side-slope conditions, a balance between melt tension and melt melt is required. Printing / Coating
    [0081] Multilayer articles can receive impressions on their surface. Surface activation can be achieved by various means known in the art, such as corona, plasma or flame treatment, or by fluorination to generate membrane surfaces with sufficient activation energy. Then, printing is carried out using state-of-the-art inks and printing processes. Methods
    [0082] The density is measured according to ASTM D 792-03, Method B, in isopropanol. Melting index - ASTM 1238, 2, 16 kg @ 190 ° C (I2); ISO 1133, 2.16 kg @ 190 ° C; ISO 1133.5 kg @ 190 ° C
    [0083] Melt flow rate - ASTM 1238, 2.16 kg @ 230 ° C; 2.16 kg @ 230 ° C; ISO 1133.5 kg @ 190 ° C
    [0084] GPC method - The permeation chromatographic system can be instruments such as models PL-210 or model PL-220 from Polymer Laboratories. The column and carousel compartments are operated at 140 ° C. Three 10 micron Mixed-B columns from Polymer Laboratories are used. The solvent is 1,2,4-trichlorobenzene. The samples are prepared at a concentration of 0.1 gram of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). The samples are prepared by gently shaking for 2 hours at 160 ° C. The injection volume used is 100 microliters and the flow rate is 1.0 ml / minute. Calibration of the GPC column set is conducted with 21 polystyrene standards with narrow molecular weight distribution with molecular weights ranging from 580 to 8,400,000, arranged in 6 "cocktail" mixtures with at least a dozen separations between the molecular weights individual. The standards are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80 ° C with slight agitation for 30 minutes. Mixtures of narrow standards are operated first and in decreasing order of the highest molecular weight component to minimize degradation. The peak molecular weights of polystyrene standard are converted to molecular weights of polyethylene using the following Equation (as described in Williams and Ward, J. Polym. Sci. Polym. Let., 6, 621 (1968)): Mpolethylene = 0.431 ( Mpolystyrene), or Mpolipropylene = 0.645 (Mpoli styrene)
    [0085] Calculations of equivalent molecular weight of polypropylene are performed using version 3.0 of TriSEC Viscotek software.
    [0086] Polydispersity (PDI) or Molecular Weight Distribution (MWD) - the polydispersity of the polymers used in the present invention is typically described as "narrow". "Narrow polydispersity", "narrow molecular weight distribution", "narrow MWD" and similar terms mean a ratio (Mw / Mn) of weight average molecular weight (Mw) to numerical average molecular weight (Mn) measured using GPC.
    [0087] The results of Differential Scanning Calorimetry are determined on a TA Instruments DS1000 QC equipped with an RCS cooling accessory and an automatic sampler. A flow of nitrogen purge gas at 50 ml / min is used. The sample is pressed into a thin film and melted in the press at about 175 ° C and then cooled in air to room temperature (25 ° C). About 3-10 mg of material is then cut into a 6 mm diameter disc, weighed accurately, and placed in a light aluminum container (ca 50 mg) which is subsequently closed by compression. The thermal behavior of the sample is investigated with the following temperature profile: the sample is quickly heated to 180 ° C and maintained isothermal for 3 minutes to remove any previous thermal history. The sample is then cooled to -40 ° C at a cooling rate of 10 ° C / min and held at -40 ° C for 3 minutes. The sample is then heated to 150 ° C at a heating rate of 10 ° C / min. The cooling curves and the second heating curve are recorded.
    [0088] The DSC melting peak, or melting temperature (Tm) is measured as the maximum in the thermal flow rate (W / g) with respect to the linear baseline drawn between -30oC and the end of the melt. The heat of fusion (ΔHf) is measured as the area under the melting curve between -30oC and the end of the fusion, using a linear baseline. The DSC calibration is performed as described below. First, a baseline is obtained by operating a DSC from -90oC without a sample in the DSC aluminum container. Then 7 milligrams of fresh indium sample is analyzed by heating the sample to 180oC, cooling the sample to 140oC at a cooling rate of 10oC / min, and then keeping the sample isothermally at 140oC for 1 minute, and then heating the sample from 140oC to 180oC at a heating rate of 10oC per minute. The heat of fusion and the start of fusion of the indium sample are determined and checked to be in the range of 0.5oC of 156.6oC for the start of fusion and in the range of 0.5 J / g of 28.71 J / g to the end of the merger. Then deionized water is analyzed by cooling a droplet of the fresh sample in the DSC container from 25oC to -30oC at a cooling rate of 10oC per minute. The sample is kept isothermally at -30oC for 2 minutes and heated to 30oC at a heating rate of 10oC per minute. The start of the fusion is determined and verified so that it is in the range of 0.5oC of 0OC.
    [0089] Crystallinity - The factor used to convert specific melting heat, ΔHf,% by nominal crystallinity weight is 165 J / g (for propylene-based polymers) and 292 J / g (for ethylene-based polymers) = 100% by weight of crystallinity. (Using a different conversion factor could change the details of the results, but not substantive conclusions). With this conversion factor, the total crystallinity of a sample (units:% weight of crystallinity) is calculated as 100% times ΔHf divided by 165 or 292 J / g. And, with this conversion factor, 1% residual crystallinity corresponds to 1.65 J / g (based on P) or 2.92 J / g (based on E).
    [0090] Tensile strength - EN ISO 527-1 at 100 mm / min.
    [0091] Module - ISO 527-3, 2% drying module
    [0092] Elongation - EN ISO 527-1 at 100 mm / min
    [0093] Weld test - Polymer welding describes the process of combining (bonding) material surfaces under pressure and temperature, usually requiring total or partial fusion of components to combine. Polymer welding requires compatibility of material pairs for combining. The heat seal described here is a type of welding. Heat sources for welding or sealing can be provided by hot air, heat conduction, infrared radiation, mechanical friction, ultrasonic exposure, or high frequency. Hot welding systems, for example, manual systems such as LEISTER's TRIAC-S (Switzerland) are commonly used for welding membranes for buildings and construction. For thermoplastic olefins, consolidation temperatures in the range of 280 to 400oC are considered for hot welding. The common test method for olefins is to clean the sample surfaces with acetone and then weld the samples over a width of 5 cm. Sample strips "1.5 cm wide by 150 mm long" were cut perpendicular to the welding joint, and along the joint (joined membranes - overlapping flow in the center of the strip). After 24 hours of storage in environmental conditions, tensile / tear tests were carried out on the welded strips. The requirement in the building and construction sector is that the sample failure occurs in the laminar area and not in the weld joint. Gasket delamination is not tolerated. The Figures illustrating various aspects of the test are shown in Figure 2 - Figure 5.
    [0094] Flammability - EN 11925-2; BS 7837; EN 13823.Examples

    [0095] Samples of these compounds are produced using an internal kneader. In principle, any continuous or discontinuous combination process can be used for the preparation of compounds, such as Banbury mixers, calenders, corrotative double screw extruders, co-kneaders, known in the art.
    [0096] In a second step, the compounds are extruded using an 80 mm mono-screw extruder under olefin extrusion conditions with a progressive temperature profile starting at 80 ° C in the funnel and ending with a flange adjustment of 210 ° C. In principle, any standard direct extrusion, extrusion or melt calendering process for olefins can be used to provide a homogeneous melt for molding or coating fabrics.
    [0097] After the extruder, the melt is molded at mass temperatures in the range of 210 ° C to 240 ° C through a slotted flat die and fed by a three-cylinder calender. In the opening between cylinders ("nip") of the first space of the calender, the cast is coated on a canvas (waxed) of resistant mesh.
    [0098] The specific data of the screen are: 3.5x3.5 circular point; 2200 PET x 2200 PET; 165g / m2; warp pull: 260 daN / 5cm; weft traction: 260 daN / 5cm.
    [0099] In principle, any canvas with sufficient mechanical and dimensional strength to meet the requirements of end use, and with sufficient adhesion to the polymer layers can be used. Carbon fiber, glass fiber, PP or PE, even metallic, can also be used.
    [0100] This extrusion coating can be carried out in separate steps, according to the desired final product design. For the examples:
    [0101] Step 1: Extrusion of the lower layer: first-pass coating of the screen.
    [0102] Step 2: Extrusion of the top layer, second pass and final coating.
    [0103] As needed, additional layers can be extruded or collaminated, such as blocking layers, colored top layers, etc.
    [0104] For the Examples, the total thickness of the membranes is between 0.55 and 0.65 mm.
    [0105] The resulting membrane design is illustrated in Figure 6.
    [0106] The physical properties of the coated membranes were then determined according to EN ISO 527-1 in a tensile tester. The tensile strength and elongation at break were measured at a drawing speed of 100 mm / min. The secant modulus was determined at the beginning of the tensile test at 2% elongation (2% secant modulus).
    [0107] In addition, the thermally welded samples were prepared with a Leister Triac manual system according to Figures 2-5. For the welded samples, the resistance to delamination was tested in a tensile tester for strips with 50 mm width under stretching speed of 100 mm / min. Table 3 lists the results of the mechanical test and the welding tests.
    [0108] It is evident that fabrics coverings meet common requirements for physical strength and flexibility. The welding tests produced excellent results of resistance to delamination, with the samples for all formulations breaking out of the weld joint.
    [0109] After the physical characterization of the coated fabrics, flame retardancy and reaction to fire are tested according to common European standards for membranes for buildings and construction. The following tests were conducted:. EN 11925-2 - Test on small burner, combustion at the edge and on the surface. BS (British Standard 7837), combustion at the edge. EN 13823 (test of isolated object in combustion).


    [0110] The approval in the test EN 11925-2 in combination with EN 13823 in the classification B-s1-d0 classifies the membranes according to EN 13501-5 in class B which is new for TPO coated fabrics and halogen-free membranes. As can be seen in Tables 3 and 5, all samples with an organic / inorganic ratio below 0.35 and a polymer / FR ratio below 0.35 meet these classifications.
    权利要求:
    Claims (8)
    [0001]
    1. Multilayer structure, characterized by the fact that it comprises a layer having a formulation comprising: (i) an olefin block copolymer comprising an ethylene content of at least 50 mole percent of the entire polymer, the olefin block copolymer having a polydispersity of 1.7 to 3.5, a density of 0.850 g / cm3 to 0.925 g / cm3, and a melting index of 0.1 g / 10 min to 30 g / 10 (according to ASTM D- 1238, at 190 ° C / 2.16 kg), the olefin block copolymer being an ethylene / octene block copolymer and being present in an amount of 10% by weight to 25% by weight, based on the total weight formulation; (ii) a propylene / α-olefin copolymer comprising between 60 and less than 100 percent by weight of units derived from propylene and between more than 0 and 40 percent of units derived from at least one ethylene and one α-olefin C4 -10, the propylene / α-olefin copolymer having a density greater than 0.855 g / cm3 and less than 0.895 g / cm3 and melt flow rate from 0.1 to 500 g / 10 min (according to ASTM D- 1238 at 230 ° C / 2.16 kg), and (iii) a halogen-free flame retardant, a polymer-to-flame retardant ratio being less than 0.35, and the halogen-free flame retardant being present in an amount greater than 60% by weight based on the total weight of the formulation.
    [0002]
    2. Structure according to claim 1, characterized by the fact that it has an organic / inorganic weight ratio of less than 0.35.
    [0003]
    3. Structure according to claim 1, characterized in that the halogen-free flame retardant includes magnesium hydroxide.
    [0004]
    4. Structure according to claim 1, characterized by the fact that the ethylene content is greater than 80 moles per cent of the entire copolymer in ethylene / octane blocks.
    [0005]
    5. Structure according to claim 4, characterized in that the melt index of the olefin block copolymer is 0.1 g / 10 min (according to ASTM D-1238 at 190 ° C / 2.16 kg).
    [0006]
    6. Structure according to claim 5, characterized in that the melt flow rate of the propylene / α-olefin copolymer is from 0.1 to 50 g / 10 min (according to ASTM D-1238 to 230 ° C / 2.16 kg).
    [0007]
    7. Structure according to claim 6, characterized in that the propylene / α-olefin copolymer has an Mw / Mn of 1.8 to 3.0.
    [0008]
    8. Structure according to claim 7, characterized in that the olefin block copolymer is present in an amount of 10% by weight to 25% by weight based on the total weight of the formulation.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-03-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-24| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-12-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-03-09| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261608089P| true| 2012-03-07|2012-03-07|
    US61/608,089|2012-03-07|
    PCT/US2013/028786|WO2013134083A1|2012-03-07|2013-03-04|Polyolefin based formulations for membranes and fabrics|
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