Process for preparing graft polymers

Abstract

The present disclosure provides a method. In an embodiment, the method includes providing an apparatus. The device comprises (A) a channel having an interior for receiving a first flow stream (FFS1) comprising a molten polymer composition, the channel having an inflow end and an opposite outflow end. The apparatus includes (B) a gear pump assembly having (i) a housing; (ii) a gear chamber in the housing; (iii) an inlet having a width (Iw) that fluidly communicates the channel outflow end with the gear chamber; (iv) a plurality of intermeshing gears mounted for rotation in the gear chamber, the gears having teeth engaged with each other in the chamber; and (v) an outlet in fluid communication with the gear chamber. The apparatus includes (C) one or more injectors upstream of the gear pump assembly for adding a second fluid to the first flow stream. The second fluid is composed of a radical-graftable substance and a peroxide. The peroxide has an activation temperature. The injector is located upstream of the inlet. The method includes introducing the second fluid from each injector into the FFS1 at a location upstream of the inlet, and feeding the FFS1 and the second fluid into the inlet. The method comprises mixing the second fluid with FFS1 in the gear chamber to form a mixed fluid flow stream (mFFS), discharging the mFFS from the outlet and into the curing chamber; and grafting the free radical graftable species to the polymer in the curing chamber to form a grafted polymer.

Description

Background Art

[0001] Extruders and static mixers are commonly used to combine or otherwise mix two or more viscous materials, such as polymer melt streams. Polymer melt streams are typically highly viscous, and the flow of the polymer melt stream in this method is usually laminar, lacking a natural mixing mechanism. The highly viscous nature of polymer melt streams makes the addition and mixing of small amounts of low-viscosity fluid products (additives) problematic. Although extruders (twin-screw or single-screw) can be used to mix lower-viscosity liquid additives into polymer melt streams, extruders are difficult to scale up, and production costs increase rapidly when increased production capacity and extruder size are required.

[0002] Using static mixers introduces the disadvantage of increased capital costs. Static mixers impede flow and consequently create the risk of introducing significant pressure drops into the polymer melt flow production process. The pressure drop caused by adding a static mixer to the flow process can lead to potential dead zones in the production flow. Dead zones can cause long-term deterioration of the polymer melt flow process.

[0003] There is an understanding in the art that alternative mixing methods are needed for polymer melt streams that avoid extruders and / or static mixers. Summary of the Invention

[0004] This disclosure provides a method. In an embodiment, the method includes providing an apparatus. The apparatus includes (A) a channel having an interior for receiving a first flow stream (FFS1) comprising a molten polymer composition, the channel having an inlet end and an opposing outlet end. The apparatus includes (B) a gear pump assembly having (i) a housing; (ii) a gear chamber within the housing; and (iii) an inlet fluidly communicating the outlet end of the channel with the gear chamber, the inlet having a width (I w (iv) A plurality of meshing gears mounted to rotate in a gear chamber, the gears having teeth that engage with each other in the chamber; and (v) an outlet in fluid communication with the gear chamber. The apparatus includes (c) one or more ejectors upstream of the gear pump assembly for adding a second fluid to the first flow stream. The second fluid consists of a free radical grafting material and a peroxide. The peroxide has an activation temperature. The ejectors are located upstream of the inlet. The method includes introducing the second fluid from each ejector into the FFS1 at a location upstream of the inlet, and feeding the FFS1 and the second fluid into the inlet. The method includes mixing the second fluid with the FFS1 in the gear chamber to form a mixed fluid flow stream (mFFS), discharging the mFFS from the outlet and allowing it to enter a curing chamber; and grafting the free radical grafting material onto the polymer in the curing chamber to form a grafted polymer. Attached Figure Description

[0005] Figure 1 This is a cross-sectional view of an apparatus with a gear pump according to an embodiment of the present disclosure.

[0006] Figure 2 yes Figure 1 A magnified view of area 2.

[0007] Figure 3A It is based on the implementation scheme of this disclosure. Figure 1 A perspective view of the device, showing the fluid plate.

[0008] Figure 3B yes Figure 3A A cross-sectional view of region 3B.

[0009] Figure 4A yes Figure 1 A cross-sectional view of the device, indicating an alternative location of the injector in the device's passageway.

[0010] Figures 4B to 4E This is a cross-sectional view of the device, showing the corresponding... Figure 4A The flow and mixing distribution at the injector location. Figures 4B to 4E The cross-sectional view of the resulting mixed fluid flow and the corresponding CoV value for each flow and mixing distribution are also shown.

[0011] Figure 5 This is a side front view of an apparatus having a tapered portion according to an embodiment of the present disclosure.

[0012] Figure 6A This is a front view of a vertically oriented jet duct according to an embodiment of the present disclosure.

[0013] Figure 6B This is a front view of a horizontally oriented jet duct according to an embodiment of the present disclosure.

[0014] Figure 7A , Figure 7B and Figure 7C Each is a perspective view of a meshing gear according to a corresponding embodiment of this disclosure.

[0015] Figure 8 It is a perspective view of a herringbone gear.

[0016] Figure 9 The additive concentration distribution of spur gears (0° helix), helical gears (7° helix), helical gears (30° helix), and herringbone gears at (A) 0° injection angle and (B) 90° injection angle.

[0017] definition

[0018] Any reference to the periodic table is as in the version published by CRC Press, Inc. in 1990-1991. A group of elements in the table is referred to using a new notation for numbering the groups.

[0019] For purposes of U.S. patent practice, any reference to the contents of a patent, patent application, or publication is incorporated by reference in its entirety (or its equivalent U.S. version thereof), particularly with respect to the definitions in the publication (to the extent that it does not differ from any definitions specifically provided in this publication).

[0020] The numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, and include both the lower limit and the upper limit. For a range containing definite values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7), any subrange between any two definite values ​​is included (e.g., the range 1 to 7 above includes subranges of 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0021] Unless stated to the contrary, implied by the context, or as is customary in the art, all parts and percentages are based on weight, and all test methods are current methods as of the date of this disclosure.

[0022] As used, the terms "blend" or "polymer blend" refer to a mixture of two or more polymers. Blends may be miscible or immiscible (not phase-separated at the molecular level). Blends may or may not be phase-separated. Blends may or may not contain one or more structural domain configurations, as determined by transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art. Blends can be achieved by physically mixing the two or more polymers at a macroscopic level (e.g., melt-blending or compounding) or a microscopic level (e.g., simultaneous formation within the same reactor).

[0023] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0024] The terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not such components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed using the term “comprising” may include any additional additives, adjuvants, or compounds, whether in polymeric or other forms. In contrast, the term “consistently comprising” excludes any other components, steps, or procedures (except those not essential to operability) from the scope of any subsequent statements. The term “consisting of” excludes any components, steps, or procedures not specifically described or listed. Unless otherwise stated, the term “or” refers to the listed members individually and in any combination.

[0025] Ethylene-based polymers (interchangeably referred to as polyethylene) are polymers comprising units of a majority amount (>50 mol%) derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include low-density polyethylene (LDPE); linear low-density polyethylene (LLDPE); ultra-low-density polyethylene (ULDPE); single-point catalytic linear low-density polyethylene, including both linear and substantially linear low-density resins (m-LLDPE); ethylene-based plastomers (POP) and ethylene-based elastomers (POE); medium-density polyethylene (MDPE); and high-density polyethylene (HDPE). These polyethylene materials are generally known in the art; however, the following description may help to understand the differences between some of these different polyethylene resins.

[0026] The term "LDPE" can also be referred to as "high-pressure ethylene polymer" or "highly branched polyethylene," and it is defined as meaning that the polymer is partially or wholly homopolymerized or copolymerized in an autoclave or tubular reactor at pressures above 14,500 psi (100 MPa) using a free radical initiator (such as peroxide) (see, for example, US 4,599,392, which is hereby incorporated herein by reference). LDPE resin typically has a viscosity of 0.916 g / cm³. 3 Up to 0.935 g / cm 3 The density within the range.

[0027] The term "LLDPE" includes the use of the conventional Ziegler-Natta catalyst system. Two resins prepared from catalyst systems and chromium-based catalyst systems and single-site catalysts (including, but not limited to, substituted mono- or dicyclopentadienyl catalysts (commonly referred to as metallocenes), confined geometry catalysts, pyridinium amine catalysts, phosphine imine catalysts, and polyvalent aryloxy ether catalysts (commonly referred to as diphenylphenoxys), and comprising linear, substantially linear, or heterogeneous polyethylene copolymers or homopolymers. Compared to LDPE, LLDPE contains less long-chain branching and comprises substantially linear ethylene polymers, which are further defined in U.S. Patents 5,272,236, 5,278,272, 5,582,923, and 5,733,155; homogeneous branched linear ethylene polymer compositions, such as those in U.S. Patent 3,645,992; heterogeneous branched ethylene polymers, such as those prepared according to the process disclosed in U.S. Patent 4,076,698; and / or blends thereof (such as those in U.S. 3,914,342 or U.S. Patent 4,076,698). (Those disclosed in 5,854,045). LLDPE can be manufactured by gas-phase, solution-phase, or slurry polymerization, or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0028] The term "MDPE" refers to a material with a density of 0.926 g / cm³. 3 Up to 0.935 g / cm 3 Polyethylene. “MDPE” is typically prepared using chromium or Ziegler-Natta catalysts or using single-point catalysts, including but not limited to substituted mono- or di-cyclopentadienyl catalysts (commonly known as metallocenes), restricted geometry catalysts, pyridinium amine catalysts, phosphine imine catalysts and polyvalent aryloxy ether catalysts (commonly known as diphenylphenoxys), and typically has a molecular weight distribution (“MWD”) greater than 2.5.

[0029] The term "HDPE" refers to a material with a density greater than approximately 0.935 g / cm³. 3 And at most about 0.980 g / cm 3 Polyethylene is generally prepared using Ziegler-Natta catalysts, chromium catalysts, or single-point catalysts (including but not limited to substituted mono- or di-cyclopentadienyl catalysts (commonly known as metallocenes), confined geometry catalysts, pyridineamine catalysts, phosphineimide catalysts, and polyvalent aryloxy ether catalysts (commonly known as bisphenylphenoxy).

[0030] The term "ULDPE" refers to a material with a density of 0.855 g / cm³. 3 Up to 0.912 g / cm 3Polyethylene, typically prepared using Ziegler-Natta catalysts, chromium catalysts, or single-site catalysts (including but not limited to substituted mono- or di-cyclopentadienyl catalysts (commonly known as metallocenes), confined geometry catalysts, pyridineamine catalysts, phosphineimide catalysts, and polyvalent catalysts (commonly known as diphenylphenoxys)). ULDPE includes, but is not limited to, polyethylene (ethylene-based) plastomers and polyethylene (ethylene-based) elastomers. Polyethylene (ethylene-based) elastomers and plastomers typically have a density of 0.855 g / cm³. 3 Up to 0.912 g / cm 3 The density.

[0031] "Alkenes" are unsaturated aliphatic hydrocarbons with carbon-carbon double bonds.

[0032] "Olefin-based polymers" (interchangeably referred to as "polyolefins") are polymers containing a majority % by weight of polymerizable olefin monomers (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers.

[0033] As used herein, the term "polymer" or "polymeric material" refers to a compound prepared by polymerizing monomers, whether of the same or different types, which, in polymeric form, provide multiple and / or repeating "units" or "monomer units" constituting the polymer. Therefore, the general term polymer encompasses the term homopolymer, which is generally used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is generally used to refer to polymers prepared from at least two types of monomers. This general term also encompasses all forms of copolymers, such as random copolymers, block copolymers, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" refer to copolymers prepared as described above by polymerizing ethylene or propylene and one or more additional polymerizable α-olefin monomers, respectively. It should be noted that although polymers are generally referred to as being "made from" one or more specified monomers, "based on" a specified monomer or monomer type, "containing" a specified monomer content, etc., in this context, the term "monomer" should be understood to refer to the polymeric residue of the specified monomer rather than the unpolymerized material. Generally, polymers are referred to herein as "units" based on the polymeric form of the corresponding monomer.

[0034] "Propylene-based polymers" (interchangeably referred to as "polypropylene") are polymers containing more than 50 mol% of polypropylene monomers (based on the total amount of polymerizable monomers) and optionally containing at least one comonomer. Propylene-based polymers include propylene homopolymers and propylene copolymers (meaning units derived from propylene and one or more comonomers). The terms "propylene-based polymers" and "polypropylene" are used interchangeably. A non-limiting example of a propylene-based polymer (polypropylene) is one having at least one C2 or C4–C... 10 propylene / α-olefin comonomers of α-olefin comonomers.

[0035] Test methods

[0036] Mixing The mixing degree is quantified by the coefficient of variation (CoV) of the local concentration of the second fluid (F2) relative to the first flow (FFS1) on a certain cross-sectional plane. CoV, as defined in Equation 1, is calculated on a cross-sectional plane perpendicular to the average flow velocity, where C is the concentration at position r and time t, and It is the average concentration.

[0037] Equation 1

[0038]

[0039] Equation 2

[0040]

[0041] Equation 3

[0042]

[0043] Where n is the sample size, which is the number of computational fluid dynamics fluid elements in the cross-section, and C i It represents the concentration of the i-th fluid element. Generally, the lower the CoV value, the higher the mixing degree.

[0044] density Measured according to ASTM D792, Method B. Results are expressed in grams (g) per cubic centimeter (g / cc or g / cm³). 3 Record the results in units of g (g) / cm³. The density of the fluid flow (in Table 1) was measured according to ASTM D 792. Results are expressed in grams (g) / cm³ (g / cc or g / cm³). 3 )Record.

[0045] Melt index(I2 or MI) Measured at 190°C and 2.16 kg according to ASTM D-1238. Values ​​are reported in g / 10 min, corresponding to the number of grams eluted per 10 minutes.

[0046] “ Viscosity "Viscosity" refers to the fluid resistance caused by deformation due to shear or tensile stress. For the purposes of this specification, viscosity was measured at 130°C using a Brinell viscometer according to ASTM D 445. Results are reported in centipoise cP. Detailed Implementation

[0047] This disclosure provides a method. In an embodiment, the method includes providing an apparatus. The apparatus includes (A) a channel having an interior for receiving a first flow (FFS1). FFS1 is a molten polymer composition. The channel has an inlet end and an opposite outlet end. The apparatus includes (B) a gear pump assembly. The gear pump assembly includes (i) a housing, (ii) a gear chamber within the housing, and (iii) an inlet that fluidly communicates the outlet end of the channel with the gear chamber. The inlet has a width (I w The gear pump assembly further includes (iv) a plurality of meshing gears mounted to rotate within a gear chamber. The gears have teeth that engage with each other within the chamber. The gear pump assembly also includes (v) an outlet in fluid communication with the gear chamber. The device further includes (c) one or more ejectors upstream of the gear pump assembly for adding a second fluid to the first flow stream. The second fluid comprises (i) a radical-graftable material and (ii) a peroxide. The peroxide has an activation temperature. The method includes introducing the second fluid from each ejector into FFS1 at a location upstream of the inlet; feeding FFS1 and the second fluid into the inlet; and mixing the second fluid with FFS1 in the gear chamber to form a mixed fluid flow stream (mFFS). The method also includes discharging the mFFS from the outlet and allowing it to enter a curing chamber, and grafting the radical-graftable material onto a polymer in the curing chamber to form a grafted polymer.

[0048] The method includes providing an apparatus. The apparatus includes (A) a channel having an interior for receiving a first flow (FFS1). The channel has an opening at an inlet end and an opening at an opposite outlet end. The apparatus includes (B) a gear pump assembly. The gear pump assembly includes (i) a housing; (ii) a gear chamber within the housing; and (iii) an inlet providing fluid communication between the channel and the gear chamber, the inlet having a width (I... w(iv) a plurality of meshing gears mounted to rotate in a gear chamber, the gears having teeth that engage with each other in the chamber; and (v) an outlet in fluid communication with the gear chamber. The apparatus includes (c) one or more ejectors located upstream of the gear pump assembly for adding a second fluid to the first flow stream. In an embodiment, each ejector is located at at least half a distance of the gear diameter upstream of the inlet. In an embodiment, each ejector has an elongated conduit extending into the channel. In an embodiment, the method includes introducing the second fluid from each corresponding elongated conduit into FFS1 at a location at least half a gear diameter upstream of the inlet. The method includes feeding FFS1 and the second fluid into the inlet, mixing the second fluid with FFS1 in the gear chamber to form a mixed fluid flow stream (mFFS), and discharging the mFFS from the outlet.

[0049] Accordingly, a description is provided with specific reference to the accompanying drawings, which illustrate features and operation of embodiments of the present disclosure but are not intended to limit the scope. In the drawings (unless otherwise indicated), the same numerals are consistently used to denote the same elements of the apparatus.

[0050] Figure 1 and Figure 2 A mixing device 10 is shown, comprising a gear pump 12, a channel 14, and an outlet cylinder 16. The channel 14 is an annular body having a substantially uniform diameter or uniform diameter along its length. The channel 14 may or may not include a tapered portion 15, as will be disclosed below. When the tapered portion is absent, the channel 14 has a substantially uniform diameter or uniform diameter along its length.

[0051] Device 10 includes a gear pump assembly. A "gear pump" is a positive displacement pump that moves fluid (or one or more fluids) by repeatedly closing a fixed volume using meshing gears within a housing. The meshing gears mechanically deliver the fluid using a circulating pumping action. The rotating gears form a liquid seal with the pump housing and generate suction at the pump inlet. Fluid drawn into the pump is confined within the chamber of the rotating gears, and the fluid is delivered to the discharge outlet.

[0052] Figure 1 This is a cross-sectional view of device 10. Figure 1Gear pump assembly 12 is shown. Gear pump assembly 12 includes a housing 18 defining a gear chamber 20. Gear chamber 20 has an inlet 19. Inlet 19 is an opening in housing 18 that allows passage 14 to fluidly communicate with gear chamber 20. Inlet 19 has an inlet width 21. Inlet width 21 is the longest length of inlet 19 extending between opposite sides of housing 18. When the top-to-bottom length of inlet 19 is not the same as the side-to-side length of inlet 19, inlet width 21 is the larger of the top-to-bottom length or the side-to-side length. When inlet 19 has a circular cross-sectional shape, inlet width 21 is the diameter of inlet 19. Since the configuration and shape of inlet 19 can vary, the length of inlet width 21 can vary accordingly. In other words, in addition to the small gap or clearance between each gear and the inner wall of gear chamber 20, inlet width 21 may or may not include the sum of the diameters of the meshing gears 22a and 22b. The length or range of inlet width 21 is interchangeably referred to as "I". w ".

[0053] Within the gear chamber 20 are multiple (or two) meshing gears (interchangeably referred to as gears or gears (singular)), gears 22a and 22b. Each gear 22a, 22b has teeth 24. The teeth 24 of gear 22a mesh (or interlock) with the teeth 24 of gear 22b. In an embodiment, gears 22a and 22b are of the same size and shape, such that each gear 22a and gear 22b has a gear diameter 25, which is of the same length. As used herein, a "gear diameter" (also referred to as an "outer gear diameter") is the length of a straight segment that begins at a gear tooth, passes through the axis of rotation, extends across the gear to the opposing gear tooth, and defines the outermost gear diameter, as shown by gear diameter 25. Gear diameter 25 is Figure 1 The straight line segment shown. Gear diameter 25 is interchangeably referred to as "G". d The term "gear diameter" can be interchangeably referred to as "gear outer diameter" and / or "pitch circle diameter". Alternatively, the size and / or shape of gear 22a may differ from that of gear 22b. Each gear 22a, 22b is supported by a separate shaft (not shown). Typically, one gear is driven by a motor, and this drives the other gear (idler). In an embodiment, both shafts may be driven by a motor. The shafts are supported by bearings on each side of the housing. Each shaft causes the corresponding gear to rotate about an axis of rotation. Gear 22a rotates about axis of rotation 26a, and gear 22b rotates about axis of rotation 26b. As each gear 22a, 22b rotates about its respective axis of rotation, the teeth 24 engage, mesh, or otherwise interlock with each other. As the rotation of the gear continues, the teeth disengage from each other.

[0054] In this embodiment, each gear has a helix angle. As used herein, "helix angle" is the angle between the axis of rotation of the gear and a line tangent to one of the teeth, as viewed from the front view of the gear. The helix angle can be from 0° to 45°. In another embodiment, the helix angle of gears 22a and 22b is from 0° to 5°.

[0055] In the implementation, each gear is a herringbone gear. A "herringbone gear" is a gear with gear teeth having a helix angle α from one end of the gear cylinder to the middle of the gear cylinder, and then an angle 360-α from the middle of the gear cylinder to the other end of the gear cylinder. This angle is measured from the edge of the helical gear teeth to the axis of the gear cylinder moving clockwise. This creates a "V-shaped pattern" (e.g., ...) on the gear teeth of the gear cylinder. Figure 8 As shown), and thus named "herring (fish) bone".

[0056] The method includes directing a first fluid flow 34 ( Figure 1 The material (in the gray shaded area) is fed into channel 14. Channel 14 has an upstream end or inlet end for receiving the first fluid flow. Channel 14 has a downstream end or outlet end in fluid communication with inlet 19. As used herein, a “fluid flow” is a material that is in a fluid state and moves as a flow or otherwise flows. Fluid flow differs from the flow of fine solid particles (e.g., the dumping of sand) because the fine solid particles (sand particles) are not in a fluid state. Flow is typically caused and sustained by gravity, but other forms of energy or force can be used to cause flow, such as flow caused by the use of a pump. Non-limiting examples of materials for the first fluid flow (interchangeably referred to as “FFS1”) include polymers in a molten, melted, or otherwise flowable state, including polyesters, polyamides, polyurethanes, polyolefins (polyethylene, polypropylene), poly(ethylene terephthalate), natural rubber, synthetic rubber, EPDM, and combinations thereof. In the implementation scheme, the viscosity of FFS1 is 0.1 g / 10 min to 1000 g / 10 min, or 0.1 g / 10 min to 100 g / 10 min, or 0.1 g / 10 min to 10 g / 10 min.

[0057] The apparatus 10 includes one or more ejectors 50 for introducing a second fluid into the FFS1. The apparatus 10 may include one, two, three, four, five, six, or more ejectors 50. The ejectors 50 are located upstream of the gear pump assembly 12. The ejectors 50 are in fluid communication with a source of the second fluid and with conduits, valves, and pumps for supplying the second fluid to the ejectors 50. The second fluid (interchangeably referred to as “F2”) contains (i) a radical initiator, such as, for example, a peroxide, and (ii) a radical-graftable substance. In an embodiment, the viscosity of the second fluid is less than the viscosity of the FFS1. It should be understood that F2 is a fluid and may or may not include solid particles dispersed therein; the viscosity of F2 is less than the viscosity of FF1. In another embodiment, the viscosity of the second fluid is from 1 centipoise (cP) to 5000 cP, or from 1 cP to 1000 cP, or from 1 cP to 100 cP, or from 1 cP to 10 cP.

[0058] Non-limiting examples of suitable free radical initiators include organic initiators such as dicumyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, benzoyl peroxide, cumene peroxide, tert-butyl peroctanoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxide)hexane, lauryl peroxide, tert-butyl peracetate, and combinations thereof. Free radical initiators (peroxides) have an activation temperature.

[0059] Various radical-graftable substances can be attached to FFS1 polymer compositions, either alone or as relatively short grafts. These radical-graftable substances include unsaturated molecules, each containing at least one heteroatom. Radical-graftable substances include, but are not limited to, silane comonomers, maleic anhydride, dibutyl maleate, dicyclohexyl maleate, diisobutyl maleate, dioctadecyl maleate, N-phenylmaleimide, citraconic anhydride, tetrahydrophthalic anhydride, bromomaleic anhydride, chloromaleic anhydride, nadic anhydride, methylnadic anhydride, alkenyl succinic anhydride, maleic acid, fumaric acid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid, and the corresponding esters, imides, salts, and Diels-Alder adducts of these compounds.

[0060] The free radical-graftable material can be a silane comonomer. A silane comonomer having the following formula can be grafted onto the polymer composition of FFS1:

[0061]

[0062] where R 1 For a hydrogen atom or a methyl group; x is 0 or 1, provided that when x is 1, n is at least 1; m and n are independently integers from 0 to 12 (inclusive), or from 1 to 4, and each R 2Independently, it is a hydrolyzable organic group, such as an alkoxy group (e.g., methoxy, ethoxy, butoxy), an aryloxy group (e.g., phenoxy), an aryloxy group (e.g., benzyloxy), an aliphatic acyloxy group (e.g., formyloxy, acetoxy, propionyloxy), an amino or substituted amino group (e.g., alkylamino, arylamino), or a lower alkyl group containing 1 to 6 carbon atoms, provided that no more than one of the three R groups is an alkyl group. These silanes can be grafted onto the polymer composition of FFS1 using an appropriate amount of organic peroxide.

[0063] Non-limiting examples of suitable silanes include unsaturated silanes comprising an vinyl unsaturated hydrocarbon group, such as vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, or γ-(meth)acryloyloxyallyl group, and a hydrolyzable group, such as a hydrocarbyloxy, hydrocarbonyloxy, or hydrocarbon amino group. Non-limiting examples of hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, and alkyl or aryl amino groups. In embodiments, the silane comonomer is selected from vinyltrimethoxysilane (VTMS), vinyltriethoxysilane, vinyltriacetoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, and combinations thereof.

[0064] In one embodiment, each injector 50 includes an elongated conduit 52 that extends, penetrates, or otherwise traverses the interior of the channel 14. Each elongated conduit 52 traverses a portion or the entire diameter of the channel 14, and each elongated conduit 52 extends across the interior of the channel 14.

[0065] In one embodiment, each elongated conduit 52 includes a plurality of spaced-apart ports 54 extending along the downstream side of each elongated conduit 52. The ports 54 discharge or otherwise dispense a second fluid along the length of each elongated conduit 52. In one embodiment, the ports 54 discharge a continuous flow of the second fluid along the length of each conduit, thereby forming a fluid sheet. As used herein, a “fluid sheet” is a substantially continuous or continuous fluid body constituted by the second fluid disposed in the FFS1, having a length, width, and height when the FFS1 is viewed in a cross-sectional view from the downstream of the elongated conduit. Figure 3A This is an exploded perspective view of device 10, with channel 14 and housing 18 removed. Figure 3A Fluid sheets 60a, 60b formed by respective injectors 50a, 50b (each injector having a corresponding elongated conduit 52 and spaced-apart ports 54) are shown. Figure 3AEach fluid sheet 60a, 60b with a corresponding body 62 is shown. Each body 62 is a continuous volume F2, and each body 62 has a corresponding dimension of length (L), width (W), and height (H).

[0066] Return to Figure 1 In the embodiment, the injector 50 is located at least half (or 0.5G) of the gear diameter upstream of the inlet 19. d At a distance of ), for example, when gear 22a (and / or gear 22b) has a diameter of 32cm, half the gear diameter (or 0.5G) d The distance is 16cm. The method includes at least half the diameter of the gear upstream of inlet 19 or 0.5G. d Or 1G upstream of entrance 19 d To 5G d or 1G d To 3G d or 1.5G d To 3G d At a distance of [distance missing], a second fluid 36 (interchangeably referred to as "F2") is introduced into FFS1 34. In an embodiment, device 10 includes two ejectors, a first ejector 50a and a second ejector 50b, ejector 50a being spaced apart from ejector 50b along a channel diameter 56, each ejector 50a, 50b (and channel diameter 56) being located at least 0.5G upstream of inlet 19. d At a distance of, such as Figure 1 As shown.

[0067] In this implementation, the length of the inlet width 21 is greater than the length of the gear diameter 25. The injector 50 is located upstream of the inlet 19 at least the inlet width 1. w At a distance of [distance missing]. The method includes at least 1I upstream of inlet 19. w , or 1I upstream of entrance 19 w Up to 5I w 、or 1I w To 3I w or 1.5I w To 3I w A second fluid 36 (interchangeably referred to as "F2") is introduced into FFS1 34 at a distance of [distance missing]. In an embodiment, device 10 includes two ejectors, a first ejector 50a and a second ejector 50b, ejector 50a being spaced apart from ejector 50b along a channel diameter 56, each ejector 50a, 50b (and channel diameter 56) being located 1I upstream of inlet 19. w At a distance of, such as Figure 1 As shown.

[0068] In the implementation, each injector includes a plurality of spaced-apart ports extending along a portion of the channel sidewall (“wall injector”). As disclosed in the co-pending case USSN _____________ (84964-US-PSP) filed in ______________, the entire contents of which are incorporated herein by reference. The wall injector may be located at least half the diameter of the gear (or 0.5G) upstream of inlet 19. d At a distance of ), or at least at an entrance width I upstream of entrance 19. w At a distance, as disclosed above relative to injector 50.

[0069] The method includes feeding FFS1 and F2 into inlet 19 and mixing F2 36 into FFS1 34 in gear chamber 20. FFS1 34 and F2 36 enter gear chamber 20 from channel 14. Counter-rotating gears 22a and 22b generate suction at region 4, thereby trapping or otherwise drawing FFS1 and F2 into gear chamber 20. As the counter-rotation of gears 22a and 22b continues, FFS1 and F2 are stretched in the space 38 between teeth 24 and the inner wall of gear chamber 20, such as... Figure 1 As indicated by arrow M, the stretching continues as the gears rotate further, and a squeezing force is generated in space 38, mixing F2 into FFS1. When tooth 24 from gear 22a engages (or re-engages) with tooth 24 from gear 22b at region 5, the trapped FFS2 mixed into FFS1 is discharged from gear chamber 20 as a mixed fluid flow 40 (or “mFFS 40”) and passes through outlet 42. As gears 22a and 22b continue to rotate in opposite directions, this “suction-stretch-squeeze-discharge” cycle repeats, with suction trapping new amounts of FFS1 34 and F2 36 between the meshing teeth and the inner wall of the gear chamber, thus continuing the cycle.

[0070] The method includes discharging mFFS 40 from outlet 42. mFFS 42 flows from outlet 42 into curing chamber 16, as... Figure 5 As shown. Non-limiting examples of suitable curing chambers include high-temperature tubes (“high-temperature tubes” are tubes or chambers that can be heated to temperatures above the peroxide activation temperature). The method includes grafting a free radical-graftable substance onto the polymer in curing chamber 16 to form a grafted polymer.

[0071] The method involves heating mFFS 40 to above the peroxide activation temperature in a curing chamber. Exposure to temperatures above the peroxide activation temperature induces the grafting of radical-graftable substances onto the polymer.

[0072] Unbound by any particular theory, it is believed that the incorporation of functional monomers into polymers is accomplished through radical-mediated grafting in the polymer's molten state. In this method, peroxides decompose into alkoxy radicals (above the peroxide activation temperature) and abstract hydrogen from the polymer, generating a polymer-centric radical. This radical then adds to the unsaturation of the monomer. Through a series of addition and growth steps, the functionalized (grafted) material is obtained.

[0073] In the implementation, the method includes maintaining the temperature of the mFFS below the peroxide activation temperature during mixing and emission to prevent peroxide decomposition (peroxide activation) before complete homogenization.

[0074] Alternatively, the desired temperature for peroxide decomposition is achieved via shear heating in a gear pump. Additional heat can also be provided externally to achieve the desired activation temperature of the peroxide. Once the temperature and homogeneity are reached, a minimum residence time is required to achieve the optimal grafting level. The desired residence time can be achieved by introducing the mFFS into a heated zone (e.g., a heating tube) after the mFFS is discharged from the gear pump.

[0075] In the implementation plan, the minimum residence time is four half-lives at the peroxide activation temperature (peroxide decomposition temperature).

[0076] Unbound by any particular theory, the applicant discovered that at a distance of at least half the diameter of the gear (or at least one I upstream of inlet 19) w The introduction of a second fluid into FFS1 at a distance from the inlet 19 inadvertently creates or otherwise defines a recirculation zone in channel 14 (or alternatively in the tapered portion). As used herein, a “recirculation zone” is a volumetric portion in channel 14 (or a volumetric portion in the tapered portion) whose downstream end is defined by a plane covering inlet 19 and whose upstream end is defined by a plane covering an elongated conduit located at least half (0.5G) of the gear diameter located remotely from and upstream of inlet 19. d (or located at least one I upstream of entrance 19) w (at a distance); the rotation of gears 22a and 22b generates (i) laminar flow of FFS1 and the second fluid and (ii) vortex flow of FFS1 and the second fluid in the volume section. The recirculation zone performs two actions: (1) the recirculation zone moves the incoming second fluid plate (F2) to the low-pressure zone at the apex of the gear meshing zone; and (2) the recirculation zone enhances the mixing of the second fluid plate (F2) because a portion of the second fluid F2 is initially mixed in the recirculation zone and then enters the gear chamber 20.

[0077] In an implementation, the method includes forming a laminar flow through the gear chamber 20. As used herein, a "laminar flow" is a flow in which small disturbances in the form of vortices or eddies do not possess sufficient energy to sustain themselves; any vortices or eddies are instantaneously dissipated; laminar flow is the opposite of turbulent flow. Figure 1 and Figure 2 The middle arrow M indicates a portion of FFS1 and a portion of F2 flowing through and around the meshing gears 22a and 22b.

[0078] In an implementation, the method further includes forming a vortex flow in the recirculation zone. As used herein, a “vortex flow” is a flow in the recirculation zone in which a portion of FFS1 and / or a portion of F2 rotates about an axis to generate vortices. The recirculation zone (consisting of FFS1 and F2) is located in the channel such that the downstream end of the recirculation zone abuts the top of the gear teeth, the channel sidewall abuts the other side, and the upstream end of the recirculation zone is defined by the position of the ejector, which is at least 0.5G upstream of the inlet 19. d (or at least 19 l from the entrance) w The upstream end of the recirculation zone remains open to the viscous flow of FFS1 and FFS2, such as... Figure 1 As indicated by arrow 1, the gear pump assembly 12, with two gears rotating in opposite directions, generates two recirculation zones, each with a separate and discrete vortex flow. Each recirculation zone is upstream of each corresponding gear 22a, 22b, as shown in the image. Figure 1 and Figure 3B As shown.

[0079] In the implementation scheme, device 10 includes, for example, Figure 3A The first ejector 50a and the second ejector 50b are shown. Each ejector includes a corresponding elongated conduit 52 with a corresponding port 54 for discharging the second fluid 36 as corresponding first flow vanes 60a and second flow vanes 60b into the FFS1 34. The first ejector 50a is spaced apart from the second ejector by a certain distance. The ejector 50a is located upstream of the inlet 19 at least half the diameter of the gear, 0.5G. d Location (or at a distance of 1I upstream of entrance 19) w The method involves introducing a second fluid from each corresponding elongated conduit (relative to port 54), and at least 0.5G upstream of inlet 19, thereby defining the recirculation zone. d (or at least one I) w At the location of ), the corresponding first flow sheet 60a and second flow sheet 60b are formed into FFS1. The method includes, as shown in... Figure 1A first vortex flow 66a and a second vortex flow 66b are formed in the corresponding first recirculation zone 70a and second recirculation zone 70b. The method includes feeding FFS1 34 and flow plates 60a, 60b into inlet 19; mixing a second fluid 36 with FFS1 34 in gear chamber 20 to form a mixed fluid flow 40 (mFF 40S); discharging mFFS 40 from outlet 42; and forming mFFS 40 with a concentration of 0.1 to 0.5.

[0080] For the purposes of evaluation, Figures 4A to 4E A device 10 with injectors at different locations within channel 14 and gear pump assembly 12 is shown. Figure 4A In the diagram, position A indicates a distance of 0.5G upstream of entrance 19. d Two injectors at a distance. Position C indicates a distance of less than 0.5G within gear chamber 20 upstream of inlet 19. d A single injector at a distance of [distance]. Position D indicates that in gear chamber 20, at space 38 and less than 0.5G upstream of inlet 19. d The two injectors, with position E representing a single injector in channel 14 and less than 0.5Gd upstream of inlet 19.

[0081] Figure 4B It shows in Figure 4A The flow and mixing distribution of the two ejectors at position A is shown in the cross-sectional view, where mFFS 40 is taken along line 4B-4B. Laminar flow M and vortex flow N form an mFFS of 0.33. An ejector is present at position A. Figure 4B This is an example of the disclosure.

[0082] Figure 4C It shows in Figure 4A The flow and mixing distribution of a single injector at position C is shown in the cross-sectional view, where mFFS 40 is taken along line 4C-4C. Laminar flow M and vortex-free flow N form an mFFS of 0.61. A single injector is present at position C. Figure 4C This is a publicly disclosed comparison sample.

[0083] Figure 4D It shows in Figure 4A The flow and mixing distribution of the two ejectors at position D is shown in the cross-sectional view, where mFFS 40 is taken along line 4D-4D. Laminar flow M and vortex-free flow N form an mFFS of 0.54. There are two ejectors at position D. Figure 4D This is a publicly disclosed comparison sample.

[0084] Figure 4E It shows in Figure 4AThe flow and mixing distribution of a single injector at position E is shown in the cross-sectional view, where mFFS 40 is taken along line 4E-4E. Laminar flow M and vortex flow N form an mFFS of 0.89. A single injector is present at position E. Figure 4E This is a publicly disclosed comparison sample.

[0085] Figure 5 An embodiment of the device 10 is shown, which has a tapered portion 15 in fluid communication with the channel 14 and located upstream of the gear assembly 12. The tapered portion 15 is in fluid communication with the gear chamber 20.

[0086] In one embodiment, the device 10 includes a tapered portion 15. The tapered portion 15 is an annular body 28 having an upstream end 30, the diameter of which is greater than the length of the inlet width 21. The tapered portion 15 has a downstream end 32, the diameter of which is the length of the inlet width 21. In other words, the diameter of the downstream end 32 is the same as or substantially the same as the inlet width 21.

[0087] Moving from the upstream end 30 to the downstream end 32, the tapered portion 15 has a body 28 with a gradually decreasing or otherwise tapering diameter, thereby contracting the internal volume within the tapered portion 15. In this way, the tapered portion 15 has an upstream diameter greater than the chamber width, which decreases to the downstream end, where the diameter is equal to or substantially equal to or less than the chamber width. As fluid flows into the gear chamber 20, the contracting diameter of the tapered portion 15 increases the pressure in the fluid flow. In an embodiment, the method includes positioning an elongated conduit at the upstream end of the tapered portion; at least one inlet width (I) upstream of the inlet... w At the location of ), a second fluid is introduced from each corresponding elongated conduit into FFS1, FFS1 and the second fluid are fed into inlet 19; the second fluid is mixed with FFS1 in the gear chamber to form a mixed fluid flow (mFFS); and the mFFS is discharged from the outlet. In another embodiment, the method includes forming mFFS with an CoV concentration of 0.1 to 0.5.

[0088] This disclosure advantageously provides a method for mixing a second fluid (F2) (such as an additive) into a polymer melt stream (FFS1) without using an extruder and a static mixer. In an embodiment, the method of the invention is implemented by utilizing a liquid additive injector system placed in a conduit that carries the polymer stream to a gear pump. This disclosure also provides a specific gear distribution for efficient mixing. Shearing and mixing provided by the gear pump are utilized to achieve the desired mixing.

[0089] Examples of implementations of this disclosure are provided below by way of example rather than limitation.

[0090] Example

[0091] Table 1 below provides the materials used in the embodiments.

[0092] Table 1 - Materials

[0093]

[0094] In the implementation plan, such as Figure 1 The apparatus 100 is shown. The apparatus 100 is similar to the apparatus 10 (disclosed above), wherein the apparatus 100 includes additional and / or alternative components for evaluating hybrid performance.

[0095] An elongated conduit 52 penetrates or otherwise traverses channel 14 and extends through the interior of channel 14. The elongated conduit 52 extends into the interior of the channel. Multiple spaced-apart ports extend along the length of the downstream side of the elongated conduit 52. The device 100 may also include an F2 source, as well as conduits, valves, and pumps for supplying F2 to the elongated conduit 52. For the device 100, the distance between the axis of rotation 26a and the elongated conduit 52 is 7.6 inches (2.5 inches). w The distance between the inlet and the injector is 1.95I. w For device 100, the length of outlet cylinder 16 is 18 inches (6.5 inches). w ).

[0096] For evaluation purposes, an elongated catheter 152 is provided, and it includes two elongated catheters 156a and 156b, which are spaced apart and parallel or substantially parallel to each other, as shown below. Figures 6A to 6B As shown. Each elongated conduit 156a and 156b is a 0.5-inch 80-gauge tube with four 3 / 32-inch ports 156 spaced 1 inch apart. Ports 156 are located on the downstream side of each elongated conduit 154a and 154b.

[0097] In configuration A, the elongated conduit 152 is vertically oriented in channel 14 such that elongated conduits 154a and 154b are each parallel to or substantially parallel to each axis of rotation 26a, 26b of the corresponding gears 22a, 22b, as shown below. Figure 6A As shown.

[0098] In configuration B, the elongated conduit 152 is horizontally oriented in channel 14, such that elongated conduits 154a and 154b are each perpendicular or substantially perpendicular to each axis of rotation 26a, 26b of the gear, as shown below. Figure 6B As shown.

[0099] In device 100, the pitch circle diameter of each gear is 2.756 inches. In gear chamber 20, (i) the tooth clearance and (ii) the clearance between the gear tip and the housing are both maintained at 0.01 inches. Gears with four different helix angles are provided for evaluation. Gears 122a and 122b have a helix angle of 0°. Figure 7A Gears 222a and 222b have a helix angle of 7°. Figure 7B Gears 322a and 322b have a helix angle of 30°. Figure 7C Gears 422a and 422b have a herringbone shape (Fig. 7D).

[0100] Table 2 below provides the CoV values ​​for the cross-sectional plane of mFFS 40 at the outlet cylinder 16. Computational fluid dynamics (CFD) is a modeling method used to simulate the flow through device 100. CFD (Starccm+V15) and the mesh tool (SCORG) were used to generate the CoV values ​​in Table 2 below. The CoV values ​​were calculated using Equation 1, where the average additive concentration is estimated based on the input mass flow rate of the additive, and the local concentration of the additive is estimated from the CFD results. The CoV values ​​are across the cross-section perpendicular to the flow (1.81I downstream of the outlet). w The standard deviation and average concentration of the second fluid (F2) are calculated as described above. As previously mentioned, CoV calculates the ratio of standard deviation to average concentration. The standard deviation and average concentration values ​​are calculated based on CFD simulation results under the aforementioned operating conditions. The simulation is run to achieve steady-state conditions when the average and standard deviation of the concentration values ​​across different cross-sectional planes no longer change. Because the CFD simulation preserves details of velocity, pressure, temperature, and concentration values ​​at each computational cell, the standard deviation and average concentration values ​​at a given cross-section can be calculated.

[0101] Table 2 - Mixed Assessment - CoV Value

[0102]

[0103] Surprisingly, the CoV value, indicating mixing efficiency, was lower for the 0° injection case (configuration A) than for its 90° injection case (configuration B), and this trend was consistent regardless of the gear design profile. It should be noted that a lower CoV value indicates better mixing, with CoV values ​​below 0.5 considered sufficient for most chemical methods (Paul et al., *Handbook of Industrial Mixing*, 2003). In addition to the injection duct orientation, the effect of the gear helix angle was also evident. Herringbone gears showed the lowest CoV values, followed by 0° helix angles (spur gears), where the CoV value increased with increasing individual helix angles. With increasing helix angles, the second fluid (additive) tended to accumulate on one side of the outlet duct due to the pressure gradient facilitated by the single helix gear. However, for herringbone gears, the additive flow became symmetrical, due to the net zero-span pressure gradient resulting from the double helix angles (left-hand and right-hand), and the symmetry they provided, where gear teeth with different helix angles were equidistant from the gear's center plane, performing best in mixing the additive.

[0104] Figure 9 The additive concentration distribution for spur gears, helical gears, and herringbone gears with 0° and 90° injection is shown. As previously mentioned, preferential flow is promoted through the helical gear, where the additive accumulates on one side. However, for the herringbone gear (… Figure 8 The flow remains uniform, with a continuous contact line (stretching), which leads to uniform mixing. Therefore, herringbone gears typically have lower CoV values ​​compared to spur and helical gears.

[0105] It was found that increasing the helix angle promotes some preferential flow at the suction side of the gear pump. The discharge volume changes along the gear span as the teeth disengage. Gear profiles with large helix angles tend to open more on one side first, resulting in a low-pressure zone. Without being bound by any particular theory, this low-pressure zone draws more additive from one side of the upstream side C of the gear chamber than the other, thus creating an uneven distribution of additives.

[0106] It is particularly desirable that this disclosure is not limited to the embodiments and descriptions contained herein, but includes modifications of those embodiments, including portions of embodiments appearing within the scope of the following claims and combinations of elements of different embodiments.

Claims

1. A method, the method comprising: Providing means, the means comprising (A) has an interior channel for receiving a first flow stream (FFS1) containing a molten polymer composition, the channel having an inlet end and an opposite outlet end; (B) A gear pump assembly, the gear pump assembly comprising... (i) Outer shell, (ii) The gear chamber in the housing. (iii) an inlet that provides fluid communication between the outlet end of the channel and the gear chamber, the inlet having a width (I) w ), (iv) A plurality of meshing gears, having teeth that engage with each other in the gear chamber, are mounted to rotate within the gear chamber. (v) An outlet in fluid communication with the gear chamber. (C) One or more ejectors upstream of the gear pump assembly, the ejectors being used to add a second fluid to the first flow stream, the second fluid comprising a free radical-graftable substance and a peroxide having an activation temperature, the ejectors being located upstream of the inlet, the method comprising The second fluid is introduced from each injector into the FFS1 at a location upstream of the inlet; The FFS1 and the second fluid are fed into the inlet; The second fluid is mixed with FFS1 in the gear chamber to form a mixed fluid flow (mFFS); The mFFS is discharged from the outlet and allowed to enter the curing chamber; as well as The free radical grafting material is grafted onto the polymer in the curing chamber to form a grafted polymer.

2. The method of claim 1, wherein the method comprises maintaining the temperature of the mFFS below the peroxide activation temperature during the mixing and the emission.

3. The method according to any one of claims 1 to 2, wherein the one or more injectors are located at a distance of at least half the gear diameter upstream of the inlet, the method comprising The second fluid is introduced from each injector into the FFS1 at a position at least half the diameter of the gear upstream of the inlet.

4. The method according to any one of claims 1 to 3, wherein the method comprises heating the mFFS in the curing chamber to a temperature above the peroxide activation temperature.

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