Waterproof film and preparation method thereof

Abstract

The present invention relates to waterproof membranes, in particular waterproof membranes for underground engineering, in particular waterproof membranes for underground engineering comprising metallocene catalyzed linear low density polyethylene and asphalt.

Description

Technical Field

[0001] This invention relates to waterproof membranes, particularly waterproof membranes for underground engineering, especially waterproof membranes for underground engineering comprising metallocene-catalyzed linear low-density polyethylene and bitumen. Background Technology

[0002] On October 24, 2022, the Ministry of Housing and Urban-Rural Development of my country approved the "General Specification for Waterproofing of Building and Municipal Engineering" (GB55030-2022), which came into effect on April 1, 2023. The newly promulgated GB55030-2022 requires underground engineering projects to use a double-layer waterproofing structure. Under the new national standard, polyethylene (PE) / asphalt has become one of the potential structural options, especially asphalt, which is favored in construction projects due to its relatively low cost.

[0003] Asphalt is a complex mixture composed of various hydrocarbons of different molecular weights and their non-metallic derivatives. During high-temperature heating, asphalt releases various substances, including volatile organic compounds (VOCs), such as benzo(a)pyrene, phenols, and naphthalenes. Therefore, there are concerns that these VOC gases released from asphalt may adversely affect the performance of polymer waterproof membranes.

[0004] However, to date, there is no research or data on the interaction between bitumen and polyethylene (PE) polymers in waterproof membrane applications. Summary of the Invention

[0005] This invention relates to novel waterproof membranes for underground engineering, and more particularly to novel waterproof membranes for underground engineering comprising metallocene-catalyzed linear low-density polyethylene and bitumen.

[0006] According to one aspect of the present invention, the present invention relates to a waterproof membrane comprising a polyethylene polymer layer and an asphalt layer, wherein the polyethylene polymer layer and the asphalt layer are adjacent to each other.

[0007] The polyethylene polymer layer comprises approximately 20 wt% to approximately 100 wt% metallocene-catalyzed linear low-density polyethylene and approximately 0 wt% to approximately 80 wt% Ziegler-Natta-catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer.

[0008] Among them, metallocene-catalyzed linear low-density polyethylene has a content of approximately 0.900 g / cm³. 3 Approximately 0.940 g / cm³ 3 The density, measured according to ASTM D-792, of which metallocene-catalyzed linear low-density polyethylene has a melt index I of approximately 0.10 g / 10 min to approximately 5.00 g / 10 min. 2.16According to ASTM D-1238 (190℃ / 2.16kg), the linear low-density polyethylene with metallocene catalysis has a melt index ratio of approximately 10 to approximately 50. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg), and

[0009] The linear low-density polyethylene catalyzed by Ziegler-Natta has a density of approximately 0.910 g / cm³. 3 Approximately 0.930 g / cm³ 3 The density, measured according to ASTM D-1505, of which Ziegler-Natta catalyzed linear low-density polyethylene has a melt index I of approximately 0.50 g / 10 min to approximately 3.00 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0010] According to an embodiment of the present invention, the metallocene-catalyzed linear low-density polyethylene comprises about 70 mol% to about 99 mol% of ethylene-derived units and about 1 mol% to about 30 mol% of polymer units derived from C3-C20 olefins, based on the total number of moles of polymer units in the metallocene-catalyzed linear low-density polyethylene.

[0011] According to an embodiment of the invention, the polyethylene polymer layer consists of metallocene-catalyzed linear low-density polyethylene and optionally Ziegler-Natta-catalyzed linear low-density polyethylene.

[0012] According to an embodiment of the present invention, metallocene-catalyzed linear low-density polyethylene has a density of approximately 0.900 g / cm³. 3 - Approximately 0.940 g / cm³ 3 Approximately 0.905 g / cm³ 3 - Approximately 0.940 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.940 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.930 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.920 g / cm³ 3 The density is measured according to ASTM D-792.

[0013] According to embodiments of the present invention, metallocene-catalyzed linear low-density polyethylene has a melt index (MI, or I) of about 0.10 g / 10 min to about 5.00 g / 10 min, about 0.10 g / 10 min to about 4.00 g / 10 min, for example about 0.10 g / 10 min to about 3.00 g / 10 min, for example about 0.10 g / 10 min to about 2.00 g / 10 min, for example about 0.10 g / 10 min to about 1.00 g / 10 min, for example about 0.10 g / 10 min to about 0.90 g / 10 min, for example about 0.10 g / 10 min to about 0.80 g / 10 min, for example about 0.10 g / 10 min to about 0.70 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg).

[0014] According to embodiments of the present invention, metallocene-catalyzed linear low-density polyethylene has a melt index ratio of about 10 to about 50, about 20 to about 50, for example about 20 to about 40. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0015] According to an embodiment of the invention, the polyethylene polymer layer comprises about 30 wt% metallocene-catalyzed linear low-density polyethylene and about 70 wt% Ziegler-Natta-catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer.

[0016] According to an embodiment of the present invention, metallocene-catalyzed linear low-density polyethylene has a density of approximately 0.916 g / cm³. 3 Its density, measured according to ASTM D-792, has a melt index I of approximately 0.50 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg), and with a melt index of approximately 38, it is comparable to I. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0017] According to an embodiment of the present invention, metallocene-catalyzed linear low-density polyethylene has a density of approximately 0.912 g / cm³. 3Its density, measured according to ASTM D-792, has a melt index I of approximately 0.50 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg), and with a melt index of approximately 35, it is comparable to I. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0018] According to an embodiment of the present invention, the Ziegler-Natta catalyzed linear low-density polyethylene has a density of approximately 0.910 g / cm³. 3 Approximately 0.930 g / cm³ 3 Its density, or approximately 0.910 g / cm³. 3 To approximately 0.925 g / cm 3 Its density, or approximately 0.910 g / cm³. 3 To approximately 0.920 g / cm 3 The density is measured according to ASTM D-1505.

[0019] According to embodiments of the present invention, the Ziegler-Natta catalyzed linear low-density polyethylene has a melt index I of about 0.50 g / 10 min to about 3.00 g / 10 min. 2.16 Or a melt index I of approximately 1.00 g / 10 min to approximately 3.00 g / 10 min. 2.16 Or a melt index I of approximately 1.00 g / 10 min to approximately 2.50 g / 10 min. 2.16 Or a melt index I of approximately 1.50 g / 10 min to approximately 2.50 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0020] According to an embodiment of the present invention, the Ziegler-Natta catalyzed linear low-density polyethylene has a density of approximately 0.918 g / cm³. 3 Its density, measured according to ASTM D-1505, has a melt index I of approximately 2.0 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0021] According to another aspect of the invention, the present invention relates to the use of metallocene-catalyzed linear low-density polyethylene in a bitumen-containing waterproof membrane for improving the puncture resistance of the membrane, wherein the waterproof membrane comprises a polyethylene polymer layer and a bitumen layer, wherein the polyethylene polymer layer and the bitumen layer are adjacent to each other.

[0022] The polyethylene polymer layer comprises approximately 20 wt% to approximately 100 wt% metallocene-catalyzed linear low-density polyethylene and approximately 0 wt% to approximately 80 wt% Ziegler-Natta-catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer.

[0023] Among them, metallocene-catalyzed linear low-density polyethylene has a content of approximately 0.900 g / cm³. 3 Approximately 0.940 g / cm³ 3 The density, measured according to ASTM D-792, of which metallocene-catalyzed linear low-density polyethylene has a melt index I of approximately 0.10 g / 10 min to approximately 5.00 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg), the linear low-density polyethylene with metallocene catalysis has a melt index ratio of approximately 10 to approximately 50. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg), and

[0024] The linear low-density polyethylene catalyzed by Ziegler-Natta has a density of approximately 0.910 g / cm³. 3 Approximately 0.930 g / cm³ 3 The density, measured according to ASTM D-1505, of which Ziegler-Natta catalyzed linear low-density polyethylene has a melt index I of approximately 0.50 g / 10 min to approximately 3.00 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0025] According to an embodiment of the present invention, the metallocene-catalyzed linear low-density polyethylene comprises about 70 mol% to about 99 mol% of ethylene-derived units and about 1 mol% to about 30 mol% of polymer units derived from C3-C20 olefins, based on the total molar number of polymer units in the metallocene-catalyzed linear low-density polyethylene.

[0026] According to another aspect of the invention, the present invention relates to a method for preparing a waterproof membrane, wherein a polyethylene polymer layer is prepared by a sheet extrusion production line conventional in the art for polyethylene membranes.

[0027] According to the method for preparing the waterproof membrane of the present invention, there may or may not be an adhesive between the polyethylene polymer layer and the asphalt layer. If an adhesive is present, adhesives commonly used in the art for waterproof membranes in underground engineering can be used in this invention.

[0028] Optionally, the waterproof membrane of the present invention uses self-adhesive bitumen; in other words, there is no adhesive between the polyethylene polymer layer and the bitumen layer.

[0029] The inventors of this invention have surprisingly discovered that, in thermal aging tests in the presence of bitumen, the polyethylene polymer layer of the present invention, comprising metallocene-catalyzed linear low-density polyethylene, exhibits beneficial dimensional stability and unexpectedly improved puncture resistance, which ensures excellent durability of the waterproof membrane of the present invention in its final use.

[0030] Metallocene-catalyzed linear low-density polyethylene (m-LLDPE)

[0031] According to an embodiment of the invention, the waterproof membrane comprises a polyethylene polymer layer and an asphalt layer, wherein the polyethylene polymer layer and the asphalt layer are adjacent to each other, wherein the polyethylene polymer layer comprises about 20 wt% to about 100 wt% of metallocene-catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer.

[0032] According to an embodiment of the present invention, the polyethylene polymer layer comprises about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt%, about 90 wt%, or about 100 wt% of metallocene-catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer. Based on the weight of the polyethylene polymer layer, the content of metallocene-catalyzed linear low-density polyethylene can be a range consisting of any two of the above values, for example, about 20 wt% to about 100 wt%, about 20 wt% to about 90 wt%, etc.

[0033] As used herein, the term "metallocene catalyst" is defined as a compound containing at least one transition metal compound having one or more substituted or unsubstituted cyclopentadienyl structural moieties (Cp) (usually two Cp structural moieties) together with transition metals of Group 4, 5 or 6 of the periodic table such as zirconium, hafnium and titanium.

[0034] Metallocene catalysts typically require activation with suitable co-catalysts or activators to produce "active metallocene catalysts," which are organometallic complexes with vacant coordination sites capable of coordinating, inserting, and polymerizing olefins. Active catalyst systems usually contain not only metallocene complexes but also activators such as aluminoxanes or their derivatives (preferably methylaluminoxanes), ionizing activators, Lewis acids, or combinations thereof. Alkylaluminoxanes (typically methylaluminoxanes and modified methylaluminoxanes) are particularly suitable as catalyst activators. The catalyst system can be supported on a support, typically an inorganic oxide or chloride or resin material, such as polyethylene or silica.

[0035] According to an embodiment of the present invention, linear polyethylene with a density falling within the following range is referred to as linear low-density polyethylene (LLDPE): approximately 0.900 g / cm³. 3 Approximately 0.940 g / cm³ 3 The density is measured according to ASTM D-792 or ASTM D-1505, where “linear” indicates that the polyethylene has no long-chain branches or only a small number of long-chain branches. As is well known in the art, linear low-density polyethylene (LLDPE) typically has a branching index (g') close to 1, for example, greater than or equal to 0.98 to less than 1, or greater than or equal to 0.99 to less than 1.

[0036] According to embodiments of the present invention, metallocene-catalyzed linear low-density polyethylene (m-LLDPE) comprises about 70 mol% to about 99 mol% of ethylene-derived units, based on the total molar number of polymer units in the metallocene-catalyzed linear low-density polyethylene. The lower limit of the range of ethylene-derived unit content based on the total molar number of polymer units in the metallocene-catalyzed linear low-density polyethylene can be 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 92 mol%, 94 mol%, 95 mol%, 96 mol%, 97 mol%, 98 mol%, or 99 mol%. The upper limit of the range of ethylene-derived unit content based on the total molar number of polymer units in the metallocene-catalyzed linear low-density polyethylene can be 80 mol%, 85 mol%, 90 mol%, 92 mol%, 94 mol%, 95 mol%, 96 mol%, 97 mol%, 98 mol%, or 99 mol%. Any of the aforementioned upper limit content can be combined with any of the aforementioned upper limit content; any of the aforementioned upper limit content can be combined with any of the aforementioned lower limit content; and any of the aforementioned upper limit content can be combined with any of the aforementioned lower limit content.

[0037] The metallocene-catalyzed linear low-density polyethylene of the present invention may have about 1 mol% to about 30 mol% of polymer units derived from C3-C20 olefins, such as C3-C20 α-olefins, such as hexene or octene. Based on the total molar number of polymer units in the metallocene-catalyzed linear low-density polyethylene, the upper limit of the content range of polymer units derived from C3-C20 olefins may be 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 8 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, or 1 mol%. Based on the total molar number of polymer units in the metallocene-catalyzed linear low-density polyethylene, the lower limit of the content range of polymer units derived from C3-C20 olefins may be 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 8 mol%, 10 mol%, 15 mol%, 20 mol%, or 25 mol%. Any of the aforementioned upper limit content can be combined with any of the aforementioned upper limit content; any of the aforementioned upper limit content can be combined with any of the aforementioned lower limit content; and any of the aforementioned upper limit content can be combined with any of the aforementioned lower limit content.

[0038] According to an embodiment of the present invention, the density of metallocene-catalyzed linear low-density polyethylene, as measured according to ASTM D-792, can be greater than or equal to about 0.900 g / cm³. 3 For example, ≥0.902 g / cm³ 3 For example, ≥0.904 g / cm³ 3 For example, ≥0.906 g / cm³ 3 For example, ≥0.908 g / cm³ 3 For example, ≥ 0.910 g / cm³ 3 For example, ≥ 0.911 g / cm³ 3 For example, ≥ 0.912 g / cm³ 3 For example, ≥ 0.913 g / cm³ 3 For example, ≥ 0.914 g / cm³ 3 For example, ≥ 0.915 g / cm³ 3 For example, ≥ 0.916 g / cm³ 3 For example, ≥ 0.917 g / cm³ 3 For example, ≥ 0.918 g / cm³ 3 For example, ≥ 0.919 g / cm³ 3 For example, ≥ 0.920 g / cm³ 3 For example, ≥ 0.925 g / cm³ 3 For example, ≥ 0.930 g / cm³3 For example, ≥ 0.935 g / cm³ 3 The density.

[0039] Alternatively, metallocene-catalyzed linear low-density polyethylene may have a density equal to or less than approximately 0.940 g / cm³, as measured according to ASTM D-792. 3 For example, ≤0.935 g / cm³ 3 For example, ≤0.930 g / cm³ 3 For example, ≤0.925 g / cm³ 3 For example, ≤0.920 g / cm³ 3 For example, ≤ 0.919 g / cm³ 3 For example, ≤ 0.918 g / cm³ 3 For example, ≤ 0.917 g / cm³ 3 For example, ≤ 0.916 g / cm³ 3 For example, ≤ 0.915 g / cm³ 3 For example, ≤ 0.914 g / cm³ 3 For example, ≤ 0.913 g / cm³ 3 For example, ≤ 0.912 g / cm³ 3 The explicitly disclosed range includes, but is not limited to, the range formed by any combination of the numerical values ​​listed above, such as approximately 0.900 g / cm³. 3 - Approximately 0.940 g / cm³ 3 For example, approximately 0.905 g / cm³ 3 - Approximately 0.940 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.940 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.930 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.920 g / cm³ 3 wait.

[0040] According to an embodiment of the present invention, the melt index (MI, or I) of metallocene-catalyzed linear low-density polyethylene is measured according to ASTM D-1238 (190°C / 2.16 kg). 2.16The values ​​can be ≥ 0.10 g / 10 min, for example ≥ 0.20 g / 10 min, for example ≥ 0.30 g / 10 min, for example ≥ 0.40 g / 10 min, for example ≥ 0.50 g / 10 min, for example ≥ 0.60 g / 10 min, for example ≥ 0.70 g / 10 min, for example ≥ 0.80 g / 10 min, for example ≥ 0.90 g / 10 min, for example ≥ 1.00 g / 10 min, for example ≥ 1.50 g / 10 min, for example ≥ 2.00 g / 10 min, for example ≥ 2.50 g / 10 min, for example ≥ 3.00 g / 10 min, for example ≥ 3.50 g / 10 min, for example ≥ 4.00 g / 10 min, for example ≥ 4.50 g / 10 min.

[0041] Alternatively, metallocene-catalyzed linear low-density polyethylene may be used according to the melt index (MI, or I) measured according to ASTM D-1238 (190°C / 2.16 kg). 2.16 It can be ≤ about 5.00 g / 10min, for example ≤ about 4.50 g / 10min, for example ≤ about 4.00 g / 10min, for example ≤ about 3.50 g / 10min, for example ≤ about 3.00 g / 10min, for example ≤ about 2.50 g / 10min, for example ≤ about 2.00 g / 10min, for example ≤ about 1.50 g / 10min, for example ≤ about 1.00 g / 10min, for example ≤ about 0.90 g / 10min, for example ≤ about 0.80 g / 10min, for example ≤ about 0.70 g / 10min, for example ≤ about 0.60 g / 10min, for example ≤ about 0.50 g / 10min, for example ≤ about 0.40 g / 10min, for example ≤ about 0.30 g / 10min, for example ≤ about 0.20 g / 10min, etc. The explicitly disclosed range includes, but is not limited to, the range formed by any combination of the numerical values ​​listed above, such as about 0.10 g / 10min to about 5.00 g / 10min, such as about 0.10 g / 10min to about 4.00 g / 10min, about 0.10 g / 10min to about 3.00 g / 10min, about 0.10 g / 10min to about 2.00 g / 10min, about 0.10 g / 10min to about 1.00 g / 10min, such as about 0.10 g / 10min to about 0.90 g / 10min, such as about 0.10 g / 10min to about 0.80 g / 10min, such as about 0.10 g / 10min to about 0.70 g / 10min, etc.

[0042] According to embodiments of the present invention, metallocene-catalyzed linear low-density polyethylene can have a melt index ratio of about 10 to about 50. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190°C / 2.16 kg). For example, metallocene-catalyzed linear low-density polyethylene can have a melt index ratio of about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, or about 50. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg). The melt index ratio of metallocene-catalyzed linear low-density polyethylene to I... 21.6 / I 2.16 It can be a range consisting of any two of the above values, for example, about 10 to about 50, about 10 to about 40, etc.

[0043] Metallocene-catalyzed linear low-density polyethylene is commercially available from ExxonMobil and is labeled as Exceed TM XP metallocene polyethylene (mPE) for sale. Exceed TM XP mPE offers advantageous properties such as dart impact strength, resistance to flexural cracking and longitudinal (MD) tearing, and maintaining stiffness at lower densities. TM XP mPE also offers a good balance of melt strength, toughness, stiffness and sealing ability.

[0044] The following metallocene-catalyzed linear low-density polyethylene is used in the embodiments of the present invention:

[0045] Exceed TM Flow+ m 0516.ML is a metallocene-catalyzed linear low-density polyethylene purchased from ExxonMobil. It is a copolymer of ethylene and 1-hexene and has the following performance parameters:

[0046] Density: Approximately 0.916 g / cm³ 3 It is measured according to ASTM D792; and

[0047] Melt index: approximately 0.50 g / 10 min, measured according to ASTM D1238 (190℃ / 2.16 kg); and

[0048] Melt index ratio I 21.6 / I 2.16 Approximately 38, of which I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0049] Exceed TM Tough+ m 0512.ML is a metallocene-catalyzed linear low-density polyethylene purchased from ExxonMobil. It is a copolymer of ethylene and 1-hexene and has the following performance parameters:

[0050] Density: 0.912 g / cm³ 3 It is measured according to ASTM D792; and

[0051] Melt index: 0.50 g / 10min, measured according to ASTM D1238 (190℃ / 2.16kg); and

[0052] Melt index ratio I 21.6 / I 2.16 Approximately 35, of which I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0053] Ziegler-Natta catalyzed linear low-density polyethylene

[0054] According to an embodiment of the invention, the waterproof membrane comprises a polyethylene polymer layer and an asphalt layer, wherein the polyethylene polymer layer and the asphalt layer are adjacent to each other. For cost considerations, the polyethylene polymer layer may comprise about 0 wt% to about 80 wt% of Ziegler-Natta catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer.

[0055] According to an embodiment of the invention, the polyethylene polymer layer comprises about 0 wt%, about 10 wt%, 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, or about 80 wt% of Ziegler-Natta catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer. Based on the weight of the polyethylene polymer layer, the content of Ziegler-Natta catalyzed linear low-density polyethylene can be a range consisting of any two of the above values, for example, about 0 wt% to about 80 wt%, about 20 wt% to about 80 wt%, etc.

[0056] According to an embodiment of the present invention, Ziegler-Natta catalyzed linear low-density polyethylene is defined as a linear low-density polyethylene copolymer produced in the presence of a Ziegler-Natta catalyst.

[0057] According to embodiments of the present invention, linear low-density polyethylene catalyzed by Ziegler-Natta commonly used in the art can be used in the present invention.

[0058] According to an embodiment of the present invention, linear polyethylene with a density falling within the following range is referred to as linear low-density polyethylene (LLDPE): approximately 0.900 g / cm³. 3 Approximately 0.940 g / cm³ 3 The density is measured according to ASTM D-792 or ASTM D-1505, where “linear” indicates that the polyethylene has no long-chain branches or only a small number of long-chain branches. As is well known in the art, linear low-density polyethylene (LLDPE) typically has a branching index (g') close to 1, for example, greater than or equal to 0.98 to less than 1, or greater than or equal to 0.99 to less than 1.

[0059] According to embodiments of the present invention, the Ziegler-Natta catalyzed linear low-density polyethylene contains at least one or more comonomers. Suitable comonomers are, for example, C3-C20 α-olefin comonomers or C3-C10 α-olefin comonomers.

[0060] For example, the comonomer may be selected from one or more of 1-butene, 1-hexene, and 1-octene.

[0061] According to an embodiment of the present invention, the Ziegler-Natta catalyzed linear low-density polyethylene has a density of approximately 0.910 g / cm³. 3 Approximately 0.930 g / cm³ 3 The density is measured according to ASTM D-1505. For example, Ziegler-Natta catalyzed linear low-density polyethylene can have a density of approximately 0.910 g / cm³. 3 Approximately 0.915 g / cm³ 3 Approximately 0.920 g / cm³ 3 Approximately 0.925 g / cm³ 3 or approximately 0.930 g / cm³ 3 The density is measured according to ASTM D-1505. For example, Ziegler-Natta catalyzed linear low-density polyethylene can have a density range consisting of any two of the above values, such as approximately 0.910 g / cm³. 3 Approximately 0.930 g / cm³ 3 Its density, or approximately 0.910 g / cm³. 3 To approximately 0.925 g / cm 3Its density, or approximately 0.910 g / cm³. 3 To approximately 0.920 g / cm 3 The density is measured according to ASTM D-1505.

[0062] According to embodiments of the present invention, the Ziegler-Natta catalyzed linear low-density polyethylene has a melt index I of about 0.50 g / 10 min to about 3.00 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg). For example, Ziegler-Natta catalyzed linear low-density polyethylene can have melt index I of approximately 0.50 g / 10min, approximately 1.00 g / 10min, approximately 1.50 g / 10min, approximately 2.00 g / 10min, approximately 2.50 g / 10min, or approximately 3.00 g / 10min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg). For example, Ziegler-Natta catalyzed linear low-density polyethylene can have a melt index I consisting of any two of the above values. 2.16 The range, for example, melt index I from about 0.50 g / 10 min to about 3.00 g / 10 min. 2.16 Or a melt index I of approximately 1.00 g / 10 min to approximately 3.00 g / 10 min. 2.16 Or a melt index I of approximately 1.00 g / 10 min to approximately 2.50 g / 10 min. 2.16 Or a melt index I of approximately 1.50 g / 10 min to approximately 2.50 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

[0063] ExxonMobil™ C4LL 2018.AY is a Ziegler-Natta catalyzed linear low-density polyethylene purchased from ExxonMobil. It is a copolymer of ethylene and butene and has the following performance parameters:

[0064] Density: 0.918 g / cm³ 3 It is measured according to ASTM D-1505; and

[0065] Melt index: 2.0 g / 10min, measured according to ASTM D1238 (190℃ / 2.16kg).

[0066] asphalt

[0067] According to an embodiment of the present invention, the waterproof membrane comprises a polyethylene polymer layer and an asphalt layer, wherein the polyethylene polymer layer and the asphalt layer are adjacent to each other.

[0068] According to embodiments of the present invention, asphalt commonly used in the art for waterproof membranes in underground engineering can also be used in the present invention.

[0069] In particular, self-adhesive bitumen, which is commonly used in the art for waterproof membranes in underground engineering, can be used in this invention.

[0070] The asphalt used in the embodiments of the present invention was purchased from Oriental Yuhong SAM-920 self-adhesive polymer modified asphalt waterproof membrane. Attached Figure Description

[0071] Figure 1 This invention demonstrates the metallocene-catalyzed linear low-density polyethylene: Exceed TM Color changes of Flow+ m 0516.ML and the Ziegler-Natta catalyzed linear low-density polyethylene of the present invention: ExxonMobil™ C4LL 2018.AY from day 1 to day 14 in a heat aging test with and without bitumen.

[0072] Figure 2 This invention demonstrates the metallocene-catalyzed linear low-density polyethylene: Exceed TM Flow+ m 0516.ML and the Ziegler-Natta catalyzed linear low-density polyethylene of the present invention: ExxonMobil™ C4LL 2018.AY, percentage change in puncture resistance from day 1 to day 14 in a thermal aging test, with and without bitumen, compared to the starting day 0.

[0073] Figure 3 This demonstrates the metallocene-catalyzed linear low-density polyethylene of the present invention at day 14 in a thermal aging test with asphalt present: Exceed TM The puncture resistance, i.e., F, of Flow+ m 0516.ML and the Ziegler-Natta catalyzed linear low-density polyethylene of the present invention: ExxonMobil™ C4LL 2018.AY 最大 Comparison of (N).

[0074] Figure 4 This invention demonstrates the metallocene-catalyzed linear low-density polyethylene: Exceed TM Flow+ m 0516.ML and the Ziegler-Natta catalyzed linear low-density polyethylene of the present invention: ExxonMobil™ C4LL 2018.AY, changes in dimensional stability from day 1 to day 14 in a thermal aging test, with and without bitumen, compared to the starting day 0.

[0075] Figure 5 The illustration shows a clamping system used to measure puncture resistance.

[0076] Figure 6 The illustration shows a punching die equipped with a "12mm Ø hole" used for specimen preparation in puncture resistance testing.

[0077] Figure 7 This invention demonstrates the metallocene-catalyzed linear low-density polyethylene: Exceed TM Tough+ m0512.ML puncture resistance (F) in thermal aging tests from day 0 to day 14, with and without asphalt. 最大 The change of (N)). Detailed Implementation

[0078] To better understand the technical solution of this invention, the applicant provides the following embodiments for illustrative purposes. These embodiments are merely illustrative and do not limit the scope of protection of this invention in any way.

[0079] Example

[0080] 1. Materials and Formula

[0081] Use the materials and formulations shown in Table 1 in the pre-applied reverse waterproofing system (PAW).

[0082] Table 1. Materials and Formulations

[0083] The asphalt used in the embodiments of the present invention was purchased from Oriental Yuhong SAM-920 self-adhesive polymer modified asphalt waterproof membrane.

[0084] 2. Thermal aging test method

[0085] To study the interaction between the asphalt and the polyethylene polymer layer, the inventors conducted thermal aging tests on the polymer and asphalt.

[0086] The inventors used a Jwell three-layer sheet extrusion production line to prepare polyethylene polymer layers, wherein all the polyethylene polymer layers prepared were single layers with a thickness of 1.2 mm, that is, the composition of the three layers of sheets in the Jwell three-layer sheet extrusion production line was consistent.

[0087] After bonding the polyethylene polymer layer with industrial waterproof asphalt, the layers were wrapped in tin foil and aged in a 70°C oven for 1, 2, 4, 7, 10, and 14 days, respectively. Meanwhile, as a reference, asphalt-free polyethylene polymer layers were wrapped in tin foil and aged in a 70°C oven for 1, 2, 4, 7, 10, and 14 days, respectively.

[0088] After thermal aging, the asphalt was peeled off from the polyethylene polymer layer, and the puncture resistance and dimensional stability of the polyethylene polymer layer were then analyzed at the STC Testing Laboratory (ExxonMobil Shanghai Technical Center Analytical and Testing Laboratory) according to the methods shown in Table 2. The same methods were used for the reference. Each formulation was tested five times, and the average value was taken.

[0089] Table 2

[0090] 2.1 Puncture resistance test method:

[0091] Puncture resistance: refers to the maximum load that a sample can withstand before or during fracture, and is measured in Newtons (N).

[0092] 2.1.1 Instruments and Equipment

[0093] a) Tensile testing machine

[0094] It can operate at a constant elongation rate (CRE) of 300 mm / min. Model: Zwick Z005 TensileTester.

[0095] b) Clamping system

[0096] A ring-shaped clamp accessory, which consists of concentric discs with an inner diameter of 45±0.025 mm.

[0097] A solid steel rod with a diameter of 8±0.1 mm, featuring a flat-top design with a 45° angle at the bottom. See the appendix of this invention for details. Figure 5 .

[0098] c) Automatic recording load-elongation recorder

[0099] It must be equipped with computer data backup function, and its operating speed must be consistent with that of the tensile testing machine.

[0100] 2.1.2. Sampling, Sample Preparation and Environmental Conditioning

[0101] a. Sampling

[0102] Cut samples from the sheet, maintaining a spacing of at least 10 mm, and avoiding the edges of the sheet.

[0103] b. Sample preparation

[0104] Six samples were cut from both sides of the sheet using an STC-109 / 112 automatic hollow die punch, equipped with a die cutter with a 12mm Ø hole. See the appendix of this invention for details. Figure 6 .

[0105] c. Sample conditioning

[0106] a) The specimens should be laid flat and placed separately with the usable side facing up, and placed in a standard atmospheric environment for textile conditioning for at least 24 hours (h).

[0107] b) The atmospheric environment used for sample preparation and testing shall meet the requirements of the standard atmospheric environment for textile testing, namely, a temperature of 23±2℃ and a relative humidity of 50±10%.

[0108] 2.1.3. Test Procedure

[0109] a) Install the puncture clamp, metal rod, and 2500 N force sensor.

[0110] b) Equipment startup: Refer to the Zwick Z005 Tensile Tester Operation Manual (OMP) and select the "Puncture Resistance Test" program.

[0111] c) In wizard mode, confirm that all parameters are set correctly, and enter the sample number, operator's name and test date in "Report Parameters".

[0112] d) Click “Force 0”, then clamp “other component layer” in the lower jaw and click “Start” to start the test.

[0113] e) Take the remaining 5 samples and repeat step d) to complete at least 5 tests.

[0114] f) Click "Save As" to save the test data, and then print the test results in PDF format to the specified path.

[0115] 2.2 Dimensional stability test method:

[0116] The dimensional stability of a material is characterized by heat treatment of the sample in an oven at a specified temperature and time, measuring the changes in length and width of the sample before and after treatment, and calculating the rate of dimensional change.

[0117] 2.2.1 Sample Preparation

[0118] a) Sampling requirements: Take a sample from each roll of material at least 1m from the end, avoiding the edge of the roll (≥100mm from the edge);

[0119] b) Specimen size: Prepare one rectangular specimen with a length (longitudinal) of (250±5) mm and a width (transverse) of (250±5) mm;

[0120] c) Mark measurement points: Mark two parallel lines (forming an “inner frame”) along the length and width directions on each sample, 50 mm from the edge. Measure the length (L0) and width (B0) of the inner frame as initial dimensions (accurate to 0.5 mm).

[0121] 2.2.2 Test Procedure

[0122] a) Initial measurement: Use a ruler to measure the inner frame length (L0) and width (B0) of each sample mark, and record the data;

[0123] b) Heat treatment: Place the sample flat on the steel plate (the samples do not overlap and the distance between the sample and the oven wall is ≥50mm), put it in the oven at the specified temperature, and keep it at the specified temperature for the specified time.

[0124] c) Cooling and remeasurement: Remove the sample and place it together with the steel plate in a desiccator to cool to room temperature (at least 2 hours), and then measure the length (L1) and width (B1) of the inner frame.

[0125] 2.2.3 Result Calculation

[0126] The rate of dimensional change is calculated using the following formula:

[0127] Length change rate (%): Δ L =(L1 – L0) / L0 ×100

[0128] Width change rate (%): Δ B =(B1 – B0) / B0 ×100

[0129] In the formula:

[0130] L0 and B0 are the length and width before heat treatment;

[0131] L1 and B1 are the length and width after heat treatment.

[0132] The results are accurate to 0.1%. A positive rate of change indicates material expansion, while a negative rate indicates contraction.

[0133] 3. Results and Discussion

[0134] 3.1 Color change of the polyethylene polymer layer during thermal aging test

[0135] Figure 1 The invention's formulation 1 (the metallocene-catalyzed linear low-density polyethylene of the present invention: Exceed) is shown. TMColor changes of Flow+ m 0516.ML) and Formulation 3 (Ziegler-Natta catalyzed linear low-density polyethylene of the present invention: ExxonMobil™ C4LL 2018.AY) from day 1 to day 14 in a heat aging test with and without asphalt.

[0136] Under asphalt-free conditions, the colors of both Formula 1 and Formula 3 remained unchanged from day 1 to day 14 in the thermal aging test.

[0137] Under asphalt conditions, in the heat aging test from day 1 to day 14, the color of the polyethylene polymer layer of both formulations 1 and 3 deepened over time; after 14 days, the polyethylene polymer layer of both formulations turned brown, and this color could not be removed with alcohol solvents.

[0138] Figure 1 This indicates that bitumen does indeed affect metallocene-catalyzed linear low-density polyethylene (LLDPE) layers and Ziegler-Natta-catalyzed LLDPE layers.

[0139] 3.2 Puncture resistance of the polyethylene polymer layer in the thermal aging test

[0140] Figure 2 The invention's formulation 1 (the metallocene-catalyzed linear low-density polyethylene of the present invention: Exceed) is shown. TM Flow+ m 0516.ML) and Formulation 3 (Ziegler-Natta catalyzed linear low-density polyethylene of the present invention: ExxonMobil™ C4LL 2018.AY) showed the percentage change in puncture resistance from day 1 to day 14 in the thermal aging test, with and without asphalt, compared to the starting day 0.

[0141] from Figure 2 It can be seen that, in the absence of asphalt, compared with the initial day 0, the puncture resistance of formulation 3 (ExxonMobil™ C4LL 2018.AY) was slightly improved or remained essentially unchanged from day 1 to day 14 in the thermal aging test.

[0142] However, in the presence of asphalt, the puncture resistance of formulation 3 (ExxonMobil™ C4LL 2018.AY) was significantly reduced from day 1 to day 14 in the thermal aging test compared to the initial day 0, with a reduction of up to approximately 10%.

[0143] from Figure 2 It can also be seen that: in the absence of asphalt, compared with the initial 0 days, in the thermal aging test, formulation 1 (Exceeding) TMThe puncture resistance of Flow+ m 0516.ML) increased slightly on day 1, then decreased: the puncture resistance on days 2, 4, 7, and 10 was essentially the same as that on day 0, and then increased slightly on day 14 compared to day 0. However, in the presence of asphalt, in the thermal aging test, from day 1 to day 14, the puncture resistance of formulation 1 (Exceeding) was significantly lower than that on day 0. TM The puncture resistance of Flow+ m 0516.ML) was slightly reduced on day 1, but unexpectedly improved on days 2, 4, 7, 10 and 14 compared to the starting day 0, with some improvements exceeding 10%.

[0144] The effect of asphalt on the puncture resistance of Formulation 1, i.e., the metallocene-catalyzed linear low-density polyethylene of the present invention, is surprising and unexpected, both compared to the puncture resistance of Formulation 1 without asphalt and compared to the puncture resistance of Formulation 3 with asphalt. Asphalt unexpectedly improves the puncture resistance of the metallocene-catalyzed linear low-density polyethylene of the present invention, by up to >about 10%.

[0145] Figure 3 This shows that, in the presence of asphalt, formulation 1 (Exceeding) showed the effect at day 14 in the thermal aging test. TM The puncture resistance of Flow+ m 0516.ML and Formulation 3 (ExxonMobil™ C4LL 2018.AY), i.e., F 最大 Comparison of (N).

[0146] from Figure 3 It can be seen that on the 14th day of the heat aging test, due to the presence of asphalt, the puncture resistance of Formula 1 is Fmax = 590.21 N; the puncture resistance of Formula 3 is Fmax = 268.9 N. Therefore, it can be concluded that the puncture resistance of Formula 1 is 2.2 times that of Formula 3.

[0147] Figure 7 Formulation 2 of the present invention (metallocene-catalyzed linear low-density polyethylene: Exceed) is shown. TM Tough+ m0512.ML) puncture resistance (F) in thermal aging tests from day 0 to day 14, with and without asphalt. 最大 The change of (N)).

[0148] from Figure 7 It can be seen that, without asphalt, compared to the initial 0 days, in the thermal aging test from day 1 to day 14, formulation 2 (Exceeding)TM The puncture resistance (F) of Tough+ m 0512.ML) 最大 (N) all decreased.

[0149] from Figure 7 It can also be found that: in the presence of asphalt, compared to the initial day 0, on days 1, 2, and 4 of the thermal aging test, formulation 2 (Exceeding) TM The puncture resistance (F) of Tough+ m 0512.ML) 最大 (N)) were all reduced; however, unexpectedly, compared to the initial day 0, on days 7, 10, and 14 of the thermal aging test, formulation 2 (Exceeding TM The puncture resistance (F) of Tough+ m 0512.ML) 最大 (N)) Surprisingly, it showed an increase.

[0150] Furthermore, in the presence of asphalt, compared to the initial 0 days, although on days 1, 2, and 4 of the thermal aging test, formulation 2 (Exceeding) showed... TM The puncture resistance (F) of Tough+ m 0512.ML) 最大 (N)) decreased, but the decrease was better than (i.e., less than) the case without asphalt.

[0151] from Figure 7 It can also be found that: in the thermal aging test from day 1 to day 14, formulation 2 (metallocene-catalyzed linear low-density polyethylene: Exceed) TM Toughness of 0.512.ML (m 0512.ML) in the presence of asphalt (F 最大 (N) is superior to the puncture resistance (F) in the absence of asphalt. 最大 (N).

[0152] 3.3 Dimensional stability of the polyethylene polymer layer in the thermal aging test

[0153] Figure 4 The invention's formulation 1 (the metallocene-catalyzed linear low-density polyethylene of the present invention: Exceed) is shown. TM Flow+ m 0516.ML) and Formulation 3 (Ziegler-Natta catalyzed linear low-density polyethylene of the present invention: ExxonMobil™ C4LL 2018.AY) showed changes in dimensional stability from day 1 to day 14 in the thermal aging test, with and without asphalt, compared to the initial day 0.

[0154] from Figure 4It can be seen that in the heat aging test, from day 1 to day 14, for both formulation 1 and formulation 3, asphalt caused the dimensional stability of linear low-density polyethylene to deteriorate.

[0155] According to the national standard GB / T23457-2017, the dimensional change rate ΔL should be ≤1.5%. Figure 4 The pink area in the middle.

[0156] from Figure 4 It can be seen that, in the presence of asphalt, the dimensional stability change of formulation 3 exceeds the requirements of the national standard GB / T23457-2017, that is, starting from the second day, the dimensional change rate ΔL of formulation 3 is > 1.5%.

[0157] However, from Figure 4 It can be seen that, unexpectedly, in the presence of asphalt, the dimensional stability change of Formula 1 did not exceed the national standard requirement of GB / T23457-2017 from day 1 to day 14, that is, the dimensional change rate ΔL of Formula 1 was always ≤1.5%.

[0158] In other words, in the presence of asphalt, the dimensional stability of the metallocene-catalyzed linear low-density polyethylene of the present invention is superior to that of the Ziegler-Natta-catalyzed linear low-density polyethylene.

[0159] Moreover, in the thermal aging test, the dimensional stability of the metallocene-catalyzed linear low-density polyethylene of the present invention meets the national standard requirements of GB / T23457-2017.

[0160] All documents described herein, including any priority documents and / or experimental procedures, are incorporated by reference to all rights, without prejudice to the present invention. It will be apparent from the foregoing overview and specific embodiments that, while the form of this disclosure has been illustrated and described, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, it is not intended that this disclosure be limited thereto. Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever a composition, element, or group of elements precedes the transitional term “comprising,” it should be understood that the same composition or group of elements preceding the enumerated composition, element, or element, and vice versa, is also considered to have the transitional terms “consistently composed of,” “composed of,” “selected from,” or “is” preceding the enumerated composition, element, or elements.

[0161] For simplicity, only certain numerical ranges are explicitly disclosed in this document. However, a lower limit can be combined with any other upper limit to define a range that is not explicitly stated, and similarly, a lower limit can be combined with any other lower limit to define a range that is not explicitly stated; likewise, an upper limit can be combined with any upper limit to define a range that is not explicitly stated. Furthermore, even if not explicitly stated, every point or individual value between the two endpoints is included within the range. Therefore, each point or individual value itself can serve as a lower or upper limit, combined with other points or individual values ​​or other lower or upper limits to define a range that is not explicitly stated.

Claims

1. A waterproof membrane comprising a polyethylene polymer layer and an asphalt layer, wherein the polyethylene polymer layer and the asphalt layer are adjacent to each other. The polyethylene polymer layer comprises approximately 20 wt% to approximately 100 wt% metallocene-catalyzed linear low-density polyethylene and approximately 0 wt% to approximately 80 wt% Ziegler-Natta-catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer. Among them, metallocene-catalyzed linear low-density polyethylene has a content of approximately 0.900 g / cm³. 3 Approximately 0.940 g / cm³ 3 The density, measured according to ASTM D-792, of which metallocene-catalyzed linear low-density polyethylene has a melt index I of approximately 0.10 g / 10 min to approximately 5.00 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg), the linear low-density polyethylene with metallocene catalysis has a melt index ratio of approximately 10 to approximately 50. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg), and The linear low-density polyethylene catalyzed by Ziegler-Natta has a density of approximately 0.910 g / cm³. 3 Approximately 0.930 g / cm³ 3 The density, measured according to ASTM D-1505, of which Ziegler-Natta catalyzed linear low-density polyethylene has a melt index I of approximately 0.50 g / 10 min to approximately 3.00 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

2. The waterproof membrane according to claim 1, wherein the metallocene-catalyzed linear low-density polyethylene comprises about 70 mol% to about 99 mol% of ethylene-derived units and about 1 mol% to about 30 mol% of polymer units derived from C3-C20 olefins, based on the total molar number of polymer units of the metallocene-catalyzed linear low-density polyethylene.

3. The waterproof membrane according to claim 1 or 2, wherein the polyethylene polymer layer comprises metallocene-catalyzed linear low-density polyethylene and optionally Ziegler-Natta-catalyzed linear low-density polyethylene.

4. The waterproof membrane according to any one of claims 1-3, wherein the metallocene-catalyzed linear low-density polyethylene has a content of about 0.905 g / cm³. 3 - Approximately 0.940 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.940 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.930 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.920 g / cm³ 3 The density, measured according to ASTM D-792; and / or The metallocene-catalyzed linear low-density polyethylene has a melt index (MI, or I0) of approximately 0.10 g / 10 min to approximately 4.00 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 3.00 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 2.00 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 1.00 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 0.90 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 0.80 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 0.70 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg); and / or Metallocene-catalyzed linear low-density polyethylene has a melt index ratio of about 20 to about 50, for example, about 20 to about 40. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

5. The waterproof membrane according to any one of claims 1-4, wherein the metallocene-catalyzed linear low-density polyethylene has a content of about 0.916 g / cm³. 3 Its density, measured according to ASTM D-792, has a melt index I of approximately 0.50 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg), and with a melt index of approximately 38, it is comparable to I. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg); or Among them, metallocene-catalyzed linear low-density polyethylene has a content of approximately 0.912 g / cm³. 3 Its density, measured according to ASTM D-792, has a melt index I of approximately 0.50 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg), and with a melt index of approximately 35, it is comparable to I. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

6. The waterproof membrane according to any one of claims 1-5, wherein the Ziegler-Natta catalyzed linear low-density polyethylene has a content of about 0.910 g / cm³. 3 To approximately 0.925 g / cm 3 Its density, or approximately 0.910 g / cm³. 3 To approximately 0.920 g / cm 3 The density, measured according to ASTM D-1505; and / or The linear low-density polyethylene catalyzed by Ziegler-Natta exhibits a melt index I of approximately 1.00 g / 10 min to approximately 3.00 g / 10 min. 2.16 Or a melt index I of approximately 1.00 g / 10 min to approximately 2.50 g / 10 min. 2.16 Or a melt index I of approximately 1.50 g / 10 min to approximately 2.50 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

7. A waterproof membrane comprising a polyethylene polymer layer and an asphalt layer, wherein the polyethylene polymer layer and the asphalt layer are adjacent to each other. The polyethylene polymer layer comprises approximately 20 wt% to approximately 100 wt% metallocene-catalyzed linear low-density polyethylene and approximately 0 wt% to approximately 80 wt% Ziegler-Natta-catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer. Among them, metallocene-catalyzed linear low-density polyethylene has a content of approximately 0.916 g / cm³. 3 Its density, measured according to ASTM D-792, has a melt index I of approximately 0.50 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg), and with a melt index of approximately 38, it is comparable to I. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg), or Among them, metallocene-catalyzed linear low-density polyethylene has a content of approximately 0.912 g / cm³. 3 Its density, measured according to ASTM D-792, has a melt index I of approximately 0.50 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg), and with a melt index of approximately 35, it is comparable to I. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg), and The linear low-density polyethylene catalyzed by Ziegler-Natta exhibits a density of approximately 0.918 g / cm³. 3 Its density, measured according to ASTM D-1505, has a melt index I of approximately 2.0 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

8. The method for preparing a waterproof membrane according to any one of claims 1-7, wherein the polyethylene polymer layer is prepared by a sheet extrusion production line for a polyethylene membrane; wherein there may or may not be an adhesive between the polyethylene polymer layer and the bitumen layer.

9. The adhesive according to claim 8, wherein the asphalt layer is self-adhesive asphalt.

10. Use of metallocene-catalyzed linear low-density polyethylene in bitumen-containing waterproof membranes to improve the puncture resistance of the membranes, wherein the waterproof membrane comprises a polyethylene polymer layer and a bitumen layer, wherein the polyethylene polymer layer and the bitumen layer are adjacent to each other. The polyethylene polymer layer comprises approximately 20 wt% to approximately 100 wt% metallocene-catalyzed linear low-density polyethylene and approximately 0 wt% to approximately 80 wt% Ziegler-Natta-catalyzed linear low-density polyethylene, based on the weight of the polyethylene polymer layer. Among them, metallocene-catalyzed linear low-density polyethylene has a content of approximately 0.900 g / cm³. 3 Approximately 0.940 g / cm³ 3 The density, measured according to ASTM D-792, of which metallocene-catalyzed linear low-density polyethylene has a melt index I of approximately 0.10 g / 10 min to approximately 5.00 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg), the linear low-density polyethylene with metallocene catalysis has a melt index ratio of approximately 10 to approximately 50. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg), and The linear low-density polyethylene catalyzed by Ziegler-Natta has a density of approximately 0.910 g / cm³. 3 Approximately 0.930 g / cm³ 3 The density, measured according to ASTM D-1505, of which Ziegler-Natta catalyzed linear low-density polyethylene has a melt index I of approximately 0.50 g / 10 min to approximately 3.00 g / 10 min. 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

11. The use according to claim 10, wherein the metallocene-catalyzed linear low-density polyethylene comprises about 70 mol% to about 99 mol% of ethylene-derived units and about 1 mol% to about 30 mol% of polymer units derived from C3-C20 olefins, based on the total number of moles of polymer units of the metallocene-catalyzed linear low-density polyethylene.

12. The use according to claim 10 or 11, wherein the metallocene-catalyzed linear low-density polyethylene has about 0.905 g / cm³. 3 - Approximately 0.940 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.940 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.930 g / cm³ 3 For example, approximately 0.910 g / cm³ 3 - Approximately 0.920 g / cm³ 3 The density, measured according to ASTM D-792; and / or The metallocene-catalyzed linear low-density polyethylene has a melt index (MI, or I0) of approximately 0.10 g / 10 min to approximately 4.00 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 3.00 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 2.00 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 1.00 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 0.90 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 0.80 g / 10 min, for example, approximately 0.10 g / 10 min to approximately 0.70 g / 10 min. 2.16 According to ASTM D-1238 (190℃ / 2.16kg); and / or Metallocene-catalyzed linear low-density polyethylene has a melt index ratio of about 20 to about 50, for example, about 20 to about 40. 21.6 / I 2.16 , where I 21.6 Measured according to ASTM D-1238 (190℃ / 21.6kg) and I 2.16 Measured according to ASTM D-1238 (190℃ / 2.16kg).

Images