Ethylene-based polymer composition containing a polyfunctional branching agent and process for producing the same

Abstract

Provide a process for producing an ethylene polymer having improved melt strength for an upward branching level. 【Solution means】This process includes providing a multifunctional branching agent (MFBA). MFBA has three or more carbon-carbon double bonds on the condition that (A) MFBA is not a polymer of butadiene and does not contain an acrylate group or a methacrylate group, and MFBA has a total reactivity R of 3 < R < 40 determined by the following formula (I). JPEG2026086607000017.jpg22170 In the formula, j = the product of exponents, p = the number of different types of carbon-carbon double bonds j in the molecule, n j = the number of each carbon-carbon double bond of type j in the molecule, r 1,j = the relative reactivity ratio (RRR) of ethylene to carbon-carbon double bond j. This process includes reacting MFBA with ethylene under polymerization conditions and forming an ethylene polymer composition composed of units of ethylene and units of MFBA.

Description

Background Art

[0001] In ethylene polymers such as low density polyethylene (LDPE), the level of branching is, for example, mainly due to the reactor design (autoclave or tubular), and the polymerization conditions used to make LDPE. The level of branching is also directly correlated with the melt strength of the final polymer. Branching agents for improving the level of branching in LDPE are known. However, the process conditions required to achieve modified LDPE with a high level of branching often result in a final product with a lower degree of crystallinity and a higher content of low molecular weight extractable fractions. Therefore, there is a continuing need in the art for LDPE having improved melt strength for an improved level of branching, and for LDPE prepared under polymerization conditions that maintain good polymer properties.

[0002]

Summary of the Invention

[0003] The present disclosure provides a process. In one embodiment, the process includes providing a multifunctional branching agent (MFBA). The MFBA has: A) (1) the MFBA is not a polymer of butadiene, and (2) the MFBA does not contain acrylate or methacrylate groups, and has three or more carbon-carbon double bonds. The MFBA has: B) a total reactivity R greater than 3 and less than 40 (3 < R < 40), where R is determined by the following formula (I),

[0004] [Number] In the formula, j is the integration of exponents, p is the number of different types of carbon-carbon double bonds j in the molecule, n ,

[0006] , 1,j , , , , , , , j , , , , , is the number of each carbon-carbon double bond of type j in the molecule, r 1,j is the relative reactivity ratio (relative reactivity ra tio, RRR) of ethylene to carbon-carbon double bond j. This process reacts MFBA with ethylene under polymerization conditions to form an ethylene polymer composition containing units of ethylene and units of MFBA and includes.

[0005] The present disclosure also provides an ethylene polymer composition resulting from this process. In one embodiment the ethylene polymer composition contains (i) units of ethylene and (ii) multifunctional branching agent (MFBA) units. MFBA (A) (1) MFBA is not a polymer of butadiene, and (2) MFBA does not contain acrylate groups or methacrylate groups, and has three or more carbon -carbon double bonds. MFBA has (B) a total reactivity R greater than 3 and less than 40 (3 < R < 40), and R is determined by the following formula (I),

[0006] [Number] In the formula, j is the integration of exponents, p is the number of different types of carbon-carbon double bonds in MFBA, n j is the number of each carbon-carbon double bond of type j in the molecule, r 1,j= This is the relative reactivity ratio (RRR) of ethylene to the carbon-carbon double bond j. [Brief explanation of the drawing]

[0007] [Figure 1] The chemical structure of a polyfunctional branching agent according to one embodiment of the present disclosure is shown. [Figure 2] The chemical structure of a polyfunctional branching agent according to one embodiment of the present disclosure is shown.

[0008] definition Any reference to the periodic table of elements can be found in CRC Press, Inc., 1990-1991. Therefore, this is a reference to a published work. The references to element groups in this table are numbered by group. This is a new notation method for that purpose.

[0009] For the purpose of U.S. patent practice, the content of any referenced patents, patent applications, or publications must be within the scope of the U.S. The entire content, in particular, is not disclosed with respect to definitions and general knowledge in the art (this disclosure is not provided). (To the extent that it does not contradict the definitions provided herein) (or the corresponding U.S. patent application in the publication is incorporated by reference in the same way.)

[0010] The numerical ranges disclosed herein include a lower limit and an upper limit, from the lower limit to the upper limit. Includes all values. Explicit values ​​(e.g., 1 or 2, or 3-5, or 6, or If the range includes 7), then any subrange between any two explicit values ​​is included. (For example, the range 1-7 above could include 1-2, 2-6, 5-7, 3-7, 5-6, etc.) (This includes the sub-range.)

[0011] Unless otherwise stated, implied by the context, or customary in the art, All parts and percentages are based on weight, and all test methods are as of the filing date of this disclosure. It is the latest model.

[0012] "Alkanes" are saturated hydrocarbons. "Alkyl" (or "alkyl group") is a compound. It is an alkane with a valence (typically monovalent).

[0013] "Alkenes" are hydrocarbons containing a carbon-carbon double bond. "Alkenyls" (also An "alkenyl group" is an alkene that has a bonding valency (typically monovalent).

[0014] The term "allyl" (or "allyl group") refers to a monovalent unsaturated C3H5 hydrocarbon. In other words, the allyl group is propene with one hydrogen atom removed.

[0015] As used herein, the terms “blend” or “polymer blend” are used in 2 This refers to a mixture of one or more polymers. The blend may be miscible or not. (Not phase-separated at the molecular level). Blends, even if they are phase-separated, are not phase-separated. It is not necessary. The blend is suitable for transmission electron spectroscopy, light scattering, X-ray scattering, and in the art. It may contain, or may contain, one or more domain configurations determined by other known methods. It's not necessary. Blending is at a macro level (e.g., melt blending or compounding of resins). Alternatively, two or more polymers can be formed at a micro level (e.g., simultaneously in the same reactor) physically This can be done by mixing.

[0016] The term "composition" refers to a mixture of materials containing the composition, as well as materials formed from the materials of the composition. This refers to the reaction products and decomposition products produced.

[0017] The terms "comprising," "including," and "possessing," and The derived words are any additional components, whether or not they are specifically disclosed. This is not intended to exclude the existence of steps or procedures. To avoid any doubt, "including" All compositions claimed through the use of the term "comprising" are, in particular, opposed to Unless otherwise stated, any additional additives, whether polymers or other, are permitted. It may contain a juvant or compound. In contrast, the term "essentially derived from" is a compound. Except for those not essential to the function, all other components and steps from the scope of all subsequent descriptions Excluding procedures or steps. The term "consisting of" is any that is not explicitly described or enumerated. Exclude any of the ingredients, steps, or procedures. The term "or" means, unless otherwise specified. The listed members are referred to individually and in any combination. The singular form is used when the plural form is used. This includes use, and vice versa.

[0018] As used herein, the term "ethylene-based polymer composition" means in its polymerized form. Based on the weight of the polymer, a mixture containing more than 50% by weight or the majority of the amount of ethylene. This refers to a product that may optionally contain at least one comonomer or other molecule.

[0019] As used herein, the term "ethylene monomer" refers to a monomer having a double bond between them. A chemical unit having two carbon atoms, each carbon atom bonded to two hydrogen atoms, is a chemical unit. The units polymerize with other such chemical units to form ethylene-based polymer compositions. A "hydrocarbon" is a compound that contains only hydrogen and carbon atoms. A (or "hydrocarbonyl group") is a hydrocarbon having a bonding value (typically monovalent). Hydrocarbons can have a linear, cyclic, or branched structure.

[0020] As used herein, the term "low-density polyethylene" (or LDPE) means 0.910g / cc to less than 0.940g / cc or 0.918g / cc to 0.930g / cc The density per cc and the broad molecular weight distribution (MWD), i.e. This refers to polyethylene having long-chain branching with a "broad MWD" of 4.0 to 20.0. .

[0021] "Olefins" are unsaturated aliphatic hydrocarbons that have a carbon-carbon double bond.

[0022] The term "phenyl" (or "phenyl group") refers to a group that has a bonding valency (typically monovalent). It is a C6H5 aromatic hydrocarbon ring.

[0023] As used herein, the terms “polymer” or “polymer material” are the same as “polymer material.” Whether it is a type or a different type, polymerizing monomers This refers to a compound prepared by and the multiple and / or repeating "units" that constitute the polymer. Alternatively, "polymer units" are provided in a polymerized form. Therefore, the general term polymer is The term "H" is commonly used to refer to polymers prepared from only one type of monomer. The term "mopolymer" refers to a polymer prepared from at least two types of monomers. The term copolymer, which is commonly used to refer to, encompasses and also, for example, Randa This also includes all forms of copolymers, such as polymers and blocks. The terms "rimer" and "propylene / α-olefin polymer" refer to ethylene, respectively. Alternatively, the above copolymer prepared by polymerizing propylene and one or more additional polymerizable α- This shows olefin monomers. Polymers are often made from one or more specific monomers. "Manufactured," "based on" a specific monomer or monomer type, and having a specific monomer content Although it is sometimes referred to as "containing," in this context, the term "monomer" refers to a specific monomer. Please note that this refers to the polymerization residue, and not to the non-polymerized species. In general, polymers in this specification are based on "units," which are the polymerization forms of the corresponding monomers. It refers to spiders.

[0024] Test method Density is measured according to ASTM D792, Method B. The result is in grams / cubic centimeter. It is reported in millimeters (g / cc).

[0025] Melt Index When used herein, "melt index" (or "melt index") The term "MI" or "I2" refers to how much a thermoplastic polymer is in a molten state. This refers to a measure of how easily something can be melted. The melt index, or I2, is based on ASTM D1. 238, measured according to the conditions 190°C / 2.16kg, with grams eluted every 10 minutes. (g / 10 mins) is reported. 10 This is according to ASTM D1238, under conditions of 190°C / 10K. It is measured according to g and reported as grams eluted per 10 minutes (g / 10 min). Toindex ratio (I 10 / I2) is a temperature of 190°C according to ASTM D1238. The measurement is taken by taking the ratio of the values ​​obtained at 10 kg and 2.16 kg.

[0026] Melt strength As used herein, the term "melt strength" refers to a measure of the maximum tensile force applied to a polymer in a molten state before the polymer breaks. It is measured at 190 °C using a Goettfert Rheotens 71.97 (Goettfert Inc., Rock Hill, SC). A Goettfert Rheotester 2000 capillary rheometer with a flat entrance angle (180 degrees), a length of 30 mm, and a diameter of 2 mm is provided to a molten sample (25 - 50 grams). The sample is fed into a barrel (L = 300 mm, diameter = 12 mm), compressed, and allowed to melt for 10 minutes, and then extruded at a constant piston speed of 0.265 mm / s (which corresponds to a wall shear rate of 38.2 s for a given die diameter). The extrudate passes through a Rheotens wheel located 100 mm below the die exit and is pulled downward by the wheel at an acceleration rate of 2.4 millimeters per square second (mm / s²). The force applied to the wheel (measured in centinewtons, cN) is recorded as a function of the wheel speed (mm / s). The sample is repeated at least twice until two curves of force (cN) as a function of strand speed (mm / s) overlap. Then, the curve showing the highest speed at strand breakage is reported. The melt strength is reported in units of centinewtons (cN) as the plateau force before the strand breaks. 融状態のポリマーに加えられる最大張力の尺度を指す。Goettfert Rheot ens 71.97(Goettfert Inc.、Rock Hill,SC)を使 用して、190℃で測定される。溶融した試料(25~50グラム)には、平坦な入口角 度(180度)を備え、長さ30mm、直径2mmのGoettfert Rheote ster 2000キャピラリーレオメーターが供給される。試料は、バレル(L=30 0mm、直径=12mm)に供給され、圧縮され、10分間溶融することを許容された後 、0.265mm / sの一定のピストン速度(これは、所与のダイの直径で38.2s - 1 の壁剪断速度に相当する)で押し出される。押出物は、ダイ出口の100mm下に位置 するレオテンのホイールを通過し、2.4ミリメートル / 平方秒(mm / s 2 )の加速速 度でホイールによって下向きに引っ張られる。ホイールにかかる力(センチニュートン、 cNで測定)は、ホイールの速度(mm / s)の関数として記録される。ストランド速度 (mm / s)の関数としての力(cN)の2つの曲線が重なるまで、試料を少なくとも2 回繰り返す。次いで、ストランド切断時に最高速度を示した曲線が報告される。溶融強度 は、ストランドが切断される前のプラトー力として、センチニュートン(centi-newton、 cN)の単位で報告される。

DETAILED DESCRIPTION OF THE INVENTION

[0027] 1. Process The present disclosure provides a process. The process includes providing a multifunctional branching agent (MFBA) and reacting the MFBA with ethylene under polymerization conditions. The process forms an ethylene polymer composition comprising units of ethylene and units of the MFBA. The process includes providing or selecting a multifunctional branching agent (or "MFBA"). As used herein, a "multifunctional branching agent" is a compound that meets or satisfies the following parameters (A) and (B): A) (1) the MFBA is not a polymer of butadiene and (2) the MFBA does not contain acrylate or methacrylate groups, provided that the MFBA has three or more carbon-carbon double bonds B) has a total reactivity R greater than 3 and less than 40 (3 < R < 40), where R is determined by Equation (I): where j is the product of the exponents, p is the number of different types of carbon-carbon double bonds in the MFBA, n j is the number of each type j of carbon-carbon double bond in the molecule, r 1,j is the relative reactivity ratio (RRR) of ethylene to carbon-carbon double bond j for free radical propagation. In the context of Equation (I), "is" is understood to be interchangeable with the equal sign "=".

[0028]

Number

[0030] MFBA consists of three or more carbon-carbon double bonds, or 3, or 5, or 10-20, or It has 30, 50, 100, or more carbon-carbon double bonds. One embodiment In this state, MFBA consists of 3 to 100 carbon-carbon double bonds, or 5 to 50 carbon-carbon double bonds. It has a double bond, or 10 to 30 carbon-carbon double bonds.

[0031] As used herein, “butadiene polymer” refers to a polymer having structure (II). Polymers containing C4H6 units:

[0032] [ka] polymers having structure (III):

[0033] [ka] In the formula, the value of m is an integer between 1 and 100, and the value of n is an integer between 0 and 100. This MFBA does not contain or excludes "butadiene polymers."

[0034] As used herein, “acrylate group or methacrylate group” refers to the following structure (IV) is a reactive group containing,

[0035] [ka] In the formula, R1 is H or CH3. Structure (IV) includes acrylates and methacrylates. This MFBA does not contain or excludes "acrylate group or methacrylate group". Exclude.

[0036] In addition to satisfying (A) above, the polyfunctional branching agent conforms to or satisfies parameter (B), and parameter (B) is a total reactivity R greater than 3 and less than 40 (3 < R < 40), and R is determined by formula (I). 、or satisfies it, and parameter (B) is a total reactivity R greater than 3 and less than 40 (3 < R < 40), and R is determined by formula (I). In the formula,

[0037]

Number

[0038] The term "j" is the product of exponents (or the lower limit of the product, the number used to generate the first term of the series). The term "p" is the number of different types of C-C double bonds (carbon-carbon double bonds) present in the MFBA. Figure 1 shows the structure of MFBA, bisallyl maleate, indicated by reference number 10. Bisallyl maleate (10) has two different types of C-C double bonds. The first C-C double bond is indicated by reference number 12. The terminal double bond, which is the second type of C-C double bond, is indicated by the reference number. used). The term "p" is the number of different types of C-C double bonds (carbon-carbon double bonds) present in the MFBA. Figure 1 shows the structure of MFBA, bisallyl maleate, indicated by reference number 10. Bisallyl maleate (10) has two different types of C-C double bonds. The first C-C double bond is indicated by reference number 12. The terminal double bond, which is the second type of C-C double bond, is indicated by the reference number. weight bond (carbon-carbon double bond). Figure 1 shows the structure of MFBA, bisallyl maleate, indicated by reference number 10. Bisallyl maleate (10) has two different types of C-C double bonds. The first C-C double bond is indicated by reference number 12. The terminal double bond, which is the second type of C-C double bond, is indicated by the reference number. BA, bisallyl maleate. (10) has two different types of C-C double bonds. The first C-C double bond is indicated by reference number 12. The terminal double bond, which is the second type of C-C double bond, is indicated by the reference number. As shown in numbers 14a and 14b, bisallyl maleate has a total of three CC double bonds. It has two terminal CC bonds (reference numbers 14a, 14b) of the same type of CC duplex. Since it is a bond, specifically a terminal CC double bond, the number of different types of bonds is 2. In bis-allyl leate, the value of "p" is 2.

[0039] Figure 2 shows another MFBA, 2,4,6,8-tetramethyl-2,4,6,8-teto Lavinyl-cyclotetrasiloxane (hereinafter referred to as "(D Vi )4) Non A limited example is given, indicated by reference number 20. (D Vi )4 (reference number 20) is, It has four CC double bonds 22a, 22b, 22c, and 22d. 22a, 22b, 22c, and 22d are all CC double bonds of the same type. As a result, (D Vi In 4, p=1.

[0040] In equation (I), the term "n" represents the number of double bonds of each type. For example, Bisallyl iodate (reference number 10 shown in Figure 1) is the first CC double bond type. It has one CC double bond 12, and two terminal C- bonds as a second CC double bond type It has C double bonds 14a, 14b. As a further example, (D Vi )4(Reference number 2 in Figure 2) 0) has four CC double bonds of the same type 22a, 22b, 22c, and 22d. ru.

[0041] The reactivity ratio is calculated as the relative reactivity of ethylene compared to the CC double bond in question. The reactivity ratio can be measured experimentally by performing the experiment. The reactivity ratio can be calculated from quantum mechanics, or its contents are incorporated herein by reference. The references by Mortimer and Ehrlich are included in Fundamenta. ls of the Free-Radical Polymerization of Ethylene,Adv. Polymer Sci,Vol.7,pp.386-4 It can be found in 48 (1970) (hereinafter referred to as Mortimer for compatibility purposes). Table 1 below shows some reactive groups (ethylene) determined by Mortimer. This provides a non-limiting example of the reactivity ratio (to n).

[0042] Table 1 below provides non-limiting examples of reactive groups and their respective reactivity ratios.

[0043] [Table 1] * Please refer to Mortimer.

[0044] Table 2 below lists non-limiting examples of suitable polyfunctional branching agents, and R, total, using formula (I). It provides reactivity calculations. The polymer formula is simplified to each repeating unit. .

[0045] [Table 2]

[0046] Table 3 below shows that parameters (A) and (B) are not met, and therefore "multifunctional branching" according to this disclosure. This shows non-restrictive examples of compounds that are not "agents." These mainly include compounds where R is less than 3, or where R is 40. It is greater than and / or the total number of CC double bonds in the molecule is less than 3, or C - The reason is that one or more of the C double bonds are acrylates or methacrylates. That is the reason.

[0047] [Table 3]

[0048] This process involves reacting MFBA with ethylene under polymerization conditions. When used, the term "polymerization conditions" refers to high pressure (11,000p) inside a polymerization reactor. Free radicals at high temperatures (200°C to 350°C) and between sig and 53,000 psig. Includes initiation polymerization.

[0049] In one embodiment, the MFBA is (D Vi 4. Bisallyl maleate, polyisoprene The following are selected: polymyrcene, polyfarnesene, and combinations thereof.

[0050] In one embodiment, the MFBA is (D Vi )4.

[0051] In one embodiment, MFBA is bisallyl maleate.

[0052] The reaction of MFBA and ethylene under polymerization conditions involves the production of units derived from ethylene and MFBA. An ethylene-based polymer having units derived from is formed, and the ethylene units are in the polymer. It constitutes the majority (by weight) of the monomers present. In other words, ethylene polymers. It contains ethylene monomer and MFBA comonomer, and ethylene and MFBA are each PO It is polymerized on the polymer main chain. In this way, this ethylene-based polymer has pendant in the polymer chain. It is structurally different from polyethylene that uses functional additives grafted with t.

[0053] Polymerization conditions include polymerization utilizing one, two, or more free radical indicators. Includes. Non-limiting examples of suitable free radical initiators include organoperoxides and cyclic compounds. Peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, Peroxy carbonate, peroxy dicarbonate, peroxy ester, peroxy Ketal, t-butyl peroxypivalate, di-t-butyl peroxide, t-butyl Peroxyacetate, t-butylperoxyethylhexanoate, and t-butylperoxyethylhexanoate Examples include luoxy-2-hexanoates and combinations thereof. In one embodiment... These organic peroxy initiators are based on the weight of the polymerizable monomer, which is 0.001 wt. It is used in amounts ranging from % to 0.2% by weight.

[0054] In further embodiments, the free radical initiator is at least one incorporated into the ring structure It contains a peroxide group. An example of such an initiator is TRIGONOX 301(3,6 ,9-triethyl-3,6,9-trimethyl-1,4,7-tripeloxonane) and T RIGONOX 311(3,3,5,7,7-pentamethyl-1,2,4-trioxet Bread) and both of which are available from Akzo Nobel, and Un HMCH-4-AL (3,3,6,6, This includes, but is not limited to, 9,9-hexamethyl-1,2,4,5-tetroxonane. stomach.

[0055] Regarding polymerization conditions, the polymerization reactor is a tubular reactor and / or an autoclave reactor. and / or a reactor configuration including a continuous stirred-tank reactor.

[0056] In one embodiment, polymerization is carried out in a reactor configuration including at least one tubular reactor. It can be done.

[0057] In one embodiment, polymerization is carried out in a reactor configuration including at least one autoclave reactor. It will be held there.

[0058] In one embodiment, the process is based on the amount of ethylene added to the polymerization reactor. Next, react with MFBA at a concentration of 5 mol ppm to 2000 mol ppm, and baseline The melt strength is 10% to 200% higher than that of ethylene homopolymers. The method used herein includes forming an ethylene-MFBA copolymer. In this case, the term "moles (ppm)" is 1 × 10⁻¹⁰. -6 1 mole of ethy This is a relationship between ethylene and ethylene. When used herein, "baseline ethylene homopolymer" It was prepared under the same polymerization conditions as those used to produce ethylene-MFBA copolymer. It is a modified ethylene homopolymer, and the baseline ethylene homopolymer is ethylene-M Same or substantially the same melt index (I2±0.5g / 10) as FBA copolymer It has (a portion).

[0059] In one embodiment, a conventional chain transfer agent (CTA) is used to transport molecules Control the amount. One or more CTAs are added during the polymerization process. Indefinitely suitable CTAs Typical examples include propylene, isobutane, n-butane, 1-butene, and methyl ethyl acetate. Ton, acetone, ethyl acetate, propionaldehyde, ISOPAR (ExxonMob Examples include methanol and isopropanol (from il Chemical Co.). In one embodiment, the amount of CTA used in this process is 0.03 by weight of the total reaction mixture. It is approximately 10 percent by weight.

[0060] In one embodiment, the process includes a process recycling loop to improve conversion efficiency. include.

[0061] In one embodiment, polymerization is carried out in a tubular reactor. The tubular reactor is a single-zone tubular reactor. It may be a ventilator or a multizone tubular reactor. In a further embodiment, the tubular reactor is multizone This is a thizone tubular reactor. Multizone tubular reactors control the ethylene-to-CTA ratio. Therefore, it includes alternative locations that supply fresh ethylene to control polymer properties. To achieve the desired ethylene monomer to chain transfer agent ratio, fresh ethylene monomer is used. , added simultaneously at multiple locations. Similarly, fresh CT is used to control polymer properties. Select the addition point A. To achieve the desired CTA to ethylene monomer ratio, fresh The CTA is added simultaneously at multiple locations. Similarly, the addition point and fresh MFBA The amount is determined to maximize the desired properties, such as improved melt strength and performance, in the target application. The gel formation is controlled to achieve the desired branching agent to ethylene monomer ratio. Therefore, fresh MFBA can be added simultaneously at multiple locations. Using MFBA, By broadening the particle distribution and improving the melt strength of the polymer, gel formation and reactors can be improved. It does not involve or have potential adverse effects such as fouling or process instability. By minimizing the amount of MFBA, the desired changes in the product properties can be achieved. To achieve this, further requirements must be met regarding the distribution of CTA and MFBA along the reactor system. This will be imposed. Non-limiting examples of suitable multizone tubular reactors are shown in International Publication No. 20 This is described in issues 13 / 059042 and 2013 / 078018, and in each reference The contents are incorporated herein by reference.

[0062] In one embodiment, polymerization is carried out in a multi-reactor where the autoclave reactor precedes the tubular reactor. This is done within the system. Fresh ethylene, fresh CTA, and fresh MFBA are added at the point of addition. The ratio is the supply to the reaction zone and / or the ratio of CTA to ethylene monomer in the reaction zone. The ratio of MFBA to ethylene monomer is controlled to achieve a desired ratio.

[0063] In one embodiment, the MFBA is supplied directly to the reaction zone through the compression step, or It is supplied directly to the feed to the reaction zone. The selection of the supply point to the reaction and / or reaction zone is , solubility of MFBA in pressurized ethylene and / or solvent, contraction of MFBA in pressurized ethylene In a preheater used to heat the contents of the reactor before the injection of the compound and / or initiator This includes, but is not limited to, fouling due to premature polymerization of MFBA, several It depends on the factors.

[0064] In one embodiment, MFBA is supplied directly to the reaction zone or supplied to the reaction zone. It is supplied directly to the rations.

[0065] In one embodiment, MFBA is supplied only to reaction zone 1.

[0066] In one embodiment, the ethylene supplied to the first reaction zone is the total ethylene supplied to polymerization. It is 10 percent to 100 percent of Ren. In a further embodiment, the first reaction zone The ethylene supplied to the polymer is 20 percent to 80 percent of the total ethylene supplied to polymerization. And, further 25 percent to 75 percent, further 30 percent to 70 percent, and The percentage is between 40 and 60 percent.

[0067] In one embodiment, the process is carried out in a reactor configuration including at least one tubular reactor. This is carried out. In further embodiments, the maximum temperature in each reaction zone is 200°C to 350°C. Furthermore, the temperature ranges from 220°C to 325°C, and then again from 225°C to 300°C.

[0068] In one embodiment, the polymerization pressure at the first inlet of the reactor is 800 bar to 3600 bar. , or 1500-3400 bar, or 2000-3200 bar.

[0069] In one embodiment, "concentration of CTA in the feed relative to reaction zone i" versus "reaction zone 1 The ratio of the concentration of CTA in the added feed is 1 or greater.

[0070] In one embodiment, "concentration of CTA in the feed relative to reaction zone i" versus "reaction zone 1 The ratio of the concentration of CTA in the added feed to the product is less than 1, or less than 0.8, or 0.6. It is less than or less than 0.4.

[0071] In one embodiment, the number of reaction zones is 3 to 6.

[0072] Non-limiting examples of ethylene monomers used in the production of ethylene polymers include new Only fresh ethylene is used to produce the ethylene-based polymer of the present invention. - By removing polar components from the recycle stream, or by the reaction system configuration Examples include purified ethylene obtained by using [a certain method]. Further ethylene monomer An example is ethylene monomer from the recycling loop.

[0073] In one embodiment, the process involves polymerizing termonomers into ethylene and MFBA under polymerization conditions. This process involves reacting units of ethylene monomer and units of MFBA. To form an ethylene-based polymer composition composed of one or more units of ter monomer. This includes. Non-limiting examples of suitable termomers include those having 20 or fewer carbon atoms each. α-olefins, acrylates, methacrylates, and vinyl acetate, vinyl trim Examples include toxicilane and anhydrous forms. The α-olefin ter monomer has 3 to 10 units It may have carbon atoms, or α-olefin ter monomers may have 3 to 8 carbon atoms It may have an atom or 4 to 8 carbon atoms. Exemplary α-olefin monomers are given below. For example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-oc Examples include tene, 1-nonene, 1-decene, and 4-methyl-1-pentene, but these Not limited to this.

[0074] In one embodiment, the process uses ethylene, MFBA (and optionally termomeres). This is reacted under polymerization conditions in the presence of one or more optional additives to produce an ethylene polymer. - Including the formation of a composition. Non-limiting examples of suitable additives include stabilizers and plasticizers. Antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, flame retardants, processing aids, smoke suppression Examples include agents, viscosity control agents, and anti-adhesive agents. This composition is, for example, based on the weight of the composition and may contain one or more additives in an amount of 0% by weight, or more than 0% by weight and less than 30 percent of the total weight. A composition containing MFBA copolymerized with ethylene and one or more optional additives is hereinafter interchangeably referred to as "MFBA(PE)".

[0075] In one embodiment, MFBA(PE) is treated with one or more stabilizers, such as antioxidants like IRGANOX1 010, IRGANOX1076, and IRGAFOS168.

[0076] 2. Polymer The present disclosure provides an ethylene-based polymer (interchangeably referred to as "MFBA(PE)") composed of units of ethylene and units of MFBA. MFBA(PE) is formed by reacting MFBA with ethylene (and optionally a comonomer) under the polymerization conditions disclosed above. MFBA(PE) consists of units of ethylene, (optionally units of a comonomer), and is formed by reacting MFBA with ethylene (and optionally a comonomer) under the polymerization conditions disclosed above. MFBA(PE) consists of units of ethylene, (optionally units of a comonomer), and (A) (1) MFBA is not a polymer of butadiene and (2) MFBA does not contain an acrylate group or a methacrylate group, provided that it has three or more carbon-carbon double bonds, (B) It has a total reactivity R greater than 3 and less than 40 (3 < R < 40), and R is determined by the following formula (I)

[0077]

Number

[0078] Without being bound by any particular theory, MFBA is a formant ethylene system. To improve the melt strength of the polymer composition. Under polymerization conditions, one or two of the MFBA molecules Or three or more carbon-carbon double bonds form the growth chain that creates the ethylene polymer. It reacts (bonds) with ethylene to become part of the polyethylene chain. Ethylene-based polymers are formed from ethylene. It has units derived from polymers and units derived from MFBA, and the units derived from ethylene are polymers. It constitutes the majority (by weight) of the units present within it. In other words, ethylene polymers. It contains ethylene monomer and MFBA comonomer, and ethylene and MFBA are each PO It is polymerized on the polymer main chain. In this way, this ethylene-based polymer has pendant in the polymer chain. It is structurally different from polyethylene that uses functional additives grafted with ethylene. n-MFBA copolymer compositions are interchangeably referred to as "MFBA(PE)".

[0079] In one embodiment, the MFBA is (D Vi 4. Bisallyl maleate, polyisoprene The following are selected: polymyrcene, polyfarnesene, and combinations thereof.

[0080] In one embodiment, the MFBA is (D Vi )4.

[0081] In one embodiment, MFBA is bisallyl maleate.

[0082] In one embodiment, MFBA(PE) is in a polymerized form at 95% by weight, or 96% by weight, is 97% by weight, or 98% to 99% by weight, or 99.5% by weight, or 99.8% by weight , or 99.9% by weight, or 99.95% by weight, or 99.99% by weight of ethylene and The quantity of MFBA, or 5.0% by weight, or 4.0% by weight, or 3.0% by weight, or 2. 0% by weight to 1.0% by weight, or 0.5% by weight, or 0.2% by weight, or 0.1% by weight, or It contains 0.05% by weight, or 0.01% by weight, of MFBA. The weight percentage is MF Based on the total weight of BA(PE). In further embodiments, MFBA(PE) is in a polymerized form. , 95% to 99.99% by weight, or 96% to 99.95% by weight, or 97% by weight It contains ethylene at ~99.9% by weight, or 98% to 99.8% by weight, and MFBA is 5 0% by weight to 0.01% by weight, or 4.0% by weight to 0.05% by weight, or 3.0% by weight to It is present in an amount of 0.1% by weight, or 2.0% to 0.2% by weight.

[0083] In one embodiment, MFBA(PE) is concentrated at 0.915 g / cc to 0.935 g / cc. It has a degree.

[0084] In one embodiment, MFBA(PE) is 0.05 g / 10 min, or 0.5 g / 10 min. Alternatively, 1.0g / 10 minutes, or 5.0g / 10 minutes, or 10g / 10 minutes, or 20g / 10 minutes, or 30g / 10 minutes, or 40g / 10 minutes to 50g / 10 minutes, or 60g / 10 minutes. Alternatively, a melt-in-your-mouth mixture of 70g / 10 minutes, 100g / 10 minutes, or 1000g / 10 minutes. It contains kus(I2). In a further embodiment, MFBA(PE) is 0.15 g / 10 min ~80g / 10 min, or 0.5g / 10 min~70g / 10 min, or 1.0g / 10 min~6 0g / 10 min, or 5.0g / 10 min to 50g / 10 min, or 10g / 10 min to 40g / It has a melt index (I2) of 10 minutes, or 20g / 10 minutes to 30g / 10 minutes. In a further embodiment, MFBA(PE) is 0.1g / 10 min to 4.5g / 10 min. Alternatively, it has a melt index of 0.5g / 10 min to 4.0g / 10 min.

[0085] In one embodiment, the ethylene polymer composition comprises ethylene monomer MFBA and one The above termomers are included. Non-limiting examples of termomers include 20 or fewer carbon atoms each. α-olefins, acrylates, methacrylates, acrylic acid, methacrylates, which have elementary atoms. Examples include lylic acid, vinyl acetate, vinyltrimethoxysilane, and anhydride. α-Oleph The intermediate monomer may have 3 to 10 carbon atoms, or α-olefins. Intermonomers may have 3 to 8 carbon atoms or 4 to 8 carbon atoms. (Example) Examples of α-olefin ter monomers include propylene, 1-butene, 1-pentene, 1- Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1 -Pentene is one example, but it is not limited to these.

[0086] In one embodiment, the ethylene polymer composition comprises one or more optional additives. Non-limiting examples of suitable additives include stabilizers, plasticizers, antistatic agents, pigments, dyes, and nucleiform compounds. Forming agents, fillers, slip agents, flame retardants, processing aids, smoke suppressants, viscosity control agents, and anti-stick agents are For example, the ethylene polymer composition is, for instance, the weight of the ethylene polymer composition Based on this, it contains 0% by weight of the total weight, or one or more additives in an amount greater than 0% by weight but less than 10%. obtain.

[0087] In one embodiment, MFBA(PE) is one or more stabilizers, for example, IRGANOX1 Treated with antioxidants such as 010, IRGANOX1076, and IRGAFOS168. It can be done.

[0088] MFBA(PE) may include combinations of two or more embodiments described herein.

[0089] This disclosure also relates to at least one component formed from the MFBA(PE) described herein. We will provide goods that include [a certain amount].

[0090] In one embodiment, the article is a coating of film.

[0091] In one embodiment, the article is a coating.

[0092] In one embodiment, the article is a film.

[0093] The articles may include combinations of two or more embodiments as described herein.

[0094] 3.Applications The MFBA(PE) in this disclosure refers to single-layer and multi-layer films; blow-molded articles, injection-molded articles. , or molded articles such as rotationally molded articles; coatings; useful including fibers, woven fabrics or nonwoven fabrics. It can be used in various conventional thermoplastic manufacturing processes for producing such articles.

[0095] This MFBA(PE) is not limited to transparent shrink film, collation shrink film, and Cast stretch film, silage film, stretch hood, sealant, and It can be used in various films, including diaper backsheets. Other suitable applications include: Wires and cables, gaskets and profiles, adhesives, footwear components, and automatic Examples include, but are not limited to, interior car parts.

[0096] The applicant has demonstrated that by adding MFBA during the polymerization of ethylene, under the same polymerization conditions, M Compared to LDPE resin produced without FBA addition, the LDPE resin at the same MI We discovered that this leads to an improvement in melt strength.

[0097] Without limiting ourselves, we will now describe some embodiments of this disclosure as examples. This will be explained in detail in the examples. [Examples]

[0098] The materials used in the examples are described in Table 1 below.

[0099] [Table 4]

[0100] Example 1: Bisallyl maleate (BAI) as a polyfunctional branching agent IM) Polymerization was carried out in a continuous stirred-tank reactor. Four electric heater bands were used to control the reactor. The mixture was heated to 220°C and / or cooled. The reactor pressure was approximately 2000 bar. The amount of propylene used as a chain transfer agent controls the polymer melt index (MI) to 4.0. (CTA) was used. Ethylene and propylene were stirred through the reactor shaft. It was supplied to the top. TPO and TPA diluted in Isopar E were poured into one side of the reactor. The reaction was initiated to maintain a total ethylene conversion rate of approximately 12%. Diluted bisallyl maleate in par E is injected into a separate injector on the side of the reactor. The fuel was supplied. The residence time in the reactor was approximately 1.5 minutes. At the single outlet on the lower part of the reactor, All unreacted reactants and polymers were contained. The spray and flow were reduced to approximately 1 bar. By doing so, and simultaneously cooling the flow to ambient temperature, the polymer is separated from the remaining reactants. Then, it was separated. Next, the polymer was collected in powder form.

[0101] The structure of bisallyl maleate is shown by reference no. 10 in Figure 1. Suaryl contains three CC double bonds and contains an acrylate or methacrylate group. It is not a product of butadiene polymerization, and thereby the parameter (A) of MFBA is To satisfy. Bisallyl maleate contains two different types of CC double bonds (p Bisallyl maleate has a reactivity ratio of 0.2, and is a dihydrotestosterone-internal maleate. It has a double bond (n1=1). Bisallyl maleate has two reactivity ratios of 3.1. It has terminal vinyl groups (n2=2). Therefore, the R value is calculated to be 5.6. Therefore, bisallyl maleate satisfies parameter (A) and parameter (B) (Equation 1) Therefore, it is an MFBA as defined herein.

[0102] Data from an invention example using bis-allyl maleate (BAIIM) as MFBA The results are shown in Table 4. Addition of 30 mol ppm to 93 mol ppm of bis-allyl maleate Therefore, baseline ethoxyethanol produced with the same or substantially the same I2 under the same polymerization conditions Lenhomopolymer (comparative sample, CS) Compared to the melt strength, the melt strength of ethylene / BAIIM copolymer ("melt strength") The ength (MS) improves. Baseline ethylene homopolymer is 4.00 g / It has an I2 value of 10 min and a melt strength of 13.84 cN. (IE1, IE2, and IE3) The ethylene / BAIIM copolymers are, respectively, IE1 3.67 / 16.36 cN. (18% improvement in melt strength above baseline), IE2 4.0 / 17.63 (baseline (27% improvement in melt strength compared to the original), and IE3 3.99 / 17.09cN (base ray). It has an I2 / melt strength value that is 23% higher than that of the previous model.

[0103] [Table 5]

[0104] Example 2: (D) as a polyfunctional branching agent Vi )4 Polymerization was carried out in a continuously stirred tank reactor operating under adiabatic conditions. The reactor pressure was approximately 200 It was 0 bar. This amount controls the final polymer melt index to approximately 4g / 10min. Propylene was used as a chain transfer agent (CTA). Ethylene and propylene were stirred together. It was supplied to the top of the reactor at a temperature of 60°C by a shaft. 1% by weight in mineral spirits. Diluted TPO is injected into one side of the reactor to maintain the reactor temperature at 220°C. The reaction was initiated. Also, diluted in mineral spirits (D Vi )4, on the side of the reactor It was supplied into a separate injector on the surface. The residence time in the reactor was approximately 1.5 minutes. All unreacted reactants and polymers were contained in a single outlet on the vessel. 200°C and Devolatilization in a low-pressure separator operating at 15 bar extracts the polymer from the remaining reactants. The polymer was separated, and then the resulting molten polymer was extruded through a pelletizer and collected.

[0105] (D Vi The structure of )4 is shown in Table 2. (D Vi )4 is acrylate or methacrylate It does not contain a group, (D Vi )4 is not a product of butadiene polymerization. (D Vi )4 is, It contains one type of carbon-carbon double bond (p=1). (D Vi )4 is the opposite of 0.4 Each molecule has four of these double bonds with a response ratio (n1=4). Therefore, The R value is calculated to be 10. Therefore, (D Vi )4 is parameter (A) and parameter It satisfies (B)(Equation 1) and is therefore an MFBA as defined herein.

[0106] As MFBA (D Vi The data from the embodiment of the invention using )4 is shown in Table 5 (below). 40 mol ppm to 130 mol ppm (D Vi )By adding 4, the same or substantially the same The melt strength of baseline ethylene homopolymers produced with the same I2 and under the same polymerization conditions Compared to the degree, ethylene / (D Vi )4 The melt strength of the copolymer is improved. (D Vi )4 The baseline ethylene homopolymer that does not contain has a melt strength of 3.3 cN, and ethylene n / (D Vi Each of the four copolymers has a melt strength of more than 6 cN.

[0107] As shown in Table 5, the baseline ethylene homopolymer was 4.15 g / 10 min It has an I2 value and a melt strength of 3.32 cN. Ethylene in IE4, IE5, and IE6. n / (D Vi )4 copolymers each have IE4 3.69 / 7.65 cN (base (130% improvement in melt strength compared to previous standards), IE5 3.79 / 6.33 (9 baseline) (1% or more improvement in melt strength), and IE6 3.68 / 8.37 (150% above baseline) It has an I2 / melt strength value that surpasses the average melt strength.

[0108] [Table 6]

[0109] This disclosure is not limited to the embodiments and examples contained herein, but also includes some embodiments and Modified forms of those embodiments, including combinations of elements from different embodiments, are described below. It is particularly intended to include to the extent that it falls within the scope of the patent claims.

Claims

1. It is a process, A polyfunctional branching agent (MFBA), A) (1) The MFBA is not a polymer of butadiene, and (2) The MFBA does not contain acrylate groups or methacrylate groups. As an example, three or more carbon-carbon double bonds, B) Having a total reactivity R greater than 3 and less than 40 (3 < R < 40), where R is given by the following formula (I) It was decided, [Math 1] During the ceremony, j = the sum of exponents, p = the number of different types of carbon-carbon double bonds j in the molecule. n ｊ = This is the number of carbon-carbon double bonds of type j in the molecule, r １，ｊ = The relative reactivity ratio (RRR) of ethylene to the carbon-carbon double bond j, polyfunctional. To provide a branching agent, Reacting the MFBA with ethylene under polymerization conditions, To form an ethylene-based polymer composition containing ethylene units and MFBA units. A process that includes "toto".

2. The process involves reacting ethylene with MFBA in a tubular reactor, To form an ethylene-based polymer composition containing ethylene units and MFBA units. The process according to claim 1, including toto.

3. The process involves reacting ethylene with the MFBA in an autoclave reactor, To form an ethylene-based polymer composition containing ethylene units and MFBA units. The process according to claim 1, including toto.

4. Ethylene, (D Ｖｉ ) ４ bisallyl maleate, polyisoprene, polymyrcene, MFBA, selected from the group consisting of polyfarnesenes and combinations thereof, reacts with To make, The present invention relates to any one of claims 1 to 3, which includes forming an ethylene-based polymer composition. The process described.

5. Reacting the ter monomer with the ethylene and the MFBA, Ethylene system including units of ethylene, units of MFBA, and units of ter monomer The process according to any one of claims 1 to 4, comprising forming a polymer composition vinegar.

6. The units of ethylene, A unit of polyfunctional branching agent (MFBA), (A) (1) The MFBA is not a polymer of butadiene, and (2) The MFBA does not contain acrylate groups or methacrylate groups. As an example, three or more carbon-carbon double bonds, (B) Having a total reactivity R greater than 3 and less than 40 (3 < R < 40), where R is given by the following formula (I) It was decided that [Math 2] During the ceremony, j = the sum of exponents, p = the number of different types of carbon-carbon double bonds in the MFBA, n ｊ = This is the number of carbon-carbon double bonds of type j in the molecule. r １，ｊ = The relative reactivity ratio (RRR) of ethylene to the carbon-carbon double bond j, polyfunctional. Units of branching agents, α-olefins, acrylates, methacrylates, vinyl acetate, and vinyl trimethoxy Ethylene, which contains an optional ter-monomer unit selected from the group consisting of sisirane. A polymer composition.

7. The aforementioned MFBA is (D Ｖｉ ) ４ Bisallyl maleate, polyisoprene, polymilce A substance selected from the group consisting of , polyfarnesene, and combinations thereof, according to claim 6. The ethylene-based polymer composition described.

8. An ethylene-based polymer composition according to claim 6 or 7, comprising units of ter monomer.

9. An article comprising the ethylene polymer composition according to any one of claims 6 to 8.

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