• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    COMPOSITION CAPABLE OF FORMING FOAM, FOAM, LAMINATE, ITEM, AND DIVING CLOTHES. A foam-capable composition comprising at least one block olefinic copolymer, one olefinic copolymer, an oil, a crosslinking agent and a blowing agent is provided. The olefinic block copolymer has an Mw / Mn of 1.7 to 3.5, and at least one melting point, Tm, in degreesC, and a density, d, in g / cm3, with the numerical values of Tm and d correspond to the ratio: Tm (highest) -2002.9 + 4538.5 (d) - 2422.2 (d) 2. Foams, laminates, articles and wetsuits made with foams are also provided.
    公开号:BR112014018134B1
    申请号:R112014018134-9
    申请日:2012-03-16
    公开日:2021-03-02
    发明作者:Yong Chen；David Wang；Jose M. Rego；Kyle G. Kummer；Kim L. Walton
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Field of invention
    [0001] This invention relates to foams comprising mixtures of polyolefins, methods of preparing them and the use of foams in various applications. History of the invention
    [0002] Conventional wetsuits that have been employed so far for spearfishing, diving, surfing, fishing, kayaking and other activities are generally laminates made of materials comprising closed-cell sponge sheet as a core layer and stretched cloths attached adhesive to the sheet on one or two surfaces. The sponge sheet provides good heat retention properties and good workability for human body movement. Neoprene (chloroprene rubber - CR) was the dominant material for about 60 years to manufacture foam due to its excellent softness, flexibility, tactile feel, mechanical strength (such as low compression deformation), weather resistance, insulation properties and waterproof. A nylon shirt or mesh having good stretch capacity provides good abrasion resistance for diving suits. The outer surface of the laminate is smooth or embossed and usually coated with adhesive with a polyurethane film that provides water repellency, durability, coloring, etc.
    [0003] It would be useful to provide a lighter and chlorine-free material suitable for diving suits, particularly for reasons of sustainability. Summary of the invention
    [0004] The invention provides a composition suitable for use in wetsuits and the like. In particular, the invention provides a foam-capable composition comprising: one or more olefinic block copolymers; one or more olefinic copolymers; an oil; a cross-linking agent; and, an expansion agent. The invention also provides a foam, a laminate, an article and a diving suit made with the composition capable of forming foam. Detailed description of the invention
    [0005] "Polymer" means a polymeric compound prepared by polymerizing monomers, whether of the same or different types. The generic term "polymer" encompasses the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer".
    [0006] Interpolymer means a polymer prepared by the polymerization of at least two different types of monomers. The generic term “interpolymer” includes the term “copolymer” (which is usually used to refer to a polymer prepared from two different monomers), as well as the term “terpolymer” (which is usually used to refer to a polymer prepared from three different types of monomers). It also covers polymers prepared by polymerizing four or more types of monomers.
    [0007] If used, the term "crystalline" refers to a polymer that has a first order transition or crystalline melting point (Tm) determined by differential scanning calorimetry (DSC) or an equivalent technique. The term can be used in such a way as to allow exchange and / or substitution for the term "semi-crystalline". The term "amorphous" refers to a polymer without a crystalline melting point determined by differential scanning calorimetry (DSC) or an equivalent technique.
    [0008] Foams or compositions capable of forming foams of the invention comprise an olefinic block copolymer. The term "olefinic block copolymer" or "OBC" is a copolymer of ethylene / α-olefin in multiblocks and includes ethylene and one or more copolymerizable comonomers of α-olefin in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. The terms "interpolymer" and "copolymer" are used here to allow for exchange or replacement. In some embodiments, the multi-block copolymer can be represented by the following formula: (AB) n 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 bond in a substantially linear manner, as opposed to a substantially branched or substantially star-shaped manner. In other embodiments, blocks A and blocks B are randomly distributed along the polymer chain. In other words, block copolymers do not usually have a structure as follows. AAA-AA-BBB-BB
    [0009] In other embodiments, block copolymers do not usually have a third type of block, which comprises different comonomers. In other embodiments, each of blocks A and B has monomers or comonomers distributed substantially at random 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 tip segment, which has a substantially different composition than the rest of the block.
    [0010] Preferably, ethylene comprises the major molar fraction of the entire block copolymer, i.e., ethylene comprises at least 50 molar percent of the entire 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 all polymer comprising at least one other comonomer which is preferably an α-olefin having 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 entire polymer and an octene content of 10 to 15, preferably 15 to 20 mole percent of the entire polymer. .
    [0011] The olefinic block copolymer includes various amounts of "hard" and "soft" segments. "Hard" segments are 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 (content of monomers 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 incorporations, the hard segments include all, or substantially all of the ethylene-derived units. "Soft" segments are blocks of polymerized units in which the comonomer content (monomer content other than ethylene) is greater than 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 may 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.
    [0012] The term “delta comonomer” (“Δcomonomero”) means the difference in molar percentage of comonomer between the hard segment and the soft segment of the block olefinic copolymer. In some embodiments, the comonomer delta is greater than 18.5 mol%, greater than 20 mol% or greater than 30 mol%. The comonomer delta can be 18.5 mol% to 70 mol%, 20 mol% to 60 mol% or 30 mol% to 50 mol%. The comonomer delta can be measured using 13C NMR as described below and in U.S. Patent No. 7,947,793. The term "separation of mesophases" means a process in which polymeric blocks are separated locally to form ordered domains. In these systems, the crystallization of ethylene segments is mainly constrained to the resulting mesodomains and such systems can be referred to as "separated into mesophases". These mesodomains can take the form of spheres, cylinders, lamellae, or other known morphologies for block copolymers. The narrowest dimension of a domain, such as perpendicular to the lamella plane, is generally greater than about 40 mm in the separate block copolymers in mesophases of the present invention. In some embodiments, the olefinic block copolymer is separated into mesophases.
    [0013] The soft segments can be present in an OBC of 1 percent by weight to 99 percent by weight of the total weight of the OBC, or from 5 percent by weight to 95 percent by weight, from 10 percent by weight 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. On the other hand, the hard segments can be present in similar bands. The percentage by weight of soft segments and the percentage by weight of hard segments can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed, for example, in US patent No. 7,608,668, entitled “Ethylene / α-Olefin Block Interpolymers” filed on March 15, 2006, on behalf of Colin LP Shan, Lonnie Hazlitt, et al. , and transferred to Dow Global Technologies Inc., the disclosure of which is incorporated herein entirely by reference. In particular, the weight percentages of hard and soft segments and the comonomer content can be determined as described in column 57 through column 63 of US 7,608,668.
    [0014] The olefinic block copolymer is a polymer comprising two chemically distinct regions or segments (referred to as "blocks") preferably joined in a linear manner, i.e., a polymer comprising chemically different units that are joined end-to-end with respect polymerized ethylene functionality, rather than pendant or grafted. In an incorporation, the blocks differ in the amount or type of comonomer incorporated, density, amount of crystallinity, crystallite size attributable to a polymer of such composition, type or degree of tacticity (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching ( including long chain branching or hyper-branching), homogeneity or any other chemical or physical property. Compared to block interpolymers of the prior art, including interpolymers produced by sequential addition of monomers, fluxionary catalysts, or anionic polymerization techniques, this OBC is characterized by unique polymer polydispersion distributions (PDI or Mw / Mn or MWD), block length distribution and / or block number distribution, due, in an incorporation, to the effect of exchange agents in combination with multiple catalysts used in their preparation.
    [0015] In an incorporation, the OBC is produced in a continuous process and has a polydispersity index, PDI, of 1.7 to 3.5, or of 1.8 to 3, or of 1.8 to 2.5, or from 1.8 to 2.2. When produced in a batch or semi-batch process, the OBC has a PDI of 1.0 to 3.5, or from 1.3 to 3, or from 1.4 to 2.5, or from 1.4 to 2.
    [0016] In addition, the olefinic block copolymer has a PDI corresponding to a Schultz-Flory distribution instead of a Poisson distribution. The present OBC has a polydispersed distribution of blocks as well as a polydispersed distribution of block sizes. This results in the formation of polymeric products having improved and noticeable physical properties. The theoretical benefits of a polydispersed block distribution were previously modeled and discussed in Potemkin, Physical Review E (1998) 57 (6), pp. 6902-6912, and in Dobrynin, J. Chem. Phys. (1997) 107 (21), pp. 9234-9238.
    [0017] In an embodiment, the present olefinic block copolymer has a very probable distribution of block lengths. In an embodiment, the olefinic block copolymer is defined as having: (A) Mw / Mn of 1.7 to 3.5, at least one melting point, Tm, in ° C, and a density, d, in g / cm3, 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, and is characterized by a heat of fusion, ΔH, in J / g, and a delta quantity, ΔT, in ° C defined as the temperature difference between the maximum peak of DSC and the maximum peak of fractionation by analysis of crystallization (“CRYSTAF”), with the numerical values of ΔT and ΔH having the following relationships: ΔT> -0.1299 (ΔH) + 62.81 p / ΔH greater than zero and up to 130 J / g, and ΔT> 48 ° C for ΔH greater than 130 J / g, the peak of CRYSTAF being 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 temperature of CRYSTAF will be 30 ° C; and / or (C) elastic recovery, Re, in percentage in deformation of 300 percent and 1 cycle measured with a film molded by compression of the ethylene / α-olefin interpolymer, and has a density, d, in g / cm3, the numerical values of Re ed satisfying the following relationship when the ethylene / α-olefin interpolymer is substantially free of cross-linked phase: Re> 1481 - 1629 (d); and / or (D) have a molecular fraction that elutes between 40 ° C and 130 ° C when fractioned using TREF, characterized by the fact that the fraction has a molar comonomer content greater than or equal to the amount (-0,2013) T + 20.07, more preferably greater than or equal to the quantity (-0,2013) T + 21.07, where T is the numerical value of the maximum elution temperature of the TREF fraction, measured in ° C; and / or (E) have a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° C, G' (100 ° C), the ratio of G '( 25 ° C) for G '(100 ° C) is in the range of about 1: 1 to about 9: 1.
    [0018] The olefinic block copolymer may also have: (F) a molecular fraction that elutes between 40 ° C and 130 ° C, when fractionated using TREF, characterized by the fact that the fraction has a block index of at least 0, 5 and up to about 1 and a molecular weight distribution, Mw / Mn, greater than about 1.3; and / or (G) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw / Mn, greater than about 1.3. It is understood that the olefinic block copolymer can have one, some, all, or any combination of properties (A) - (G). The block index can be determined as described in detail in U.S. Patent No. 7,608668 incorporated herein by reference for that purpose. Analytical methods for determining properties (A) to (G) are disclosed, for example, in US Patent No. 7,608,668, column 31, row 26 through column 35, row 44, incorporated herein by reference for that purpose .
    [0019] Monomers suitable for use in the preparation of the present OBC include ethylene and one or more monomers polymerizable by addition other than ethylene. Non-limiting examples of suitable comonomers include normal or branched chain α-olefins of 3 to 30 carbon atoms, 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, tetra-cyclododecene, and 2-methyl-1,4,5, 8-dimethane-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene; diolefins 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, ethylidene-norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4 -ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decathriene; and 3-phenyl-propene, 4-phenyl-propene, 1,2-difluoro-ethylene, tetrafluoro-ethylene, and 3,3,3-trifluoro-1-propene.
    [0020] The olefinic block copolymer has a density of 0.850 g / cm3 to 0.925 g / cm3, or 0.860 g / cm3 to 0.88 g / cm3, or 0.860 g / cm3 to 0.879 g / cm3. OBC has a Shore A index 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 min, or from 0.1 g / 10 min to 20 g / 10 min, or from 0.1 g / 10 min to 15 g / 10 min, measured by 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.
    [0021] The olefinic block copolymers are produced via a chain exchange process as described in U.S. Patent No. 7,858,706, which is hereby incorporated by reference. In particular, appropriate chain exchange agents and related information are listed in column 16, line 39 through column 19, line 44. Suitable catalysts are described in column 19, line 45 through column 46, line 19 and appropriate 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 US patents no. 7,608,668, 7,893,166, and 7,947,793.
    The foams and foaming compositions of the invention may also include another olefinic copolymer. Any other olefinic copolymer known to those of ordinary skill in the art may be used in the invention disclosed herein. Non-limiting examples of olefinic copolymers include copolymers derived from ethylene and an alkene having 3 or more carbon atoms. Non-limiting examples of the alkene having 3 or more carbon atoms include propene, butenes (for example, 1-butene, 2-butene and isobutene) and alkyl-substituted butenes, pentenes (for example, 1-pentene and 2-pentene) and alkyl substituted pentenes (eg 4-methyl-1-pentene), hexenes (eg 1-hexene, 2-hexene and 3-hexene) and alkyl substituted hexenes, heptenes (eg 1-heptene, 2 -heptene and 3-heptene) and alkyl-substituted heptenes, octenes (for example, 1-octene, 2-octene, 3-octene and 4-octene) and alkyl-substituted octenes, for example, 1-nonene, 2 -nonene, 3-nonene, and 4-nonene) and alkyl-substituted nonenes, decenes (for example, 1-decene, 2-decene, 3-decene, 4-decene and 5-decene) and alkyl-substituted decines, dodecenes and alkyl-substituted dodecenes, and butadiene. In some embodiments, the olefinic copolymer is an ethylene / alpha-olefin (EAO) copolymer or an ethylene / propylene copolymer (EPM). In some embodiments, the olefinic copolymer is a homogeneous ethylene-based random copolymer and, preferably, is an ethylene / α-olefin copolymer, more preferably an ethylene / octene copolymer. Such polymers are commercially obtainable under the trade names ENGAGE (The Dow Chemical Company) and EXACT (ExxonMobil Chemical Company). The olefinic copolymer has a density of 0.850 g / cm3 to 0.908 g / cm3, preferably 0.850 g / cm3 to 0.900 g / cm3 and a Shore A index of 40 to 70, preferably 45 to 65 and more preferably 50 to 65 The olefinic copolymer can be present in an amount of 0% by weight to 60% by weight, from 15% by weight to 60% by weight, preferably from 20% by weight to 60% by weight, more preferably from 30% by weight at 55% by weight, based on the total weight of the composition.
    [0023] In an embodiment, the foam or foam-capable composition comprises an ethylene / propylene / diene monomer (EPDM) rubber. EPDM materials are linear interpolymers of ethylene, propylene, and an unconjugated diene such as 1,4-hexadiene, dicyclopentadiene, or noridene ethylidene. A preferred class of interpolymers is obtained having the properties disclosed herein of the polymerization of ethylene, propylene, and an unconjugated diene to prepare the EPDM elastomer. The appropriate unconjugated diene monomers can be normal chain, branched chain or cyclic hydrocarbon dienes having 6 to 15 carbon atoms. Examples of suitable unconjugated dienes include, but are not limited to, normal chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, acyclic chain dienes branched, such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene and mixtures of dihydromyricene and dihydro-ocinene isomers, alicyclic dienes single-ring, such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclodecadiene, and fused and bridged multiple ring alicyclic dienes, such as tetrahydroindene , methyl tetrahydroindene, dicyclopentadiene, bicyclo- (2,2,1) -hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene. Of the dienes typically used to prepare EPDMs, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2- norbornene (MNB), and dicyclopentadiene (DCPD). Especially preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
    [0024] In some embodiments, EPDM polymers have an ethylene content of 50% to 75% by weight, a propylene content of 20% to 49% by weight, and an unconjugated diene content of 1% to 10 % by weight, all percentages by weight based on the total weight of the polymer. Examples of representative EPDM polymers for use include NORDEL IP 3640, NORDEL IP 4520 and NORDEL IP 4570 obtainable from The Dow Chemical Company, Midland, MI, VISTALON 2504 obtainable from ExxonMobil, Baton Rouge, LA, and KELTAN 4550 obtainable from DSM Elastomers Americas , Addis, LA.
    [0025] EPDM polymers, also known as ethylene elastomeric copolymers, a higher alpha-olefin and a polyene, have molecular weights of 20,000 to 2,000,000 Dalton or more. Its physical form ranges from waxy materials to rubbers to hard polymers such as plastics. They have viscosities in diluted solution (DSV) of 0.5 to 10 dL / g, measured at 30 ° C in a solution of 0.1 g of polymer in 100 cm3 of toluene. EPDM polymers also have a Mooney viscosity of 10 to 100 ML (1 + 4) at 125 ° C, preferably from 10 to 70 ML (1 + 4) at 125 ° C or from 10 to 50 ML (1 + 4) at 125 ° C. EPDM polymers have a density of 0.850 g / cm3 to 0.90 g / cm3, 0.855 g / cm3 to 0.885 g / cm3 or 0.860 g / cm3 to 0.880 g / cm3.
    [0026] In some incorporations, EPDM has a crystallinity less than 10% measured by DSC, preferably greater than 0% to 10%, from 0.001% to 10% or from 0.001% to 5%.
    [0027] In some embodiments, EPDM is present in an amount of 0% by weight to 50% by weight, preferably from 5% by weight to 40% by weight, more preferably from 5% by weight to 30% by weight, with based on the total weight of the composition.
    [0028] The composition may also include a styrenic copolymer in blocks. Generally speaking, block styrenic copolymers include at least two blocks of monoalkenyl arene, preferably two blocks of polystyrene, separated by a block of a saturated conjugated diene, preferably a block of saturated polybutadiene. Preferred styrenic block copolymers have a linear structure, although branched or radial polymers of functionalized block copolymers prepare useful compounds. The total numerical average molecular weight of the styrenic block copolymer is preferably 30,000 to 250,000 if the copolymer has a linear structure. Such block copolymers can have an average polystyrene content of 10% by weight to 40% by weight. Suitable block copolymers having unsaturated rubber monomer units include, but are not limited to, styrene / butadiene (SB), styrene / ethylene / butadiene (SEB), styrene / isoprene (SI), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), α-methyl-styrene / butadiene / α-methyl-styrene and α-methyl-styrene / isoprene / α-methyl-styrene. The styrenic block copolymer can be present in an amount of 0% by weight to 50% by weight, preferably from 5% by weight to 40% by weight, more preferably from 5% by weight to 30% by weight, based on weight total composition.
    [0029] The composition may also include an acrylonitrile / butadiene rubber, a silicone rubber or a chlorinated polyethylene rubber which can be present in amounts from 0% by weight to 50% by weight, preferably from 5% by weight to 40 % by weight, more preferably from 5% by weight to 30% by weight, based on the total weight of the composition.
    [0030] The composition includes an oil. The oil can be an aromatic oil, a mineral oil, a naphthenic oil, a paraffinic oil, a vegetable oil based on triglycerides such as castor oil, a synthetic hydrocarbon oil such as polypropylene oil, a silicone oil, or any combination of them. A non-limiting example of an appropriate oil is a white mineral oil sold under the trade name HYDROBRITE® 550 (Sonneborn). The oil is present in an amount of 10% by weight to 45% by weight, preferably from 20% by weight to 40% by weight, more preferably from 25% by weight to 35% by weight, based on the total weight of the composition.
    [0031] The foams disclosed herein can be prepared from a foam-capable composition comprising at least one blowing agent, at least one cross-linking agent and at least one of the polyolefins described above and, optionally, at least one other additive or a combination of them. Non-limiting examples of other suitable additives include grafting initiators, crosslinking catalysts, blowing agent activators (for example, zinc oxide, zinc stearate and the like), coagents (for example, trialyl cyanurate, trimethylolpropane trimethacrylate), plasticizers, dyes or pigments, stability controlling agents, nucleating agents, fillers, antioxidants, acid purgers, ultraviolet stabilizers, flame retardants, lubricants, processing aids, extrusion aids, and combinations thereof. Some suitable additives have been described in Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition (2001), which is incorporated herein entirely by reference. The blowing agent is present in an amount of 1 phr to 8 phr, preferably 2 phr to 6 phr. The cross-linking agent is present in an amount of 1 phr to 6 phr, preferably 2 phr to 5 phr. When present, blowing agent activators can be present in an amount greater than 0 phr to 2.0 phr, preferably from 0.05 phr to 1.0 phr. When present, the charge can be present in an amount greater than 0 phr to 20 phr, preferably from 0.05 phr to 10 phr. When present, processing aids can be present in an amount of 0.1 phr to 2.0 phr; antioxidant in an amount of 0.1 phr to 1.0 phr; and, UV stabilizer in an amount of 0.1 phr to 1.0 phr. The term "phr" means parts per hundred of resin, as is commonly understood in the art.
    [0032] The foams disclosed herein may be substantially cross-linked. A foam is substantially cross-linked when it contains more than 5% gel by Method A of ASTM D-2765-84. In some embodiments, the foam disclosed here contains more than 5% gel, more than 10% gel, more than 15% gel, more than 20% gel, more than 25% gel, more than 30% gel , more than 35% gel, or more than 40% gel by Method A of ASTM D- 2765-84. In other embodiments, the foam disclosed here contains less than 99% gel. In additional embodiments, the foam disclosed here contains less than 85% gel. In additional embodiments, the foam disclosed here contains less than 75% gel. The foam may have 5% gel to 99% gel, 15% gel to 85% gel, or 25% gel to 75% gel.
    The foams or compositions capable of foaming disclosed herein can have a density of 0.05 g / cm3 to 0.2 g / cm3, preferably from 0.06 g / cm3 to 0.16 g / cm3, more preferably from 0.08 g / cm3 to 0.16 g / cm3, measured according to ASTM 792. Foams can have a 60% modulus from 0.60 kg / cm2 to 1.50 kg / cm2, preferably from 0.60 kg / cm2 to 0.8 kg / cm2, more preferably from 0.65 kg / cm2 to 0.75 kg / cm2. Foams can have a permanent deformation of 15% to 35%, preferably from 15% to 30%.
    [0034] The foams or compositions capable of forming foam disclosed herein may be open cells or closed cells. A foam disclosed herein is a closed cell foam when the foam contains 80% or more closed cells or less than 20% open cells according to ASTM D2856-A.
    [0035] Suitable blowing agents for preparing the foams disclosed herein may include, but are not limited to, inorganic blowing agents, organic blowing agents, chemical blowing agents and combinations thereof. Some expansion agents are disclosed in Sendijarevic et al., “Polymeric Foams And Foam Technology”, Hanser Gardner Publications, Cincinnati, Ohio, 2nd edition, chapter 18, pages 505-547 (2004), which is incorporated by reference.
    [0036] Non-limiting examples of suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, and helium. Non-limiting examples of suitable organic blowing agents include aliphatic hydrocarbons having 1 to 6 carbon atoms, aliphatic alcohols having 1 to 3 carbon atoms, and fully and partially halogenated aliphatic hydrocarbons having 1 to 4 carbon atoms. Non-limiting examples of suitable aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, and the like. Non-limiting examples of suitable aliphatic alcohols include methanol, ethanol, n-propanol, and isopropanol. Non-limiting examples of suitable fully and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons, and chlorofluorocarbons. Non-limiting examples of fluorocarbons include methyl fluoride, perfluoro-methane, ethyl fluoride, 1,1-difluoro-ethane (HFC-152a), 1,1,1-trifluoro-ethane (HFC-143a), 1,1, 1,2-tetrafluoro-ethane (HFC-134a), pentafluoro-ethane, difluoro-methane, perfluoro-ethane, 2,2-difluoro-propane, 1,1,1-trifluoro-propane, perfluoro-propane, dichloro-propane , difluoro-propane, perfluoro-butane, perfluoro-cyclobutane. Non-limiting examples of partially halogenated chlorocarbons and chlorofluorocarbons include methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloro-ethane, 1,1-dichloro-1-fluorine-ethane (HCFC-141b) , 1-chloro-1,1-difluoro-ethane (HCFC-142b), 1,1-dichloro-2,2,2-trifluoro-ethane (HCFC-123) and 1-chloro-1,2,2,2 -tetrafluoro-ethane (HCFC-124). Non-limiting examples of suitable completely halogenated chlorofluorocarbons include trichloro-monofluoro-methane (CFC-11), dichloro-difluoro-methane (CFC-12), trichloro-trifluoro-ethane (CFC-113), 1,1,1- trifluoro-ethane, pentafluoro-ethane, dichloro-tetrafluoro-ethane (CFC-114), chloroheptafluoro-propane, and dichloro-hexafluoro-propane. Non-limiting examples of suitable chemical blowing agents include azodicarbonamide, azo-isobutyronitrile, benzene-sulfo-hydrazide, 4,4-oxybenzene-sulfonyl-semicarbazide, p-toluene sulfonyl semicarbazide, barium azodicarboxylate, N, N'-dimethyl -N, N'-dinitro-terephthalamide, and trihydrazine triazine. In some embodiments, the blowing agent is azodicarbonamide, isobutane, CO2, or a mixture thereof. Preferably, the blowing agent has a decomposition temperature of 150 ° C to 210 ° C.
    [0037] One can induce the crosslinking of the foams by activating the crosslinking agent in the composition capable of forming foam. The crosslinking agent can be activated by exposing it to a temperature above its decomposition temperature. Alternatively, the cross-linking agent can be activated by exposing it to radiation that causes the generation of free radicals from the cross-linking agent. Similarly, the formation of foams or expansion of the foams disclosed herein can be induced by activating the blowing agent in the composition capable of foaming. In some embodiments, the blowing agent is activated by exposing it to a temperature above its decomposition temperature. Generally, activations of crosslinking and foaming can occur simultaneously or sequentially. In some incorporations, activations occur simultaneously. In other embodiments, the activation of the crosslinking occurs first and the activation of the foaming occurs afterwards. In additional incorporations, the activation of the foaming occurs first and the activation of the crosslinking occurs next.
    [0038] The composition capable of foaming can be prepared or processed at a temperature below 150 ° C to prevent decomposition of the blowing agent and the crosslinking agent. When radiation crosslinking is used, the foam-capable composition can be prepared at a temperature below 160 ° C to prevent decomposition of the blowing agent. In some embodiments, the foam-capable composition can be extruded or processed through a matrix in a desired manner to form a foam-capable structure. Then, the foam-capable structure can be expanded and cross-linked at an elevated temperature (for example, from 150 ° C to 250 ° C) to activate the blowing agent and the cross-linking agent to form a foam structure. In some embodiments, the foam-capable structure can be irradiated to crosslink the polymeric material, which can then be expanded at elevated temperature as described above.
    [0039] Some appropriate crosslinking agents have been disclosed in Zweifel Hans et al., "Plastics Additives Handbook", Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, chapter 14, pages 725-812 (2001); in the Encyclopedia of Chemical Technology, volume 17, 2nd edition, Interscience Publishers (1968); and in Daniel Seern, “Organic Peroxides”, volume 1, Wiley-Interscience (1970), all of which are incorporated by reference. In some embodiments, there is no crosslinking agent in the compositions capable of foaming or in the foams disclosed herein.
    [0040] Non-limiting examples of suitable cross-linking agents include peroxides, phenols, azides, aldehyde / amine reaction products, substituted ureas, substituted guanidines, substituted xanthates, substituted dithiocarbamates, sulfur-containing compounds, such as thiazoles, sulfenamides, disulfides tiurami, para-quinone-dioxima, dibenzo-para-quinone-dioxima, sulfur, imidazoles, silanes and combinations thereof.
    [0041] Non-limiting examples of suitable organic peroxide crosslinking agents include alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacyl peroxides, peroxycetals, cyclic peroxides and combinations thereof. In some embodiments, organic peroxide is dicumyl peroxide, t-butyl-isopropylidene peroxybenzene, 1,1-di- (terciobutyl peroxy) -3,3,5-trimethyl-cyclohexane, 2,5-dimethyl-2, 5-di- (t-butyl peroxy) hexane, t-butyl-cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexine or a combination of themselves. In an embodiment, the organic peroxide is dicumyl peroxide. Additional teachings are disseminated with respect to organic peroxide crosslinking agents in C.P. Park, “Polyolefin Foam”, chapter 9 of Handbook of Polymer Foams and Technology, edited by D. Klempner and K.C. Frisch, Hanser Publishers, pp. 198-204, Munich (1991), which is incorporated by reference.
    [0042] Optionally, the foam capable composition disclosed herein may comprise a catalyst. Any crosslinking catalyst that can promote crosslinking of the ethylene / α-olefin interpolymer or polymeric mixture can be used. Non-limiting examples of suitable catalysts include organic bases, carboxylic acids, and organometallic compounds. In some embodiments, the catalyst includes organic and complex titanates or lead, cobalt, iron, nickel, zinc and tin carboxylates. In other embodiments, the catalyst is or comprises dibutyl tin dilaurate, tin dioctyl maleate, dibutyl tin diacetate, dibutyl tin dioctanoate, stannous acetate, stannous octanoate, lead naphthenate, zinc caprylate, cobalt naphthenate or a combination of themselves. In additional embodiments, the catalyst is or comprises a tin carboxylate such as dibutyltin dilaurate and tin dioctyl maleate.
    [0043] Alternatively, the crosslinking of foams or compositions capable of forming foams disclosed herein can be carried out using radiation. Non-limiting examples of appropriate radiation include beta rays or electron beams, gamma rays, X-rays, or neutron rays. Radiation is believed to activate crosslinking by generating radicals in the polymer that can subsequently combine and crosslink. Additional teachings about radiation crosslinking are disclosed in C.P. Park, supra, pages 198-204, which is incorporated herein by reference. In some embodiments, the foam or foam-capable composition is not crosslinked by radiation.
    [0044] In general, the radiation dosage depends on several factors. Those skilled in the art will be able to quickly select appropriate levels of radiation based on the thickness and geometry of the article to be irradiated, as well as the characteristics of the composition capable of forming foam or of the components such as molecular weight, molecular weight distribution, content of comonomer, the presence of crosslinking enhancing coagents, additives (for example, oil), and the like. In general, the dosage does not exceed what is required to effect the desired level of crosslinking. In some embodiments, the dosage does not cause more than 5% of gel in the foam by method A of ASTM D-2765-84.
    [0045] In some embodiments, double curing systems comprising at least two activation methods selected from crosslinking and radiation agents can be effectively employed. For example, it may be desirable to employ a peroxide crosslinking agent together with a silane crosslinking agent, a peroxide crosslinking agent together with radiation, a sulfur containing crosslinking agent together with a silane crosslinking agent, or the like.
    [0046] Foams or compositions capable of forming foams disclosed herein may optionally comprise a stability-controlling or gas permeation modifying agent. Any stability-controlling agent that can improve the dimensional stability of the foams can be used. Non-limiting examples of suitable stability controlling agents include C10-24 fatty acid amides and esters. Such agents are described in U.S. Patent Nos. 3,644,230 and 4,214,054, which are incorporated herein by reference. In some embodiments, stability-controlling agents include stearyl stearamide, glycerol monostearate, glycerol monobeenate, sorbitol monostearate and combinations thereof. In general, the amount of stability-controlling agents is 0.1 to 10 parts, 0.1 to 5 parts, or 0.1 to 3 parts by weight per hundred parts by weight of the polymer. In some embodiments, the stability-controlling agent is glycerol monostearate.
    [0047] Foams or compositions capable of forming foams disclosed herein may optionally comprise a nucleating agent. Any nucleating agent that can control the size of the foam cells can be used. Non-limiting examples of suitable nucleating agents include inorganic substances such as calcium carbonate, talc, clay, titanium oxide, silica, barium sulfate, diatomaceous earth, citric acid, sodium bicarbonate, sodium carbonate, and combinations thereof. In some embodiments, the nucleating agent is a combination of citric acid and sodium bicarbonate or a combination of citric acid and sodium carbonate. In other embodiments, the nucleating agent is HYDROCEROL® CF 20 from Clariant Corporation, Charlotte, NC. The amount of nucleating agent used can vary from 0.01 to 5 parts by weight per hundred parts by weight of the polymer.
    [0048] In some embodiments, the foams or compositions capable of forming foams disclosed herein comprise an antioxidant. In the foams disclosed here, any antioxidant that may prevent the oxidation of polymeric components and additives in the foams can be added. Non-limiting examples of appropriate antioxidants include aromatic or hindered amines such as alkyl diphenylamines, phenyl-α-naphthylamine, phenyl-α-naphthylamine substituted with alkyl or aralkyl, alkylated p-phenylene diamines, tetramethyl-diamine-diphenylamine and the like; phenols such as 2,6-ditherciobutyl-4-methyl-phenol, 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-ditherciobutyl-4'-hydroxy-benzyl) benzene, tetrakis [ (methylene (3,5-ditherciobutyl-4-hydroxy-hydrocinamate)] methane (eg, IRGANOX ™ 1010, from Ciba Geigy, New York), acryloyl-modified phenols, octadecyl-3,5-ditherciobutyl-4-hydroxy- cinnamate (for example, IRGANOX ™ 1076, obtainable from Ciba Geigy), phosphites and phosphonites, hydroxylamines, benzofuranone derivatives, and combinations thereof. Some antioxidants have been described in Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications , Cincinnati, Ohio, 5th edition, chapter 1, pages 1-140 (2001), which is incorporated herein by reference.
    [0049] In other embodiments, the foams or compositions capable of forming foams disclosed herein comprise a UV stabilizer. In the foams disclosed here, you can add any UV stabilizer that can prevent or reduce the degradation of foams by UV radiation. Non-limiting examples of suitable UV stabilizers include benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidines, carbon black, hindered amines, nickel coolers, hindered amines, phenolic antioxidants, metal salts, zinc compounds and combinations of the themselves. Some UV stabilizers have been described in Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, chapter 2, pages 141-426 (2001), which is incorporated herein by reference.
    [0050] In additional embodiments, the foams or compositions capable of forming foams disclosed herein comprise a dye or pigment. In the foams disclosed here, any dye or pigment that can change the appearance of the foams in human eyes can be added. Non-limiting examples of suitable dyes or pigments include inorganic pigments such as metal oxides, for example, iron oxide, zinc oxide, and titanium dioxide, mixtures of metal oxides, carbon black, organic pigments such as anthraquinones, ananthrone, azo and monoazo compounds, arylamides, benzimidazolone, BONA lacquers, diceto-pyrrole-pyrroles, dioxazins, diazo compounds, diarylide compounds, flavantrones, indantrones, isoindolinones, isoindolines, metal complexes, monoazo salts, naphthols, b-naphthols, naftol lacquers of naphthol, perylene, perinones, phthalocyanines, pyrantrone, quinacridones, and quinophthalones, and combinations thereof. Where used, the amount of dye or pigment in the foam may be more than 0 to 10% by weight, 0.1% to 5% by weight, or 0.25 to 2% by weight of the total weight of the foam. Some colorants have been described in Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, chapter 15, pages 813-882 (2001), which is incorporated herein by reference.
    [0051] Optionally, the foams or compositions capable of forming foams disclosed herein may comprise a filler. In the foams disclosed here, you can add any load that can adjust, among others, volume, weight, costs, and or technical performance. Non-limiting examples of appropriate fillers include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed colloidal silica, wollastonite, feldspar, aluminum silicate, calcium silicate, carbon black, alumina, alumina hydrated such as aluminum hydroxide, glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, sawdust, glass fibers, carbon fibers, marble powder, cement powder, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanates and combinations thereof. In some embodiments, the filler is barium sulfate, talc, calcium carbonate, silica, glass, fiberglass, alumina, titanium dioxide, or a mixture thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, fiberglass or a mixture of them. Some charges were disclosed in US Patent No. 6,103,803 and in Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, chapter 17, pages 901-948 (2001), which here are incorporated by reference.
    [0052] Optionally, the foams or compositions capable of forming foams disclosed herein may comprise a lubricant. In the foams disclosed herein, any lubricant that can be used, among others, can be used to modify the rheology of compositions capable of forming molten foams, to improve the surface finish of molded foam articles, and / or to facilitate dispersion. of fillers or pigments. Non-limiting examples of suitable lubricants include fatty alcohols and their esters of dicarboxylic acids, fatty acid esters of short-chain alcohols, fatty acid esters of long-chain alcohols, lignite waxes, polyethylene waxes, polypropylene waxes natural and synthetic paraffin, fluorinated polymers and combinations thereof. Where used, the amount of the lubricant in the foam may be more than 0 to 5% by weight, 0.1 to 4% by weight, or 0.1 to 3% by weight of the total weight of the foam. Some suitable lubricants have been disclosed in Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, chapter 5, pages 511-552 (2001), which is incorporated by reference.
    [0053] Optionally, the foams or compositions capable of forming foams disclosed herein may comprise an antistatic agent. In the foams disclosed here, any antistatic agent that can increase the conductivity of the foams and prevent the accumulation of static charge can be added. Non-limiting examples of suitable antistatic agents include conductive fillers (for example, carbon black, metallic particles and other conductive particles), fatty acid esters (for example, glycerol monostearate), ethoxylated alkylamines, diethanolamides, ethoxylated alcohols, alkyl sulfonates , alkyl phosphates, quaternary ammonium salts, alkyl betaines and combinations thereof. Where used, the amount of antistatic agent in the foam may be more than 0 to 5% by weight, 0.01 to 3% by weight, or 0.1 to 2% by weight of the total weight of the foam. Some appropriate antistatic agents have been disclosed in Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, chapter 10, pages 627-646 (2001), which is incorporated by reference.
    [0054] The processes for producing polyolefin foams are described in C.P. Park, “Polyolefin Foam”, chapter 9 of Handbook of Polymer Foams and Technology, edited by D. Klempner and K.C. Frisch, Hanser Publishers, Munich (1991), which is incorporated by reference.
    [0055] The ingredients of the foaming composition can be mixed or combined in any mixing or combination devices known to those skilled in the art. The ingredients of the foaming composition can be mixed at a temperature below the decomposition temperature of the blowing agent and the crosslinking agent to ensure that all ingredients are mixed homogeneously and remain intact. After the foam-capable composition is relatively homogeneously mixed, the composition is molded and then exposed to conditions (for example, heat, pressure, shear, etc.) for a period of time sufficient to activate the blowing agent and the blowing agent. cross-linking to produce the foam.
    [0056] In some embodiments, the ingredients of the foam-capable composition can be mixed and matched in any mixing or combination devices known to those skilled in the art. Non-limiting examples of suitable mixing or blending devices include extruders, mixers, mills, dispersers, homogenizers and the like. In other embodiments, the blowing agent is dry blended with the ethylene / α-olefin interpolymer or with the polymeric mixture before heating the foaming composition to a molten form. In additional embodiments, the blowing agent is added when the foam-capable composition is in a molten phase. In some embodiments, the composition capable of forming foam disclosed here is extruded through a matrix where the crosslinking is activated. Then, the composition capable of forming extruded foam can be exposed to an elevated temperature to activate the blowing agent to form the foam.
    [0057] The foams disclosed herein can be prepared by conventional extrusion foaming processes. In general, the foam can be prepared by heating the polymeric components to form a melted or plasticized polymeric material, incorporating a blowing agent into it to form a foam-capable composition, and extruding the foam-capable composition through a matrix to form a foam. form foam products. Before mixing them with the blowing agent, the polymers can be heated to a temperature equal to or above their glass transition temperatures or melting points. The blowing agent can be incorporated or mixed into the molten polymer by any means known in the art such as an extruder, mixer, and the like. The blowing agent can be mixed with the melted polymer at a high enough pressure to prevent substantial expansion of the melted polymer and to homogeneously disperse all of the blowing agent therein. Optionally, a nucleating agent can be mixed in the polymer melt or mixed dry with the polymer before plasticizing or melting. The foam-capable composition can be cooled to a lower temperature to optimize the physical characteristics of the foam structure. The foam-capable composition can then be extruded or transported through a matrix in a desired manner to a lower or reduced pressure zone to form the foam structure. The lower pressure zone may be at a lower pressure than that in which the foam-capable composition is maintained prior to extrusion through the die. The lower pressure can be superatmospheric or subatmospheric (vacuum), but preferably at an atmospheric level.
    [0058] In some embodiments, the foams disclosed here are molded into a coalesced row form by extruding the polymer through a multiple orifice matrix. The holes can be arranged so that contact occurs between adjacent streams of the molten extrudate during the foaming process and the surfaces in contact adhere to each other with sufficient adhesion to result in a unitary foam structure. The streams of the molten extrudate coming out of the die can take the form of rows or profiles, which can desirably foam, coalesce, and adhere to one another to form a unitary structure. Desirably, individual coalesced profiles or rows should remain adhered to a unitary structure to prevent row delamination under stresses found in the preparation, molding, and use of foams. Apparatus and methods for producing foam structures in the form of coalesced tiers are disclosed in U.S. Patent Nos. 3,573,152 and 4,824,720 which are hereby incorporated by reference.
    [0059] In other embodiments, the foams disclosed herein are formed by an accumulative extrusion process as seen in U.S. Patent No. 4,323,528, which is incorporated herein by reference. In the accumulative extrusion process, low density foams are prepared having large areas of lateral cross section: (1) forming under pressure the composition capable of foaming the polymers and a blowing agent at a temperature in which the viscosity of the composition capable of foaming is sufficient to retain the blowing agent when the foaming composition is allowed to expand; (2) extruding the composition capable of foaming in a retention zone maintained at a temperature and pressure that does not allow the composition capable of foaming to form foam, the retention zone having an outlet matrix defining an orifice opening in a pressure zone smaller in which the composition capable of forming foam forms foam, and a hatch capable of opening closing the die hole; (3) opening the gate periodically; (4) applying substantially simultaneously mechanical pressure by a movable plunger to the composition capable of foaming to eject it from the retention zone through the matrix orifice to the lower pressure zone, at a rate greater than that in which substantial foaming occurs in the matrix orifice and smaller than that in which substantial irregularities in the shape or area of cross section occur; and (5) allowing the composition capable of forming ejected foam to expand uncontrollably in at least one dimension to produce the foam structure.
    [0060] In some embodiments, the foams disclosed herein can be prepared by compression molding or by injection molding. In other embodiments, the foams are prepared by compression molding at a temperature above the decomposition temperatures of the peroxide and the blowing agent and under pressure for a defined period of time which is followed by an expansion step when the mold opens and the pressure is released. In additional embodiments, the foams are prepared by injection molding the compound comprising the polymers that melt at temperatures below the decomposition temperatures of the peroxide and the blowing agent in mold at temperatures above the decomposition temperatures of the peroxide and the blowing agent. The material remains at temperature and under pressure until the mold opens and the pressure is reduced at that point where the material will expand. Mixing foam ingredients
    [0061] The ingredients of the composition capable of forming foam can be mixed or combined using methods known to those skilled in the art. Non-limiting examples of appropriate mixing methods include melt mixing, solvent mixing, extrusion, and the like.
    [0062] In some embodiments, the foam ingredients are mixed melted by a method described by Guerin et al., In U.S. Patent No. 4,152,489. First, remove any solvents from the ingredients by heating to an appropriate elevated temperature of 100 ° C to 200 ° C or 150 ° C to 175 ° C at a pressure of 667 Pa (5 Torr) to 1333 Pa (10 Torr) . Then, the ingredients are weighed in a container in the desired proportions and the foam is formed by heating the contents of the container to a molten state with agitation.
    [0063] In other embodiments, the foam ingredients are processed using solvent mixing. First, the ingredients of the desired foam are dissolved in an appropriate solvent and then the mixture is combined. Then the solvent is removed to provide the foam.
    [0064] In some embodiments, in the preparation of homogeneous mixtures, physical mixing devices that can provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing may be used. You can use continuous or batch methods of physical mixing. Non-limiting examples of batch methods include those methods that use BRABENDER® mixing equipment (for example, BRABENDER PREP CENTER®, obtainable from CW Brabender Instruments, Inc., South Hackensach, NJ) or BANBURY® lamination and internal mixing equipment ( obtainable from Farrel Company, Ansonia, Conn.). Non-limiting examples of continuous methods include single spindle extrusion, double spindle extrusion, disc extrusion, reciprocating single spindle extrusion, and single spindle barrel extrusion. In some embodiments, additives can be added to an extruder through a feed funnel or feed throat during the extrusion of the polymers or foam. Mixing or combining polymers by extrusion has been described in C. Rauwendaal, "Polymer Extrusion", Hanser Publishers, New York, NY, pages 322-334 (1986), which is incorporated herein by reference.
    [0065] When one or more additives are required in the foams, the desired amounts of the additives can be added in a single charge or in multiple charges in any of the component polymers separately or together. In addition, the addition can occur in any order.
    [0066] Embodiments of the invention also comprise articles comprising the foam or foam-capable composition described above. In particular, items can be wetsuits for diving, spearfishing, surfing, fishing, canoeing and other such activities. Diving suits can be manufactured from compositions capable of forming inventive foams by laminating the foams in appropriate cloths using methods known in the art. Wetsuit articles are described, for example, in U.S. Patent Nos. 3,660,849 and 4,274,158.
    [0067] The following examples are presented to exemplify embodiments of the invention. All numerical values are approximate. When numerical ranges are given, it should be understood that incorporations outside the declared ranges may still fall within the scope of the invention. Specific details described in each example should not be construed as necessary features of the invention. EXAMPLES Testing methods Compression deformation
    [0068] Compression strain is measured based on method B of ASTM D 395. The thickness of the sample is around 19 mm, diameter of (29 ± 0.5) mm, cut from foam sheet with a thickness of ( 19 ± 0.5) mm. The samples were tested in a constant 50% depression around (23 ± 1) ° C for 23 hours and then removed and relaxed around (23 ± 1) ° C for 1 hour and then measured. Compression strain = [(original thickness - final thickness) / original thickness] x 100%. 13C NMR analysis
    [0069] Samples are prepared by adding approximately 3 g of a 50/50 mixture of tetrachloroethane-d2 / ortho-dichlorobenzene in 0.4 g of sample in a 10 mm NMR tube. The samples are dissolved and homogenized by heating the tube and its contents to 150 ° C. Data is collected using a 400 MHz Eclipse ™ JEOL spectrometer or a 400 MHz Varian Unity Plus ™ spectrometer, corresponding to a resonance frequency of 13C of 100.5 MHz. Data is acquired using 4000 transients per data file , a 6-second pulse repetition delay. To achieve minimum signal-to-noise for quantitative analysis, multiple data files are added together. The spectral width is 25,000 Hz with a minimum file size of 32K data points. The samples are analyzed at 130 ° C in a 10 mm wide band probe. Comonomer incorporation is determined using the Randall triad method (Randall. J.C .; JMSRev. Macromol. Chem. Phys., C29, 201-317 (1989), which is incorporated here entirely by reference. Density
    [0070] Samples for measuring foam density are prepared from cake foams with or without a fixed coating layer. The foam density is measured using a cake foam sample after removing any integral coating each by accurately measuring the length (L) x width (W) and height (H) of the foam and the mass to the nearest 0.1 g. The density is calculated by dividing the mass of the foam sample by the product of L x W x H, all in cm.
    [0071] You can measure the density of polymers by preparing the samples according to ASTM D 1928 and then measuring the density within one hour of sample compression according to method B of ASTM D 792. Melting temperature, Tm, via DSC
    [0072] Differential scanning calorimetry (DSC) results are determined using a DSC model Q1000 from TAI equipped with an RCS cooling accessory and automatic feeding system. A flow of nitrogen purge gas of 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 with air to room temperature (25 ° C). 3-10 mg of material is cut on a 6 mm diameter disc, accurately weighed, placed in a light aluminum pan (approximately 50 mg) and then closed by crimping. The thermal behavior of the sample is investigated with the following temperature profile. The sample is heated quickly to 180 ° C and maintained isothermally for 3 minutes in order to remove any previous thermal history. The sample is then cooled to -40 ° C at a cooling rate of 10 ° C / min and maintained at -40 ° C for 3 minutes. Then, the sample is heated to 150 ° C at a heating rate of 10 ° C / min. The cooling and second heating curves are recorded.
    [0073] The DSC melting peak is measured as the maximum heating flow rate (W / g) with respect to the linear baseline between -30 ° C and end of melting. The heat of fusion is measured as the area under the melting curve between -30 ° C and the end of the fusion using a linear baseline. GPC (Mw / Mn determination)
    [0074] The gel permeation chromatographic system (GPC) consists of a Model PL-210 instrument from Polymer Laboratories or Model PL-220 from Polymer Laboratories. The carousel and speaker 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 in a concentration of 0.1 g of polymer in 50 ml of solvent containing 200 ppm of butylated hydroxy-toluene (BHT). The samples are prepared by gently shaking at 160 ° C for 2 hours. The injection volume is 100 μ L, and the flow rate is 1.0 mL / min.
    [0075] Calibration of the set of GPC columns is performed with 21 polystyrene patterns of narrow molecular weight distribution with molecular weights ranging from 580 to 8,400,000, arranged in 6 “cocktail” mixtures, with at least a dozen separation between individual molecular weights. The standards are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared in 0.025 g in 50 mL of solvent for molecular weights greater than or equal to 1,000,000 and 0.05 g in 50 mL 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 patterns are used first and in descending order from the highest molecular weight component to minimize degradation. The maximum molecular weights of polystyrene standards are converted to molecular weights of polyethylene using the following equation (described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): Mpolethylene = 0.431 ( Polystyrene)
    [0076] Calculations of equivalent molecular weight of polypropylene are performed using the Viscotek Version 3.0 TriSEC software. Table 1. Additional test methods
    Components • POE: ENGAGE ™ 8842, density 0.857 g / cm3 (ASTM D792), MI 1 g / 10 min (ASTM D1238, at 190 ° C / 2.16 kg), Shore A = 54 (ASTM D2240). • OBC1: INFUSE ™ 9807, density 0.866 g / cm3 (ASTM D792), MI 15 g / 10 min (ASTM D1238, at 190 ° C / 2.16 kg), Shore A = 55 (ASTM D2240). • OBC2: INFUSE ™ 9107, density 0.866 g / cm3 (ASTM D792), MI 1 g / 10 min (ASTM D1238, at 190 ° C / 2.16 kg), Shore A = 60 (ASTM D2240). • OBC3: density 0.870 g / cm3 (ASTM D792), MI 0.5 g / 10 min (ASTM D1238, at 190 ° C / 2.16 kg), Shore A = 51 (ASTM D2240); 1-octene content in the soft segment of 27 mol%. • Crosslinking agent: LUPEROX ™ DC40 SP2 (40% by weight of active percentage) from Arkema. • Mineral oil: paraffin oil, HYDROBRITE 550, obtainable from SONNEBORN. • Expansion agent: AC3000, by Kum Yang Chemical Company. • Mica: particle size around 205 microns; supplied locally. • ZnO: zinc oxide, Horsehead Corporation. • ZnSt: zinc stearate; Fisher Scientific. • EPDM1: NORDEL ™ IP 3430, Mooney viscosity (ML1 + 4, 125 ° C) = 27 MU, obtainable from The Dow Chemical Company. • EPDM1: NORDEL ™ IP 3640, Mooney viscosity (ML1 + 4, 125 ° C) = 40 MU, obtainable from The Dow Chemical Company. • Comparative A: neoprene rubber foam. Table 2. Inventive formulations for cake foam preparation

    phr - parts per hundred of resin Sample preparation 1. Batch mix
    [0077] The ingredients were added to the 3.5 L KOBELCO mixer in the following order: polymer followed by ZnO, ZnSt, talc and oil in 3 successive quantities after melting the polymer. Then the blowing agent and peroxide were added and mixed for an additional 3 to 5 minutes for a total mixing time of 15 minutes keeping the batch temperature below 125 ° C. The resulting batch was finished in a two-cylinder laminator to thoroughly mix any remaining ingredients on the surface when it fell out of the mixer. 2. Foam preparation
    [0078] Finished laminated layers were cut into squares such that 200 grams were introduced into the compression molding groove to prepare the cake foams. The pre-foams were preheated for 8 minutes at 120 ° C and compressed into 20 tons for 4 minutes to form a solid mass in the mold before foaming. The preheated mass was transferred to a foaming press and kept for 8 minutes at 66K psi and 180 ° C. Once the pressure was released, the foam was removed, measured and allowed to cool. The foams were cut and sliced into thin layers or the desired shape for testing. Table 3. Foams of inventive examples against comparative foam (3 mm foam sheet)

    [0079] From the test results in Table 3, it is observed that foams of surprisingly lower densities (light weight) prepared with the inventive formulations showed physical properties that are comparable to the reference standard neoprene foam, which is typical for wetsuit applications, especially for the 60% modulus and compression strain, which are key requirements for applications such as wetsuits. Although the tensile strength and elongation are slightly less than that of neoprene foam, these can be compensated by laminating with elastic cloths.
    [0080] Although the invention has been described with respect to a limited number of embodiments, the specific characteristics of an embodiment can be attributed to other embodiments of the invention. No embodiment alone is representative of all aspects of the invention. In some embodiments, the compositions or methods may include numerous compounds or steps not mentioned here. In other embodiments, the compositions or methods do not include, or are substantially free from, any compounds or steps not mentioned here. There are variations and modifications to the described incorporations. Finally, any number disclosed here must be constructed to mean approximate, regardless of whether the term “about” or “approximately” is used in the description of the number. The appended claims are intended to cover all such modifications and variations as being within the scope of the invention.
    权利要求:
    Claims (7)
    [0001]
    1. Composition capable of forming foam, for use in the manufacture of diving suits, characterized by the fact that it comprises: (a) one or more olefinic block copolymers having hard blocks in which ethylene is present in an amount greater than 95% in weight based on the weight of the polymer, and soft blocks, in which the comonomer content, corresponding to the content of monomers in addition to ethylene is greater than 5% by weight based on the weight of the polymer, said olefin block copolymers having an Mw / Mn from 1.7 to 3.5, and at least one melting point, Tm, in ° C, and a density, d, in g / cm3, with the numerical values of Tm and d corresponding to the relationship: Tm> -2002, 9 + 4538, 5 (d) - 2422.2 (d) 2; (b) one or more olefinic copolymers; (c) an oil; (d) a cross-linking agent; and (e) a blowing agent; the olefin copolymer comprising ethylene-propylene-diene monomer rubber and / or an ethylene / α-olefin copolymer; said molecular weight distribution Mw / Mn being determined by gel permeation chromatography, as described in the description; said density, d, being measured according to ASTM 792; and said melting point, Tm, being determined via differential scanning calorimetry.
    [0002]
    2. Composition capable of forming foam, according to claim 1, characterized by the fact that one or more of the olefinic block copolymers are separated by mesophase and have a comonomer delta greater than 18.5 mol%, the said comonomer delta it is the difference, in mol% of the comonomer, between the hard block and the soft block of the copolymer in olefin blocks.
    [0003]
    A foam-forming composition according to either of Claims 1 or 2, characterized in that: (a) the olefinic block copolymer is present in an amount of 5% by weight to 40% by weight, preferably 10 % by weight to 30% by weight, more preferably from 10% by weight to 25% by weight; (b) the ethylene / propylene / diene monomer rubber is present in an amount of 5% by weight to 40% by weight, preferably from 5% by weight to 30% by weight; (c) the mineral oil is present in an amount of 15% by weight to 45% by weight, preferably from 20% by weight to 40% by weight, more preferably from 25% by weight to 35% by weight; (d) the cross-linking agent is present in an amount of 1-6 phr, preferably 2-5 phr; (e) the blowing agent is present in an amount of 18 phr, preferably 2-6 phr.
    [0004]
    4. Foam for use in the manufacture of diving suits, characterized in that said foam is prepared from the composition capable of forming foam as defined in any one of claims 1 to 3.
    [0005]
    5. Foam according to claim 4, characterized in that the foam has a density of 0.05 g / cm3 to 0.2 g / cm3, a 60% modulus of 0.60 kg / cm2 to 1, 50 kg / cm2, and a compression strain of 15% to 35%, measured according to ASTM D 395, method B.
    [0006]
    6. Laminate, for the manufacture of wetsuits characterized by the fact that the laminate comprises foam as defined in any of claims 4 or 5.
    [0007]
    7. Diving suit, characterized by the fact that it comprises foam as defined in any of claims 4 or 5.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014018134B1|2021-03-02|composition capable of forming foam for use in the manufacture of wetsuits, foam for use in the manufacture of wetsuits, laminates, and wetsuits
    TWI375681B|2012-11-01|Foams made from interpolymers of ethylene/α-olefins
    KR100798204B1|2008-01-24|Composition for polyolefin resin foam, foam of the same, and process for producing foam
    BR112015003776B1|2021-03-09|composition, foam and article
    CN106536191B|2019-06-28|Self-adhering film
    KR100695546B1|2007-03-15|Lower foggy thermoplastic elastomer composition, and process for producing the composition and its use
    CN101175801A|2008-05-07|Crosslinked polyolefin resin foam
    MX2011003534A|2012-06-27|Compositions for abrasion resistant foams and methods for making the same.
    JP6843077B2|2021-03-17|Blends for foams, foams produced from them and articles containing them
    WO2002002316A1|2002-01-10|Layered product of olefin foam and use
    JP6804549B2|2020-12-23|Process for preparing foamed articles made from ethylene / α-olefin interpolymers
    TW201739819A|2017-11-16|Cross-linked foams made from interpolymers of ethylene/alpha-olefins
    JPH09157426A|1997-06-17|Production of olefin-based thermoplastic elastomer injection molded foamed body
    TWI660000B|2019-05-21|Blends for foams, foams manufactured therefrom and articles comprising the same
    JP4254434B2|2009-04-15|Ethylene / α-olefin / non-conjugated diene copolymer rubber composition for molding foam and peroxide cross-linked foam comprising the same
    US5585411A|1996-12-17|Plastic foams made from polybutylene blends
    JP3012277B2|2000-02-21|Partially crosslinked thermoplastic elastomer foam and method for producing the same
    JP2665373B2|1997-10-22|Partially crosslinked thermoplastic elastomer foam and method for producing the same
    JP7014361B2|2022-02-01|Blends for foams, foams produced from them and articles containing them
    JP2020183533A|2020-11-12|Blend for foam, foam produced from the same and article including the same
    JP2020158632A|2020-10-01|Foam sheet
    JP3784226B2|2006-06-07|Expandable olefinic thermoplastic elastomer composition and foamed product thereof
    BR112021007533A2|2021-07-27|article of manufacture, and, method of making an extrusion foam polymer composition
    同族专利:
    公开号 | 公开日
    CN104245807A|2014-12-24|
    EP2825585A4|2015-11-04|
    JP6147281B2|2017-06-14|
    CN104245807B|2017-09-05|
    JP2015514825A|2015-05-21|
    EP2825585B1|2020-07-08|
    KR20140146065A|2014-12-24|
    EP2825585A1|2015-01-21|
    WO2013134945A1|2013-09-19|
    SG11201404498SA|2014-10-30|
    KR101951068B1|2019-02-21|
    US20150025165A1|2015-01-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3644230A|1968-02-19|1972-02-22|Haskon Inc|Extrusion process for polyolefin foam|
    US3573152A|1969-07-29|1971-03-30|Foster Grant Co Inc|Thermoplastic elongated cellular products|
    US3660849A|1970-07-13|1972-05-09|Minnesota Mining & Mfg|Deep submergence diving suit and insulative material therefor|
    US4045517A|1975-11-24|1977-08-30|Rohm And Haas Company|Polyacrylic hot melt adhesives|
    US4214054A|1977-10-21|1980-07-22|Asahi-Dow Limited|Expanded olefin polymer|
    CA1117252A|1978-04-14|1982-02-02|Her Majesty The Queen, In Right Of Canada, As Represented By The Minister Of National Defence|Evacuated diving suit insulation|
    US4323528A|1980-08-07|1982-04-06|Valcour Imprinted Papers, Inc.|Method and apparatus for making large size, low density, elongated thermoplastic cellular bodies|
    US4824720A|1988-02-11|1989-04-25|The Dow Chemical Company|Coalesced polyolefin foam having exceptional cushioning properties|
    US5932659A|1994-09-19|1999-08-03|Sentinel Products Corp.|Polymer blend|
    US5973049A|1997-06-26|1999-10-26|The Dow Chemical Company|Filled polymer compositions|
    KR101382699B1|2005-03-17|2014-04-08|다우 글로벌 테크놀로지스 엘엘씨|FOAMS MADE FROM INTERPOLYMERS OF ETHYLENE/α-OLEFINS|
    US7666918B2|2004-03-17|2010-02-23|Dow Global Technologies, Inc.|Foams made from interpolymers of ethylene/α-olefins|
    US7858706B2|2004-03-17|2010-12-28|Dow Global Technologies Inc.|Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation|
    US8084537B2|2005-03-17|2011-12-27|Dow Global Technologies Llc|Polymer blends from interpolymers of ethylene/α-olefin with improved compatibility|
    BRPI0609833B1|2005-03-17|2017-04-18|Dow Global Technologies Inc|soft foam, foamable composition and foam article|
    US7608668B2|2004-03-17|2009-10-27|Dow Global Technologies Inc.|Ethylene/α-olefins block interpolymers|
    US7786216B2|2005-03-17|2010-08-31|Dow Global Technologies Inc.|Oil based blends of interpolymers of ethylene/α-olefins|
    EP2170993B1|2007-07-13|2019-05-15|Dow Global Technologies LLC|Catalytic olefin block copolymers with controlled block sequence distribution and at least one low crystallinity hard block|
    CN101983214A|2008-01-30|2011-03-02|陶氏环球技术公司|Ethylene/alpha-olefin block interpolymers|
    US9193856B2|2008-12-01|2015-11-24|Mitsui Chemicals, Inc.|Copolymer, rubber composition, cross-linked rubber, cross-linked foam, and uses thereof|JP6018495B2|2012-12-14|2016-11-02|株式会社イノアック技術研究所|Olefin resin foam and method for producing the same|
    US10040888B1|2013-06-14|2018-08-07|Cooper-Standard Automotive Inc.|Composition including silane-grafted polyolefin|
    US10100139B2|2013-08-01|2018-10-16|Cooper-Standard Automotive Inc.|Hose, composition including silane-grafted polyolefin, and process of making a hose|
    CN104610563A|2013-11-05|2015-05-13|晋江凯基高分子材料有限公司|Preparation method of olefin block copolymer material foam, and application of foam|
    CN103992610A|2014-05-20|2014-08-20|泉州三盛橡塑发泡鞋材有限公司|Environment-friendly olefin segmented copolymer foam material and preparation method thereof|
    CN103992609A|2014-05-20|2014-08-20|泉州三盛橡塑发泡鞋材有限公司|Olefin block copolymer foam material and preparation method thereof|
    CN111853380A|2014-07-02|2020-10-30|库博标准汽车配件有限公司|Hose, abrasion resistant composition and hose manufacturing process|
    KR101466388B1|2014-07-16|2014-11-28|화인케미칼 주식회사|Cleaning foam for concrete pump|
    CN104804358B|2015-04-24|2018-03-30|茂泰鞋材有限公司|A kind of ageing-resistant thermoplasticity sole of light weight and preparation method thereof|
    CN107531958B|2015-05-08|2020-11-06|陶氏环球技术有限责任公司|Process for foaming polyolefin compositions using azodicarbonamide/citrate mixtures as nucleating agents|
    CN105199298A|2015-10-28|2015-12-30|辽宁石油化工大学|Olefin blocked copolymer foam material|
    KR20170049255A|2015-10-28|2017-05-10|주식회사 동진쎄미켐|Heat-decomposed compound and method for gasification using the same|
    US9999815B2|2015-12-09|2018-06-19|Eaton Intelligent Power Limited|Lightweight multicolor compression molded grip|
    US11098188B2|2016-09-29|2021-08-24|Dow Global Technologies Llc|Blends for foams, foams manufactured therefrom and articles comprising the same|
    CN109563329A|2016-12-10|2019-04-02|库珀标准汽车公司|Polyolefin elastomer composition and preparation method thereof|
    US10570236B2|2016-12-10|2020-02-25|Cooper-Standard Automotive Inc.|Combined seals, compositions, and methods of making the same|
    CN112513153A|2018-06-29|2021-03-16|陶氏环球技术有限责任公司|Foam bead and sintered foam structure|
    CN109251388B|2018-07-04|2020-12-01|湖北祥源新材科技股份有限公司|High-temperature-resistant cross-linked polyolefin foam material and preparation method thereof|
    CN111303541A|2018-12-12|2020-06-19|上海宜珂橡胶科技有限公司|Wear-resistant rubber particle capable of being formed by injection molding and preparation method and application thereof|
    TW202112955A|2019-09-19|2021-04-01|台橡股份有限公司|Thermoplastic elastomer composition, foamed material and manufacturing method thereof|
    WO2021056406A1|2019-09-27|2021-04-01|Dow Global Technologies Llc|SILANE CROSSLINKED ETHYLENE/α‐OLEFIN BLOCK COPOLYMER BEAD FOAM|
    US10995466B1|2020-02-24|2021-05-04|Saudi Arabian Oil Company|Polymer geo-injection for protecting underground structures|
    KR102361628B1|2020-11-12|2022-02-14|한국신발피혁연구원|Bio epdm foam composition for ocean suit|
    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-03-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/CN2012/072418|WO2013134945A1|2012-03-16|2012-03-16|Foamable compositions, foams and articles thereof|
    [返回顶部]