Thermoplastic polyolefin composition

Abstract

The present invention provides a thermoplastic polyolefin composition that reduces rigidity while exhibiting a balanced combination of mechanical and rheological properties. [Solution] A thermoplastic polyolefin (TPO) composition comprising (a) polypropylene impact copolymer (ICP), (b) a polymer selected from (bi) hydrogenated styrene block copolymer (HSBC) and (b-ii) polypropylene elastomer (PBE), (c) a filler, (d) optionally a polyolefin elastomer (POE), and (e) optionally an additive. The HSBC comprises at least one block "S" composed of vinyl aromatic units and at least one block "R" composed of hydrogenated diene units and optionally vinyl aromatic units, with a vinyl aromatic unit content (VAC) of 5 to 45% by weight and a molecular weight (M) of block "S" of 2 to 20 kg / mol. p ) has.

Description

[Technical Field]

[0001] This disclosure relates to thermoplastic polyolefin (TPO) compositions, methods for preparing the same, and their use in roofing applications. [Background technology]

[0002] Roofing membranes are widely used to cover flat, low-slope, and steep-slope roofs of commercial and industrial buildings such as shopping centers, hospitals, warehouses, and factories. These membranes are typically prepared from polymer compounds formulated with ethylene-propylene-diene monomer (EPDM), poly(vinyl chloride) (PVC), or thermoplastic olefin (TPO). One or more challenges associated with such membranes include color limitations (e.g., blackening with carbon black), the need for special adhesives for attachment to roofing substrates, and the use of volatile organic compound (VOC) solvents during installation.

[0003] The development of thermoplastic polyolefin (TPO) films has provided a more sustainable alternative. TPO combines elastomeric properties with thermoplastic processability, allowing for the production of reflective films without carbon black. Unlike EPDM and PVC films, TPO films can be installed by robotic thermal welding without adhesives or VOC-based solvents, offering advantages in sustainability, installation efficiency, and environmental impact. However, existing TPO films often lack the desirable balance of mechanical and rheological properties. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Thermoplastic polyolefin (TPO) compositions containing polypropylene impact copolymers in combination with elastomers selected from hydrogenated styrene block copolymers (HSBCs) and polypropylene elastomers (PBEs) are still in demand. Such compositions offer reduced stiffness and a balanced combination of other properties. [Means for solving the problem]

[0005] (Summary of the invention) In one embodiment, the present disclosure relates to a thermoplastic polyolefin (TPO) composition comprising, essentially, or consisting of, polypropylene impact copolymers, polymers, fillers, polyolefin elastomers and additives, wherein, with respect to the total weight of the TPO composition, (a) 15 to 50% by weight of polypropylene impact copolymer (ICP) having a melt flow rate (MFR) <1.0 g / 10 min as measured according to ASTM D1238 at 230°C and a 2.16 kg load; (bi) 10 to 45% by weight of (b) polymer selected from the group consisting of hydrogenated styrene block copolymer (HSBC) and (b-ii) polypropylene elastomer (PBE); (c) 5 to 50% by weight of fillers; (d) 0 to 30% by weight of polyolefin elastomer (POE); and (e) 0 to 10% by weight of additives. HSBC comprises at least one block "S" composed of vinyl aromatic units and at least one block "R" composed of hydrogenated diene units and optionally vinyl aromatic units. 1 Total vinyl aromatic unit content (VAC) of 5–45 wt% as measured by 1H NMR and molecular weight (M) of block "S" of 2–20 kg / mol as measured according to ASTM D5296 p ) has a PBE with an ethylene content of 14–18 wt% and a melt flow index (MFI) of <5 g / 10 min, measured at 190°C and a 2.16 kg load according to ASTM D1238. The above transitional phrases (e.g., “contains,” “essentially consists of,” and “consists of”) are intended to have their conventional meanings as understood in patent law or as defined where appropriate.

[0006] In a second embodiment, the TPO composition has a flexural modulus of <850 MPa as measured according to ASTM D790, and a melt flow rate (MFR) of >1.3 dg / min as measured at 230 °C with a 2.16 kg load according to ASTM D1238.

[0007] In a third embodiment, the TPO composition exhibits at least a 10% decrease in flexural modulus compared to a TPO composition that does not contain the polymer of component (b).

[0008] In a fourth embodiment, the ICP is a heterophasic polypropylene comprising (i) a crystalline polypropylene homopolymer matrix phase and (ii) a dispersed phase of an ethylene-propylene copolymer.

Mode for Carrying Out the Invention

[0009] The following terms are used throughout this specification.

[0010] "Consisting essentially of" means that the composition mainly contains the listed components and may further contain one or more components that do not substantially affect the novel features or intended functions of the present invention. In embodiments, such additional components are present in an amount of <30 wt%, <20 wt% or <10 wt% based on the total weight of the composition.

[0011] "At least one of (a group such as A, B, and C)" or "any of (a group such as A, B, and C)" means a single member from the group, two or more members from the group, or a combination of members from the group. For example, at least one of A, B, and C includes, for example, only A, only B, or only C, as well as A and B, A and C, B and C, or A, B, and C, or any other all combinations of A, B, and C.

[0012] A list of embodiments presented as "A, B or C" should be construed to include embodiments of only A, only B, only C, "A or B", "A or C", "B or C", or "A, B or C".

[0013] "Any of A, B, or C" refers to one choice from A, B, or C.

[0014] "Any of A, B, and C" refers to one or more choices from A, B, and C.

[0015] The "vinyl aromatic unit content" (VAC) of a block copolymer refers to the weight percentage of polymerized vinyl aromatic monomers, such as styrene and para-methylstyrene, in the block copolymer. VAC is calculated by dividing the total molecular weight of all vinyl aromatic units by the total molecular weight of the block copolymer. VAC is determined by proton nuclear magnetic resonance spectroscopy. 1 H (Worldwide) and / or 13 This can be determined using 13C NMR. VAC is sometimes used interchangeably with PSC (polystyrene content).

[0016] "Butylene unit content" refers to the weight percentage of butylene units ("B") relative to all diene units in a given polymer (e.g., a hydrogenated block copolymer). Butylene units are formed by polymerization of 1,3-butadiene monomer by 1,2-addition, followed by hydrogenation. 1,3-butadiene monomer can also be polymerized by 1,4-addition, which yields ethylene units ("E") upon hydrogenation. Both butylene and ethylene units may be present in the hydrogenated block copolymer, which may contain other units derived from vinyl aromatic units and / or conjugated diene monomers, arranged in any order. The butylene unit content is: 1 1H NMR and / or 13 It can be measured by 13C NMR. The butylene unit ("B") content is sometimes used interchangeably with the "vinyl content" before hydrogenation.

[0017] "Molecular weight" or Mw refers to the polystyrene equivalent molecular weight in kg / mol of a polymer block or block copolymer. Mw can be measured by gel permeation chromatography (GPC) using a polystyrene calibration standard, for example, performed in accordance with ASTM D5296. The GPC detector may be an ultraviolet or refractive index detector or a combination thereof. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The Mw of the polymer measured using GPC calibrated in this way is the polystyrene equivalent molecular weight or apparent molecular weight. The Mw represented herein is measured at the peak of the GPC trace and is generally referred to as the polystyrene equivalent "peak molecular weight" designated as M p and is referred to as the polystyrene equivalent "peak molecular weight".

[0018] "Hydrogenated SBC" or HSBC refers to a styrenic block copolymer (SBC) in which the diene units are hydrogenated to a hydrogenation level of >90 mol% or preferably >95 mol% or more preferably >98 mol% or <100 mol%, and the vinyl aromatic units are hydrogenated to <20 mol% or preferably <10 mol% or more preferably <5 mol%.

[0019] "Hydrogenation level" refers to the level (percentage) of saturation of the double bonds (e.g., olefin, aromatic, etc.) of the block copolymer and 1 can be measured by 1H NMR.

[0020] "Residual unsaturation" or RU refers to the level of unsaturation, i.e., the carbon-carbon double bonds per gram of the block copolymer. RU 1 can be measured using 1H NMR or ozone decomposition titration.

[0021] "Unit" refers to a structural building block derived from one or more polymerized monomers and represents a repeating element that forms part of a polymer or copolymer chain. Different from a "monomer", which is an individual molecule before polymerization, a "unit" is the transformed form of a monomer after the polymerization process.

[0022] "Coupling efficiency" or CE refers to the weight percentage of coupled polymer molecules relative to the total weight of both coupled and uncoupled polymer molecules. CE is expressed as a percentage (%) and can be used to estimate the content of diblock structures or, more generally, the proportion of "uncoupled arms" in a block copolymer. For example, a CE of 80% indicates that the block polymer contains 20% by weight of diblock (uncoupled) species and 80% by weight of triblock and multi-arm species.

[0023] The "polydispersion index" or PDI is the weight-average molecular weight (M w ) Number average molecular weight (M n It refers to the ratio to ) and is sometimes called the molecular weight distribution. PDI is used to indicate the distribution of polymer chain molecular weight in a given polymer.

[0024] This disclosure relates to thermoplastic polyolefin (TPO) compositions comprising (a) polypropylene impact copolymer (ICP), (b) a polymer component selected from hydrogenated styrene block copolymer (HSBC) and polypropylene elastomer (PBE), (c) one or more fillers, (d) optionally a polyolefin elastomer (POE), and (e) optionally an additive. The TPO compositions exhibit enhanced durability and mechanical properties and are particularly suitable for use in roofing applications, including roofing membranes.

[0025] (Polypropylene Impact Copolymer (ICP)) ICP is a heterogeneous polypropylene comprising (i) a crystalline polypropylene homopolymer matrix phase and (ii) a dispersed ethylene propylene copolymer phase. The presence of the dispersed ethylene propylene phase results in enhanced toughness and impact resistance compared to crystalline polypropylene homopolymer alone. In embodiments, the ethylene propylene copolymer contains ethylene units in an amount of 40-70, or 45-65, or 40-55, or <60, or <55% by weight of the total weight of the ethylene propylene copolymer.

[0026] In embodiments, the dispersed phase of ICP comprises ethylene propylene copolymer in an amount of 10-40, 15-35, 20-30, 10-30, 15-30, <30, or <25% by weight of the total weight of ICP, with the remainder being a polypropylene homopolymer matrix.

[0027] In the embodiment, the ICP has an ethylene content of 25-50, 30-45, 25-40, 30-40, >25, <50, or <45% by weight of the total weight of the ICP.

[0028] In embodiments, the dispersed phase of the ICP further comprises other (co)polymers such as ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer (EPDM) rubber, polyethylene, plastomers, and mixtures thereof. Such (co)polymers may be present in amounts of 1 to 40, 5 to 35, or 10 to 25% by weight relative to the total weight of the dispersed phase.

[0029] In embodiments, the crystalline polypropylene homopolymer matrix contains small amounts of comonomers, such as <10 or <5% by weight of ethylene, butene, 1-hexene, 1-octene, or similar α-olefins.

[0030] The ICP as a whole, measured at 230°C and a 2.16 kg load according to ASTM D1238, can indicate a melt flow rate (MFR) of 0.10-1.0, or 0.10-0.80, or 0.10-0.50, or 0.15-0.45, or 0.20-0.40, or 0.25-0.35, or 0.25-0.50, or 0.10-0.40, or >0.15, or <1.0, or <0.50 g / 10 min.

[0031] In the embodiment, the ICP is measured according to ASTM D792, and is 0.80-1.0, or 0.82-0.98, or 0.85-0.95, or 0.88-0.92 g / cm³. 3 It has a density of .

[0032] In an embodiment, the ICP has a Vicat softening temperature of 130-160°C, or 135-155°C, or 140-150°C, or 130-150°C, or 140-160°C, as determined by ASTM D1525.

[0033] ICP can be produced using conventional reactor techniques. In embodiments, propylene is polymerized in a first reactor to form a highly crystalline polypropylene homopolymer, which is then transferred to a second reactor where additional propylene and ethylene are copolymerized in the presence of the polypropylene homopolymer. In embodiments, the ICP is cross-copolymerized in a single reactor rather than in two series reactors. The resulting ICP, whether prepared in a single-reactor process or a multi-reactor process, can be further blended with other polymers or components.

[0034] In the embodiment, the TPO composition contains ICP in an amount of 15-50, 18-48, or 19-47% by weight of the total weight of the TPO composition.

[0035] (Polymer components) The TPO composition contains a polymer selected from the group consisting of hydrogenated styrene block copolymers (HSBCs) and polypropylene elastomers (PBEs).

[0036] In some embodiments, the polymer is added in an amount of 10-45, 12-40, 15-45, 10-25, 12-22, 20-45, 25-40, >10, or <45% by weight relative to the total weight of the TPO composition.

[0037] (Hydrogenated styrene block copolymer (HSBC)) HSBC can be a linear, branched, or radial block copolymer comprising at least one block "S" composed of vinyl aromatic units and at least one rubbery block "R" (block "R") composed of hydrogenated diene units and optionally vinyl aromatic units. The vinyl aromatic units are derived from polymerized vinyl aromatic monomers, while the hydrogenated diene units are derived from polymerized conjugated diene monomers prior to hydrogenation.

[0038] In one embodiment, HSBC is SR, (SR) n X, SRS, SRSR, RSRSR, (RSR) n X, SRSRS, (SRS) n X is either a linear or branched (multi-armed) block copolymer having a general structure selected from X and mixtures thereof, where n is an integer between 2 and 30, or between 2 and 20, or between 2 and 10, and X is a residue of the coupling agent.

[0039] In this embodiment, each block "R" is a block selected from E / B, E / B / S, EP / MB, EP / MB / S, E / B / EP / MB, and combinations thereof.

[0040] In this embodiment, block "R" is in the form of E / B, consisting of ethylene ("E") units and butylene ("B") units, which are hydrogenated 1,4-butadiene units and hydrogenated 1,2-butadiene units, respectively.

[0041] In this embodiment, block "R" is in the form of E / B / S, consisting of ethylene ("E") units, butylene ("B") units, and vinyl aromatic units.

[0042] In the embodiment, block "R" is in the form of EP / MB, consisting of ethylene propylene (EP) units and methylbutylene (MB) units. Each EP unit is a hydrogenated 1,4-isoprene unit, and each MB unit is a hydrogenated 3,4-isoprene unit and a hydrogenated 1,2-isoprene unit.

[0043] In this embodiment, block "R" is in the form of EP / MB / S, composed of EP units, MB units, and vinyl aromatic units.

[0044] In this embodiment, block "R" is in the form of E / B / EP / MB, consisting of ethylene ("E") units, butylene ("B") units, EP units, and MB units.

[0045] In embodiments, the coupling agent "X" includes, for example, halides of aliphatic or aromatic aliphatic hydrocarbons such as divinylbenzene, e.g., 1,2-dibromoethane, bis(chloromethyl)benzene, silicon tetrachloride, dialkyl or diaryl silicon dichloride, alkyl or aryl silicon trichloride, tin tetrachloride, alkyl silicon methoxide, alkyl silicon ethoxide, polyfunctional aldehydes such as terephthalic acid dialdehyde, ketones, esters, anhydrides, or epoxides, and other difunctional or polyfunctional compounds. In embodiments, the coupling agent is selected from methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, dimethyl adipate, gamma-glycidoxypropyltrimethoxysilane, and mixtures thereof. In embodiments, the HSBC has a coupling efficiency (CE) of >60%, <98%, 60-98%, or 65-95%.

[0046] In embodiments, the vinyl aromatic monomer is selected from the group consisting of styrene, para-methylstyrene, para-ethylstyrene, para-n-propylstyrene, para-iso-propylstyrene, para-n-butylstyrene, para-sec-butylstyrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, isomers of para-dodecylstyrene, ortho-substituted styrene, meta-substituted styrene, alpha-methylstyrene, 1,1-diphenylethylene, and mixtures thereof.

[0047] In embodiments, the conjugated diene monomer is selected from the group consisting of isoprene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, farnesene, myrcene, piperylene, cyclohexadiene, and mixtures thereof.

[0048] In the embodiment, each block "S" has a hydrogenation level of <30%, <20%, <10%, or <5% relative to all double bonds present in block "S". In the embodiment, the diene units in each block "R" have a hydrogenation level of >80%, >90%, >95%, >98%, or up to 100%, or 80-99%, or 90-98%.

[0049] In embodiments, HSBC is a mixture of at least two block copolymers selected from the group consisting of diblock species and species having two or more blocks (e.g., triblock, tetrablock, pentablock, etc.). In embodiments, diblock species constitute 1 to 40, or 2 to 35, or 3 to 15, or 15 to 35, or >3, or <35% by weight of the total weight of HSBC, and species having two or more blocks constitute up to 99% by weight, or 60 to 99, or 65 to 98, or 85 to 97, or 65 to 85, or >65, or <97% by weight.

[0050] In this embodiment, the HSBC has a residual unsaturated (RU) of 0-0.5, or 0.01-0.4, or 0.05-0.5, or <0.5, or <0.4, or <0.3, or <0.2, or <0.1 meq / g. 1 It can be measured by 1H NMR or ozonolysis.

[0051] In the embodiment, the HSBC has a butylene unit ("B") content of 30-90, 35-85, 40-80, 30-55, 65-85, >35, or <85% by weight relative to the total weight of hydrogenated diene units in the HSBC.

[0052] In the embodiment, the HSBC has a vinyl aromatic unit content (VAC) of 5 to 45, 8 to 40, 10 to 35, 7 to 18, 25 to 45, >8, >10, or <40% by weight relative to the total weight of the HSBC.

[0053] In this embodiment, each block "S" has a molecular weight (M) of 2-20, or 3-18, or 4-15, or 3-12, or 5-15, or >2, or >4, or <15 kg / mol. p ) has.

[0054] In the embodiment, block E / B (if present) has a molecular weight (M) of 90-240, or 95-230, or 100-220, or 110-210 kg / mol. p ) has.

[0055] In the embodiment, block E / B / S (if present) has a molecular weight (M) of 90-240, or 95-230, or 100-220, or 110-210 kg / mol. p ) has.

[0056] In this embodiment, HSBC has a molecular weight (M) of 80-250, or 90-245, or 100-240, or 105-230, or 110-250, or 120-160, or 180-225, or 130-215, or 105-150 kg / mol. p ) has.

[0057] In embodiments, the HSBC has a melt flow rate (MFR) of 10–40, or 12–35, or 15–30, or 10–25, or 18–35, or >15, or <30 dg / min, measured at 230°C and a 5 kg load. In embodiments, the HSBC has an MFR of 2–55, or 7–50, or 9–48, or 10–45, or 5–15, or 35–50, or 2–10, or >2, or <50 dg / min, measured at 230°C and a 2.16 kg load. All MFRs conform to ASTM D1238.

[0058] In this embodiment, HSBC has a molecular weight (M) relative to block "S" of block E / B in the range of 15:1 to 40:1, or 18:1 to 38:1, or 20:1 to 35:1, or 22:1 to 37:1. p It has a ratio.

[0059] In embodiments, HSBC has a molecular weight (M) relative to block "S" of block E / B / S in the range of 10:1 to 25:1, or 12:1 to 22:1, or 14:1 to 20:1, or 10:1 to 18:1, or 14:1 to 25:1. p It has a ratio.

[0060] In this embodiment, HSBC contains 30-55% by weight of butylene units ("B"), 7-18% by weight of VAC, and 3-12 kg / mol of block "S". p , M of block copolymers with a concentration of 120-160 kg / mol p , MFR of 15-30 dg / min at 230℃ / 5kg, diblock content of 15-35 wt% and molecular weight (M) of block E / B relative to block "S" in the range of 22:1-37:1 p It has a general structure SE / BS with a ratio of ).

[0061] In the embodiment, the HSBC contains 65-85% by weight of butylene units ("B"), 25-45% by weight or 7-18% by weight of VAC, and 3-12 kg / mol of block "S". p M of block copolymers with a concentration of 105-150 kg / mol or 180-225 kg / mol p , MFR of 2-15 dg / min or 35-50 dg / min at 230℃ / 2.16kg, diblock content of 3-15% by weight, molecular weight (M) of block E / B (if present) relative to block "S" in the range of 22:1-37:1 p ) ratio and molecular weight (M) of block E / B / S (if present) relative to block "S" in the range of 14:1 to 20:1 p The general structure of SE / BS, SE / B / SS, and mixtures thereof has a ratio of ).

[0062] In embodiments, HSBC is functionalized with at least one functional group, such as a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group, an epoxy group, an isocyanate group, a silanol group, or a silane group.

[0063] (Polypropylene elastomer (PBE)) In the embodiment, the TPO composition includes PBE, which is a copolymer of propylene and ethylene monomer.

[0064] In this embodiment, the PBE contains ethylene units in an ethylene unit content of 14-18, 14-17, 15-17, 14-16, 15-16, >14, or <18% by weight relative to the total weight of the PBE, with the remainder being propylene units.

[0065] In embodiments, PBE is measured according to ASTM D792, ranging from 0.850 to 0.920, or 0.855 to 0.910, or 0.860 to 0.900 g / cm³. 3 It has a density of .

[0066] In the embodiment, the PBE has a glass transition temperature of -40 to -20°C or -35 to -25°C, as measured by DSC.

[0067] In an embodiment, PBE has a melting temperature of 50-120°C, 55-100°C, 60-80°C, or 50-70°C, as measured by DSC.

[0068] In an embodiment, the PBE has a melt flow index (MFI) of 0.1 to 15, or 0.5 to 8, or 0.5 to 5, or 0.1 to 3, or >0.1, or >0.5, or <5 g / 10 min, as measured at 190°C and a 2.16 kg load according to ASTM D1238.

[0069] (Filler) The TPO composition contains one or more fillers to provide bulk reinforcement and processing advantages. Examples of fillers include magnesium carbonate hydrate, magnesium carbonate, magnesium calcium carbonate hydrate, magnesium calcium carbonate, magnesium hydroxide (Mg(OH)2·xH2O), calcium carbonate, aluminum trihydrate, magnesium silicate, sepiolite, wollastonite (calcium silicate), kaolin clay, montmorillonite, boehmite, alumina trihydrate, perlite, vermiculite, glass fibers, glass microspheres, and mixtures thereof.

[0070] In embodiments, the filler also acts as a flame retardant, decomposing endothermally to release water or carbon dioxide, diluting the flammable polymer contents, forming an insulating barrier layer, and thereby contributing to improved fire resistance of the composition. Examples include aluminum trihydrate, boehmite, huntite and hydromagnesite, magnesium carbonate (MgCO3) and dolomite (CaMg(CO3)2), wollastonite, calcium carbonate and magnesium hydroxide.

[0071] In one embodiment, the filler is magnesium hydroxide (Mg(OH)2·xH2O). In a further embodiment, the filler is aluminum trihydrate, hanthite-hydromagnesite, alone or in combination.

[0072] In embodiments, the filler is pre-blended into a masterbatch containing one of the following: ICP, low-density polyethylene (LDPE), POE, polypropylene, SBC, etc. Such a masterbatch may contain >40, or >50, or >60, or >70, or 45-80, or 50-75% by weight of the filler, with the remainder being ICP.

[0073] In one embodiment, the filler is added in an amount of 5 to 50, 10 to 45, 15 to 40, 20 to 50, 25 to 45, >5, or <50% by weight relative to the total weight of the TPO composition.

[0074] (Optional polyolefin elastomer (POE)) In one embodiment, the TPO composition further comprises POE selected from ethylene-α-olefin copolymers, propylene-α-olefin copolymers, and mixtures thereof.

[0075] In the embodiment, the ethylene-α-olefin copolymer is composed of ethylene and at least one C3-C 20 It is a copolymer with α-olefins, containing ethylene units in an amount of >50, >60, >70, >80, or >90% by weight of the total weight of the copolymer, with the remainder being C3-C 20 It is an α-olefin unit.

[0076] In one embodiment, the propylene-α-olefin copolymer comprises propylene and at least one C4-C 20 It is a copolymer with α-olefins, containing propylene units in an amount of >50, >60, >70, >80, or >90% by weight of the total weight of the copolymer, with the remainder being C4-C 20 It is an α-olefin unit.

[0077] Appropriate C3~C 20 Or C4~C 20 Examples of α-olefins include propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and related α-olefins.

[0078] Examples of POEs include ethylene / butene copolymers, ethylene / hexene copolymers, ethylene / octen copolymers, ethylene / α-olefin / diene-modified interpolymers (e.g., ethylene / propylene / diene-modified interpolymers, ethylene / propylene / octen copolymers, etc.), ethylene / propylene copolymers, propylene / 1-butene copolymers, propylene / hexene copolymers, propylene / 4-methyl-1-pentene copolymers, propylene / 1-octen copolymers, propylene / ethylene / 1-butene copolymers, propylene / ethylene / ethylidene norbornene copolymers, propylene / ethylene / 1-hexene copolymers, propylene / ethylene / 1-octen copolymers, propylene / styrene copolymers, and propylene / ethylene / styrene copolymers.

[0079] In this embodiment, the POE is prepared by a metallocene catalytic polymerization process. The resulting material has the same types and weight percentages of comonomers but can exhibit measurable properties that distinguish it from polyolefins produced by conventional Ziegler-Natta polymerization processes.

[0080] In the embodiment, POE is C4~C 18 Further comprising diolefins and / or alkenylbenzenes.

[0081] In embodiments, POE is measured according to ASTM D792, and is 0.850-0.920, or 0.855-0.915, or 0.860-0.910, or 0.865-0.905 g / cm³. 3 It has a density of .

[0082] In an embodiment, the POE has a melt flow index (MFI) of 0.1–50, or 0.5–30, or 0.1–20, or 0.1–10, or 0.5–8, or >0.5, or <10 g / 10 min, as measured at 190°C and a 2.16 kg load according to ASTM D1238.

[0083] In this embodiment, POE has a number average molecular weight (M) of 20-400, 30-350, 40-300, 50-200, 20-100, or 40-90 kg / mol. n ) has.

[0084] In this embodiment, the POE has a PDI of 1.7 to 3.5, or 1.8 to 3.0, or 1.9 to 2.8, or 2.0 to 2.5, or >2.0, or <2.5.

[0085] In the embodiment, POE has a glass transition temperature (T) of <0, <-10°C, >-40°C, or >-30°C. g ) has.

[0086] In embodiments, POE has a melting point (M) of >60°C, >70°C, <100°C, 60-100°C, 65-95°C, or 70-90°C. p ) has.

[0087] In embodiments, POE, if present, is added in an amount of up to 30% by weight, or 5-30%, 7-25%, or 5-22% by weight, relative to the total weight of the TPO composition.

[0088] (Optional additives) The TPO composition further comprises additives selected from the group consisting of activators, curing agents, UV stabilizers, neutralizing agents, thickeners, fusion aids, slip agents, mold release agents, antimicrobial agents, surfactants, flame retardants (other than the fillers listed above), antioxidants, ozone cracking inhibitors, color change pH indicators, plasticizers, tackifiers, film-forming additives, pigments, catalysts, other resins, redox pairs, viscosity modifiers, degassing agents, strengthening agents, adhesion promoters, heat stabilizers, lubricants, flow regulators, anti-dripping agents, anti-blocking agents, antistatic agents, processing aids, stress relief additives, and mixtures thereof.

[0089] Examples of pigments include titanium dioxide, zinc oxide, lithopone, antimony oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, and mixtures thereof. The pigment can be incorporated as a masterbatch containing the pigment and a polymer matrix such as polypropylene homopolymer, polyethylene, HSBC, PBE, or POE. The polymer matrix of the masterbatch can have an MFR of 10-300 g / 10 min, measured at 230°C and a 2.16 kg load according to ASTM D1238, and can be present in an amount of 20-40% by weight relative to the total weight of the masterbatch.

[0090] Examples of UV stabilizers include hindered amine light stabilizers (HALS), benzotriazoles, benzophenones, triazines, and related compounds. UV stabilizers can also be incorporated as masterbatches containing the UV stabilizer and a polymer matrix such as polypropylene homopolymer, polyethylene, HSBC, PBE, or POE. The polymer matrix of the masterbatch can have an MFR of 10-300 g / 10 min, measured at 230°C and a 2.16 kg load according to ASTM D1238, and can be present in an amount of 70-90% by weight relative to the total weight of the masterbatch.

[0091] In embodiments, if the additive is added, it is in an amount of up to 10, or 0.5 to 10, or 1 to 5, or 2 to 5% by weight of the total weight of the TPO composition.

[0092] (Thermoplastic polyolefin (TPO) composition) The TPO composition comprises, based on the total weight of the composition, (a) 15 to 50% by weight of ICP, (b) 10 to 45% by weight of a polymer selected from either HSBC or PBE, (c) 5 to 50% by weight of at least a filler, and (d) up to 30% by weight of POE.

[0093] (Preparation of TPO composition / articles) TPO compositions can be processed by conventional methods known to those skilled in the art, which involve combining and blending individual components by melt mixing. In some embodiments, the melt-mixed composition can be extruded into pellets for further processing. In other embodiments, the individual components may be melt-mixed and directly converted into articles such as sheets without the need for pre-formulation. Articles can be formed by techniques such as injection molding, blow molding, overmolding, rotational molding, thermoforming, casting, extrusion, and morph extrusion.

[0094] In embodiments, the TPO composition is formulated at temperatures in the range of 150-250°C, 180-245°C, 200-240°C, 180-235°C, or 210-250°C. The various components can be added in any order or simultaneously. In embodiments, the additives are incorporated in the form of a pre-mixed masterbatch.

[0095] In embodiments, the roof membrane is prepared from a TPO composition using a conventional extrusion molding process and optionally laminated onto a multilayer sheet. The roof membrane may include two or more sheets that are joined together to form a laminated structure.

[0096] In this embodiment, the roof membrane has a thickness of 0.1 to 50 mm, or 0.5 to 20 mm, or 1 to 10 mm, or 0.5 to 5 mm.

[0097] (Properties of TPO composition) The film obtained from the TPO composition exhibits flexibility over an operating temperature range of -40 to 50°C while maintaining resistance to roll blocking at high temperatures, such as >100°C. Furthermore, the film is characterized by low rigidity, contributing to improved ease of installation and durability.

[0098] In an embodiment, the TPO composition has a flexural modulus of <850, or <800, or >40, or 40-750, or 80-720, or 100-700, or 100-680, or 200-700, or 500-700, or 100-350 MPa, as measured according to ASTM D790.

[0099] In embodiments, the TPO composition has a yield point tensile strength of >5, <30, 5-30, 6-25, 7-22, 8-20, 7-16, or 10-15 MPa, as measured according to ASTM D638.

[0100] In the embodiment, the TPO composition has a tensile strength at break of >5, <30, 5-30, 6-25, 7-22, 7-16, or 10-15 MPa, as measured according to ASTM D638.

[0101] In an embodiment, the TPO composition has an elongation at break of >350%, or <1200%, or 350-1200%, or 370-1150%, or 390-1100%, or 400-1050%, or 700-1000%, as measured according to ASTM D638.

[0102] In one embodiment, the TPO composition has an MFR of >1.3, <15, 1.3-15, 1.5-12, 1.7-10, 1.3-8, 1.4-7, or 2.5-5.5 dg / min, as measured at 230°C and a 2.16 kg load according to ASTM D1238.

[0103] The elastic modulus of the TPO composition is measured by dynamic viscoelasticity measurement (DMA), for example, using a Discovery DMA 850 instrument manufactured by TA Instruments, at temperatures in the range of -70 to 110°C and a frequency of 1 Hz.

[0104] In the embodiment, the TPO composition has an elastic modulus of <9000, >1000, or 1000-9000, or 1100-8800, or 1200-8500, or 3000-8300 MPa at -40°C.

[0105] In the embodiment, the TPO composition has an elastic modulus of <5000, or >800, or 300-5000, or 320-4800, or 340-4600, or 600-3000 MPa at -20°C.

[0106] In this embodiment, the TPO composition has an elastic modulus of <3000, or >100, or 100-3000, or 120-2800, or 200-2600, or 100-800 MPa at 0°C.

[0107] In this embodiment, the TPO composition has an elastic modulus of <1300, >50, 50-1300, 70-1200, 500-1200, or 50-300 MPa at 20°C.

[0108] In the embodiment, the TPO composition has an elastic modulus of <800, >40, 40-800, 50-600, 100-600, 400-600, or 50-200 MPa at 40°C.

[0109] In the embodiment, the TPO composition exhibits one or more of the following performance advantages compared to a TPO composition that does not contain polymer component (b).

[0110] A decrease of at least 10% in the flexural modulus, An increase of at least 5% in elongation at break. A decrease of at least 5% in the modulus of elasticity at 0°C. A decrease of at least 5% in the modulus of elasticity at 20°C and A decrease of at least 5% in the modulus of elasticity at 40°C.

[0111] (Uses of TPO composition) The TPO composition can be processed into a roofing membrane suitable for application on flat, low-slope, or steep-slope substrates. The roofing membrane can be fixed to the underlying roof structure by conventional methods such as adhesive bonding, ballast systems, spot bonding, or mechanical fastening.

[0112] In the embodiment, the roof membrane is provided as a single sheet or as a laminate that forms an integrated structure by including two or more joined layers.

[0113] The roof membrane can also be reinforced with scrim, which can be selected from woven or nonwoven fabrics or mixtures thereof, such as polyester, glass fiber, glass fiber reinforced polyester, polypropylene, and nylon.

[0114] In the embodiment, the surface of the roof membrane is textured on either the top or bottom surface with a pattern such as polyhedral shapes, conical protrusions, or random surface designs. Such texturing increases the surface area of ​​the membrane, reduces glare, and enhances slip resistance.

[0115] (Analysis method) To identify and quantify the ICP and PBE components, techniques such as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) can be used to distinguish crystalline polypropylene homopolymer domains from the amorphous elastomer phase. Fourier transform infrared spectroscopy (FTIR) can be used to determine the ethylene content of PBE and the comonomer content, including the distribution of diene units in HSBC. 1 1H NMR and 13 13C NMR may be useful. Gel permeation chromatography (GPC) can be used to measure the molecular weight, including the molecular weight of block "S" in HSBCs.

[0116] The vinyl aromatic unit content in HSBC can be quantified using NMR and ultraviolet (UV) spectroscopy. The relative amounts of the HSBC phase and the PBE phase can also be determined by transmission electron microscopy (TEM) or atomic force microscopy (AFM), which reveal the phase morphology and dispersion within the matrix.

[0117] The melt flow rate (MFR) and melt flow index (MFI) of the composition can be directly measured under specific temperature and load conditions according to ASTM D1238. The filler can be detected and quantified using techniques such as energy-dispersive X-ray spectroscopy (EDX), X-ray fluorescence (XRF), inductively coupled plasma spectroscopy (ICP-OES or ICP-MS), or TGA.

[0118] Additives such as UV stabilizers, antioxidants, pigments, and processing aids can be identified and quantified using chromatography (e.g., GC-MS or HPLC), FTIR, or UV spectroscopy. The relative weight percentages of ICP, HSBC, or PBE, packing materials, additives, and POE can be determined by gravimetric analysis supported by compositional analysis from NMR and FTIR, and by a combination of selective solvent extraction and thermal fractionation. [Examples]

[0119] The following examples are intended to be non-limiting.

[0120] The following test method will be used.

[0121] The following components are used in the examples.

[0122] ICP-1 was measured at 230°C / 2.16kg with an MFR of 0.35g / 10min and a concentration of 0.90g / cm³. 3This is a polypropylene impact copolymer having a density of 145°C, a Vicat softening temperature of 145°C, 15-30% by weight of ethylene propylene copolymer, 40-55% by weight of ethylene units in the ethylene propylene copolymer, and 30-40% by weight of total ethylene units. ICP-1 is available from LyondellBasell.

[0123] HSBC-1 is 13.3 wt% VAC, 5.3 kg / mol block "S" M p , M of block copolymer at 145 kg / mol p It is a linear hydrogenated triblock copolymer (SE / BS) having a butylene unit ("B") content of 44% by weight, an MFR of 22 dg / min at 230°C / 5kg, 71% CE, and 29% by weight diblock content.

[0124] HSBC-2 is 34.5 wt% VAC, 7.2 kg / mol block "S" M p , M of block copolymer at 125 kg / mol p It is a linear hydrogenated triblock copolymer (SE / B / SS) having a butylene unit ("B") content of 78% by weight, 93% CE, an MFR of 43 g / 10 min at 230°C / 2.16 kg, 93% CE, and a diblock content of 7% by weight.

[0125] HSBC-3 contains 12.3 wt% VAC and 5.7 kg / mol of block "S" M p , M of block copolymer at 203 kg / mol p It is a linear hydrogenated triblock copolymer (SE / BS) having a butylene unit ("B") content of 78% by weight, an MFR of 11 dg / min at 230°C / 2.16 kg, 95% CE, and a diblock content of 5% by weight.

[0126] HSBC-4 is 12.5 wt% VAC, 6.4 kg / mol block "S" M p , M of block copolymer at 201 kg / mol pIt is a linear hydrogenated triblock copolymer (SE / BS) having a butylene unit ("B") content of 78% by weight, an MFR of 3.3 dg / min at 230°C / 2.16 kg, 93% CE, and a diblock content of 7% by weight.

[0127] POE-1 undergoes MFI at 190°C / 2.16kg with 5g / 10min and 0.885g / cm³. 3 It is an ethylene-hexene copolymer having a density of [density].

[0128] POE-2 undergoes MFI at 190°C / 2.16kg with a 1g / 10min injection and 0.885g / cm³ injection. 3 It is an ethylene-hexene copolymer having a density of [density].

[0129] PBE-1 has an ethylene content of 16% by weight, 0.862 g / cm³. 3 It is a polypropylene-based elastomer with a density and an MFI of 1.4 g / 10 min at 190°C / 2.16 kg.

[0130] A masterbatch having a polypropylene homopolymer matrix containing 20-40% by weight of titanium dioxide (TiO2).

[0131] UV-S: A masterbatch having 2-(2-hydroxy-5-methylphenyl)benzotriazole, a UV stabilizer, and a polypropylene homopolymer matrix of 70-90% by weight.

[0132] (Examples 1-17) TPO compositions were prepared by dry mixing the individual components and then compounding them in a twin-screw extruder at a temperature of 225-235°C. Test specimens for property measurement were prepared by injection molding using a mold temperature of 50°C. The formulations and mechanical properties of the TPO compositions of Examples 1-17 are shown in Table 1. Comparative Examples C-Ex-1, C-Ex-4, and C-Ex-7 are provided for reference.

[0133] [Table 1]

[0134] Table 2

Claims

1. A thermoplastic polyolefin composition, wherein, with respect to the total weight of the thermoplastic polyolefin composition, (a) 15 to 50% by weight of polypropylene impact copolymer having a melt flow rate of <1.0 g / 10 min as measured at 230°C and a 2.16 kg load according to ASTM D1238, (b-i) A hydrogenated styrene-based block copolymer comprising at least one block "S" composed of vinyl aromatic units and at least one block "R" composed of hydrogenated diene units and optionally vinyl aromatic units, １ The total vinyl aromatic unit content (VAC) of 5–45% by weight, as measured by 1H NMR, and Molecular weight (M) of block "S" in the range of 2-20 kg / mol, as measured by ASTM D5296. ｐ A hydrogenated styrene-based block copolymer having ) and (b-ii) Polypropylene elastomer having an ethylene content of 14-18% by weight and a melt flow index (MFI) of <5 g / 10 min as measured at 190°C and a 2.16 kg load according to ASTM D1238. Selected from the group consisting of (b) Polymer in an amount of 10 to 45% by weight, (c) Filler in an amount of 5 to 50% by weight, (d) 0 to 30% by weight of polyolefin elastomer, (e) Additives in a weight of 0 to 10% A thermoplastic polyolefin composition.

2. Flexural modulus of elasticity of <850 MPa, as measured according to ASTM D790, The melt flow rate (MFR) was measured at 230°C and a 2.16 kg load according to ASTM D1238, and was >1.3 dg / 10 min. A thermoplastic polyolefin composition according to claim 1, having the following characteristics.

3. A thermoplastic polyolefin composition according to any one of claims 1 to 2, which exhibits at least a 10% decrease in flexural modulus compared to a thermoplastic polyolefin composition that does not contain the polymer of component (b).

4. The thermoplastic polyolefin composition according to any one of claims 1 to 3, wherein the polypropylene impact copolymer is a heterogeneous polypropylene comprising (i) a crystalline polypropylene homopolymer matrix phase and (ii) a dispersed phase of ethylene propylene copolymer.

5. The thermoplastic polyolefin composition according to claim 4, wherein the ethylene propylene copolymer contains 40 to 70% by weight of ethylene units relative to the total weight of the ethylene propylene copolymer.

6. The thermoplastic polyolefin composition according to claim 4, wherein the dispersed phase of the polypropylene impact copolymer contains 10 to 40% by weight of the ethylene propylene copolymer based on the total weight of the polypropylene impact copolymer.

7. The aforementioned polypropylene impact copolymer The ethylene content is 25 to 50% by weight relative to the total weight of the polypropylene impact copolymer. The melt flow rate was measured at 230°C and a 2.16 kg load, and the melt flow rate was 0.10 to 0.80 g / 10 min. 0.80~1.0g / cm ３ density A thermoplastic polyolefin composition according to any one of claims 1 to 3, having at least one of the above.

8. The polymer of component (b) is S-R, (S-R) ｎ X, S-R-S, S-R-S-R, R-S-R-S-R, (R-S-R) ｎ X, S-R-S-R-S, (S-R-S) ｎ A hydrogenated styrene-based block copolymer represented by a general structure selected from X and mixtures thereof, where n is an integer from 2 to 30, and X is a residue of a coupling agent. Each block "S" is composed of vinyl aromatic units. Each block "R" is a block selected from E / B, E / B / S, EP / MB, EP / MB / S, E / B / EP / MB, and combinations thereof. Each block E / B consists of ethylene ("E") units and butylene ("B") units. Each block E / B / S is composed of ethylene ("E") units, butylene ("B") units, and vinyl aromatic units. Each block EP / MB is composed of ethylene propylene (EP) units and methylbutylene (MB) units. Each block EP / MB / S is composed of ethylene propylene (EP) units, methyl butylene (MB) units, and vinyl aromatic units. Each block E / B / EP / MB consists of ethylene ("E") units, butylene ("B") units, ethylenepropylene (EP) units, and methylbutylene (MB) units. A thermoplastic polyolefin composition according to any one of claims 1 to 3.

9. The aforementioned hydrogenated styrene-based block copolymer The butylene unit ("B") content is 30 to 90% by weight relative to the total weight of hydrogenated diene units, and Vinyl aromatic unit content (VAC) of 10-35% by weight The thermoplastic polyolefin composition according to claim 8, having at least one of the above.

10. Block "S" has a molecular weight of 4-15 kg / mol (M ｐ ) has, The hydrogenated styrene-based block copolymer has a molecular weight (M) of 80 to 250 kg / mol. ｐ The thermoplastic polyolefin composition according to claim 8, having ).

11. The hydrogenated styrene-based block copolymer is represented by the general structure S-E / B-S, Butylene unit ("B") content of 30-55% by weight, Vinyl aromatic unit content (VAC) of 7-18% by weight, Molecular weight (M ｐ ) of block "S" of 3 to 12 kg / mol Molecular weight (M) of 120-160 kg / mol ｐ ), and 15-35% by weight of Zibloc content A thermoplastic polyolefin composition according to claim 8, having the following characteristics.

12. The hydrogenated styrene-based block copolymer is represented by a general structure selected from S-E / B-S, S-E / B / S-S, and mixtures thereof. Butylene unit ("B") content of 65-85% by weight, Vinyl aromatic unit content of 25-45% by weight or 7-18% by weight, Molecular weight (M) of block "S" in the range of 3-12 kg / mol ｐ ), Molecular weight (M) of 105-150 kg / mol or 180-225 kg / mol ｐ ), and 3-15% by weight of Zibloc content A thermoplastic polyolefin composition according to claim 8, having the following characteristics.

13. The polymer of component (b) is a polypropylene-based elastomer, and the polypropylene-based elastomer is Ethylene content of 14-17% by weight, The melt flow index (MFI) was measured at 190°C and a 2.16 kg load, and the values ​​were 0.5 to 5 g / 10 min. 0.850~0.920g / cm ３ density A thermoplastic polyolefin composition according to any one of claims 1 to 3, having the following characteristics.

14. The thermoplastic polyolefin composition comprises 5 to 30% by weight of the polyolefin elastomer, and the polyolefin elastomer is The melt flow index (MFI) was measured according to ASTM D1238 at 190°C and a 2.16 kg load, with a value of >0.5 g / 10 min. A thermoplastic polyolefin composition according to any one of claims 1 to 3, having the following characteristics.

15. The thermoplastic polyolefin composition according to any one of claims 1 to 3, wherein the filler is selected from the group consisting of magnesium carbonate hydrate, magnesium carbonate, magnesium calcium carbonate hydrate, magnesium calcium carbonate, magnesium hydroxide, calcium carbonate, aluminum trihydrate, magnesium silicate, sepiolite, wollastonite (calcium silicate), kaolin clay, montmorillonite, boehmite, alumina trihydrate, perlite, vermiculite, glass fibers, glass microspheres, and mixtures thereof.

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