Polymer compositions to reduce nozzle stop during extrusion and related methods

Abstract

A manufacturing process comprising the steps of: compounding a composition having a polyolefin, a first component, which is polyethylene glycol, polyethylene glycol monoester, or polyethylene glycol diester, and a second component, which is a phosphorus-containing compound having one of the following two structures: wherein each R1, R2, R3, R4, and R5 is independently selected and is a C10-C18 alkyl moiety; n is an integer in the range of 3-11; and the sum of x1 + x2 is an integer in the range of 1-251, or wherein each R1, R2, R3 and R4 is independently selected and is a C10-C18 alkyl moiety; m is an integer in the range of 3-11; and x is an integer in the range of from 1 to 122 wherein the composition does not include fluorine-containing compounds; and extruding the compounded composition through a die, and wherein the manufacturing process has a reduced die build-up rate relative to an otherwise identical manufacturing process that does not include the first component or the second component.

Description

[0001] Cross-reference to related applications

[0002] This patent application claims priority to U.S. Provisional Patent Application Serial No. 63439041, filed January 13, 2023. The subject matter of U.S. Provisional Patent Application Serial No. 63439041, filed January 13, 2023, is incorporated herein by reference. Background Technology

[0003] In polymer extrusion processing, it remains necessary to eliminate or reduce the rate of accumulation of unwanted material on the heated die (die head, mold, die), i.e., to eliminate or reduce the rate of unwanted die buildup (die buildup, mold buildup, mold buildup) on the heated die. Die buildup can adversely affect the quality of the extrudate (i.e., the composition extruded from the heated die) because some of the accumulated die buildup can detach or peel off from the heated die and appear in the extrudate as black specks or other types of contamination. Contamination caused by die buildup often results in extrudates or extruded products, such as extruded polymer films, failing to meet quality standards. This, of course, leads to inefficiencies in manufacturing.

[0004] Due to the die buildup rate in extrusion processes, the manufacturing process must periodically shut down for maintenance for a period at least equal to the time spent clearing the buildup from the heated die. These periods of inactivity result in lost production, which in turn leads to additional manufacturing costs. Summary of the Invention

[0005] A manufacturing method includes the step of: compounding (kneading, mixing, compounding) a composition having the following characteristics:

[0006] The composition comprises a polyolefin, a first component, and a second component, wherein the first component is polyethylene glycol, polyethylene glycol monoester, or polyethylene glycol diester, and the second component is a phosphorus-containing compound having one of the following two structures:

[0007]

[0008] Among them, each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3-11; and the sum of x1+x2 is an integer in the range of 1-251, or

[0009]

[0010] Among them, each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 The alkyl portion; m is an integer in the range of 3-11; and x is an integer in the range of 1-122, wherein the composition does not contain fluorinated compounds; and the compounded composition is extruded through a die (die), and wherein a manufacturing method that is otherwise identical except for the first or second component has a reduced die buildup rate.

[0011] A manufacturing method includes the step of: compounding a composition having the following components: a polyolefin, a first component, and a second component, wherein the first component is polycaprolactone, and the second component is a phosphorus-containing compound having one of the following two structures:

[0012]

[0013] Among them, each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3-11; and the sum of x1+x2 is an integer in the range of 1-251, or

[0014]

[0015] Among them, each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 The alkyl portion; m is an integer in the range of 3-11; and x is an integer in the range of 1-122, wherein the composition does not contain fluorinated compounds; and the compounded composition is extruded through a die, wherein the manufacturing method has a reduced die accumulation rate relative to a manufacturing method that is otherwise identical but does not include the first or second component.

[0016] A manufacturing method includes the step of: compounding a composition having the following components: a polyolefin, a first component, and a second component, wherein the first component is polypropylene glycol, polypropylene glycol monoester, or polypropylene glycol diester, and the second component is a phosphorus-containing compound having one of the following two structures:

[0017]

[0018] Among them, each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3-11; and the sum of x1+x2 is an integer in the range of 1-251, or

[0019]

[0020] Among them, each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 The alkyl portion; m is an integer in the range of 3-11; and x is an integer in the range of 1-122, wherein the composition does not contain fluorinated compounds; and the compounded composition is extruded through a die, wherein the manufacturing method has a reduced die accumulation rate relative to a manufacturing method that is otherwise identical but does not include the first or second component.

[0021] A manufacturing method includes the step of: compounding a composition having the following components: a polyolefin, a first component, and a second component, wherein the first component is a polyethylene glycol-polypropylene glycol copolymer, a polyethylene glycol-polycaprolactone copolymer, a polypropylene glycol-polycaprolactone copolymer, or a 1,4-butanediol-polycaprolactone copolymer, and the second component is a phosphorus-containing compound having one of the following two structures:

[0022]

[0023] Among them, each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18Alkyl moiety; n is an integer in the range of 3-11; and the sum of x1+x2 is an integer in the range of 1-251, or

[0024]

[0025] Among them, each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 The alkyl portion; m is an integer in the range of 3-11; and x is an integer in the range of 1-122, wherein the composition does not contain fluorinated compounds; and the compounded composition is extruded through a die, wherein the manufacturing method has a reduced die accumulation rate relative to a manufacturing method that is otherwise identical but does not include the first or second component.

[0026] A manufacturing method includes the step of: compounding a composition having the following components: a polyolefin, a first component, and a second component, wherein the first component is an ester prepared from a copolymer of polyethylene glycol and polypropylene glycol, and the second component is a phosphorus-containing compound having one of the following two structures:

[0027]

[0028] Among them, each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3-11; and the sum of x1+x2 is an integer in the range of 1-251, or

[0029]

[0030] Among them, each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 The alkyl portion; m is an integer in the range of 3-11; and x is an integer in the range of 1-122, wherein the composition does not contain fluorinated compounds; and the compounded composition is extruded through a die, wherein the manufacturing method has a reduced die accumulation rate relative to a manufacturing method that is otherwise identical but does not include the first or second component. Attached Figure Description

[0031] This patent or application document contains at least one drawing executed in color. Upon request and payment of the necessary fees, the Patent Office will provide a published copy of this patent or application document with one or more color drawings.

[0032] Figure 1 A color photograph of the die deposit produced using the formulation AG described in the experimental section of this application is shown.

[0033] Figure 2A A color photograph of the stand die deposit produced using formulation A described in the experimental section of this application is shown.

[0034] Figure 2B A color photograph of the vertical die-gap accumulation produced using formulation B described in the experimental section of this application is shown.

[0035] Figure 2C A color photograph of the vertical die-gathering material produced using formulation C described in the experimental section of this application is shown.

[0036] Figure 2D A color photograph of the vertical die-gap material produced using formulation D described in the experimental section of this application is shown. Detailed Implementation

[0037] The embodiments generally relate to polymer-extrusion manufacturing methods employing non-fluorinated polymeric processing aids, which result in a reduced die build-up rate compared to manufacturing methods that are otherwise identical but do not employ non-fluorinated polymeric processing aids.

[0038] Very generally, embodiments relate to a method of manufacturing a composition in which a non-fluorinated polymer processing aid is used, the composition comprising: a polyolefin, a first component, and a second component.

[0039] Regarding the chemical nomenclature used herein, copolymers are involved in several instances where a hyphen, i.e., the "-" symbol, is used to indicate the distinction between the first and second copolymer units. For example, AB copolymer indicates that "A" refers to the first copolymer unit and "B" is the second copolymer unit. Furthermore, in the description of the chemical structure of copolymers herein, "A..." n -B mThe quotation marks indicate that the first repeating copolymer unit "A" is repeated "n" times and the second repeating copolymer unit "B" is repeated "m" times. Furthermore, regarding the description of the copolymer structure, the repeating copolymer units enclosed in parentheses (as opposed to brackets) should be understood as teaching both one or more block copolymer embodiments and one or more random copolymer embodiments. For example, in the following illustrative copolymer structure:

[0040]

[0041] in

[0042] n is an integer in the range of 1 to 10;

[0043] m is an integer in the range 1-10; and

[0044] x is an integer in the range of 1 to 1000.

[0045] It should be understood that when x > 1, the parenthetical units referred to by x can be the same or different. When they are the same, a block copolymer is obtained, and when they are different, a random copolymer is obtained.

[0046] Polymer extrusion manufacturing methods, including the step of extruded a polymer composition through a heated die (die), are well known. Those skilled in the art can determine useful die temperatures without excessive experimentation. As a non-limiting example, useful compounding and extrusion temperatures for manufacturing blown polymeric films can be determined by those skilled in the art without excessive experimentation. In embodiments, useful blown film manufacturing temperatures range from 190°C to 250°C; in other embodiments, temperatures of approximately 220°C are useful for manufacturing blown films. Useful temperatures for manufacturing cast films can also be determined by those skilled in the art without excessive experimentation. In embodiments, useful cast film manufacturing temperatures typically range from 250°C to 330°C. In other embodiments, useful cast film manufacturing temperatures typically range from 240°C to 330°C.

[0047] All polyolefins known to be useful for manufacturing cast and blown films can be used in the embodiments. In specific embodiments, useful polyolefins include: polyethylene (PE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), and combinations thereof.

[0048] In one embodiment, the first component is polyethylene glycol, polyethylene glycol monoester, or polyethylene glycol diester. In another embodiment, the polyethylene glycol has the following structure:

[0049]

[0050] in

[0051] n is an integer in the range of 3 to 500.

[0052] In embodiments, polyethylene glycol in the range of 1000 g / mol (n is about 23) to 10,000 g / mol (n is about 227) is useful.

[0053] In this embodiment, polyethylene glycol monoester has the following structure:

[0054]

[0055] in

[0056] n is an integer in the range of 3 to 500, and

[0057] R is C1-C 28 Saturated or unsaturated portions.

[0058] Useful embodiments also include polyethylene glycol monoesters having the following structure:

[0059]

[0060] in

[0061] n is an integer in the range of 3 to 500, and

[0062] R is C6-C 20 Saturated or unsaturated portions.

[0063] In the embodiments, polyethylene glycol diester has the following structure:

[0064]

[0065] in

[0066] n is an integer in the range of 3 to 500, and

[0067] Each R is chosen independently and is C1-C. 28 Saturated or unsaturated portions.

[0068] In other embodiments, the first component is polycaprolactone. In one embodiment, polycaprolactone has the following structure:

[0069]

[0070] in

[0071] n is an integer in the range of 3 to 500.

[0072] In other embodiments, the first component is polypropylene glycol, polypropylene glycol monoester, or polypropylene glycol diester. In one embodiment, the polypropylene glycol has the following structure:

[0073]

[0074] in

[0075] n is an integer in the range of 3 to 500;

[0076] Polypropylene glycol monoester has the following structure:

[0077]

[0078] in

[0079] n is an integer in the range of 3 to 500, and

[0080] R is C1-C 28 Saturated or unsaturated portions; and

[0081] Polypropylene glycol diester has the following structure:

[0082]

[0083] in

[0084] n is an integer in the range of 3 to 500, and

[0085] Each R is chosen independently and is C1-C. 28 Saturated or unsaturated portions.

[0086] In other embodiments, the first component is a polyethylene glycol-polypropylene glycol copolymer. In one embodiment, the polyethylene glycol-polypropylene glycol copolymer has the following structure:

[0087]

[0088] in

[0089] n is an integer in the range of 1 to 500.

[0090] m is an integer in the range of 1-500, and

[0091] x is an integer in the range of 1 to 500.

[0092] In other embodiments, the first component is an ester prepared from a copolymer of polyethylene glycol and polypropylene glycol. In these embodiments, the ester prepared from the copolymer of polyethylene glycol and polypropylene glycol has one of two structures:

[0093]

[0094] in

[0095] n is an integer in the range of 1 to 500.

[0096] m is an integer in the range of 1 to 500.

[0097] x is an integer in the range of 1-500, and

[0098] R is C1-C 28 Saturated or unsaturated parts

[0099] or

[0100]

[0101] in

[0102] n is an integer in the range of 1 to 500.

[0103] m is an integer in the range of 1 to 500.

[0104] x is an integer in the range of 1-500, and

[0105] Each R is independently selected from C1-C 28 Saturated or unsaturated portions.

[0106] In other embodiments, the first component is (i) a polyethylene glycol-polycaprolactone copolymer or (ii) a polypropylene glycol-polycaprolactone copolymer. In those embodiments where the first component is a polyethylene glycol-polycaprolactone copolymer, the polyethylene glycol-polycaprolactone copolymer has one of the following three structures:

[0107]

[0108] Where n is an integer in the range of 1 to 500, m is an integer in the range of 1 to 500, and x is an integer in the range of 1 to 500; or

[0109]

[0110] Where n is an integer in the range of 1 to 500, m is an integer in the range of 1 to 500, x is an integer in the range of 1 to 500, and R is a C1-C2 integer. 28 Saturated or unsaturated portion; or

[0111]

[0112] in

[0113] n is an integer in the range of 1 to 500.

[0114] m is an integer in the range of 1 to 500.

[0115] x is an integer in the range of 1-500, and

[0116] Each R is independently selected from C1-C 28 Saturated or unsaturated portions.

[0117] Furthermore, in those embodiments where the first component is a polypropylene glycol-polycaprolactone copolymer, the polypropylene glycol-polycaprolactone copolymer has one of the following three structures:

[0118]

[0119] in

[0120] n is an integer in the range of 1 to 500.

[0121] m is an integer in the range of 1-500, and

[0122] x is an integer in the range of 1 to 500.

[0123] or

[0124]

[0125] Where n is an integer in the range of 1 to 500, m is an integer in the range of 1 to 500, x is an integer in the range of 1 to 500, and R is a C1-C2 integer. 28 Saturated or unsaturated portion; or

[0126]

[0127] Where n is an integer in the range of 1 to 500, and m is an integer in the range of 1 to 500.

[0128] x is an integer in the range of 1-500, and

[0129] Each R is independently selected from C1-C 28 Saturated or unsaturated portions.

[0130] In other embodiments, the first component is a 1,4-butanediol-polycaprolactone copolymer having one of the following three structures:

[0131]

[0132] in

[0133] n is an integer in the range of 1 to 500.

[0134] m is an integer in the range of 1 to 500.

[0135] x is an integer in the range of 1 to 500.

[0136] or

[0137]

[0138] in

[0139] n is an integer in the range of 1 to 500.

[0140] m is an integer in the range of 1 to 500.

[0141] x is an integer in the range of 1-500, and

[0142] R is C1-C 28 Saturated or unsaturated portions;

[0143] or

[0144]

[0145] in

[0146] n is an integer in the range of 1 to 500.

[0147] m is an integer in the range of 1 to 500.

[0148] x is an integer in the range of 1-500, and

[0149] R is C1-C 28 Saturated or unsaturated portions.

[0150] In this embodiment, the polycaprolactone copolymer can be a diol whose polymer chains are partially capped at both ends with hydroxyl groups.

[0151] In this embodiment, the amount of the first component in the composition is in the range of 250-5000 ppm.

[0152] In this embodiment, the second component is a phosphorus-containing compound having one of the following two structures:

[0153]

[0154] in

[0155] Each R 1 R 2 R 3 R 4 and R5 It is an independent choice and is C. 10 -C 18 Alkyl moiety;

[0156] n is an integer in the range of 3-11; and

[0157] The sum of x1 + x2 is an integer in the range of 1-251.

[0158] or

[0159]

[0160] in

[0161] Each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 Alkyl moiety;

[0162] m is an integer in the range of 3-11; and

[0163] x is an integer in the range of 1-122.

[0164] The second component can be commercially available, or it can be manufactured using known methods.

[0165] In this embodiment, the amount of the second component in the composition is in the range of 250-5000 ppm.

[0166] Methods for compounding and extruding polymer compositions are well known, and any of them can be used. Those skilled in the art will be able to determine compounding conditions without excessive experimentation. Non-limiting examples of known compounding methods include Banbury mixing, single-screw compounding, and twin-screw compounding.

[0167] All embodiments described herein explicitly exclude the use of fluorinated compounds.

[0168] Compared to manufacturing methods that are otherwise identical but do not employ polymer compositions having a first or second component, all embodiments described herein have a reduced die buildup rate.

[0169] Various methods can be used to evaluate the die-gap accumulation rate of a manufacturing method. Non-limiting examples include: 1) visually inspecting the die (and die-gap accumulation) at fixed (periodic, regular) time intervals (see attached figures); 2) taking photographs of the die (and die-gap accumulation) at fixed time intervals and then calculating the area of ​​the die-gap accumulation shown in the photographs by integration; and 3) scraping the die-gap accumulation from the die at fixed time intervals and then weighing the scraped die-gap accumulation. Those skilled in the art will be able to calculate the die-gap accumulation rate of the manufacturing method without conducting excessive experimentation.

[0170] Any one or more additives known to be useful for polymer compounding or processing may be used in the disclosed embodiments.

[0171] experiment

[0172] Processing aid packages containing polymeric phosphite combined with lubricants were evaluated under various processing temperatures and conditions, as well as resin grades, to demonstrate their effectiveness.

[0173] Polyphosphite 1

[0174]

[0175] Each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3 to 11; and the sum of x1 + x2 is an integer in the range of 1 to 251.

[0176] Phosphite 2

[0177]

[0178] Where R is a branched or straight-chain nonyl group.

[0179] Phosphite 3

[0180]

[0181] Example 1: CaCO3-filled membrane

[0182] The processing aid package of the present invention was evaluated to demonstrate the synergistic properties of the polymeric phosphite 1 combined with a 1,4-butanediol-polycaprolactone copolymer with an average molecular weight of 4000 g / mol. The formulation was compounded into 1 M LLDPE resin using a 3 / 4-inch single-screw Brabender extruder. The polymer was extruded through a 2-inch × 0.02-inch die at 80 rpm and 250°C to produce a 0.02-inch thick film.

[0183] One hour after extruding each formulation, inspect the die and visually estimate the amount of material accumulated at the die edge. The formulation containing the combination of polymeric phosphite 1 and polycaprolactone copolymer exhibits only a small amount of material accumulation compared to other formulations. Adding phosphite 3 to the formulation containing polymeric phosphite 1 and polycaprolactone copolymer increases the amount of material accumulated at the die. See also Figure 1 .

[0184] formula A B C D E F G 1MI LLDPE 80％ 80％ 80％ 80％ 80％ 80％ 80％ <![CDATA[CaCO3]]> 20％ 20％ 20％ 20％ 20％ 20％ 20％ Polyphosphite 1 1600 1600 1600 Phosphite 2 1500 Phosphite 3 1500 1500 Polycaprolactone copolymer 800 800 Fluoropolymer PPA 500 500 % of the die opening covered with accumulated material 35 25 3 5 15 15 60

[0185] Example 2

[0186] The processing aid package of the present invention was evaluated to demonstrate the synergistic performance of the combination of polymeric phosphite 1 and polycaprolactone, which is a >90% homopolymer with an average molecular weight of 80,000 g / mol, when extruded through different types of dies. The formulation was compounded into 1 M LLDPE resin using a 3 / 4-inch single-screw Brabender extruder. The polymer was extruded through a dual strand die at 80 rpm and 250°C.

[0187] Extruding each formulation for one hour followed by die inspection and visual estimation of the amount of material accumulated covering the die edge. The formulation containing the combination of polymeric phosphite 1 and polycaprolactone copolymer showed no visible material accumulation compared to other formulations. See also Figure 2A-2D .

[0188] formula A B C D 1MI LLDPE X X X X Phosphite 3 1500 1500 1500 1500 Polyphosphite 1 1600 1600 Polycaprolactone 1200 1200 % of the die opening covered with accumulated material >90 80 5 0 .

Claims

1. A manufacturing method, comprising the steps of: The following compositions are formulated: Polyolefins The first component, wherein the first component is polyethylene glycol, polyethylene glycol monoester, or polyethylene glycol diester, and The second component is a phosphorus-containing compound having one of the following two structures: in Each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3-11; and The sum of x1 + x2 is an integer in the range of 1-251. or in Each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 Alkyl moiety; m is an integer in the range of 3-11; and x is an integer in the range of 1 to 122. in, The composition does not include fluorinated compounds; and The compounded composition is extruded through a die, and Among them, compared with other manufacturing methods that are the same but do not include the first component or the second component, the manufacturing method has a reduced die-gap accumulation rate.

2. The manufacturing method according to claim 1, wherein, The polyethylene glycol has the following structure: in n is an integer in the range of 3 to 500; The polyethylene glycol monoester has the following structure: in n is an integer in the range of 3 to 500, and R is C1-C 28 Saturated or unsaturated portions; and The polyethylene glycol diester has the following structure: in n is an integer in the range of 3 to 500, and Each R is chosen independently and is C1-C. 28 Saturated or unsaturated portions.

3. The manufacturing method according to claim 1, wherein, The amount of the first component in the composition is in the range of 250-5000 ppm, and The amount of the second component in the composition is in the range of 250-5000 ppm.

4. A manufacturing method, comprising the steps of: The following compositions are formulated: Polyolefins The first component, wherein the first component is polycaprolactone, and The second component is a phosphorus-containing compound having one of the following two structures: in Each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3-11; and The sum of x1 + x2 is an integer in the range of 1-251. or in Each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 Alkyl moiety; m is an integer in the range of 3-11; and x is an integer in the range of 1 to 122. in, The composition does not include fluorinated compounds; and The compounded composition is extruded through a die, and Among them, compared with other manufacturing methods that are the same but do not include the first component or the second component, the manufacturing method has a reduced die-gap accumulation rate.

5. The manufacturing method according to claim 4, wherein, The polycaprolactone has the following structure: in n is an integer in the range of 3 to 500.

6. The manufacturing method according to claim 4, wherein, The amount of the first component in the composition is in the range of 250-5000 ppm, and The amount of the second component in the composition is in the range of 250-5000 ppm.

7. A manufacturing method, comprising the steps of: The following compositions are formulated: Polyolefins The first component, wherein the first component is polypropylene glycol, polypropylene glycol monoester, or polypropylene glycol diester, and The second component is a phosphorus-containing compound having one of the following two structures: in Each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3-11; and The sum of x1 + x2 is an integer in the range of 1-251. or in Each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 Alkyl moiety; m is an integer in the range of 3-11; and x is an integer in the range of 1 to 122. in, The composition does not include fluorinated compounds; and The compounded composition is extruded through a die, and Among them, compared with other manufacturing methods that are the same but do not include the first component or the second component, the manufacturing method has a reduced die-gap accumulation rate.

8. The manufacturing method according to claim 7, wherein, The polypropylene glycol has the following structure: in n is an integer in the range of 3 to 500; The polypropylene glycol monoester has the following structure: in n is an integer in the range of 3 to 500, and R is C1-C 28 Saturated or unsaturated portions; and The polypropylene glycol diester has the following structure: in n is an integer in the range of 3 to 500, and Each R is chosen independently and is C1-C. 28 Saturated or unsaturated portions.

9. The manufacturing method according to claim 7, wherein, The amount of the first component in the composition is in the range of 250-5000 ppm, and The amount of the second component in the composition is in the range of 250-5000 ppm.

10. A manufacturing method, comprising the steps of: The following compositions are formulated: Polyolefins The first component is a polyethylene glycol-polypropylene glycol copolymer, a polyethylene glycol-polycaprolactone copolymer, a polypropylene glycol-polycaprolactone copolymer, or a 1,4-butanediol-polycaprolactone copolymer, and The second component is a phosphorus-containing compound having one of the following two structures: in Each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3-11; and The sum of x1 + x2 is an integer in the range of 1-251. or in Each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 Alkyl moiety; m is an integer in the range of 3-11; and x is an integer in the range of 1 to 122. in, The composition does not include fluorinated compounds; and The compounded composition is extruded through a die, and Among them, compared with other manufacturing methods that are the same but do not include the first component or the second component, the manufacturing method has a reduced die-gap accumulation rate.

11. The manufacturing method according to claim 10, wherein, The polyethylene glycol-polypropylene glycol copolymer has the following structure: in n is an integer in the range of 1 to 500. m is an integer in the range of 1-500, and x is an integer in the range of 1 to 500; The polyethylene glycol-polycaprolactone copolymer has one of the following three structures: in n is an integer in the range of 1 to 500. m is an integer in the range of 1-500, and x is an integer in the range of 1 to 500; or in n is an integer in the range of 1 to 500. m is an integer in the range of 1 to 500. x is an integer in the range of 1-500, and R is C1-C 28 Saturated or unsaturated portions; or in n is an integer in the range of 1 to 500. m is an integer in the range of 1 to 500. x is an integer in the range of 1-500, and Each R is independently selected from C1-C 28 Saturated or unsaturated portions; The polypropylene glycol-polycaprolactone copolymer has one of the following three structures: in n is an integer in the range of 1 to 500. m is an integer in the range of 1-500, and x is an integer in the range of 1 to 500. or in n is an integer in the range of 1 to 500. m is an integer in the range of 1 to 500. x is an integer in the range of 1-500, and R is C1-C 28 Saturated or unsaturated portions; or in n is an integer in the range of 1 to 500. m is an integer in the range of 1 to 500. x is an integer in the range of 1-500, and Each R is independently selected from C1-C 28 Saturated or unsaturated portions; and The 1,4-butanediol-polycaprolactone copolymer has one of the following three structures: in n is an integer in the range of 1 to 500. m is an integer in the range of 1 to 500. x is an integer in the range of 1 to 500. or in n is an integer in the range of 1 to 500. m is an integer in the range of 1 to 500. x is an integer in the range of 1 to 500, and R is a C1-C2 integer. 28 Saturated or unsaturated portion; or in n is an integer in the range of 1 to 500. m is an integer in the range of 1 to 500. x is an integer in the range of 1-500, and R is C1-C 28 Saturated or unsaturated portions.

12. The manufacturing method according to claim 10, wherein, The amount of the first component in the composition is in the range of 250-5000 ppm, and The amount of the second component in the composition is in the range of 250-5000 ppm.

13. A manufacturing method, comprising the steps of: The following compositions are formulated: Polyolefins The first component is an ester prepared from a copolymer of polyethylene glycol and polypropylene glycol, and The second component is a phosphorus-containing compound having one of the following two structures: in Each R 1 R 2 R 3 R 4 and R 5 It is an independent choice and is C. 10 -C 18 Alkyl moiety; n is an integer in the range of 3-11; and The sum of x1 + x2 is an integer in the range of 1-251. or in Each R 1 R 2 R 3 and R 4 It is an independent choice and is C. 10 -C 18 Alkyl moiety; m is an integer in the range of 3-11; and x is an integer in the range of 1 to 122. in, The composition does not include fluorinated compounds; and The compounded composition is extruded through a die, and Among them, compared with other manufacturing methods that are the same but do not include the first component or the second component, the manufacturing method has a reduced die-gap accumulation rate.

14. The manufacturing method according to claim 13, wherein, The ester prepared from the copolymer of polyethylene glycol and polypropylene glycol has one of the following two structures: in n is an integer in the range of 1 to 500. m is an integer in the range of 1 to 500. x is an integer in the range of 0-500, and R is C1-C 28 Saturated or unsaturated portions, or in n is an integer in the range of 1 to 500. m is an integer in the range of 1 to 500. x is an integer in the range of 0-500, and Each R is independently selected from C1-C 28 Saturated or unsaturated portions.

15. The manufacturing method according to claim 13, wherein, The amount of the first component in the composition is in the range of 250-5000 ppm, and The amount of the second component in the composition is in the range of 250-5000 ppm.

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