JP2019512576A - Propylene-based elastomer for roofing compositions and method of preparing same - Google Patents

Abstract

Provided herein are elastomer blends and membranes comprising a blend of a propylene based elastomer, a thermoplastic resin, a flame retardant and a UV light stabilizer. [Selected figure] Figure 1

Description

Inventors Li, Lian; Zacharias, Felix Em, Dharmarajan, Naraya Naswami; Calfas, Jean; Hagadon, John Earle; and Gian, Pey Jun
CROSS-REFERENCES TO RELATED APPLICATIONS This application is related to US Provisional Patent Application Nos. 62 / 306,253 filed Mar. 10, 2016 and European Patent Application No. 16172423.2 filed on Jun. 1, 2016 Priority is claimed and its benefits, the contents of which are incorporated herein by reference.
Technical field

  Described herein are formulations comprising a propylene based elastomer useful in roofing applications, such as thermoplastic roofing applications.

  Compositions and membranes comprising thermoplastic olefin (TPO) polymers have become widely used in the roofing industry for commercial buildings. TPO films are often reflective films (40 to 60 mils thick) (1 to 1.5 mm thick), reinforced polyester scrim fabrics (1 to 2 mils thick) (0.03 to 0.05 mm thick) And pigment layers (40 to 60 mils thick) (1 to 1.5 mm thick) as a composite construction. When this film is applied to the roof, the reflective white layer is exposed to sunlight while the pigment layer (which is under the reflective layer) is attached to the roof insulation.

  For roofing and other sheeting applications, the product is typically manufactured as a membrane sheet having a standard width of 10 feet (3 meters) or more. However, narrower widths may also be available. Sheets are typically sold in rolls, transported and stored. For roofing membrane applications, several sheets are unrolled from the roll at the installation site, laid end to end next to each other to cover the roof and sealed together by the heat welding method during installation. During transport and storage, the rolls may be exposed to extreme thermal conditions, such as 40 ° C. to 100 ° C., which may cause the rolls to block during storage. After installation, the membrane may be exposed to a wide range of conditions that can degrade or destroy the structural integrity of the membrane while in use. As such, it is desirable that the membrane be able to withstand a wide range of service temperatures, such as -40 ° C to 40 ° C.

  WO 2010/115079 A1 relates to a roofing membrane, which comprises (a) 30 to 50% by weight of a propylene-based elastomer, (b) 9 to 20% by weight of a plastomer, (c ) 7 to 20% by weight impact polypropylene-ethylene copolymer, (d) 20 to 35% by weight magnesium hydroxide, (e) 5 to 10% by weight titanium dioxide and (f) 1 to 2% by weight additives Or a composition of Formulation I comprising; or (a) 32 to 48% by weight of a propylene based elastomer, (b) 9 to 18% by weight of a plastomer, (c) 7 to 20% by weight of impact polypropylene-ethylene Copolymer, (d) 25 to 35% by weight of magnesium hydroxide, (e) 4 to 6% by weight of titanium dioxide, (f) 0.75 to 1.5% by weight of UV inhibitors, (g) 0.2 to 0.45% by weight of antioxidants / stabilizers, (h) 0.15 to 0.4% by weight of heat stabilizers and (i) It contains the composition of formulation II which contains 0.1 to 0.2% by weight of a lubricant. The propylene-based elastomer used in WO 2010/115079 A1 is VistamaxxTM 6102, the lubricant used is Asahi AX 71, which is a mono- or distearic acid phosphate . The roofing membrane of WO 2010/115079 A1 is formed around a scrim with a reinforced polyester yarn.

  WO 2014/001224 A1 relates to a composition comprising 40 to 75% by weight of at least one polypropylene based elastomer and about 25 to 60% by weight of a random copolymer of at least one polypropylene. The polypropylene-based elastomer used in International Patent Publication No. WO 2014/001224 A1 was VistamaxxTM 3980, 6102 and 6202.

  International Application Publication No. WO 2014/040914 A1 relates to a thermoplastic mixture comprising at least one impact polypropylene copolymer and at least one ethylene-1-octene copolymer, wherein the impact polypropylene copolymer and ethylene The weight ratio to the 1-octene copolymer is in the range of 35:65 to 65:35.

  WO 2016/137558 A1 is a roofing film of 10 to 50% by weight of propylene based elastomer, 5 to 40% by weight of thermoplastic resin, at least one flame retardant and at least one UV stabilizer It relates to a composition.

  U.S. Patent Application No. 15 / 259,750, filed September 8, 2016, relates to a reactor blend composition for roofing applications of 70-95 wt% propylene based elastomer and 5-30 wt% ethylene copolymer .

  There is still a need for roofing membranes, in particular soft (i.e. low modulus) membranes, which demonstrate flexibility at operating temperatures of -40C to 40C and roll blocking resistance at elevated temperatures.

FIG. 6 shows the storage modulus (E ′) of samples C1, C2, 1, 2 and 3.

It is a figure which shows the storage elastic modulus (E ') of sample C3, C4, C4, 5 and 6. FIG.

It is a figure which shows the storage elastic modulus (E ') of the samples C1, C2, and 7.

It is a figure which shows the storage elastic modulus (E ') of sample C3, C4 and 8.

  Provided herein is a propylene based elastomeric blend composition, which is weight based on a propylene based elastomeric blend having an ethylene content of about 17 wt% or more to about 20 wt% or less. By about 70% to about 95% by weight of the first propylene-based elastomer component; and based on the weight of the propylene-based elastomer blend having an ethylene content of about 6% by weight to about 20% by weight. About 5% to about 30% by weight of the second propylene-based elastomer component is included.

  Provided herein is a propylene based elastomeric blend composition, which comprises the weight of a propylene based elastomeric blend having an ethylene content of about 10 wt% or more to about 13 wt% or less. About 70% to about 95% by weight of the first propylene-based elastomer component based on weight; and weight based on the propylene-based elastomer blend having an ethylene content of about 6% to about 20% by weight or less And about 5% to about 30% by weight of the second propylene-based elastomer component.

  Provided herein is a membrane composition comprising about 20% to about 50% by weight of a propylene based elastomeric blend, wherein the membrane composition comprises (i) at least about 10% by weight About 70% to about 95% by weight of the first propylene-based elastomer component, based on the weight of the propylene-based elastomer blend, having an ethylene content of about 20% or less by weight, and (ii) about 6% by weight About 5 wt% to about 30 wt% of a second propylene-based elastomeric component, based on the weight of the propylene-based elastomeric blend, having an ethylene content of greater than or equal to about 20 wt% or less; About 20% to about 40% by weight of a thermoplastic resin; at least one magnesium hydroxide masterbatch; and at least one ultraviolet light stabilizer

  Various specific embodiments and versions of the present invention are now described, including preferred embodiments and the definitions adopted herein. Although the following detailed description of the invention gives specific preferred embodiments, those skilled in the art will understand that these embodiments are for illustration only and that the present invention can be practiced in other ways. I will. Any reference to the "invention" may refer to one or more but not necessarily all of the embodiments defined by the claims. The use of titles is for convenience only and does not limit the scope of the invention.

  Described herein is a composition comprising a propylene based elastomer suitable for roofing applications, in particular roofing membranes. In a preferred embodiment, the composition comprises a propylene based elastomer which is a reactor blended polymer as described herein. In a preferred embodiment, the composition further comprises a polyalphaolefin. The composition provides a balance of properties over a wide range of temperatures. For example, the composition exhibits flexibility at temperatures of -40 ° C to 40 ° C and improved properties at elevated temperatures.

  All numerical values within the detailed description of the invention of the present specification and claims are modified by the values "about" or "approximate", and experimental error that would be expected by a person skilled in the art And variables are taken into account.

  The term "copolymer" as used herein is intended to include polymers having two or more monomers, optionally also having other monomers, including interpolymers, terpolymers, etc. There is also something to say. The term "polymer" as used herein includes, but is not limited to, homopolymers, copolymers, terpolymers, etc., and alloys and blends thereof. The term "polymer" as used herein also includes impact, block, graft, random and alternating copolymers. The term "polymer" is further intended to encompass all possible geometrical configurations, unless stated otherwise. Such arrangements include isotactic, syndiotactic and atactic symmetries. The term "blend" as used herein refers to a mixture of two or more polymers. The term "elastomer" is intended to mean any polymer that exhibits some degree of elasticity, which refers to the material that was being deformed by a force (e.g. stretching force) to its original dimensions when the force is removed. The ability to at least partially return.

  As used herein, the terms "monomer" or "comonomer" can refer to the monomer used to form the polymer, ie, unreacted chemical compound in the form prior to polymerization, and It may also refer to the monomer after it has been incorporated into the polymer, in the latter case also referred to herein as "[monomer] derived unit". Various monomers, such as propylene monomers, ethylene monomers and diene monomers are discussed herein.

  As used herein, "reactor grade" means a polymer that has not been chemically or mechanically treated or blended after polymerization in an attempt to alter the average molecular weight, molecular weight distribution or viscosity of the polymer. . Particularly excluded from such polymers, which are described as reactor grade, are those which have been visbroken, or otherwise treated or coated with a prodegradant such as peroxide. However, for purposes of the present disclosure, reactor grade polymers include polymers that are reactor blends.

As used herein, “reactor blend” refers to polymerization of one or more monomers sequentially or in parallel as a result of one polymer being formed in the presence of another In-situ) means a mechanically inseparable blend in which two or more polymers are dispersed in a highly dispersed manner, by solution blending polymers produced separately or prepared separately in parallel reactors. Reactor blends may be produced in single reactors, in-line reactors or in parallel reactors, which are reactor grade blends. The reactor blend may be manufactured by any polymerization method, such as batch, semi-continuous or continuous equipment. Particularly excluded from “reactor blend” polymers are polymers that are ex situ, eg, two or more physically or mechanically blended in a mixer, extruder or other similar device It is a blend of polymers.
Propylene-based elastomer

The polymer blends described herein comprise one or more propylene based elastomers ("PBE"). The PBE comprises propylene, about 5 to about 30% by weight of one or more comonomers selected from ethylene and / or C ₄ -C ₁₂ α-olefins and optionally one or more dienes . For example, the comonomer units may be derived from ethylene, butene, pentene, hexene, 4-methyl-1-pentene, octene or decene. In a preferred embodiment, the comonomer is ethylene. In some embodiments, an elastomeric composition based on propylene consists essentially of propylene and ethylene derived units, or consists only of propylene and ethylene derived units. In some embodiments described below, ethylene is discussed as a comonomer, but these embodiments are equally applicable to other copolymers with other higher alpha-olefin comonomers. In this regard, the copolymer may be referred to simply as PBE, referring to ethylene as the alpha-olefin.

  PBE is at least about 5% by weight, at least about 7% by weight, at least about 9% by weight, at least about 10% by weight, at least about 12% by weight, at least about 13% by weight, at least about 14% by weight based on the total weight of PBE. %, At least about 15% by weight, or at least about 16% by weight of alpha-olefin derived units. PBE is up to about 30 wt%, up to about 25 wt%, up to about 22 wt%, up to about 20 wt%, up to about 19 wt%, up to about 18 wt%, or about 17 wt% based on the total weight of PBE. It may contain up to% α-olefin derived units. In some embodiments, PBE is about 5 to about 30 wt%, about 6 to about 25 wt%, about 7 wt% to about 20 wt%, about 10 to about 19 wt%, based on the total weight of PBE. About 12 wt% to about 19 wt%, or about 15 wt% to about 18 wt%, or 16 wt% to about 18 wt% of alpha-olefin derived units may be included.

  PBE is at least about 70%, at least about 75%, at least about 78%, at least about 80%, at least about 81%, at least about 82% or at least 83% by weight based on the total weight of PBE. Of propylene-derived units. PBE is up to about 95 wt%, up to about 93 wt%, up to about 91 wt%, up to about 90 wt%, up to about 88 wt%, or up to about 87 wt%, or about 86 wt% based on the total weight of PBE. Up to weight percent, or up to about 85 weight percent, or up to about 84 weight percent propylene derived units may be included.

  PBE can be characterized by a melting point (Tm), which can be measured by differential scanning calorimetry (DSC). Using the DSC test method described herein, the melting point corresponds to the largest heat absorption peak in the range of the melting temperature of the sample as the sample is continuously heated at a programmed rate. It is the recorded temperature. If a single melting peak is observed, that peak is considered to be the "melting point". If multiple peaks (e.g. main and secondary peaks) are observed, the melting point is considered to be the largest of those peaks. It is noted that the melting point peak may be at a low temperature and may be relatively flat, making it difficult to determine the exact peak position, as many PBEs have a low degree of crystallinity. "Peak" in this context means that when the DSC curve (heat flow vs. temperature curve) is plotted as the endothermic reaction is shown as a positive peak, the overall slope of the DSC curve is the baseline It is defined as a change point that changes from positive to negative without change and forms a maximum value.

  The PBE Tm (first melt measured by DSC) is less than about 120 ° C., less than about 115 ° C., less than about 110 ° C., less than about 105 ° C., less than about 100 ° C., less than about 90 ° C., less than about 80 ° C. It may be less than about 70 ° C., less than about 65 ° C., or less than about 60 ° C. In some embodiments, the PBE may have a Tm of about 20 to about 110 ° C., about 30 to about 110 ° C., about 40 to about 110 ° C., or about 50 to about 105 ° C., with any desired range. The range from the lower limit to any upper limit may be included. In some embodiments, PBE may have a Tm of about 40 to about 70 ° C., or about 45 to about 65 ° C., or about 50 to about 60 ° C., and the desired range is from any lower limit to any upper limit You may include the range to. In some embodiments, PBE may have a Tm of about 80 to about 110 ° C., or about 85 to about 110 ° C., or about 90 to about 105 ° C., and the desired range is from any lower limit to any upper limit You may include the range to.

  The procedure of DSC used herein to measure Tm is as follows. The polymer is press molded in a heated press at a temperature of about 200 ° C. to about 230 ° C., and the resulting polymer sheet is annealed and cooled in the atmosphere under ambient conditions of about 23.5 ° C. About 6-10 mg of polymer sheet is cut out using a punch die. The 6-10 mg sample is annealed at room temperature (about 23.5 ° C.) for about 80-100 hours. At the end of this period, the sample is placed in a DSC (Perkin Elmer Pyris One Thermal Analysis System), cooled to about -30 ° C to about -50 ° C and held at -50 ° C for 10 minutes. The sample is then heated at 10 ° C / min to reach a final temperature of about 200 ° C. The sample is held at 200 ° C. for 5 minutes. This is the first melting. Next, a second cooling-heating cycle (to obtain a second melt) is performed where the sample is cooled to about -30 ° C to about -50 ° C and held at -50 ° C for 10 minutes, and then Reheated to a final temperature of about 200 ° C. at 10 ° C./min. Unless otherwise stated, Tm and Hf as referred to herein refer to the first melting.

  PBE is characterized by its percent crystallinity, measured by x-ray diffraction, also known as wide angle x-ray scattering (WAXS). The PBE may have a percent crystallinity of at least about 0.5, at least about 1.0, or at least about 1.5. PBE may be characterized by a percent crystallinity of less than about 2.0, less than about 2.5, or less than about 3.0. For polyethylene and polyethylene copolymers, WAXS can be used to probe the semi-crystalline nature of these materials. Polyethylene forms crystals which are orthorhombic in nature with unit cell sizes: a = 7.41 Å, a = 4.94 Å, a = 2.55 Å and α = β = γ = 90 °. The unit cells of the polyethylene crystals are then stacked together to form crystallites, and the planes of these crystals then diffract incident X-rays. The plane of the crystal that diffracts X-rays is characterized by its Miller index (hkl), and in the case of polyethylene, the three main diffraction planes appearing as peaks in the WAXS pattern are (110), (200) and (020) . The total range of crystallinity for these materials is calculated from the area under each (hkl) value divided by the area of the entire WAXS trace. The minimum range of crystallinity required to observe crystals using the WAXS technique is about 0.5% by volume.

  Preferably, PBE has crystalline regions interrupted by non-crystalline regions. Amorphous regions may be derived from regions of propylene segments that are not crystallizable, incorporation of comonomer units, or both. In one or more embodiments, PBE has a degree of crystallinity derived from propylene, which is isotactic, syndiotactic, or a combination thereof. In a preferred embodiment, PBE has an isotactic linkage. The presence of the isotactic chain can be determined by NMR measurements which show two or more propylene derived units arranged isotactically. In some cases, such isotactic chains are interrupted by propylene units that are not arranged isotactically, or by other monomers that otherwise interfere with the degree of crystallinity derived from isotactic chains. There is something to be done. In addition to differences in stereoregularity, PBE polymers may also have regiospecific defect structures.

PBE is a triad stereoregularity of three propylene units (measured by ¹³ C NMR at 75% or more, 80% or more, 85% or more, 90% or more, 92% or more, 95% or more, or 97% or more) mmm stereoregularity). In one or more embodiments, the triad stereoregularity is about 75 to about 99%, about 80 to about 99%, about 85 to about 99%, about 90 to about 99%, about 90 to about 97% or about 80 It may be in the range of-about 97%. Triad stereoregularity is measured by the method described in US Pat. No. 7,232,871.

PBE may have a stereoregularity index m / r ranging from a lower limit of 4 or 6 to an upper limit of 8 or 10 or 12. The stereoregularity index, expressed herein as "m / r", is measured by ¹³ C nuclear magnetic resonance ("NMR"). The stereoregularity index m / r is described in Macromolecules, Vol. 17, pp. 1950 to 1955 (1984). N. Calculated as defined by Cheng, which is incorporated herein by reference. The symbols "m" or "r" describe the stereochemistry of a pair of consecutive propylene groups, "m" representing meso and "r" representing racemate. An m / r ratio of 1.0 generally describes syndiotactic polymers, and an m / r ratio of 2.0 describes atactic materials. Isotactic materials may theoretically have ratios approaching infinity, and many atactic polymer byproducts have sufficient isotactic content to provide a ratio of greater than 50.

The comonomer content and chain distribution of the polymer can be measured using ¹³ C nuclear magnetic resonance (NMR) by methods well known to the person skilled in the art. The comonomer content of the discrete molecular weight range is a method well known to the person skilled in the art, for example Fourier transform infrared with a sample by GPC as described in Wheeler and Willis, Applied Spectroscopy, 1993, 47, 1128-1130. It can be measured using spectroscopy (FTIR). In the case of propylene-ethylene copolymers containing more than 75% by weight of propylene, the comonomer content (ethylene content) of such polymers can be measured as follows: Thin homogeneous films are above about 150 ° C. And pressed into a Perkin Elmer PE 1760 infrared spectrophotometer. 600cm full spectrum of the sample ^{-1 ~4000cm -1} is recorded, can be the monomer weight percent of ethylene can be calculated by the following equation: Ethylene wt% = 82.585-111.987X + 30.045X ^2. In this equation, X is the ratio of the peak height at 1155 cm ^{−1 to} the peak height at either 722 cm ⁻¹ or 732 cm ⁻¹ , whichever is higher. In the case of propylene ethylene copolymers having a propylene content of 75% by weight or less, the comonomer (ethylene) content can be measured using the procedure described in the Wheeler and Willis literature. Reference is made to US Pat. No. 6,525,157, which contains more details on the determination of ethylene content by measurement of GPC, measurement of NMR and DSC.

PBE is, ASTM D-1505 of about 0.84 g / cm ³ at room temperature as measured by the test method to about 0.92 g / cm ^3, from about 0.85 g / cm ³ to about 0.90 g / cm ³ or from about 0 may have a density of .85g / cm ³ ~ about 0.87 g / cm ^3, a desirable range may include a range of from any lower limit to any upper limit.

  PBE has a melt index (MI) of about 10 g / 10 min or less, about 8.0 g / 10 min or less, about 5.0 g / 10 min or less, or about 3.0 g / 10 min or less, or about 2.0 g / 10 min or less ) (ASTM D-1238, 2.16 kg @ 190 ° C). In some embodiments, the PBE may have a MI of about 0.5 to about 3.0 g / 10 min or about 0.75 to about 2.0 g / 10 min, a desirable range being any lower limit May range from any upper limit to any upper limit.

  PBE is an ASTM D of greater than about 0.5 g / 10 min, about 1.0 g / 10 min, about 1.5 g / 10 min, about 2.0 g / 10 min or about 2.5 g / 10 min. It may have a melt flow rate (MFR) measured by -1238 (2.16 kg load @ 230 ° C.). The PBE may have an MFR of less than about 25 g / 10 minutes, less than about 15 g / 10 minutes, less than about 10 g / 10 minutes, less than about 7 g / 10 minutes, or less than about 5 g / 10 minutes. In some embodiments, the PBE may have a MFR of about 0.5 to about 10 g / 10 min, about 1.0 to about 7 g / 10 min, or about 1.5 to about 5 g / 10 min. The desirable range may include a range from any lower limit to any upper limit.

この式で、η_ｂはポリマーの固有粘度であり、η_ｌはそのポリマーと同じ粘度平均分子量（Ｍｖ）の直鎖状ポリマーの固有粘度である。η_ｌ＝ＫＭｖαであり、Ｋおよびαは直鎖状ポリマーについての測定値であり、ｇ’指数測定に使用された測定器と同じ測定器を用いて得られなければならない。 PBE may have a g 'index of greater than or equal to 0.95 or at least 0.97 or at least 0.99, where g' is the Mw of the polymer using the intrinsic viscosity of isotactic polypropylene as a baseline Be done. As used herein, the g 'index is defined as:

In this formula, η _b is the intrinsic viscosity of a polymer and 固有₁ is the intrinsic viscosity of a linear polymer of the same viscosity average molecular weight (Mv) as the polymer. η _l = KM v α, K and α are measurements for linear polymers and must be obtained using the same instruments as those used for g ′ index measurements.

  The PBE may have a Shore D hardness (ASTM D2240) of less than about 50, less than about 45, less than about 40, less than about 35, or less than about 20.

  The PBE may have a Shore A hardness (ASTM D2240) of less than about 100, less than about 95, less than about 90, less than about 85, less than about 80, less than about 75 or less than 70. In some embodiments, PBE may have a Shore A hardness of about 10 to about 100, about 15 to about 90, about 20 to about 80, or about 30 to about 70, with a desirable range being any lower limit. May range from any upper limit to any upper limit.

In some embodiments, PBE is a propylene-ethylene having at least 4 or at least 5 or at least 6 or at least 7 or at least 8 or all 9 of the following properties: Copolymer:
(I) about 10 to about 25 wt%, or about 12 to about 20 wt%, or about 16 wt% to about 17 wt% ethylene-derived units, based on the weight of PBE;
(Ii) a Tm of 80 to about 110 ° C., or about 85 to about 110 ° C., or about 90 to about 105 ° C .;
(Iii) less than about 75 J / g, or less than 50 J / g, or less than 30 J / g, or about 1.0 to about 15 J / g, or about 3.0 to about 10 J / g of Hf;
(Iv) MI of about 0.5 to about 3.0 g / 10 min, or about 0.75 to about 2.0 g / 10 min;
(V) MFR of about 0.5 to about 10 g / 10 min, or 0.75 to about 8 g / 10 min, or about 0.75 to about 5 g / 10 min;
(Vi) about 175,000 to about 260,000 g / mole, or about 190,000 to about 250,000 g / mole, or about 200,000 to about 250,000 g / mole, or about 210,000 to about 240, Mw of 000 g / mol;
(Vii) Mn of about 90,000 to about 130,000 g / mol, or about 95,000 to about 125,000 g / mol, or about 100,000 to about 120,000 g / mol;
(Viii) about 1.0 to about 5, or about 1.5 to about 4, or about 1.8 to about 3 MWD; and / or (ix) less than 30, or less than 25, or less than 20 Shore D hardness.
In some embodiments, such PBE is a reactor blended PBE as described herein.

  Optionally, PBE may also contain one or more dienes. The term "diene" is defined as a hydrocarbon compound having two sites of unsaturation, ie a compound having two double bonds connecting carbon atoms. Depending on the context, the term "diene" as used herein is a diene monomer prior to polymerization, such as that which forms part of the polymerization medium, or a diene monomer (diene monomer units or diene-derived after polymerization has already begun) Also referred to as a unit. In some embodiments, the diene is 5-ethylidene-2-norbornene (ENB); 1,4-hexadiene; 5-methylene-2-norbornene (MNB); 1,6-octadiene; 5-methyl-1, 4-hexadiene; 3,7-dimethyl-1,6-octadiene; 1,3-cyclopentadiene; 1,4-cyclohexadiene; vinyl norbornene (VNB); dicyclopentadiene (DCPD) and combinations thereof It is also good. In embodiments where the propylene-based polymer comprises a diene, the diene is 0.05 wt% to about 6 wt%, about 0.1 wt% to about 5.0 wt%, based on the total weight of PBE. About 0.25 wt% to about 3.0 wt% or about 0.5 wt% to about 1.5 wt% of diene derived units may be present.

  Optionally, PBE may be grafted (i.e. "functionalized") using one or more grafting monomers. The term "grafting" as used herein means that the grafting monomer is covalently attached to the polymer chain of the propylene-based polymer. The grafting monomer can be or include at least one ethylenically unsaturated carboxylic acid or acid derivative such as an acid anhydride, ester, salt, amide, imide, acrylate, and the like. Exemplary grafting monomers include, but are not limited to: acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohexene -1, 2-dicarboxylic acid anhydride, bicyclo (2.2.2) octene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2 , 3-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro (4.4) nonene, bicyclo (2.2.1) heptene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophthalic anhydride , Norbornene-2,3-dicarboxylic anhydride, nadic anhydride, methyl nadic anhydride, hymic anhydride, methyl hymic anhydride Preliminary 5- methyl bicyclo (2.2.1) heptene-2,3-dicarboxylic anhydride. Other suitable grafting monomers include methyl acrylate and higher alkyl acrylates, methyl methacrylate and higher alkyl methacrylates, acrylic acid, methacrylic acid, hydroxymethyl methacrylate, hydroxyethyl methacrylate and hydroxy higher alkyl methacrylates and methacrylates. Acid glycidyl is mentioned. Maleic anhydride is a preferred grafting monomer. In embodiments where the grafting monomer is maleic anhydride, the maleic anhydride concentration in the grafted polymer preferably ranges from about 1% to about 6% by weight, at least about 0.5% by weight or at least about 1. It is 5% by weight.

  In a preferred embodiment, PBE is a reactor grade or reactor blended polymer as defined above. That is, in a preferred embodiment, PBE is a reactor blend of a first polymer component and a second polymer component. Thus, the comonomer content of PBE may be adjusted by adjusting the comonomer content of the first polymer component, by adjusting the comonomer content of the second polymer component, and / or the first one present in the PBE. It can be adjusted by adjusting the ratio of the polymer component to the second polymer component.

In embodiments PBE is a polymer which is a reactor blend, alpha-olefin content of the first polymer component ( "R _1") is 5 wt.% Based on the total weight of the first polymer component, 7 weight %, 10%, 12%, 15% or 17% by weight. The alpha-olefin content of the first polymer component is less than 30% by weight, less than 27% by weight, less than 25% by weight, less than 22% by weight, less than 20% by weight or 19 based on the total weight of the first polymer component. It may be less than% by weight. In some embodiments, the alpha-olefin content of the first polymer component is 5% to 30%, 7% to 27%, 10% to 25%, 12% to 22% by weight. %, 15 wt.% To 20 wt.%, Or 17 wt.% To 19 wt.%. Preferably, the first polymer component comprises propylene derived units and ethylene derived units, or consists essentially of propylene derived units and ethylene derived units.

In embodiments PBE is a polymer which is a reactor blend, alpha-olefin content of the second polymer component ( "R _2") is 1.0 wt.% Based on the total weight of the second polymer component, It may be more than 1.5 wt%, more than 2.0 wt%, more than 2.5 wt%, more than 2.75 wt% or more than 3.0 wt% α-olefin. The alpha-olefin content of the second polymer component is less than 10% by weight, less than 9% by weight, less than 8% by weight, less than 7% by weight, less than 6% by weight or 5 based on the total weight of the second polymer component It may be less than% by weight. In some embodiments, the alpha-olefin content of the second polymer component is 1.0 wt% to 10 wt%, 1.5 wt% to 9 wt%, or 2.0 wt% to 8 wt% or The 2.5 wt% to 7 wt% or 2.75 wt% to 6 wt% may range from 3 wt% to 5 wt%. Preferably, the second polymer component comprises units derived from propylene and units derived from ethylene, or consists essentially of units derived from propylene and units derived from ethylene.

  In embodiments where PBE is a reactor blended polymer, PBE is 1 to 25 wt% of the second polymer component, 3 to 20 wt% of the second polymer component, 5 to 18 wt% based on the weight of PBE. % Of the second polymer component, 7 to 15% by weight of the second polymer component or 8 to 12% by weight of the second polymer component, and the desired range is from any lower limit to any upper limit It may include a range. PBE is 75-99% by weight of the first polymer component, 80-97% by weight of the first polymer component, 85-93% by weight of the first polymer component or 82-92% by weight based on the weight of PBE. The desired range may include a range from any lower limit to any upper limit.

  PBE is preferably prepared using uniform conditions, such as a continuous solution polymerization process. In some embodiments, PBE is prepared as follows in parallel solution polymerization reactors. That is, the first reactor component is prepared in the first reactor, the second reactor component is prepared in the second reactor, and the reactor effluents from the first and second reactors are combined and blended together. A single reactor effluent is formed, from which the final PBE is separated. Typical methods for preparing PBE are described in U.S. Patent Nos. 6,881,800, 7,803,876, 8,013,069 and 8,026,323 and WO Application No. WO 2011/087729, WO 2011/087730 and WO 2011/087311 can be found, the contents of which are incorporated herein by reference.

この式で、Ｍ、Ｘ、Ｎ、Ｒ^５１、Ｒ^５２、Ｒ^５４、Ｒ^５５、Ｒ^６１〜Ｒ^６６は、式（６）および（６ａ）として既に定義され；Ｒ^７０およびＲ^７１はそれぞれ、水素、ヒドロカルビル、置換ヒドロカルビル、アルコキシ、アリールオキシ、ハロゲン、アミノおよびシリルから成る群から独立して選ばれ、任意の１種以上の隣接するＲ^７０〜Ｒ^７１は連結されて置換または非置換のヒドロカルビルまたは複素環状の環を形成してもよく、その環は５、６、７または８個の原子を有し、その環上の置換基は連結して追加の環を形成することができ；ｔは（シクロペンチルおよびシクロヘキシル環にそれぞれ対応して）２または３である。 Preferably, the first reactor component of PBE is prepared by metallocene catalyst or prepared by pyridyldiamide catalyst, and the second reactor component of PBE is prepared by metallocene catalyst. If the second reactor component is prepared with a metallocene catalyst, the metallocene catalyst may be the same as or different from the catalyst used to prepare the first reactor component. Preferably, it is the same catalyst. When the first reactor component is prepared with pyridyldiamide catalyst, it has the following structural formula:

In this formula M, X, N, R ⁵¹ , R ⁵² , R ⁵⁴ , R ⁵⁵ , R ^{61 to} R ⁶⁶ are already defined as formulas (6) and (6a); R ⁷⁰ and R ⁷¹ are each It is independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, aryloxy, halogen, amino and silyl, and any one or more adjacent R ^{70 to} R ⁷¹ are linked and substituted or unsubstituted hydrocarbyl Or it may form a heterocyclic ring, which ring has 5, 6, 7 or 8 atoms, and substituents on the ring may be linked to form an additional ring; t Is 2 or 3 (corresponding to cyclopentyl and cyclohexyl rings respectively).

In an embodiment of the present invention, R ^{61 to} R ⁶⁶ are hydrogen.

In an embodiment of the present invention, R ⁷⁰ and R ⁷¹ are each independently hydrogen and t is 2 or 3, preferably 2.

In an embodiment of the present invention, R ⁵⁴ and R ⁵⁵ are each independently hydrogen, an alkyl group or an aryl group or a substituted aryl group; preferably, one or both of R ⁵⁴ or R ⁵⁵ is hydrogen, or One of R ⁵⁴ or R ⁵⁵ is hydrogen, and the other is an aryl group or a substituted aryl group. Preferred aryl groups include, but are not limited to, phenyl and 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl and naphthyl.

In an embodiment of the present invention, R ⁵² and R ⁵¹ are independently aryl or substituted aryl; preferably, R ⁵¹ is a substituted phenyl group, such as 2,6-diisopropylphenyl, 2,6-diethylphenyl, 2 , 6-dimethylphenyl, mesityl and the like, but is not limited thereto, and preferably R ⁵² is a phenyl group or a substituted phenyl group such as 2-tolyl, 2-ethylphenyl, 2-propylphenyl, Fluoromethylphenyl, 2-fluorophenyl, mesityl, 2,6-diisopropylphenyl, 2,6-diethylphenyl, 2,6-dimethylphenyl, 3,5-di-tert-butylphenyl etc., but limited thereto I will not.

In an embodiment of the present invention, R ⁵⁴ , R ⁵⁵ , R ^{61 to} R ⁶⁶ , each R ⁷⁰ and R ⁷¹ is hydrogen, R ⁵² is phenyl, R ⁵¹ is 2,6-diisopropylphenyl, t Is two.

Non-limiting examples of pyridyldiamide catalysts that are chelated transition metal complexes (type 3) are exemplified below, and X is methyl, benzyl or chloro:

  Further particularly useful chelated transition metal complexes (type 3), such as pyridyldiamide transition metal complexes, are disclosed in U.S. Pat. No. 134615, WO 2012/134613, U.S. Patent Application Publication Nos. 2012/0071616, 2011/030310, and 2010/0022726, the contents of which are incorporated herein by reference.

PBE suitable for use in the present invention is VistamaxxTM polymer commercially available from ExxonMobil Chemical Company. The invention is not limited to the use of VistamaxxTM as PBE.
Thermoplastic resin

  The compositions described herein may comprise one or more olefinic thermoplastic resins. The "olefinic thermoplastic resin" may be any material that is not the "propylene-based elastomer" or the "ethylene-based polymer" described herein. For example, the thermoplastic resin may be a polymer or polymer blend that is considered by those skilled in the art to be inherently thermoplastic, such as a polymer that softens when exposed to heat and returns to its original state when cooled to room temperature. It may be. The olefinic thermoplastic resin component may comprise one or more polyolefins, such as polyolefin homopolymers or polyolefin copolymers. Unless otherwise specified, the term "copolymer" means a polymer (including terpolymers, tetrapolymers, etc.) derived from two or more monomers, and the term "polymer" is one or more different This refers to any carbon-containing compound having repeating units from monomers.

  Illustrative polyolefins are monoolefin monomers, for example monomers having 2 to 7 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 3-methyl-. It may be prepared from 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, mixtures thereof and copolymers thereof, but is not limited thereto. Preferably, the olefinic thermoplastic resin is not vulcanized or crosslinked.

In a preferred embodiment, the olefinic thermoplastic resin comprises or consists of polypropylene. As used herein, the term "polypropylene" refers broadly to any polymer considered by the person skilled in the art as "polypropylene" and includes homo, impact and random copolymers of propylene. Preferably, the polypropylene used in the composition described herein has a melting point above 110 ° C. and contains at least 90% by weight of propylene derived units. The polypropylene may also comprise isotactic, atactic or syndiotactic chains, preferably comprising isotactic chains. Polypropylene is derived exclusively from propylene monomers (ie, having only propylene derived units), or at least 90% by weight or at least 93% by weight or at least 95% by weight or at least 97% by weight or at least 98% by weight or at least 99% by weight of units derived from propylene, the remainder being derived from olefins, such as ethylene and / or C ₄ -C ₁₀ α-olefins.

  The olefinic thermoplastic resin may have a melting temperature of at least 110 ° C., or at least 120 ° C., or at least 130 ° C. as measured by DSC, and the melting temperature may be in the range of 110 ° C. to 170 ° C. or more.

  The thermoplastic resin may have a melt flow rate "MFR" measured by ASTM D 1238 at 230 ° C. and a 2.16 kg load of about 0.1 to 100 g / 10 min. In some embodiments, the thermoplastic resin may have a very small MFR, such polypropylene may be less than about 2 g / 10 min, or less than about 1.5 g / 10 min, or about 1 g / 10 min. It has a very small MFR of less than a minute. In some embodiments, the thermoplastic resin is about 37, 38, 39, 40, 41, 42, 43, from a lower limit of about 25, 26, 27, 28, 29, 30, 31, 32 or 33 g / 10 min. It may have an MFR up to an upper limit of 44 or 45 g / 10 min, and a desirable range may include a range from any lower limit to any upper limit. In some embodiments, the thermoplastic resin, eg, polypropylene, may have a MFR from a lower limit of about 5, 10 or 15 g / 10 min to an upper limit of about 20, 25 or 30 g / 10 min, a desirable range May include a range from any lower limit to any upper limit.

A thermoplastic resin suitable for use in the present invention is the propylene homopolymer PP7032 commercially available from ExxonMobil Chemical. The present invention is not limited to the use of PP7032 as a thermoplastic resin.
Fillers and additives

  The compositions described herein may also incorporate various additives. Additives include reinforcing and non-reinforcing fillers, antioxidants, stabilizers, processing oils, compatibilizers, lubricants (eg oleamide), antiblocking agents, antistatic agents, waxes, fillers and / or pigments Coupling agents, pigments, flame retardants, antioxidants and other processing aids known in the art. In some embodiments, the additive may comprise up to about 65% by weight, or up to about 60% by weight, or up to about 55% by weight, or up to about 50% by weight of the roofing composition. In some embodiments, the additive is at least 5%, or at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30% by weight of the roofing composition. Alternatively, it may constitute at least 35% by weight, or at least 40% by weight.

  In some embodiments, the roofing composition may include fillers and colorants. Typical materials include inorganic fillers such as calcium carbonate, clay, silica, talc, titanium dioxide or carbon black. Any type of carbon black can be used, such as channel black, furnace black, thermal black, acetylene black, lamp black and the like.

  In some embodiments, the roofing composition may include a flame retardant such as calcium carbonate, an inorganic clay containing water of hydration, such as trihydrated alumina ("ATH") or magnesium hydroxide. For example, calcium carbonate or magnesium hydroxide may be preblended in the masterbatch with a thermoplastic resin such as polypropylene or polyethylene, for example linear low density polyethylene. For example, the flame retardant may be preblended with polypropylene, impact polypropylene-ethylene copolymer or polyethylene, in which case the masterbatch is at least 40 wt%, or at least 45 wt%, or at least 45 wt% based on the weight of the masterbatch. 50% by weight, or at least 55% by weight, or at least 60% by weight, or at least 65% by weight, or at least 70% by weight, or at least 75% by weight of a flame retardant. The flame retardant masterbatch may then constitute at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt% of the roofing composition. In some embodiments, the roofing composition comprises 5 wt% to 40 wt%, or 10 wt% to 35 wt%, or 15 wt% to 30 wt% of the flame retardant masterbatch, with a desirable range being A range from any lower limit to any upper limit may be included.

  In some embodiments, the roofing composition may comprise a UV stabilizer such as titanium dioxide or TinuvinTM XT-850. UV stabilizers may be introduced into the roofing composition as part of a masterbatch. For example, the UV stabilizers may be preblended in the masterbatch with a thermoplastic resin, such as polypropylene or polyethylene, for example linear low density polyethylene. For example, the UV stabilizer may be pre-blended with polypropylene, impact polypropylene-ethylene copolymer or polyethylene, in which case the masterbatch is at least 5% by weight, or at least 7% by weight based on the weight of the masterbatch, or At least 10% by weight, or at least 12% by weight, or at least 15% by weight of a UV stabilizer. The UV stabilizer masterbatch may then constitute at least 5 wt%, or at least 7 wt%, or at least 10 wt%, or at least 15 wt% of the roofing composition. In some embodiments, the roofing composition comprises 5 wt% to 30 wt%, or 7 wt% to 25 wt%, or 10 wt% to 20 wt% of a UV stabilizer masterbatch, the preferred range being A range from any lower limit to any upper limit may be included.

Still other additives may include antioxidants and / or heat stabilizers. In an exemplary embodiment, IRGANOXTM B-225 and / or IRGANOXTM 1010, which are commercially available from BASF, may be mentioned as thermal stabilizers during processing and / or use.
Roofing composition

  The roofing compositions described herein are particularly useful for roofing applications, such as thermoplastic polyolefin roofing membrane applications. Films produced from roofing compositions can exhibit a beneficial combination of properties, in particular flexibility at temperatures of -40 ° C to 40 ° C and high temperatures, for example at temperatures of 40 ° C to 100 ° C. It can show an improved balance with stability.

  The roofing composition described herein may be precompounded or compounded in situ using a polymer manufacturing process such as a Banbury mixer or a twin screw extruder. May be produced by The composition may then be formed into a roofing membrane. Roofing membranes can be particularly useful in commercial roofing applications, for example, on flat, loose-slope or steep-slope substrates.

  The roofing membrane may be fixed on the roofing substrate by any means known in the art, for example by adhesives, ballast materials, spot bonding or mechanical spot fasteners. For example, the roofing membrane may be attached using mechanical fasteners and plates placed along the end sheet and secured through the membrane to be a roof deck. Adjacent flexible membrane sheets may be stacked over fasteners and plates and joined, for example, preferably using hot air welding. The membrane may also be fully bonded or self-bonded to the insulating material or deck material using an adhesive. The insulating material is typically secured to the deck with mechanical fasteners and a flexible membrane is adhered to the insulating material.

  The roofing membrane may be reinforced with any type of scrim, such as polyester, fiberglass, fiberglass reinforced polyester, polypropylene, woven or non-woven textiles (eg nylon) or combinations thereof But not limited thereto. Preferred scrims are fiberglass and / or polyester.

  In some embodiments, the surface layer on the top and / or bottom of the membrane may be roughened in various patterns. The rough texture increases the surface area of the membrane, reduces glare and makes the membrane surface less slippery. Examples of texture styles include polyhedra with polygonal bases and triangular faces tangent at a common vertex, such as pyramidal bases; conical arrangements with circular or elliptical arrangements; and random pattern arrangements However, it is not limited to these.

  Useful roofing membranes may have a thickness of 0.1 to 5 mm or 0.5 to 4 mm.

The roofing film composition described herein comprises a blend composition of a propylene-based elastomer, a thermoplastic resin, at least one flame retardant, and at least one UV light stabilizer. In some embodiments, the blend composition further comprises a polyalphaolefin.
[Example]

  The following non-limiting examples are provided to provide a better understanding of the foregoing discussion. Although these examples may be directed to particular embodiments, they should not be considered as limiting the invention in any particular respect. All parts, percentages and percentages are by weight unless otherwise indicated.

The test methods used in the examples are shown in Table 1 below.

  Dynamic mechanical thermal analysis ("DMTA") tests were performed on the samples produced in the examples to provide information about the small strain mechanical response of the sample as a function of temperature. Samples The samples were tested using a commercially available DMA instrument (eg, TA Instruments DMA 2980 or Rheometrics RSA) equipped with a dual cantilever test apparatus. The sample was cooled to -70 ° C and then heated to 100 ° C at a rate of 2 ° C / min while being subjected to oscillatory deformation at a strain of 0.1% and a frequency of 6.3 radians / sec. The outputs of the DMTA test are the storage modulus (E ') and the loss modulus (E "). The storage modulus indicates the elastic response, ie the ability of the material to store energy, the loss modulus is the viscous response, ie Indicates the ability of the material to dissipate energy.

  "PP 7032" is ExxonMobil (TM) PP 7032E2, a polypropylene available from ExxonMobil Chemical Company. PP7032 is a polypropylene impact copolymer with a density of 0.9 g / cc and a melt mass flow rate (MFR) (230 ° C., 2.16 kg) of 4.0 g / 10 min (ASTM D 1238).

  Polymer A of the Comparative Example is a propylene based elastomer containing 16 wt% ethylene derived units and 3 g / 10 min (ASTM D 1238) melt mass flow rate (MFR) (230 ° C., 2.16 kg).

  Comparative polymer B is a propylene based elastomer containing 17 wt% ethylene derived units and 3 g / 10 min (ASTM D 1238) melt mass flow rate (MFR) (230 ° C., 2.16 kg).

  "EXACT (R) 9061" is a plastomer available from ExxonMobil Chemical Company. EXACTTM 9061 is an ethylene-butene plastomer having a melt index (190 ° C., 2.16 kg) of 0.55 g / 10 min and a density of 0.863 g / cc. The formulation of the comparative example contains EXACT9061.

  The magnesium hydroxide masterbatch used in the examples is described in J. M. Vertex 60 HST from Huber. It contains 70% by weight magnesium hydroxide and 30% by weight polypropylene impact copolymer AdflexTM KS 311 P from Lyondell Basell.

  The white concentrate masterbatch used in the examples contains more than 50% by weight of titanium dioxide, the balance being polypropylene homopolymer.

  The UV stabilizer masterbatch used in the examples is a masterbatch comprising a UV stabilizer additive, titanium dioxide as a white pigment and a carrier resin, this masterbatch having a density of 1.04 g / cc. Was.

In the examples, polymers A and B of the comparative examples are propylene-ethylene copolymers of the comparative example prepared with a metallocene catalyst in two reactors. The catalyst used to prepare the polymers of all the comparative examples is 1,1′-bis (4-triethylsilylphenyl) methylene- (cyclopentadienyl) (2,7-di-tert-butyl-9- The fluorenyl) hafnium dimethyl and the activator is dimethylanilinium tetrakis (pentafluorophenyl) borate. Comparative polymers A and B were polymerized by the process described herein. The copolymerization was carried out in a single-phase, liquid-filled, stirred tank reactor, the feed was fed to the apparatus in a continuous stream and the product was withdrawn continuously under equilibrium conditions. All polymerizations, using a non-coordinating borate anion individuality as a soluble metallocene catalyst and cocatalyst were mainly carried out in a solvent comprising a C ₆ alkane. Tri-n-octylaluminum was used as a scavenger at an appropriate concentration to maintain the reaction. Hydrogen was added as needed to control molecular weight. Hexane solvent was purified on a bed of 3A molecular sieves and basic alumina. All feedstocks except ethylene were pumped into the reactor by the metering pump and ethylene was flowed as a gas through the mass flow meter / regulator. The reactor temperature was adiabatically controlled by controlled cooling of the feedstock and using the heat of polymerization to heat the reactor. The reactor was maintained at a pressure above the vapor pressure of the reactant mixture to maintain the reactant in the liquid phase. In this way, the reactor was operated with a uniform single phase liquid fill. The ethylene and propylene feeds were combined into one stream and then mixed with the precooled solvent stream. The mixture of catalyst components in the solvent was sent separately to the reactor and put through separate ports. The reaction mixture was vigorously stirred to achieve complete mixing over a wide range of solution viscosity. The flow rate was set such that the average residence time in the reactor was maintained at about 10 minutes. After leaving the reactor, the copolymer mixture was subjected to a quenching step, a series of concentration steps, heating and vacuum stripping and pelletizing. These general conditions are described in International Patent Application Publication WO 99/45041, the contents of which are hereby incorporated by reference in their entirety.

  In the examples, P1 to P4 were metallocene catalyzed copolymers of propylene and ethylene prepared in a single reactor. The catalyst used for the preparation of P1 to P4 was dimethylsilyl bis (indenyl) hafnium dimethyl and the activator was dimethylaluminum tetrakis (heptafluoronaphthyl) borate. P5 is a pyridyldiamide catalyzed copolymer of propylene and ethylene prepared in a single reactor. The catalyst used to prepare P5 is already disclosed as compound 1 in US Patent Application Publication No. 2015/0141601, the contents of which are incorporated herein by reference, and the activator is dimethylaluminum tetrakis. It is (pentafluorophenyl) borate. P1-P5 were polymerized by the process described herein.

The polymerization was carried out in a continuous stirred tank reactor apparatus. The 1 liter autoclave reactor was equipped with a water / steam heating element equipped with a stirrer, a pressure regulator and a temperature controller. The reactor was operated in liquid fill at a reactor pressure above the bubble point pressure of the reactant mixture to maintain the reactants in the liquid phase. All feeds (solvent and monomers) were fed into the reactor by Pulsa feed pump and flow rates were adjusted using a Coriolis mass flow controller (Quantim series from Brooks, Inc.) except ethylene. Ethylene was flowed as a gas under its own pressure through the Brooks flow controller. Similarly, the H ₂ feed was adjusted using a Brooks flow controller. The ethylene, H ₂ and propylene feeds were combined into one stream and then mixed with the pre-cooled isohexane stream which had already been cooled to at least 0 ° C. This mixture was then fed to the reactor through a single line. A scavenger solution was added to the combined stream of solvent and monomer just prior to entering the reactor to further reduce possible catalyst poisons. Similarly, the activated catalyst solution was fed to the reactor through a separate line using an ISCO syringe pump.

  The polymer produced in the reactor was withdrawn through a back pressure regulator to reduce the pressure to atmospheric pressure. This caused unconverted monomer in solution to flash into the gas phase, which was vented from the top of the gas-liquid separator. A liquid phase containing mainly polymer and solvent was collected for polymer recovery. The collected samples were first air dried in a hood to evaporate most of the solvent and then dried in a vacuum oven at a temperature of about 90 ° C. for about 12 hours. The vacuum oven dried samples were weighed to obtain a yield.

  Isohexane (solvent) and monomers (ethylene and propylene) were purified on a bed of alumina and molecular sieves. The toluene for preparing the catalyst solution was purified by the same procedure. A solution of tri-n-octylaluminum (TNOA) (25 wt% in hexane, Sigma Aldrich) in isohexane was used as a scavenger solution. The pyridyldiamide catalyst was activated with about 1: 1 molar ratio of N, N-dimethylanilium tetrakis (pentafluorophenyl) borate in 900 ml of toluene. rac-Dimethylsilylbis (indenyl) hafnium dimethyl (M1) was activated with about 1: 1 molar ratio of N, N-dimethylanilium tetrakis (heptafluoro-2-naphthyl) borate in 900 ml of toluene.

Detailed polymerization process conditions and some characteristic properties are shown in Table 2. The scavenger feed was adjusted to optimize the catalytic efficiency, and the feed was varied from 0 (no scavenger) to 15 μmol / min. The catalyst feed rate may also be adjusted according to the level of impurities in the system to reach the targeted conversion indicated in the table. All reactions were performed at a pressure of about 2.4 MPa gauge unless otherwise specified. Additional process conditions for P1-P4 polymerization processes and PBE properties are included in Table 2 below.

  The TPO roofing formulation was compounded in a BrabenderTM batch mixer. The batch size was 260 g when compounding in a batch mixer.

  Compounding in the BrabenderTM batch mixer was performed by first cutting the PBE polymer sample into small pieces and introducing it into the preheated mixing chamber. The polymer was fluidized with the other compounding ingredients. After the polymer was fluidized and homogenized, the screw speed of the batch mixer was increased to 50 rpm. Mixing was continued for 3 minutes, after which the batch was discharged from the mixing chamber. The compound from the mixer was manually separated into smaller pieces and allowed to cool under ambient temperature. Formulations prepared with either an extruder or a batch mixer were compression molded into test pieces and evaluated using the appropriate tests and methods shown in Table 1.

In Example 1, samples of the formulations of Table 3 were prepared. The amounts of each component in the formulation are shown in Table 3 in weight percent based on the total weight of the formulation. C1 to C4 are samples of comparative examples, and samples 1 to 6 are examples of the present invention. The resulting samples were tested for various properties and the results are shown in Table 4.

  Table 3 shows TPO formulations comprising commercially available PBE resins and the polymers according to the invention. Formulations C1 and C2 are controls made into formulations using Polymer A of the Comparative Example and Polymer B of the Comparative Example, respectively. Examples 1 and 2 show that the first component (reactor 1) has an ethylene content of 17.6% by weight and 18.6% by weight, respectively, and the second component (reactor 2) is 8.5% by weight Containing a mixture of PBE resins to have an ethylene content of These examples are shown as physical blends to mimic the properties of the two-reactor polymer, where the components of reactor 1 are 90% by weight of the polymer and the components of reactor 2 are polymers 10% by weight of (ie, 90% polymer split ratio). The controls C1 and C2 have the components of the reactor 2 of 5 wt% ethylene, in contrast to the inventive formulation with an ethylene fraction of 8.5 wt% reactor 2. Table 4 shows the characteristics of the comparative example and the example of the present invention. Inventive Examples 1 and 2 have lower flexural modulus compared to the control formulations C1 and C2, respectively. Both tensile stress at break and tensile strain at break of Examples 1 and 2 are respectively higher compared to control formulations C1 and C2.

Control formulations C3 and C4 in Table 3 contain plastomer components (EXACTTM 9061) and have enhanced low temperature properties. Examples 4 and 5 are similar formulations as control examples having a polymer of the present invention. In examples 4 and 5, the flexural modulus is lower compared to the control formulations C3 and C4, respectively. In Example 4, as shown in Table 4, both tensile at break and tensile strain at break are higher compared to control formulations C3 and C4, respectively.

  Figures 1 and 2 show plots of elastic modulus E 'versus temperature. In FIG. 1, both Examples 1 and 2 exhibit similar or lower modulus compared to that of control compound C1 in the temperature range of −40 ° C. to 40 ° C. Example 3 is a formulation containing PBE resin, in which the PBE reactor 1 fraction is 18.6 wt% ethylene and the reactor 2 fraction is 8.5 wt% ethylene. It is. The formulation of Example 3 contains a higher polypropylene impact copolymer content and has a fraction of impact copolymer PP7032 (ICP) at 50% by weight based on the weight of all polymer components. Higher ICP fractions lead to lower compounding costs. In contrast, control formulation C1 and inventive examples 1 and 2 contain 40% ICP, based on the weight of all polymer components. Example 3 with the higher ICP component has equivalent or lower elastic modulus over its temperature range as compared to Control Comparative Example C1. FIG. 2 shows a plot of elastic modulus for a formulation containing a plastomer component. Example 6 with a higher ICP fraction is equivalent or lower in elastic modulus compared to control formulation C4.

In Example 2, samples of the formulations of Table 5 were prepared. The amounts of each component in the formulation are shown in Table 5 in weight percent based on the total weight of the formulation. C1 to C4 are samples of comparative examples, and samples 7 and 8 are samples of the present invention. The resulting samples were tested for various properties and the results are shown in Table 6.

  Table 5 shows TPO formulations comprising commercially available PBE resins and polymers according to the invention. Formulations C1 and C2 are controls formulated with Polymer A of the Comparative Example and Polymer B of the Comparative Example, respectively. Example 7 shows that one component (reactor 1) is synthesized using a pyridyldiamide catalyst and has an ethylene content of 11.9% by weight, while the second component (reactor 2) is dimethylsilylbis (indenyl). 2.) Containing a mixture of PBE so as to be synthesized with a hafnium dimethyl catalyst and having an ethylene content of 8.5% by weight. In both cases, dimethylaluminum tetrakis (heptafluoronaphthyl) borate is used as an activator. These examples are shown as physical blends to mimic the properties of the two-reactor polymer, where the components of reactor 1 are 90% by weight of the polymer and the components of reactor 2 are polymers 10% by weight of In contrast to the inventive formulation, the control compounds C1 and C2 have the components of reactor 2 of 5% by weight of ethylene. As shown in Table 6, Example 7 of the present invention has lower flexural modulus as compared to each of the control formulations C1 and C2. The tensile stress at break and the elongation at break of Example 7 are respectively higher than the control formulations C1 and C2.

  Control formulations C3 and C4 in Table 5 contain plastomer components (EXACTTM 9061) and have enhanced low temperature properties. Example 8 is a formulation similar to the control example having a polymer of the present invention. As shown in Table 6, in Example 8, the flexural modulus is lower compared to each of the control formulations C3 and C4. In Example 8, both tensile at break and tensile strain at break are higher compared to control formulations C3 and C4, respectively.

  Figures 3 and 4 show plots of elastic modulus E 'versus temperature. In FIG. 3, Example 7 exhibits a similar or lower modulus compared to that of Control Compound C1 in the temperature range of -10 ° C to 40 ° C. FIG. 4 shows a plot of elastic modulus for a formulation containing a plastomer component. Example 8 exhibits equivalent or lower modulus in the temperature range of -10 ° C to 40 ° C as compared to control formulation C4.

  Specific embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be understood that ranges from any lower limit to any upper limit are contemplated, unless otherwise specified. All numerical values are those indicated "about" or "approximately" and take into account experimental errors and variances predicted by one skilled in the art.

  As used herein, the phrases "substantially ... not" and "substantially free" refer to the environment where the item of interest is not intentionally used or added in any amount. It is intended to mean that very small amounts present as impurities due to the above or process conditions may be included.

  To the extent that the terms used in the claims are not defined above, it is most likely as reflected in at least one printed publication or issued patent the person skilled in the art gave to the terms A broad definition must be given. Moreover, all patents, test methods, etc. documents cited in the present application are incorporated herein by reference, but such disclosure content is not inconsistent with the present application, and all laws that allow such incorporation. Limit for purposes in jurisdictions.

  Although the foregoing description relates to embodiments of the present invention, other and further embodiments of the present invention may be devised and without departing from the basic scope of the present invention. Is determined by the claims that follow.

Claims (25)

A propylene based elastomeric blend composition comprising
(A) 70% to 95% by weight of the first propylene-based elastomer component based on the weight of the propylene-based elastomer blend, wherein the ethylene content is 17% to 20% by weight; A first propylene-based elastomer component, and (b) 5% to 30% by weight of the second propylene-based elastomer component based on the weight of said propylene-based elastomer blend, A propylene based elastomeric blend composition comprising a second propylene based elastomeric component having an ethylene content of greater than or equal to 20 wt% by weight.   The composition of claim 1, wherein the propylene based polymeric elastomer blend has an ethylene content of 16 wt% to 18 wt%.   A method according to claim 1 or 2, wherein said first propylene based elastomeric component is prepared using a metallocene catalyst and said second propylene based elastomeric component is prepared using a metallocene catalyst. Composition. A propylene based elastomeric blend composition comprising
(A) 70% to 95% by weight of the first propylene-based elastomer component based on the weight of the propylene-based elastomer blend, wherein the ethylene content is 10% to 13% by weight; A first propylene-based elastomer component, and (b) 5% to 30% by weight of the second propylene-based elastomer component based on the weight of said propylene-based elastomer blend, A propylene based elastomeric blend composition comprising a second propylene based elastomeric component having an ethylene content of greater than or equal to 20 wt% by weight.   5. The composition of claim 4, wherein said first propylene based elastomeric component is prepared using a pyridyldiamide catalyst and said second propylene based elastomeric component is prepared using a metallocene catalyst. object.   5. The method of claim 4, wherein the first propylene based elastomeric component is prepared using a pyridyldiamide catalyst and the second propylene based elastomeric component is prepared using a pyridyldiamide catalyst. Composition. The composition according to claim 5 or 6, wherein the pyridyldiamide catalyst has the following structural formula:

In this formula, M is a Group 4 metal; X is each independently a monovalent anionic ligand, or two X are linked and linked to the metal atom to form a metallocene ring, or Two X's are linked to form a chelating ligand, a diene ligand or an alkylidene ligand; R ⁴¹ -R ⁴⁴ are hydrogen, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl or independently selected from silyl groups, but may be one or more adjacent R ⁴¹ to R ⁴⁴ to form a connection has been fused ring derivatives together; R ⁵¹ and R ⁵² is a hydrocarbyl, substituted hydrocarbyl, silylcarbyl R ⁵⁴ and R ⁵⁵ are hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy; and independently selected from the group consisting of and substituted silylcarbyl groups; And independently selected from the group consisting of silyl, amino, aryloxy, halogen and phosphino, provided that R ⁵⁴ and R ⁵⁵ may be linked to form a saturated heterocycle ring or a saturated substituted heterocycle ring In certain instances, substituents on the ring may be linked to form an additional ring; and R ^{60 to} R ⁶⁶ may be hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, aryloxy, halogen, amino and silyl And optionally any one or more adjacent R ^{60 to} R ⁶⁶ may be linked to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, in which case the ring is 5, It has 6, 7 or 8 ring atoms, and substituents on the ring may be linked to form an additional ring. A membrane composition,
(A) from 20% to 50% by weight of a propylene based elastomer blend,
(I) 70% to 95% by weight of the first propylene-based elastomer component based on the weight of the propylene-based elastomer blend, wherein the ethylene content is 10% to 20% by weight A first propylene-based elastomer component, and (ii) 5% to 30% by weight of the second propylene-based elastomer component based on the weight of said propylene-based elastomer blend, A propylene-based elastomer blend comprising a second propylene-based elastomer component having an ethylene content of greater than or equal to 20 wt% by weight;
(B) 20 wt% to 40 wt% thermoplastic resin based on the composition;
A membrane composition comprising (c) at least one magnesium hydroxide masterbatch; and (d) at least one UV light stabilizer.   9. The membrane of claim 8, wherein the propylene based elastomer is a reactor blend of the first propylene based elastomeric component and the second propylene based elastomeric component.   9. The membrane of claim 8, wherein the propylene based elastomer is a physical blend of the first propylene based elastomer component and the second propylene based elastomer component.   The membrane according to any one of claims 8 to 10, wherein the thermoplastic resin is a propylene homopolymer.   A membrane according to any one of claims 8 to 11, wherein the thermoplastic resin has a melt flow rate (230 ° C; 2.16 kg) of 2 to 15 g / 10 min.   A membrane according to any one of claims 8 to 11, wherein the thermoplastic resin has a melt flow rate (230 ° C; 2.16 kg) of less than 5 g / 10 min.   A membrane according to any one of claims 8 to 13, wherein the thermoplastic resin is a propylene impact copolymer.   A membrane according to any one of claims 8 to 14, wherein the propylene based elastomer has an ethylene content of 16 to 18 wt% based on the weight of the propylene based elastomer.   A membrane according to any one of claims 8 to 15, wherein the thermoplastic resin is present in the composition in an amount of 20% to 30% by weight.   A membrane according to any one of claims 8 to 16, wherein the blend composition comprises 10 to 30 wt% magnesium hydroxide masterbatch based on the weight of the blend composition.   The film according to any one of claims 8 to 17, wherein the blend composition comprises 1 to 10% by weight of a UV light stabilizer based on the weight of the blend composition.   19. Any of the claims 8-18, wherein said first propylene based elastomeric component is prepared using a metallocene catalyst and said second propylene based elastomeric component is prepared using a metallocene catalyst. The membrane according to item 1.   19. Any of claims 8 to 18, wherein said first propylene based elastomeric component is prepared using a pyridyldiamide catalyst and said second propylene based elastomeric component is prepared using a metallocene catalyst. The membrane according to claim 1 or 2.   19. The first propylene based elastomeric component is prepared using a pyridyldiamide catalyst, and the second propylene based elastomeric component is prepared using a pyridyldiamide catalyst. The membrane according to any one of the preceding claims. 22. The membrane according to claim 20 or 21, wherein the pyridyl diamide catalyst has the following structural formula:

In this formula, M is a Group 4 metal; X is each independently a monovalent anionic ligand, or two X are linked and linked to the metal atom to form a metallocene ring, or Two X's are linked to form a chelating ligand, a diene ligand or an alkylidene ligand; R ⁴¹ -R ⁴⁴ are hydrogen, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl or independently selected from silyl groups, but may be one or more adjacent R ⁴¹ to R ⁴⁴ to form a connection has been fused ring derivatives together; R ⁵¹ and R ⁵² is a hydrocarbyl, substituted hydrocarbyl, silylcarbyl R ⁵⁴ and R ⁵⁵ are hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy; and independently selected from the group consisting of and substituted silylcarbyl groups; And independently selected from the group consisting of silyl, amino, aryloxy, halogen and phosphino, provided that R ⁵⁴ and R ⁵⁵ may be linked to form a saturated heterocyclic ring or a saturated substituted heterocyclic ring, In certain instances, substituents on the ring may be linked to form an additional ring; and R ^{60 to} R ⁶⁶ may be hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, aryloxy, halogen, amino and silyl And optionally any one or more adjacent R ^{60 to} R ⁶⁶ may be linked to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, in which case the ring is 5, It has 6, 7 or 8 ring atoms, and substituents on the ring may be linked to form an additional ring.   22. A membrane according to claim 20 or 21, wherein the first propylene based elastomeric component has an ethylene content of 10% to 13% by weight based on the weight of the propylene based elastomer.   20. A method according to any one of claims 8 to 19, wherein said first propylene based elastomer component has an ethylene content of at least 17 wt% and not more than 20 wt% based on the weight of said propylene based elastomer. Membrane described.   A roofing composition comprising a membrane according to any of claims 8 to 24.

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