Reinforced melt-strength low-density polyethylene for use in films or blends.

Abstract

This invention provides a novel ethylene-based polymer with an optimized balance of melt strength, processability, and density (rigidity). [Solution] The melt strength measured at 190°C is 5.5 cN or higher, and 0.9210 g / cm³ 3 The above and 0.9275 g / cm³ 3 Low-density polyethylene is provided, having a density below the specified value and a melt index I2 measured at 190°C of 4.5 g / 10 min or more.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 005,798, filed on April 6, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] (Field of the Invention) Embodiments of the present disclosure generally relate to low - density polyethylene, particularly low - density polyethylene having enhanced melt strength.

Background Art

[0003] Properties of resins used to manufacture films, such as melt strength, viscosity, molecular weight distribution, density, etc., can affect the performance of films such as cast films, inflation films, or thermoformed films. By blending different types of ethylene - based polymers, such as low - density polyethylene (LDPE) having linear low - density polyethylene (LLDPE), some properties can be improved, but this blend can sometimes result in inconsistencies between batches. sity Polyethylene, LLDPE), some properties can be improved, but this blend can sometimes result in inconsistencies between batches. ene, LDPE), some properties can be improved, but this blend can sometimes result in inconsistencies between batches. 性のいくつかを改善することができるが、このブレンドはバッチ間の不一致をもたらす場 合がある。

[0004] Ethylene - based polymers are disclosed in the following references: International Publication No. WO 2017 / 1 4698, WO 2010 / 042390, WO 2010 / 144784, WO 20 11 / 019563, WO 2012 / 082393, WO 2006 / 049783 、同第2009 / 114661号、米国特許出願公開第2008 / 0125553号、米 ​​​National Patent Nos. 7,741,415, 8,916,667, and 9,303,107 , and European Patent No. 2239283(B1). However, such polymers have been improved. It does not provide an optimized balance between melt strength and film properties. Therefore, a new material with an optimized balance of melt strength, processability, and density (rigidity) There is still a need for ethylene-based polymers, such as LDPE. [Overview of the project]

[0005] In this embodiment, the low-density polyethylene was measured at 190 degrees Celsius (°C) and yielded 5.5 centimeters. Melt strength of thinewtons (cN) or more, and 0.9210 grams / cubic centimeter (g / cm 3 ) or more and 0.9275 g / cm³ 3 The following densities and 4.5 measured at 190°C Includes a melt index of I2 of g / 10 minutes or more.

[0006] In this embodiment, low-density polyethylene has a solvent content exceeding 5.5 cN as measured at 190°C. Melting strength and 0.9210 g / cm³ 3 The above and 0.9275 g / cm³ 3 The following densities and include nothing.

[0007] Additional features and advantages are described in the following detailed description, and will be understood by those skilled in the art. It is somewhat easy to understand, or, as detailed below, the claims, and By carrying out the embodiments described herein, including the attached drawings, it is recognized It is likely.

[0008] Both the general description above and the detailed description below illustrate various embodiments and patent This is intended to provide an overview or framework for understanding the nature and characteristics of the subject matter being claimed. Please understand the following. The attached drawings are included to provide a further understanding of various embodiments. , and incorporated herein, and constituting a part thereof. The drawings are various as described herein. This provides examples of embodiments and, along with descriptions, helps to explain the principles and operation of the claimed subject matter. stand. [Brief explanation of the drawing]

[0009] [Figure 1] A schematic diagram of the process system according to the embodiments disclosed and described herein is shown. [Figure 2] This figure shows a CDFI® chromatogram of low-density polyethylene according to embodiments disclosed and described herein. [Figure 3] This figure shows a CDFD V chromatogram of low-density polyethylene according to embodiments disclosed and described herein. [Figure 4] This figure shows a CDFL S chromatogram of low-density polyethylene according to embodiments disclosed and described herein. [Figure 5] This figure shows an LSP chromatogram of low-density polyethylene according to the embodiments disclosed and described herein. [Figure 6] This graph overwrites the melt strength at 190°C of low-density polyethylene according to the embodiments disclosed and described herein. [Modes for carrying out the invention]

[0010] Herein, we will describe specific embodiments of this application. However, this disclosure is not limited to different forms. It may be further elaborated in this way, and should be interpreted as being limited to the embodiments described herein. No. Rather, these embodiments make this disclosure thorough and complete, and cover the subject matter. The scope is provided in a manner that fully conveys the scope to those skilled in the art.

[0011] According to the embodiment, the low-density polyethylene has a density of 5.5 cN or higher as measured at 190°C. Melt strength and 0.9210 g / cm³ 3 The above and 0.9275 g / cm³ 3 The density is as follows: , including a melt index of I2, which is 4.5 g / 10 min or more as measured at 190°C, According to the embodiment, low-density polyethylene has a density exceeding 5.5 cN as measured at 190°C. Melt strength and 0.9210 g / cm³ 3 The above and 0.9275 g / cm³ 3 The density is as follows: , including.

[0012] definition As used herein, the term “composition” means a mixture of materials that constitute the composition. , and also encompass reaction products and decomposition products formed from the materials of the composition.

[0013] As used herein, the terms “blend” or “polymer blend” are: A blend refers to a mixture of two or more polymers. A blend is miscible, whether miscible or not (at the molecular level). (Phase separation may occur in the blend.) Lend uses transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art. As determined by the method, it may contain one or more domain configurations. It is not necessary. Blending is done at a macro level (for example, molten blended resin or compounding). ) or two or more polymers at the micro level (e.g., simultaneous molding in the same reactor) This can be achieved by mixing them together.

[0014] The terms "comprising", "including", "having" and their derivatives, whether or not they are specifically disclosed, are not intended to exclude the presence of any additional components, steps or procedures. To avoid doubt, all compositions claimed through the use of the term "comprising" will, unless otherwise stated, whether polymeric or not, include any additional additives, adjuvants or compounds. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other components, steps or procedures, except for those that are not essential to the operation. The term "consisting of" excludes any component, step or procedure not specifically depicted or listed. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The terms "comprising", "including", "having" and their derivatives, whether or not they are specifically disclosed, are not intended to exclude the presence of any additional components, steps or procedures. To avoid doubt, all compositions claimed through the use of the term "comprising" will, unless otherwise stated, whether polymeric or not, include any additional additives, adjuvants or compounds. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other components, steps or procedures, except for those that are not essential to the operation. The term "consisting of" excludes any component, step or procedure not specifically depicted or listed. The terms "comprising", "including", "having" and their derivatives, whether or not they are specifically disclosed, are not intended to exclude the presence of any additional components, steps or procedures. To avoid doubt, all compositions claimed through the use of the term "comprising" will, unless otherwise stated, whether polymeric or not, include any additional additives, adjuvants or compounds. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other components, steps or procedures, except for those that are not essential to the operation. The term "consisting of" excludes any component, step or procedure not specifically depicted or listed. The terms "comprising", "including", "having" and their derivatives, whether or not they are specifically disclosed, are not intended to exclude the presence of any additional components, steps or procedures. To avoid doubt, all compositions claimed through the use of the term "comprising" will, unless otherwise stated, whether polymeric or not, include any additional additives, adjuvants or compounds. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other components, steps or procedures, except for those that are not essential to the operation. The term "consisting of" excludes any component, step or procedure not specifically depicted or listed. The terms "comprising", "including", "having" and their derivatives, whether or not they are specifically disclosed, are not intended to exclude the presence of any additional components, steps or procedures. To avoid doubt, all compositions claimed through the use of the term "comprising" will, unless otherwise stated, whether polymeric or not, include any additional additives, adjuvants or compounds. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other components, steps or procedures, except for those that are not essential to the operation. The term "consisting of" excludes any component, step or procedure not specifically depicted or listed. The terms "comprising", "including", "having" and their derivatives, whether or not they are specifically disclosed, are not intended to exclude the presence of any additional components, steps or procedures. To avoid doubt, all compositions claimed through the use of the term "comprising" will, unless otherwise stated, whether polymeric or not, include any additional additives, adjuvants or compounds. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other components, steps or procedures, except for those that are not essential to the operation. The term "consisting of" excludes any component, step or procedure not specifically depicted or listed. The terms "comprising", "including", "having" and their derivatives, whether or not they are specifically disclosed, are not intended to exclude the presence of any additional components, steps or procedures. To avoid doubt, all compositions claimed through the use of the term "comprising" will, unless otherwise stated, whether polymeric or not, include any additional additives, adjuvants or compounds. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other components, steps or procedures, except for those that are not essential to the operation. The term "consisting of" excludes any component, step or procedure not specifically depicted or listed. The terms "comprising", "including", "having" and their derivatives, whether or not they are specifically disclosed, are not intended to exclude the presence of any additional components, steps or procedures. To avoid doubt, all compositions claimed through the use of the term "comprising" will, unless otherwise stated, whether polymeric or not, include any additional additives, adjuvants or compounds. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent description any other components, steps or procedures, except for those that are not essential to the operation. The term "consisting of" excludes any component, step or procedure not specifically depicted or listed.

[0015] The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. 3 The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.915 - 0.935 g / cm. As referred to herein, terms such as low density polyethylene, LDPE, etc. refer to the polyethylene polymer itself and, unless otherwise specified, do not include any additives that may be blended with the low density polyethylene. Thus, the properties of the low density polyethylene referred to in the present disclosure, unless otherwise specified, refer to the properties of the low density polyethylene polymer itself without additives. The term "low density polyethylene", abbreviated herein as "LDPE", may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene". LDPE is known in the art and herein refers to an ethylene homopolymer prepared using free radical high pressure (≧100 MPa (e.g., 100 - 400 MPa)) polymerization. LDPE resins typically have a density within the range of 0.9

[0016] As used herein, "LLDPE" is an abbreviation for "linear low-density polyethylene." The term refers to resins produced using the Ziegler-Natta catalyst system, and is limited to... However, it does not contain bis-metallocene catalysts (sometimes referred to as "m-LLDPE"), or phosphine. Single-site catalysts such as imides and geometrically constrained catalysts are used. Resins manufactured using the same method, and, but not limited to, bis(biphenylphenoxy) catalysts (polyvalent Manufactured using post-metallocene molecular catalysts such as reel oxyether catalysts. LLDPE includes a resin that has been processed. LLDPE is linear, substantially linear, or heterogeneous ethylene It contains a copolymer or homopolymer. LLDPE is classified as 5,272,236 in the United States. Nos. 5,278,272, 5,582,923, and 5,733,15 A substantially linear ethylene polymer, as further defined in Article 5, U.S. P. 3,6 Homogeneously branched ethylene polymer compositions such as those described in Patent No. 45,992, U.S. Patent No. 4, Heterogeneous branched materials, such as those prepared according to the process disclosed in Patent No. 076,698. Ethylene polymers and blends thereof (U.S. Patent No. 3,914,342 or No. 5) This includes those disclosed in patents 854, 045, etc. LLDPE resin is the said technical component Using any type of reactor or reactor configuration known in the field, gas phase, solution phase, or These can be produced by slurry polymerization, or any combination thereof.

[0017] Process Embodiment To produce low-density polyethylene, high-pressure free radical-initiated autoclave tubular A reactor combination polymerization process was used. Two different high-pressure free radical-initiated polymerization processes were employed. Types of reaction systems are known. In the first type, a stirring oven with one or more reaction zones is used. Autoclave vessels are used. Autoclave reactors typically use initiators or monomers. It has several injection points for the feed, or both. In the second type, the jacket The attached tube is used as a tubular reactor having one or more reaction zones. There is no such thing, but the length of the reactor is 100 to 3000 meters (m), or 1000 to 2000 meters. m may be preferable. The start of the reaction zone in the reactor is typically initiated by the reaction initiator, ethyl N, chain transfer agents (or telomeres), comonomers, and any combination thereof The high-pressure process is defined by one of the side injection methods. Furthermore, in an autoclave or tubular reactor having one or more reaction zones, A combination of autoclaves and tubular reactors, each containing one or more reaction zones. Even if they exist, it can still be implemented.

[0018] The molecular weight can be controlled using a chain transfer agent. In a preferred embodiment, 1 One or more chain transfer agents (CTAs) can be added to the polymerization process. Typical CTAs include propylene, isobutane, n-butane, 1-butene, and methyl Examples include, but are not limited to, ethyl ketones, acetone, and propionaldehyde. No. In one embodiment, the amount of CTA used in the process is 0.03% of the total reaction mixture. It is 10 percent by weight.

[0019] Ethylene used in the production of low-density polyethylene is obtained from loop recycling flows and polarized This may be purified ethylene obtained by removing certain components. Low-density polyethylene can be produced. It is not typical for purified ethylene to be required for this purpose. In such cases, recirculation Ethylene can be used from the piping.

[0020] Next, low-density polyethylene is produced according to the embodiments disclosed and described herein. Embodiments of systems and processes for achieving this will be described in detail.

[0021] Reaction sys of the process used to produce low-density polyethylene according to the embodiment Referring to Figure 1, which is a block diagram of the system, the process reaction system 100 shown in Figure 1 is It is a partially closed-loop, double-recycling, high-pressure, low-density polyethylene system. According to the embodiment shown in Figure 1, the process reaction system 100 is a booster / primary. Adiabatic autoclave reactor coupled with compressor 110, supercompressor 120, and tube reactor 140 Autoclave reactor 1 may include 130, a high-pressure separator 150, and a low-pressure separator 160. 30 may include three zones 130A, 130B, and 130C according to the embodiment. The peroxide initiator stream 124 flows into zone 130A of each zone 1 of the autoclave reactor 130. The third peroxide initiator stream 125 may be injected into zone 3 of the autoclave reactor 130. It can be injected at 130°C. The second peroxide initiator stream 123 is mixed with the side stream 122. Alternatively, it may be injected into either zone 2 of reactor 130B. Similarly, peroxide initiator stream 1 32 can be injected into the inlet of the tube reactor 140. The tube reactor 140 is outside the tube reactor 140. A cooling jacket (not shown) attached around the shell may be used. Tube reactor 140 The cooling jacket can use high-pressure water to cool or regulate the temperature inside the tube reactor 140.

[0022] Fresh ethylene supply stream 101 is connected to chain transfer agent (CTA) stream 1 Mixed with 02 and ethylene-rich flow 162, the first mixed flow (i.e., fresh ethylene This can form a mixed flow of high-pressure ethylene recycling and CTA. It is sequentially connected to the supercompressor 120 located downstream of the booster / primary compressor 110. It can be introduced into the booster / primary compressor 110. Then, the mixed flow is compressed and exits the booster / primary compressor 110 as the compressed flow 111. The compressed flow 111 is part of the ethylene-rich flow 152 of the high-pressure separator 150. Mixed with the Kur flow 154, the second mixed flow (i.e., overcompressed fresh ethylene and, High-pressure ethylene recycling can form a mixed flow of CTA and high-pressure ethylene recycling. This second mixed flow may be introduced into the supercompressor 120, which then overcompresses It is sequentially connected to the booster / primary compressor 110 located upstream of machine 120, and is overcompressed The machine 120 is sequentially connected to the autoclave reactor 130 located downstream. At 0, the second mixed flow is further compressed into the supercompressed flow 121 and exits the supercompressor 120.

[0023] The overcompressed flow 121 is introduced into the autoclave reactor 130, and the autoclave reactor The reactor 130 is sequentially connected to the supercompressor 120 located upstream of the autoclave reactor 130. It is also connected sequentially to the tube reactor 140 located downstream of the autoclave reactor 130. For example, a separator (not shown) separates the side flow 122 from the overcompressed flow 121. The side flow 122 is introduced into the reactor 130. The portions of 122 and the overcompressed flow 121 may be in equal proportions. The portion of the overcompressed flow 121 is Autoclave reactor 130, zone 1, 130A, etc. It can be supplied to the top. Side flow 122 is used in autoclave reactor 1 such as zone 2, 130B. It can be supplied to side 30. In the autoclave reactor 130, the supercompressed flow 121 and The side flow 122 can be partially polymerized and used as polymerization flow 131 in an autoclave reactor. It exits 130. The flow 131 can then be supplied to the tube reactor 140. 0 is sequentially connected to the autoclave reactor 130 located upstream of the tube reactor 140. It is sequentially connected to the high-pressure separator 150 located downstream of the tube reactor 140. The flow 131 is further polymerized and can exit the tube reactor 140 as polymerization flow 141. ru.

[0024] According to the embodiment, polymerization is carried out in an autoclave reactor 13 with the help of four mixtures. It can be started in 0 and tube reactor 140. Each mixture can be injected into the inlet of each reaction zone. It contains one or more free radical initiation systems. The first peroxide initiator flow 124 is It can be introduced into zone 1, 130A of autoclave reactor 130. Second peroxide initiation The agent stream 123 can be introduced into zone 2, 130B of the autoclave reactor 130. The peroxide initiator stream 125 is introduced into zone 3 of autoclave reactor 130 at 130°C. This is possible. Finally, a fourth peroxide initiator stream 132 can be introduced into the tube reactor 140.

[0025] The polymerization flow 141 is introduced into the high-pressure separator 150, and the high-pressure separator 150 performs high-pressure separation It is sequentially connected to reactor 140 located upstream of vessel 150, and also sequentially connected to low-pressure separator 160. In the high-pressure separator 150, the polymerization flow 141 is mixed with the ethylene-rich flow 152 and polymer The ethylene-rich flow 153 is separated into two parts. The first part of the ethylene-rich flow 153 is the process reaction. The second portion of the ethylene-rich flow 154, purged from system 100, is cooled and over-processed. The ethylene-rich flow 152 is recirculated to the compressor 120, where it is introduced into the supercompressor 120. It is mixed with the compressed flow 111.

[0026] The polymer-rich flow 151 is introduced into the low-pressure separator 160, and the low-pressure separator 160 The low-pressure separator 160 is sequentially connected to the high-pressure separator 150 located upstream of it, and the low-pressure separator The booster / primary compressor 110 located downstream of the unit 160 is sequentially connected. Low-pressure separator In 160, polymer-rich flow 151 is followed by a second polymer-rich flow 161 and a second ethyl It is separated into Lenrich stream 162. The second polymer-rich stream 161 is used for process reaction systole. The second ethylene-rich flow 162 can exit Tem 100 and be introduced into an extruder (not shown). This is introduced into the booster / primary compressor 110, which is sequentially connected to the low-pressure separator 160. It is mixed with fresh ethylene supply stream 101 beforehand.

[0027] According to the embodiment, the initiator is t-butyl peroxypivalate (t-butyl peroxypi valate, TBPIV), t-butyl peroxy-2 ethylhexanoate (t-butyl pero xy-2 ethylhexanoate (TBPO), tert-butylperoxyacetate (tert-buty (L peroxyacetate, TBPA), di-tert-butyl peroxide The following may be selected: oxide, DTBP, and mixtures thereof.

[0028] Low-density polyethylene properties of the embodiment Low melt strength and desirable melt index and density or modulus Density polyethylene is provided in the embodiments disclosed and described herein. The properties of low-density polyethylene as shown and described are as follows. The properties listed below are Although described in separate paragraphs, by changing the various process conditions mentioned above, The characteristics of any of the paragraphs below can be combined with the characteristics of any of the other paragraphs below. Please understand that. Therefore, any combination of the various characteristics listed below is Low-density polyethylene is intended and can be manufactured according to the embodiment.

[0029] According to the embodiment, low-density polyethylene is 0.921 per cubic centimeter. Density (g / cm³) of 0 or more and 0.9275 grams or less 3 ) may have. Density measurement is AS The procedure was performed within 1 hour after pressing the sample using TM D792-08, Method B. The density of polyethylene is 0.9215 g / cm³. 3 The above and 0.9270 g / cm³ 3 Below, 0 0.9220g / cm³ 3 The above and 0.9265 g / cm³ 3 Below, 0.9225g / cm 3 Below Above 0.9260 g / cm³ 3Below, 0.9230g / cm 3 More than 0.9255g / cm 3 Below, 0.9235g / cm 3 The above and 0.9250 g / cm³ 3 The following, or 0.9 240g / cm 3 The above and 0.9245 g / cm³ 3 It has the following density:

[0030] In this embodiment, low-density polyethylene is heated to 190°C according to ASTM D 1238. Furthermore, measured with a load of 2.16 kg, the amount was 4.5 grams per 10 minutes (g / 10 mins). It has the above, for example, 4.6g / 10 min or more, 4.7g / 10 min or more, 4.8g / 10 min or more Above, 4.9g / 10 minutes or more, 5.0g / 10 minutes or more, 5.1g / 10 minutes or more, 5.2g / 10 minutes or more, 5.3g / 10 minutes or more, 5.4g / 10 minutes or more, 5.5g / 10 minutes or more, 5 .6g / 10 minutes or more, 5.7g / 10 minutes or more, 5.8g / 10 minutes or more, 5.9g / 10 minutes It has a melt index (I2) of 6.0 g / 10 min or more. In the embodiment, it has a melt index (I2) of 6.0 g / 10 min or more. The melt index (I2) is 7.5g / 10 min or less, for example, 7.4g / 1 0 minutes or less, 7.3g / 10 minutes or less, 7.2g / 10 minutes or less, 7.1g / 10 minutes or less, 7. 0g / 10 minutes or less, 6.9g / 10 minutes or less, 6.8g / 10 minutes or less, 6.7g / 10 minutes or less Bottom, 6.6g / 10 minutes or less, 6.5g / 10 minutes or less, 6.4g / 10 minutes or less, 6.3g / The duration is 10 minutes or less, 6.2g / 10 minutes or less, or 6.1g / 10 minutes or less. In the embodiment, The melt index (I2) is between 4.5g / 10 min and 7.5g / 10 min. For example, 4.6g / 10 min or more and 7.5g / 10 min or less, 4.7g / 10 min or more and 7 0.5g / 10 mins or less, 4.8g / 10 mins or more and 7.5g / 10 mins or less, 4.9g / 10 5 minutes or more and 7.5g / 10 minutes or less, 5.0g / 10 minutes or more and 7.5g / 10 minutes or less, 0.1g / 10 minutes or more and 7.5g / 10 minutes or less, 5.2g / 10 minutes or more and 7.5g / 1 Less than 0 minutes, 5.3g / 10 minutes or more and 7.5g / 10 minutes or less, 5.4g / 10 minutes or more and 7.5g / 10 minutes or less, 5.5g / 10 minutes or more and 7.5g / 10 minutes or less, 5.6g / 1 0 minutes or more and 7.5g / 10 minutes or less, 5.7g / 10 minutes or more and 7.5g / 10 minutes or less, 5.8g / 10 minutes or more and 7.5g / 10 minutes or less, 5.9g / 10 minutes or more and 7.5g / The duration is 10 minutes or less, or 6.0 g / 10 minutes or more and 7.5 g / 10 minutes or less. In the embodiment, The melt index (I2) is 4.5g / 10 min or more and 7.0g / 10 min or less. For example, 5.0g / 10 min or more and 6.5g / 10 min or less, or approximately 6.0g / 10 min That is the case.

[0031] The melt strength is measured using a capillary rheometer, as disclosed below. It is measured using tens. In the embodiment, the melt strength is 5.5 centinewtons ( cN) or greater, for example, 5.6 cN or greater, 5.7 cN or greater, 5.8 cN or greater, 5.9 cN or more, 6.0cN or more, 6.1cN or more, 6.2cN or more, 6.3cN or more, 6.4 cN or more, 6.5cN or more, 6.6cN or more, 6.7cN or more, 6.8cN or more, 6.9 cN or more, 7.0cN or more, 7.1cN or more, 7.2cN or more, 7.3cN or more, 7.4 cN or more, 7.5cN or more, 7.6cN or more, 7.7cN or more, 7.8cN or more, 7.9 cN or more, 8.0 cN or more, 8.1 cN or more, 8.2 cN or more, 8.3 cN or more, or 8 It is 0.4 cN or more. In the embodiment, the melt strength is 5.5 cN or more and 8.5 cN or less. Yes, for example, 5.6 cN or more and 8.5 cN or less, or 5.7 cN or more and 8.5 cN or less. , 5.8 cN or more and 8.5 cN or less, 5.9 cN or more and 8.5 cN or less, 6.0 cN Above and below 8.5 cN, above 6.1 cN and below 8.5 cN, above 6.2 cN and below 8. 5 cN or less, 6.3 cN or more and 8.5 cN or less, 6.4 cN or more and 8.5 cN or less, 6.5 cN or more and 8.5 cN or less, 6.6 cN or more and 8.5 cN or less, 6.7 cN or less Above and 8.5 cN or less, 6.8 cN or more and 8.5 cN or less, 6.9 cN or more and 8.5 cN or less, 7.0 cN or more and 8.5 cN or less, 7.1 cN or more and 8.5 cN or less, 7 0.2 cN or more and 8.5 cN or less, 7.3 cN or more and 8.5 cN or less, 7.4 cN or more and 8.5 cN or less, 7.5 cN or more and 8.5 cN or less, 7.6 cN or more and 8.5 c Less than or equal to N, 7.7 cN or more and 8.5 cN or less, 7.8 cN or more and 8.5 cN or less, 7. 9 cN or more and 8.5 cN or less, 8.0 cN or more and 8.5 cN or less, or 8.1 cN or more. 8.5 cN or less, 8.2 cN or more and 8.5 cN or less, 8.3 cN or more and 8.5 cN The melt strength is less than or equal to 8.4 cN and 8.5 cN. In the embodiment, the melt strength is 5. It is 5 cN or more and 8.5 cN or less, for example, 5.5 cN or more and 8.3 cN or less, 5 0.5 cN or more and 8.2 cN or less, 5.5 cN or more and 8.1 cN, 5.5 cN or more and 8.0 cN or less, 5.5 cN or more and 7.9 cN or less, 5.5 cN or more and 7.8 cN or less Below, 5.5 cN or more and 7.7 cN or less, 5.5 cN or more and 7.6 cN or less, 5.5 c N or more and 7.5 cN or less, 5.5 cN or more and 7.4 cN or less, 5.5 cN or more and 7 Less than 0.3 cN, 5.5 cN or more and 7.2 cN or less, 5.5 cN or more and 7.1 cN or less , 5.5 cN or more and 7.0 cN or less, 5.5 cN or more and 6.9 cN or less, 5.5 cN Above and below 6.8 cN, above 5.5 cN and below 6.7 cN, above 5.5 cN and below 6. 6 cN or less, 5.5 cN or more and 6.5 cN or less, 5.5 cN or more and 6.4 cN or less, 5.5 cN or more and 6.3 cN or less, 5.5 cN or more and 6.2 cN or less, 5.5 cN or less Above and 6.1 cN or less, 5.5 cN or more and 6.0 cN or less, 5.5 cN or more and 5.9 cN or less, 5.5 cN or more and 5.8 cN or less, 5.5 cN or more and 5.7 cN or less, and It is 5.5 cN or more and 5.6 cN or less. According to the embodiment, the melt strength is 5.5 c It is greater than or equal to N and less than or equal to 8.5 cN, for example, 6.0 cN or greater and less than or equal to 8.0 cN, 6.0 cN or more and 7.5 cN or less, 6.4 cN or more and 7.0 cN or less, or 6.4 cN or more Furthermore, it is 6.8 cN or less.

[0032] According to the embodiment, the relationship between melt strength and melt index is measured at 190°C. The melting strength at cN may be determined by the following formula. Melt strength (cN) ≥ [-0.780 * (melt index, I2) + 9.9cN] ±5% Alternatively, the melt strength measured at 190°C can be determined by the following alternative formula. Melt strength (cN) ≥ [-0.780 * (melt index, I2) + 10.3cN] ]±5%

[0033] According to the embodiment, the hexane extract of low-density polyethylene is 2.60% by weight. It is less than or equal to (by weight), for example, 2.50% by weight or less, 2.40% by weight or less, 2.30% by weight or less. Weight % or less, 2.20 weight % or less, 2.10 weight % or less, 2.00 weight % or less, 1.90 Weight % or less, 1.80 weight % or less, 1.70 weight % or less, 1.60 weight % or less, 1.50 It is less than or equal to % by weight, or 1.40% by weight or less. In the embodiment, a low density is obtained using the hexane method. The polyethylene extract is 0.50% by weight or more and 2.60% by weight or less, for example. , 0.60% by weight or more and 2.50% by weight or less, 0.70% by weight or more and 2.40% by weight The following applies: 0.80% by weight or more and 2.30% by weight or less, 0.90% by weight or more and 2.30% by weight Less than or equal to a certain amount, 1.00% by weight or more and 2.20% by weight or less, 1.10% by weight or more and 2.1 0% or less by weight, 1.20% or more by weight and 2.00% or less by weight, 1.20% or more by weight and 1 0.90% by weight or less, 1.20% by weight or more, and 1.80% by weight or less, 1.20% by weight or more 1.70% by weight or less, 1.20% by weight or more and 1.60% by weight or less, 1.20% by weight or less It is above 1.50% by weight or less, or approximately 1.40% by weight.

[0034] Number average molecular weight of low-density polyethylene measured by conventional GPC method ( According to the embodiment, Mn(conv) is 12,000 grams per mole (g / mo). l) or more and 18,500 g / mol or less, for example, 13,000 g / mol or more 18,500 g / mol or less, 14,000 g / mol or more, and 17,000 g / mol or less l or less, 14,000 g / mol or more and approximately 17,000 g / mol or less, or approximately 14, It is 500 g / mol. Mn(conv) is a gel permeation chromatograph disclosed herein. GPC (Gel Permeation Schema) Protocol (Conventional) It is measured according to the law.

[0035] Weight-average molecular weight of low-density polyethylene measured according to the conventional GPC method. (Mw(conv)) is, according to the embodiment, 110,000 grams per mole (g / It is greater than or equal to 140,000 g / mol and less than or equal to 115,000 g / m³. ol or more and 135,000 g / mol or less, 117,500 g / mol or more and 130 It is less than 1,000 g / mol, or approximately 125,000 g / mol. Mw(conv) is The measurements are taken in accordance with the conventional GPC protocol disclosed herein.

[0036] z-average molecular weight of low-density polyethylene measured according to the conventional GPC method ( Mz(conv)) is, according to the embodiment, 500,000 grams per mole (g / m³). (ol) or more, for example, 500,000 g / mol or more and 650,000 g / mol or more. l or less, for example, 510,000 g / mol or more and 640,000 g / mol or less, 5 20,000 g / mol or more and 630,000 g / mol or less, 530,000 g / m³ ol or more and 620,000 g / mol or less, 540,000 g / mol or more and 610 0,000 g / mol or less, 550,000 g / mol or more, and 600,000 g / mol Below, 560,000 g / mol or more and 590,000 g / mol or less, 570,000 0 g / mol or more and 590,000 g / mol or less, or approximately 580,000 g / mol Mz(conv) is a conventional GPC protocol disclosed herein. It is measured according to the col.

[0037] In the embodiment, measurements were taken according to the conventional GPC method for low-density polyethylene. The molecular weight distribution (Mw(conv) / Mn(conv)) is 7.2 or greater, for example, 7.3 The above is 7.4 or higher, or 7.5 or higher. In the embodiment, Mw(conv) / Mn(c onv) is 9.5 or less, for example, 9.0 or less, 8.8 or less, 8.6 or less, or 8.2 or less. It is below.

[0038] Weight-average molecular weight of low-density polyethylene measured according to the absolute method provided below. According to the embodiment, the amount Mw(abs) is 225,000 g / mol or more and 325,0 00 g / mol or less, 235,000 g / mol or more, and 315,000 g / mol or less , 245,000 g / mol or more and 305,000 g / mol or less, 255,000 g / mol or more and 295,000 g / mol or less, 265,000 g / mol or more and 2 It is 85,000 g / mol or less, or approximately 275,000 g / mol. Mw(abs) This is measured in accordance with the absolute GPC protocol disclosed herein.

[0039] The weight of low-density polyethylene, measured according to the absolute method disclosed herein. Ratio of average molecular weight to weight-average molecular weight measured according to conventional GPC method (Mw( According to the embodiment, abs) / Mw(conv)) is 2.1 or greater and 2.7 or less. For example, 2.1 or higher and 2.4 or lower, or 2.15 or higher and 2.35 or lower.

[0040] According to the embodiments, low-density polyethylene measured by the absolute technique disclosed herein Len's GPC branch ratio (gpcBR) is between 2.3 and 3.2, for example, 2. 4 or more and 3.1 or less, 2.5 or more and 3.0 or less, or 2.6 or more and 2.9 or less ru.

[0041] The light scattering properties (LSP) of low-density polyethylene are as follows: Depending on the form, it is less than 3.8, for example, 3.7 or less, 3.6 or less, or 3.5 or less. Yes. In the embodiment, the LSP is 2.5 or higher, 2.6 or higher, or 2.7 or higher. In terms of morphology, the LSP is 2.5 or higher and 3.5 or lower, for example, 2.6 or higher and 3.4 The following, or 2.7 or higher and 3.3 or lower.

[0042] In the embodiment, low-density polyethylene is 0.1 radians / second (rad / sec) and The viscosity measured at 190°C is between 2,250 Pa·s and 4,250 Pa·s. For example, 2,400 Pa·s or more and 4,000 Pa·s or less, 2,600 Pa·s or less Above and below 3,800 Pa·s, 2,800 Pa·s or more and below 3,600 Pa·s, Alternatively, 2,900 Pa·s or more and 3,400 Pa·s or less, or approximately 3,200 Pa·s The viscosity is s. The viscosity is measured according to the protocol disclosed herein.

[0043] In the embodiment, low-density polyethylene is 100 radians / second (rad / sec) and The viscosity measured at 190°C is 250 Pa·s or higher and 400 Pa·s or lower, for example. , 270 Pa·s or higher and 380 Pa·s or lower, 290 Pa·s or higher and 360 Pa·s The viscosity is less than or approximately 320 Pa·s. It is measured as follows.

[0044] In the embodiment, the low-density polyethylene was measured at 0.1 radians / second and 190°C. The ratio of viscosity to viscosity measured at 100 radians / second and 190°C (V@0.1 / V@1 The temperature (00°C and 190°C) is 8.0 or higher, for example, 8.5 or higher, 9.0 or higher, or 9. It is 5 or greater. In the embodiment, viscosity is measured at 0.1 radians / second and 190°C. The viscosity percentage measured at 0 radians / second and 190°C is between 8.0 and 12.0. Yes, for example, 8.5 or higher and 11.0 or lower, 9.0 or higher and 10.5 or lower, or 9.2 It is greater than or equal to 10.8 and less than or equal to 10.8.

[0045] In the embodiment, infrared spectral analysis is performed at molecular weights of less than 5,000 g / mol ( CDF IR The cumulative distribution fraction (CDF) for ) is 0 It is less than or equal to 0.081, for example, less than or equal to 0.079, less than or equal to 0.077, less than or equal to 0.075, 0. The molecular weight is 0.73 or less, or 0.071 or less. In the embodiment, the molecular weight is 5,000 g / mol. CDF below IR It is 0.040 or greater and 0.081, for example, 0.040 or greater. For example, 0.055 or more and 0.079 or less, 0.055 or more and 0.077 or less, 0 The value is 0.055 or greater and 0.075 or less, or 0.055 or greater and 0.075 or less.

[0046] In the embodiment, the CDF is used with a molecular weight exceeding 200,000 g / mol. IR is 0.135 The above applies, for example, 0.145 or higher, 0.150 or higher, 0.155 or higher, or 0.16 It is 0 or greater. In the embodiment, the CDF is greater than 200,000 g / mol. IR teeth, It must be between 0.135 and 0.180, for example, between 0.145 and 0.175. , 0.150 or higher and 0.170 or lower, or 0.155 or higher and 0.163 or lower.

[0047] In this embodiment, viscometer analysis (CDF) is performed when the molecular weight is less than 25,000 g / mol. DV ) The CDF for this is 0.130 or less, for example, 0.127 or less, 0.126 or less, It is 0.125 or less, 0.123 or less, 0.121 or less, or 0.119 or less. In this state, the CDF is less than 25,000 g / mol in molecular weight. DV is 0.050 or greater and 0 It is 0.130 or less, for example, 0.100 or more and 0.128 or less, 0.110 or more and It is 0.125 or less, or 0.115 or more and 0.126 or less.

[0048] In the embodiment, the CDF has a molecular weight greater than 1,000,000 g / mol. DV is 0.0 It is 42 or greater, for example, 0.048 or greater, 0.053 or greater, 0.058 or greater, or 0. The molecular weight is 0.61 or higher. In the embodiment, the CDF is such that the molecular weight is greater than 1,000,000 g / mol. DV This is 0.042 or greater and 0.070 or less, for example, 0.048 or greater and 0.0 It is 65 or less, or 0.053 or more and 0.064 or less.

[0049] In the embodiment, light scattering analysis (CDF) is performed when the molecular weight is less than 100,000 g / mol. LS The cumulative distribution rate (CDF) for ) is 0.140 or less, for example, 0.130 or less. The molecular weight is 0.120 or less, or 0.110 or less. In this embodiment, the molecular weight is 100,000 g. CDF below / mol LSIt is 0.075 or greater and 0.140 or less, for example, 0 It is 0.085 or higher and 0.130 or lower, or 0.095 or higher and 0.115 or lower.

[0050] In the embodiment, the CDF has a molecular weight greater than 1,500,000 g / mol. LS is 0.1 It must be 10 or greater, for example, 0.120 or greater, 0.130 or greater, 0.135 or greater, 0.14 It is 0 or greater, or 0.145 or greater. In the embodiment, the molecular weight is 1,500,000 g / m³. CDF in ol LS It is between 0.110 and 0.160, for example, 0.12 It is greater than or equal to 0 and less than or equal to 0.155, or greater than or equal to 0.130 and less than or equal to 0.155.

[0051] In the embodiment, low-density polyethylene is 13 When measured by 13C NMR, total carbon Amyl groups (C5) of 1.5 or more per 1000 elementary atoms and per 1000 total carbon atoms It has an amyl group (C5) with a coefficient of 3.0 or less.

[0052] In this embodiment, the polymer has C1 branching (methyl branching) per 1000 total carbon atoms. It does not have.

[0053] In this embodiment, the low-density polyethylene has a concentration of 1.5 or more per 1000 total carbon atoms. ,3-diethyl branched and 1,3-diethyl branched with 5.0 or fewer per 1000 total carbon atoms It holds.

[0054] In the embodiment, the low-density polyethylene has a ratio of 3.0 or more per 1000 total carbon atoms and C below 4.0 6+ It has branches.

[0055] In this embodiment, the low-density polyethylene has a density of 0.018 or more per 1000 total carbon atoms. It is a vinyl material having a vinyl content of 0.043 or less per 1000 total carbon atoms.

[0056] In this embodiment, the low-density polyethylene has 0.01 cis per 1000 total carbon atoms. and trans groups (vinylene) with cis and to groups of 0.03 or less per 1000 total carbon atoms. It has a lance group (vinylene).

[0057] In this embodiment, the low-density polyethylene has a density of 0.05 or more per 1000 total carbon atoms. It is vinylidene and has a vinylidene content of 0.25 or less per 1000 total carbon atoms.

[0058] additives The compositions of the embodiments may contain one or more additives. These additives may include stabilizers and plasticizers. Agents, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents (e.g., ercamid, olea) Mido and stearamide), flame retardants, processing aids, smoke suppressants, viscosity modifiers, blocking inhibitors Examples include stoppers (containing talc and silicon dioxide) and oils such as mineral oil. Polymer compounds The finished product is, for example, based on the weight of the low-density polyethylene of the embodiment, 10 (in total weight). It may contain one or more additives in less than a percent. In embodiments, low-density polyethylene is One or more stabilizers, e.g., IRGANOX1010, IRGANOX1076 and IR It may be treated with antioxidants such as GAFOS168 (BASF). In embodiments, stabilizers Please understand that this will not be used.

[0059] Blending and mixing of the low-density polyethylene of the embodiment with other polymers can be carried out. Suitable polymers for blending with the low-density polyethylene of the embodiment include natural and Examples include synthetic polymers. Exemplary polymers for blending include propylene-based polymers. Polymers (both are impact-modified polypropylene, isotactic polypropylene) Atactic polypropylene and random ethylene / propylene copolymer), various Various types of ethylene-based polymers, such as high-pressure free radical LDPE, Ziegler-Natta acetate. LLDPE prepared using a medium, PE prepared using a single-site catalyst, for example , numerous reactor PE (Ziegler-Natta PE and single-site catalyst PE, for example, US special No. 6,545,088 (Kolthammer et al.), No. 6,538, No. 070 (Cardwell, et al.), No. 6,566,446 (Parik h, et al.), No. 5,844,045 (Kolthammer et al. ), Nos. 5,869,575 (Kolthammer et al.), and Nos. 6, Products disclosed in patents 448,341 (Kolthammer et al.) EVA, ethylene / vinyl alcohol copolymer, polystyrene, impact-reduced poly Styrene, ABS, styrene / butadiene block copolymers and their hydrogenated derivatives Examples include (SBS and SEBS), and thermoplastic polyurethanes. Homogeneous polymers, e.g. For example, olefin plastomers and elastomers, ethylene and propylene copolymers. (For example, VERSIFY (trademark) Plastoms & Elastomers ( The Dow Chemical Company and VISTAMAXX (Exx The polymer available under the trade name of onMobil Chemical Co. is also actually (May be useful as an ingredient in blends containing low-density polyethylene in application form). LLDP E. For example, INNATE (trademark), DOWLEX (trademark), and DOWLEX (trademark) GM (The Dow Chemical Company), as well as Exceed and E Xceed XP (Exxon Chemical Company) may also be used.

[0060] Additives, such as lubricants, antioxidants, or anti-tacks, can affect the properties of the resin. There is a combination. Furthermore, oils, such as mineral oil which can be used as a carrier for additives, are also resin-specific. It can affect the properties. Low-density polyethylene can be further modified using various methods, for example, as follows. The slip additive method, primary and secondary antioxidant method, anti-tack method, and mineral oil described below The presence of additives can be measured using a specific method.

[0061] The presence of additives can affect molecular weight, hexane extract, and density. For example, The low molecular weight properties of the additive can reduce the molecular weight of the ethylene-based polymer. Therefore, As detailed in the specification, in the low molecular weight region of the GPC elution curve, antioxidant Or when there is a peak that is known to be caused by the presence of other additives. Underestimation of the number-average molecular weight (Mn) of polymer samples. This causes Mw / Mn (where Mw is the weight-average molecular weight). The polydispersity of a sample, defined as t), may be overestimated. Similarly, in the presence of additives, At that time, hexane extract measurement includes all hexane-soluble additives, but hexane extract measurement The formula will likely not contain additives that do not dissolve in hexane, such as anti-tack agents. Therefore, The hexane extract percentage of resins containing additives is different from that of ethylene-based polymers without additives. Percent hexane extract and hexane-soluble additives (e.g., slip agents and antioxidants) (Stoppers) and / or any hexane-soluble oil (e.g., used as a carrier for additives) It will be equal to the sum of the percentages obtained. Finally, additives such as anti-tack agents This can increase the density of ethylene-based polymers. Any additive (additives may be talc or dioxide) Density (g / cm³) of ethylene-based polymers that do not contain anti-tack agents such as silicon 3 )teeth This can be expressed by the following formula.

[0062]

number

[0063] Purpose The low-density polyethylene of the embodiment is useful for articles such as single-layer and multi-layer films. Shaped articles, for example, blow-molded articles, injection-molded articles, cast articles, or rotationally molded articles Various conventional thermoplastic manufacturing processes for producing coatings, fibers, woven fabrics or nonwoven fabrics It can be used in sess. The low-density polyethylene of the embodiment is, but is not limited to, extruded. Coatings, food packaging, consumer, industrial, agricultural (coatings or films), laminates Film, fresh cut, produced film, cast film, inflation Film, thermoformed film, meat film, cheese film, candy film, Transparent shrink film, collated shrink film, stretched film, silage film, greenhouse film Film, fumigation film, lining film, stretchable hood, durable transport bag, pet food, Various films such as sandwich bags, sealants, and diaper backsheets. It can be used.

[0064] The low-density polyethylene of this embodiment is also useful in other direct end-use applications. The low-density polyethylene of the embodiment is used for coating wires and cables. Sheet extrusion for vacuum forming operations, and injection molding, blow molding or rotational molding processes It can be used in the formation of molded articles, such as in the use of sess. Embodiments for low-density polyethylene Other suitable applications include elastic films and fibers, and soft-touch materials such as electrical appliance handles. Products such as gaskets and profiles, automotive interior parts and profiles, foam products (O Impact modifiers for other thermoplastic polymers (both open-cell and closed-cell), for example For example, high-density polyethylene or other olefin polymers, cap liners, and flow A ring was mentioned.

[0065] In the embodiments disclosed and described herein, low-density polyethylene is otherwise explicitly stated. Unless otherwise specified, additive-free low-density polyethylene is disclosed herein. The properties described relate to additive-free low-density polyethylene unless otherwise disclosed. .

[0066] Test method The test method includes the following:

[0067] density Samples for density measurement were prepared according to ASTM D 4703-10. 37 samples were prepared. The material was pressed at 10,000 psi (68 MPa) for 5 minutes at 4°F (190°C). Maintain the temperature at 374°F (190°C) for the above 5 minutes, then increase the pressure to 30,000 psi. The pressure was increased to 207 MPa for 3 minutes. This was followed by 70°F (21°C) and 30,0 The pressure was maintained at 00 psi (207 MPa) for 1 minute. The measurement was performed according to ASTM D792-08. Method B was used, performed within one hour of sample pressing.

[0068] Melt Index The melt flow index, or melt index, or I2 is based on ASTM D1. 238-10, under conditions of 190℃ / 2.16kg, measured according to Method B, dissolution per 10 minutes I reported the amount in grams provided.

[0069] Nuclear magnetic resonance ( 13 (C NMR) The sample consisted of approximately 3g of 12% by weight of TCE-d2 and 0.0 in a 10mm NMR tube. 1,1,2,2-tetrachloroethane (TCE) containing 025M Cr(AcAc)3 It was prepared by adding "0.25~0.40g" of polymer sample. The head space Oxygen was removed from the sample by purging with nitrogen. Then, the heating block and the heater... Using a togun, the tube and its contents are heated to 120-140°C to extract the sample. The samples were dissolved and homogenized. Each dissolved sample was visually inspected to ensure homogeneity. Immediately before analysis, the samples were... The sample was not thoroughly mixed and allowed to cool before being inserted into the heated NMR sample holder.

[0070] All data was obtained using a Bruker 60 equipped with a 10mm extended temperature cryoprobe. Data was collected using a 0 MHz spectrometer. The sample temperature was 120°C, and the pulse repetition rate was 7.8 seconds. Data was acquired using a 90-degree flip angle and inverse gated decoupling. All measurements were performed on non-rotating samples in lock mode. The samples were left to stand for 7 minutes before data acquisition. The solution was brought into thermal equilibrium. The 13C NMR chemical shift showed the EEE triad at 30.0 ppm. See section C. 6+ The value is C in low-density polyethylene. 6+ It is a direct measure of branching. Furthermore, long branches are not distinguished from "chain ends." This refers to the ends of any chain or branch with six or more carbon atoms. Using the peak at "32.2 ppm" which represents the third carbon, we get "C 6+ Determine the value do.

[0071] [Table 1]

[0072] Nuclear magnetic resonance ( 1 (H NMR) The sample was prepared by dissolving approximately 120 mg of the sample in a 10 mm NMR tube in 0.001 M Cr(A) solution. 3.25g of tetrachloroethane-d2 / par in a 50 / 50 weight ratio containing cAc)3 It was prepared by adding it to chloroethylene. To prevent oxidation, it was inserted into a tube. The sample was purged by passing N2 through the solvent via a pipette for approximately 5 minutes. Each tube was capped and sealed with TEFLON tape. The sample was heated to 110-115°C and then... Lutex was used to ensure homogeneity.

[0073] A Bruker 600MHz spectrometer with a 10mm extended temperature cryoprobe. at 1 1H NMR was performed. The data was obtained using ZG pulses, 64 scans, and a 15.8-second pulse. The results were obtained using a repeating delay method at a sample temperature of 120°C.

[0074] The signal from the entire polymer (approximately 3 to -0.5 ppm) is taken as an arbitrary value (typically 20, Set to 000). The corresponding integral value of unsaturated vinylene (approximately 5.40-5.60 ppm). Approximately 5.16-5.35 ppm of trisubstituted compounds, approximately 4.95-5.15 ppm of vinyl, approximately 4 A concentration of vinylidene (0.70-4.90 ppm) was obtained.

[0075] The integral value of the entire polymer from the control experiment was divided by 2 to obtain a value representing X thousand carbon atoms. That is, if the integral value of the polymer is 20,000, then this corresponds to 10,000 carbon atoms and X = 1 (Represents 0).

[0076] The unsaturated group integral, obtained by dividing by the corresponding number of protons contributing to that integral, is equivalent to X thousand carbon atoms. This represents the number of unsaturated moles of each type. Dividing the number of unsaturated moles of each type by X gives 10 The number of moles of unsaturated groups per 00 moles of carbon is obtained.

[0077] Melt strength Melt strength measurement was performed using a Gottfert Rheotester 2000 capillary. Gottfert Rheotens 71.97 (Gott) coupled to a rheometer The experiment was conducted at fert Inc. (Rock Hill, SC). The molten sample (approximately 25-30g) A flat ram with a length of 30 mm, a diameter of 2.0 mm, and an aspect ratio (length / diameter) of 15. Gettfert Rheotester 2000 Fine with an inlet angle (180 degrees) The sample was supplied using a tube rheometer. After equilibrating the sample at 190°C for 10 minutes, the piston was moved to 0.2 The machine operated at a constant piston speed of 65 mm / second. The standard test temperature was 190°C. This is applied to a pair of acceleration nips located 100 mm below the die, at a rate of 2.4 mm / second. 2 acceleration Uniaxial stretching was performed at a certain degree. The tensile force was recorded as a function of the winding speed of the nip roll. The degree was reported as the average plateau force (cN) before the strand fractured. The following conditions were met: The parameters used for the melt strength measurement were: plunger speed = 0.265 mm / sec, wheel acceleration = 2. 4mm / sec 2 Capillary diameter = 2.0 mm, capillary length = 30 mm, and barrel Diameter=12mm.

[0078] Dynamic Mechanical Spectroscopy (DMS) The resin was exposed to air at a pressure of 25,000 psi for 5 minutes at 177°C, resulting in a thickness of 3 mm × It was compressed into a 1-inch circular plaque. Next, the sample was removed from the compressor and placed on a counter. It was placed there and cooled.

[0079] Constant temperature frequency sweep under nitrogen purge with TA equipped with 25mm (diameter) parallel plates Instruments' "Advanced Rheometric Expansi" The procedure was performed using the "on System (ARES)". The sample was placed on a plate and heated to 190°C. It was melted at °C for 5 minutes. Then, the plate was closed to a gap of "2 mm" and the sample was trimmed. (Remove excess sample that extends beyond the circumference of the "25mm diameter" plate), Then, the test was started. This method incorporates an additional 5-minute delay to allow for temperature equilibrium. The experiment was conducted at 190°C over a frequency range of 0.1 to 100 rad / second. The strain amplitude was constant at 10%. Complex viscosity η * , tan(δ) i.e., 0.1r Loss tangent at ad / s, viscosity at 0.1 rad / s (V0.1), at 100 rad / s The viscosity (V100) and viscosity ratio (V0.1 / V100) were calculated from these data. .

[0080] GPC Triple Detector Gel Permeation Chromatography (ography, TDGPC) The chromatography system uses an internal IR5 infrared detector. PolymerChar GPC-IR (Valencia, Sp) with r, IR5) ain) High-temperature GPC chromatograph, and Precision Detectors (current Currently, Agilent Technologies uses 2-angle laser light scattering. r light scattering (LS) detector model 2040 coupled to 4-capillary viscometer It consisted of a (4-capillary viscometer, DV). All light scattering measurements were taken at 15 degrees. Used for measuring angles. Set the autosampler oven compartment to 160 degrees Celsius. The column compartment was set to 150°C. Four Agil tubes were installed in the column. ent "Mixed A" 30cm 20 micron linear mixed bed column and 20um pre A column was used. The chromatography solvent used was 1,2,4-trichlorobene It is Zen, and 200 ppm butylated hydroxytoluene, It contained BHT. The solvent source was spurged with nitrogen. The injection volume used was 200 The volume was in microliters, and the flow rate was 1.0 milliliter / minute.

[0081] Following a method similar to the conventional GPC procedure, the conventional molecular weight Calibration and calculations were performed on the spectroscopy and distribution (20um "Mixed A" color). (Uses Mu).

[0082] A systematic approach to determining the multiple detector offset is described by Balke, Mour ey,et.al.(Mourey and Balke,Chromatograph y Polym.Chpt 12,(1992))(Balke,Thitiratsa kul,Lew,Cheung,Mourey,Chromatography Pol It was carried out in a format consistent with that published by ym.Chpt 13, (1992)). Using PolymerChar GPCOne™ software, wide homopoly Triple detector logs (MW and I) from rimmer polyethylene standard material (Mw / Mn>3) The result of V) is optimized for the result of narrow standard column calibration from the narrow standard calibration curve. As used herein, "MW" refers to molecular weight.

[0083] Absolute molecular weight data is obtained using PolymerChar GPCOne® software. Use Zimm(Zimm,BH,J.Chem.Phys.,16,109 9 (1948)) and Kratochvil (Kratochvil, P., Class ical Light Scattering from Polymer Solut Released by ions, Elsevier, Oxford, NY (1987) It was obtained in a manner consistent with that. The total injection concentration used in determining the molecular weight was suitable for linear Polyethylene homopolymers, or polyethylene standard materials of known weight-average molecular weights The mass detector area and mass detector constant were derived from one of the data points. (GPCOne(commercial The molecular weight calculated using one of the polyethylene standard materials described below is calculated using the standard material. From the above, the light scattering constant and the refractive index concentration coefficient of 0.104, dn / dc, can be used. Obtained using: Generally, the mass detector response (determined using GPCOne®) IR5) and the light scattering constant are obtained from linear standards with a molecular weight exceeding approximately 50,000 g / mol. It should be determined from the substance. Viscometer calibration (determined using GPCOne®) (The standard reference material) is used in the manner described by the manufacturer, or as an alternative. (Standard Reference Material, SRM) 1475a (National Institute of Standards and Technology) Suitable linear chains (available from the Institute of Standards and Technology, NIST) This can be achieved by using the publicly available values ​​of calibration standards. The specific viscosity area (DV) and injected mass related to the quality are expressed as its intrinsic viscosity (intrinsic vi By relating it to scosity, IV), the viscometer constant (using GPCOne(trademark)) can be determined. The chromatographic concentration is calculated using the second viral coefficient. It is assumed that the concentration is low enough to eliminate the effect on molecular weight.

[0084] The absolute weight-average molecular weight (Mw(Abs)) is measured by light (using GPCOne®). The area integral chromatogram of scattering (LS) (factored by the light scattering constant) is obtained using the mass constant and It is obtained by dividing by the mass recovered from the area of ​​the mass detector (IR5). Molecular weight And the intrinsic viscosity response is extrapolated at the edge of the chromatography where the signal-to-noise ratio is low. (Using GPCOne™). Mn is the other moment. (Abs) and M z (Abs)It is calculated according to the following formulas (1) to (2).

[0085] [Number]

[0086] Conventional GPC The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) coupled to a Precision Detectors (now Agilent Technologies) dual laser light scattering (LS) detector model 2040. For all light scattering measurements, a 15-degree angle was used for measurement purposes. The autosampler oven compartment was set at 160°C, and the column compartment was set at 150°C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene, which contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen-sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliter / minute. Agilent Technologies) dual laser light scattering (LS) detector model 2040 coupled with an internal IR5 infrared detector (IR5), PolymerCha r GPC-IR (Valencia, Spain) high-temperature GPC chromatograph consisted of For all light scattering measurements, a 15-degree angle was used for measurement purposes. The autosampler oven compartment was set at 160°C, and the column compartment was set at 150°C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent used was 1, 2,4-trichlorobenzene, which contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen-sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliter / minute. 20 micron linear mixed-bed columns. The chromatography solvent used was 1, 2,4-trichlorobenzene, which contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen-sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliter / minute. T) and the solvent source was nitrogen-sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliter / minute. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliter / minute.

[0087] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards having molecular weights in the range of 580 g / mol to 8,400,000 g / mol. The standards were prepared in six "cocktail" mixtures in which the individual molecular weights were at least 10-fold apart. The standards were purchased from Agilent Technologies. Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards having molecular weights in the range of 580 g / mol to 8,400,000 g / mol. The standards were prepared in six "cocktail" mixtures in which the individual molecular weights were at least 10-fold apart. The standards were purchased from Agilent Technologies. The standards were prepared in six "cocktail" mixtures in which the individual molecular weights were at least 10-fold apart. The standards were purchased from Agilent Technologies. The standards were prepared in six "cocktail" mixtures in which the individual molecular weights were at least 10-fold apart. The standards were purchased from Agilent Technologies. For lithstyrene standard materials with a molecular weight of 1,000,000 g / mol or more, use 50 ml of solvent. For a molecular weight of less than 1,000,000 g / mol, with 0.025 grams per liter. It was prepared at a concentration of 0.05 grams in 50 milliliters of solvent. The polystyrene standard was gently mixed. The polystyrene standard substance was dissolved at 80 degrees Celsius for 30 minutes while stirring. The quantities were converted to polyethylene molecular weight using Equation 1 (Williams and Wa As noted in rd, J. Polym. Sci., Polym. Let., 6, 621 (1968). (As stated).

[0088]

number

[0089] A quintic polynomial was used to fit each polyethylene equivalent calibration point. For A Then, small adjustments (approximately 0.3950 to 0.440) are made to linear homopolymer polyethylene. To obtain the standard material at 120,000 Mw, the column resolution and band expansion effects are compensated for. Corrected.

[0090] The total plate count for the GPC column set is 0 in 50 ml of TCB. The procedure was performed using a 0.04g solution. Plate count (equation 4) and symmetry (equation) Equation 5) was measured for a 200 microliter injection according to the following equation.

[0091]

number

[0092]

Number

[0093] The sample was prepared semi-automatically using PolymerChar "Instrument Control" software with air. The target weight of the sample was 2 mg / ml. Through the PolymerCh ar high-temperature autosampler, a solvent (containing 200 ppm of BHT) was added to a vial with a septum cap previously sparged with nitrogen. The sample was dissolved at 160 °C for 2 hours under "low-speed" shaking.

[0094] The calculations of Mn(conv), Mw(conv), and Mz(conv) were performed using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph and, according to Formulas 6 to [8], using PolymerChar GPCOne (trademark) software to subtract the baseline from the IR chromatogram at equally spaced data collection points (i) and using the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve at point (i) from Formula 1.

[0095]

[0096]

[0097]

[0098] <00,01026>

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109] <00011 This was done based on the results of GPC.

[0095]

number

[0096] In the low molecular weight region of the GPC elution curve, the presence of antioxidants or other additives may occur. When a peak known to be triggered is present, the number-average molecular weight of the polymer sample This leads to an underestimation of (Mn), so it is defined as Mw / Mn (where Mw is the weight-average molecular weight). The polydispersity of the sample will be overestimated. Therefore, the true molecular weight of the polymer sample The distribution should be calculated from GPC elution by eliminating this extraneous peak. This process is a peak removal feature in the data processing procedure for liquid chromatography analysis. It is generally explained as a property. In this process, this additive peak is GPC Before the molecular weight of the sample is calculated from the elution curve, it is removed from the GPC elution curve. Chromatography The plate count of the Graph system should exceed 24,000, and the symmetry should be 0. It should be between 0.98 and 1.22.

[0097] To monitor deviations over time, the PolymerChar GPC-IR system A flow marker (decane) was introduced into each sample via a controlled micropump. Using a flowrate marker (FM), each decane peak in the sample ( RV(FM sample) and decane peak within narrow standard calibration (RV(FM calibrated)) By matching this with RV, the pump flow rate (apparent flow rate) of each sample can be linearized. Corrected. Then, any changes in the timing of the Decane marker peaks over the entire run. It is presumed to be related to a linear shift in flow rate (effective flow rate). To facilitate the highest accuracy of RV measurement, the peak of the flow marker concentration chromatogram is A least-squares fitting routine is used to fit the quadratic equation. Then, the linear quadratic equation is used. The true peak location is solved using the derivative. The system is based on the peak of the flow marker. After calibration, the effective flow rate (for a narrow standard calibration) is calculated as shown in equation 9. Marker peak processing is performed using PolymerChar GPCOne™ software. This was done via [method / method]. The permissible flow rate correction is when the effective flow rate is within + / - 1% of the apparent flow rate. That is the case. Effective flow rate = Apparent flow rate * (RV (FM calibrated) / RV (FM sample)) (Equation 9)

[0098] A systematic approach to determining the multiple detector offset is described by Balke, Mour ey,et.al.(Mourey and Balke,Chromatograph y Polym.Chpt 12,(1992))Balke,Thitiratsak ul,Lew,Cheung,Mourey,Chromatography Poly It was done in a format consistent with that published by m.Chpt 13,(1992)), Using PolymerChar GPCOne™ software, broad homopoly Triple detector logs (MW and IV) from polyethylene standard material (Mw / Mn>3) The results of ) are optimized for the results of narrow standard column calibration from a narrow standard calibration curve.

[0099] Absolute molecular weight data is obtained using PolymerChar GPCOne® software. Use Zimm(Zimm,BH,J.Chem.Phys.,16,109 9 (1948)) and Kratochvil (Kratochvil, P., Class ical Light Scattering from Polymer Solut Released by ions, Elsevier, Oxford, NY (1987) It was obtained in a manner consistent with that. The total injection concentration used in determining the molecular weight was suitable for linear Polyethylene homopolymers, or polyethylene standard materials of known weight-average molecular weights The mass detector area and mass detector constant were derived from one of the data points. (GPCOne(commercial The molecular weight calculated using one of the polyethylene standard materials described below is calculated using the standard material. From the above, the light scattering constant and the refractive index concentration coefficient of 0.104, dn / dc, can be used. Obtained using [this method]. Generally, the mass detector response (I) (determined using GPCOne®) is obtained. R5) and the light scattering constant are obtained from linear standards with a molecular weight exceeding approximately 50,000 g / mol. It should be determined by the substance.

[0100] CDF calculation method IR5 measurement detector ("CDF") IR The cumulative distribution rate (CDF) of the viscosity detector, and the viscosity detector Equivalent detector fraction ("CDF") DV ) and cumulative detection from low-angle laser light scattering detectors Instrument fraction ("CDF LS The calculation of '' is performed in the following steps (CDF IR CDF D V , and CDF LS This is illustrated in Figures 2, 3, and 4. 1) The relative retention volume ratio of the decane peak between the sample and a certain narrow standard cocktail mixture. Based on this, the chromatogram is linearly corrected for flow rate. 2) As described in the Gel Permeation Chromatography (GPC) section, use a refractometer. The offset of the corresponding light scattering detector is corrected. 3) Based on the polystyrene calibration curve, each retention volume (RV) data The molecular weight of the slicing is calculated, and this is then used in gel permeation chromatography (GPC). The conversion coefficient from polystyrene to polyethylene listed in the document (0.3950~0.44) Correct it by [this method]. 4) Subtract the baseline from the chromatograms of the light scattermeter and refractometer, and calculate the refractometer chromatogram. The entire low molecular weight retention volume range of the light scattering chromatogram observable from the togram is reliably integrated. Use a standard GPC to divide and set the integration window (i.e., the upper limit of RV) (Set the same index for each chromatogram). Substances equivalent to less than 50 g / mol are not included in the integral. 5) In the case of Example 1, according to formulas 10A, 10B, 10C, 10D, 10E and 10F, Figure 2. In each data slice (j) shown in Figures 3 and 4, the baseline is subtracted. Based on molecular weight and the peak height (H) of low molecular weight molecules (low to high retention volume), the IR5 measurement sensor... Sir (CDF) IR ), viscosity chromatogram (CDF DV ), and low-angle laser light scattering (Lo w-Angle Laser Light Scattering (LALLS) Chromatogram (CDF) LS ) cumulative amount Calculate the Coverage Factor (CDF).

[0101]

number

[0102] GPCBR analysis using Triple Detector GPC (3D-GPC) branch index As mentioned above, the gpcBR branching index is first measured by light scattering, viscosity, and concentration detectors. It is determined by calibration. Then the baseline is determined by light scattering, viscometer, and concentration It is subtracted from the chromatogram. Then, an integration window is set, and infrared (IR5) is used. ) Light scattering and viscometer chromatography showing the presence of detectable polymers from chromatograms. The entire low molecular weight retention volume range of the linear polyethylene standard is integrated. Using this material, the Mark-Houwink constants for polyethylene and polystyrene were established. After obtaining the constant, use the two values ​​as shown in equations (11) and (12) to solve. Two linear references for polyethylene molecular weight and polyethylene intrinsic viscosity as functions of output volume A conventional calibration method will be established.

[0103]

number

[0104] The gpcBR branch index is described in Yau, Wallace W., "Examples of Using 3D-GPC-TREF for Polyolefin Charac terization”,Macromol.Symp.,2007,257,29-4 As described in 5, this is a robust method for characterizing long-chain branching. This index is Prioritizing the entire polymer detector area, conventional methods were used in determining the g' value and calculating the branching frequency. Avoid the previously used "per-slice" 3D-GPC calculation. Using a light scattering (LS) detector with peak area method, the bulk absolute weight average molecular weight of the sample is determined. The quantity (Mw(abs)) can be obtained. This method is required in conventional g' determination. Avoid the "per slice" ratio of the light scattering detector signal to the concentration detector signal. .

[0105] Using 3D-GPC, the intrinsic viscosity of the sample can also be independently obtained using equation (13). This area calculation is performed as the overall sample area, relative to the baseline and integration limit of detection. Because the impact of instrument noise and variations caused by 3D-GPC settings is very small, High accuracy is provided. More importantly, the peak area calculation is performed using the volume of the detector. It is not affected by the fucset. Similarly, the area method shown in equation (13) can be used to determine the inherent properties of the sample. Viscosity (IV) can be obtained with high precision.

[0106]

number

[0107] To determine the gpcBR branching index, the light scattering elution area of ​​the sample polymer is used. Determine the molecular weight of the sample. The dissolution area of ​​the viscosity detector for the sample polymer is the intrinsic viscosity of the sample ( It is used to determine IV or [η]).

[0108] First, the molecular weight of a linear polyethylene standard sample such as SRM1475a or its equivalent, and The intrinsic viscosity and molecular weight as a function of the amount of elution are given by equations (14) and (15). Conventional calibration method ("conventional calibration, cc") for both viscosity and viscosity. Determine using ).

[0109]

number

[0110]

number

[0111] All statistics with the subscript "cc" indicate the respective elution amounts and the corresponding values ​​mentioned above. Conventional calibration and concentration (Ci) are used for determination. Values ​​without subscripts are also determined. These are measurements based on the mass detector, LALLS, and viscometer area. PE The value is linear The reference sample is repeatedly adjusted until it has a gpcBR measurement of zero. For example, this particular The final values ​​of α and Log K for determining gpcBR in the case of polyethylene are The combined values ​​are 0.725 and -3.391 respectively, and for polystyrene, they are 0.722 and The value is -3.993. Once the K and α values ​​are determined using the procedure described above, the branched sample Repeat the procedure using the following: The branched sample is the final Mark-Hou sample obtained from the linear reference. The analysis is performed using the Wink constant as the optimal "cc" calibration value. (For linear polymers) The values ​​measured by LS and viscometers will be close to the conventional calibration standard, The gpcBR calculated from equation (15) is expected to be close to zero. Branched polymer In this case, the measured molecular weight of the polymer is higher than the calculated Mw,cc, and the calculation Because the IVcc is higher than the polymer IV measured, the level of long-chain branching is particularly high. In this case, the gpcBR will be higher than zero. In fact, the gpcBR value is determined by the polymer This represents the fractional change in IV due to the molecular size contraction effect resulting from the branching. 0.5 or The gpcBR value of 2.0 is 50% and of the equivalent weight of linear polymer molecules, respectively. This represents a molecular size contraction effect of IV at a level of 200%. In these specific embodiments, Compared to the conventional "g' index" and branch frequency calculation, use gpcBR. The advantage lies in the higher accuracy of gpcBR. All parameters used are obtained with high precision, and low 3D at high molecular weight from the concentration detector. - Not adversely affected by the response of the GPC detector. Errors in the alignment of the detector volume are also not affected by gpcB This does not affect the accuracy of the R-index determination.

[0112] LSP parameters Typical values ​​of GPC light scattering parameters (LSP) are shown in Tables 1 and 2 of Example 1, and This can be seen in Figure 5. The material analysis is based on U.S. Patent No. 8,916,667 (B2) The procedure was carried out similarly to that of Karjala et al. The X-axis of the plot was conventional. This is the logarithm of the molecular weight calculated by LS detection, or the molecular weight calculated by cc-GPC. The y-axis is LS detection. This is the instrument's response. The specific characteristics of the LS elution profile are determined by two logarithmic molecular weight limits. It is captured as defined. The lower limit corresponds to the MW1 value of 100,000 g / mol. The upper limit corresponds to an MW2 value of 900,000 g / mol. These two molecular weight limits The vertical line intersects the LS elution curve at two points. Draw the line segment connecting these two intercept points. The height of the LS signal at the first intercept (log MW1) indicates the amount of LS1. The height of the LS signal in one sample (log MW2) indicates the amount of LS2. Within two molecular weight limits The area under the LS elution curve represents the area B. The LS curve is divided into two segments by a line segment connecting the two intercepts. In comparison, the line segment is above (see A2 in Figure 5, defined as a negative value) or below (see A in Figure 5) There may be a portion of the separation area that is defined as a positive value, as in 1. A1 and The sum of A2 gives the area A and the total area A. This total area A is the area B and the line segment It can be calculated as the difference between the area below and the area below.

[0113] The step of calculating the amount of "LS" is illustrated by Example 1 shown in Tables 2 and 3. be.

[0114] Step 1: Calculate SlopeF in Table 1 using equations 16-17 below. Slope_value=[(LS2-LS1) / LS2] / dLogMW (Equation 16) SlopeF = gradient function = abs(Slope_value - 0.42) + 0.00 1 (Equation 17)

[0115] Step 2, use equations 18-19 below to find "AreaF" and "LS" in Table 2. Calculate F Area F = Area function = Abs(Abs(A / B) + 0.033) - 0.005) (Equation 18) In the formula, A / B=(Area A) / (Area B) LSP=Log(Area F*SlopeF)+4 (Equation 19)

[0116] [Table 2]

[0117] [Table 3]

[0118] Hexane extract Polymer pellets (from the polymerization pelletization process, without further modification, "1 inch x 1") Each inch square film sheet weighs approximately 2.2 grams, and the Carver Press uses 3 sheets. The pellets were pressed to a thickness of 0.0 to 4.0 mils. The pellets were heated at 190°C and 8,000 psi for 3 minutes. Press for 3 minutes, then cool for 3 minutes, then press again at 190°C at 40,000 psi for 3 minutes. Pressed and then cooled (total 12 minutes). Non-residual gloves (PIP) * CleanTea m * CottonLisle Inspection Gloves, Part Number: 97- 501) was worn to prevent contamination of the film by residual oil from the workers' hands. The film was trimmed into a 1-inch x 1-inch square and weighed (2.5 ± 0.05). g) Place the film in a heated water bath at 49.5±0.5℃ with approximately 1000 ml of hexane. Extraction was performed for 2 hours in a hexane container containing the hexane. The hexane is an isomer "hexane" mixture ( For example, hexane (Optima), Fisher Chemical, for HPLC. It was a high-purity mobile phase and / or extraction solvent for GC applications. After 2 hours, the film was removed. Remove, rinse in clean hexane, and place in a vacuum oven (80±5℃) to complete vacuum (ISO Dry in a TEMP vacuum oven, Model 281A, approximately 30 inches (Hg) for 2 hours. Next... Then, the film was placed in a desiccator and cooled to room temperature for at least one hour. After that, The film was reweighed, and the mass loss due to extraction in hexane was calculated. This method is 2 1 Based on CRF 177.1520(d)(3)(ii), but n-hexane Using hexane instead deviates from the FDA protocol by one point. The average of the measured values ​​was reported.

[0119] lubricant Approximately 5 grams of the sample was weighed (recorded precisely to the nearest 0.0001 g), and then measured out in 16 ounces. It was placed in a glass bottle. Polytetrafluoroethylene (PTF) E) The stirring rod coated with 120% xylene was dispensed using a solvent dispenser. It was placed in a glass bottle with mL of 0.04% triethyl phosphite. The bottle was loosely sealed. The mixture was heated at 130°C for 30 minutes while stirring, and placed on a stirrer. After 30 minutes, the bottle was removed and allowed to cool at room temperature. The solution was cooled while stirring for at least 2 hours. Using a solvent dispenser, 250 ml was dispensed into a bottle. mL of methanol was added to further precipitate the polymer. The solution was stirred during this addition. The solution was stirred for another 2 hours. After 2 hours of stirring, the bottle was removed and the solid was allowed to settle. Remove the aliquot using a glass pipette and transfer it to a 2 mL glass autosampler vial. The vial was then capped and placed in the gas chromatograph for analysis. The sample and standards were also used. Gas chromatography with solution, pulse splitless injection, and flame ionization detector. Analysis was performed using -. The concentration of the extract was measured using an external standard calibration procedure. In the resin The data for erucamide, oleamide, or stearamide are expressed in parts per million (ppm, μg / g ) was reported.

[0120] Antioxidant (AO) Approximately 5 grams of the sample was weighed (recorded precisely to the nearest 0.0001 g), and then 4 ounces of the sample were used. It was placed in a glass bottle. A PTFE-coated stirring rod was used with a solvent dispenser. Place the o-xylene in a glass bottle with 25 mL of 0.04% triethyl phosphite. The bottle was loosely sealed and placed on a heating device at 130°C for 30 minutes while stirring. After 30 minutes... Then, remove the bottle and let the solution cool at room temperature while stirring for at least 2 hours. Solvent dispenser Using this method, 50 mL of methanol was added to the bottle to further precipitate the polymer. The solution was stirred. The solution was stirred for a further 2 hours. After stirring for 2 hours, the bottle was removed and the solid was removed. It was allowed to settle. An aliquot of the solution was taken out with a glass pipette and placed on a 0.2 μm PTFE(2 Filter using a 5mm syringe filter and a polypropylene syringe, then add 2 mL of glass oak. The sample was placed in a sampler vial. The vial was sealed, and liquid chromatography was performed for analysis. The sample and standard solution were placed in reverse-phase liquid chromatography using a UV / Vis absorbance detector. Analysis was performed using the Graph method. The concentration of the extract was measured using an external standard calibration procedure. The AO data in the resin is reported in parts per million (ppm, μg / g). Further details Green, S.; Bai, S.; Cheatham, M.; Cong, R.; Ya u, W., “Determination of Antioxidants in P olyolefins Using Total Dissolution Metho dology Followed by RPLC”, Journal of Sepa Rational Science, 33(22), 3455-3462 (2010) Odor It can be found.

[0121] Anti-sticking agent Metal levels were measured by X-ray fluorescence using ASTM D6247. Talc Alternatively, silicon dioxide can be obtained from elemental silicon (Si) or magnesium (Mg) by XRF. It can be measured. In laboratories where many different types of materials are analyzed, Si and Mg Both may be measured. The talc result will be either Si or Mg, as needed. It may be reported as being calculated from the following. For example, the level of talc is measured using Mg and Si. It can be calculated by determining the percentage of residual ash. In the presence of only Mg and Si (no other additives are present), three measurements are performed. The values ​​(XRF and residual ash %) should match. talc (Mg) = Talc (Si) = Talc (ash) Talc can be measured using both Mg and Si. The two values ​​are different. In such cases, further analysis may be required to determine the level of talc. For example, Si If calculated using the XRF value of Si, the talc value for O2 should be higher. Talc (Mg) <Talc (Si) It is thought that the amount of SiO2 can be calculated using this difference. After determining the bell, the correction for the talc value can be calculated from the measured residual ash percentage. talc (Ash corrected) = Talc (Ash) -talc (SiO2) Furthermore, if SiO2 is present but Mg is not, talc can be elementally determined from Mg. This means the talc content can be zero. Residual ash content is as defined by ASTM D5630: in plastics. It can be measured by standard test methods for ash content.

[0122] mineral oil Weigh approximately 5 grams of the sample into a 4-ounce glass bottle (marking precisely to the nearest 0.0001g). (Recorded), then 20 mL of methylene chloride was added. The bottle was lined with PTFE. The sample was sealed in a cap. The sample was extracted on a wrist shaker at room temperature for 24 hours. The coat was removed using a glass pipette and transferred to a 2 mL glass autosampler vial. The vial was capped and placed in the gas chromatograph for analysis. (Sample and standard solution) The standard solution was analyzed using gas chromatography with a flame ionization detector. This was prepared in methylene chloride using the same mineral oil reference material as found in resins. The mineral oil peak in the matogram was integrated. Oligomers and oligomers within the same retention time window as mineral oil. Subtract the additive peak area from the mineral oil peak area. The extract concentration is determined using the external standard calibration procedure. Measurements were taken using [a specific method]. The data for mineral oil in the resin is reported in parts per million (ppm; μg / g). It can be done. [Examples]

[0123] Example 1 and Comparative Example 1: Preparation of Low-Density Polyethylene Following the above explanation regarding Figure 1, t-butylperoxy-2ethylhexanoic acid (T It contains BPO and an iso-paraffinic hydrocarbon solvent with a boiling range exceeding 179°C. The mixture was used as an initiator mixture for the first and second injection points. TBPO, t- Contains butyl peroxyacetate (TBPA) and an iso-paraffinic hydrocarbon solvent. The mixture was used as an initiator mixture for the third injection point. Di-t-butylpel Oxide (DTBP), TBPA, TPBO, and iso-paraffinic hydrocarbon solvents A mixture containing was used for the fourth injection point. Table 4 shows the mixture used for each injection point. The composition of the peroxide initiator and solvent solution used is shown in weight percent.

[0124] [Table 4]

[0125] Isobutane was used as a chain transfer agent. Ethylene was used on the suction side of the booster / primary compressor. Isobutane was injected into the stream. The composition of the CTA feed into the process was determined to achieve the desired product composition. The lut index can be adjusted as needed to maintain it.

[0126] Table 5 shows the process conditions used to produce examples and comparative examples without additives. The reaction temperature for each autoclave zone and the reaction temperature to the tube are shown below. The reactor pressure and reactor control temperature are controlled by adjusting the peroxide flow to each. The degree is used to ultimately control the molecular weight distribution of the product.

[0127] [Table 5]

[0128] The examples and comparative examples were tested according to the test procedures disclosed herein to determine density, melt, and The index (I2), melt strength, and hexane extract were measured. Examples 1 and Comparative Examples The density, melt index (I2), melt strength, and hexane extraction results for 1 are as follows: This is shown in Table 6. Referring to Figure 6, the melt strength curves for Example 1 and Comparative Example 1 are shown, and the data ends. Before breaking (strand fracture), a horizontal line is drawn that approximates the average melting strength at high speed. It is graphically depicted along with the melt strength plateau region.

[0129] [Table 6]

[0130] The molecular weight data of various examples was measured according to the test procedures disclosed herein, and Results obtained using both the convolutional (conv) method and the light scattering or absolute (abs) GPC method. The results are shown in Table 7 below.

[0131] [Table 7]

[0132] CDF and LSP data from various examples were measured according to the test procedures disclosed herein. The results are shown in Table 8 below.

[0133] [Table 8]

[0134] The viscosity data of various examples was measured according to the test procedures disclosed herein, and the results The results are shown in Table 9 below.

[0135] [Table 9]

[0136] Various embodiments 13 Fractional branching per 1000 carbon atoms by 13C NMR The data was measured according to the test procedures disclosed herein, and the results are shown in Table 10 below. vinegar.

[0137] [Table 10]

[0138] With regard to various comparative examples and examples, according to the test procedures disclosed herein 1 H NM Unsaturated data was measured using R, and the results are shown in Table 11 below.

[0139] [Table 11]

Claims

1. The melt strength measured at 190°C is 5.5 cN or higher, 0.9210g / cm ３ The above and 0.9275 g / cm³ ３ The density is as follows: Melt index I measured at 190°C with a concentration of 4.5 g / 10 minutes or more. ２ and, including Hmm, low-density polyethylene homopolymer.

2. The melt index I measured at 190°C ２ However, 4.5g / 10 minutes or more and 7 The low-density polyethylene homopolymer according to claim 1, wherein the density is 5 g / 10 min or less.

3. The melt index I measured at 190°C ２ However, 4.5g / 10 minutes or more and 6 The low-density polyethylene homopolymer according to claim 1 or 2, wherein the density is 5 g / 10 min or less.

4. The melt strength measured at 190°C is 6.0 cN or more and 8.5 cN or less. The low-density polyethylene homopolymer according to any one of claims 1 to 3.

5. The melt strength measured at 190°C is 6.4 cN or more and 7.0 cN or less. The low-density polyethylene homopolymer according to any one of claims 1 to 4.

6. The melt strength measured at 190°C in cN is -0.780* (melt index). S, I ２ ) + 9.9 cN ± 5% or more, the low density according to any one of claims 1 to 5 Polyethylene homopolymer.

7. The low-density polyethylene has a molecular weight distribution (Mw(conv) / Mn) of 7.2 or higher. (conv)) including the low-density polyethylene homopoly according to any one of claims 1 to 6 Rimmer.

8. The density is 0.9220 g / cm³. ３ The above and 0.9265 g / cm³ ３ The following is: The low-density polyethylene homopolymer according to any one of claims 1 to 7.

9. The hexane extract level is 2.60% or less, as described in any one of claims 1 to 8. Low-density polyethylene homopolymer.

10. The low-density polyethylene has a z-average molecular weight Mz(co) greater than 500,000 g / mol A low-density polyethylene homopolymer according to any one of claims 1 to 9, comprising nv.

11. The low-density polyethylene is 530,000 g / mol or more and 620,000 g / The following is a description of any one of claims 1 to 10, including a z-average molecular weight Mz(conv) of mol or less. Low-density polyethylene homopolymer.

12. The low-density polyethylene includes a GPC light scattering parameter (LSP) greater than 2.

5. The low-density polyethylene homopolymer according to any one of claims 1 to 11.

13. The low-density polyethylene homopolymer comprising the low-density polyethylene homopolymer according to any one of claims 1 to 12 Room.

14. Linear low-density polyethylene (LLDPE) and the material described in any one of claims 1 to 12. A film containing a mixture with low-density polyethylene homopolymer.

15. A carrier comprising the low-density polyethylene homopolymer described in any one of claims 1 to 12. Sterling film, inflation film, or thermoformed film.

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