TWI251003B - Process aid for melt processable polymers - Google Patents

Abstract

Extrusion processability of non-fluorinated melt-processable polymers is improved by introducing a fluoropolymer process aid by means whereby the weight average particle size of the fluoropolymer is greater than 2 microns as it reaches the extruder die entrance.

Description

1251003 V. INSTRUCTION DESCRIPTION OF THE INVENTION (The present invention relates to the extrusion of a non-baby gamma-producing melt-processable polymer, which has a fluoropolymer processing aid. ^ 曰ϋϋ , κ σ, such as hydrocarbon polymers and polyamines, melt-extruded into a process structure such as gp total „ ^ _ & ^ tube, wire mirror coating or film process

By means of a well-known method, it is a violation of the method, in which the rotary screw pushes the viscous polymer melt and passes it through the casting cylinder to press the plate, wherein the polymer is formed into a desired In the form of a report, it is then cooled and solidified into a product having the general shape of the extrusion plate. In order to achieve low manufacturing costs, it is desirable to sow the polymer at high rates. A higher extrusion rate can be easily achieved by increasing the rate of rotation of the casting screw. However, this technique is limited by the viscoelastic properties of the polymer substrate. At the rate of extrusion of the gate, an unacceptable amount of polymer hot knife is produced. In addition, an extruded material having a rough surface is often obtained, resulting in an undesired pattern on the surface of the plastic. . These surface defects are also known as melt cracks. Extrusion at high temperatures avoids this type of stomach, but increases processing costs and the cooling of the plastic is a problem. Further, if the polyolefin is extruded at a temperature close to the decomposition point, polymer degradation occurs. Therefore, it is desirable to find a method for effectively increasing the extrusion rate without increasing the melt/JZL degree to produce an article having a smooth surface. Variations in the extruder and the exit structure can improve polymer melt flow, but such improvements are always practical or economical. Another study included the addition of conventional wax-type processing aids to reduce bulk viscosity and, in some cases, improve the paper size for the Chinese National Standard (CNS) A4 specification (210X297 mm) -4 1251003 A7 广____B7 , invention description (2) nature. However, this efficiency is extremely low and the high concentration of additives required often has a negative impact on his properties. In U.S. Patent No. 3,125,547 to the entire disclosure of U.S. Patent No. 3,125,547, the disclosure of which is incorporated herein by reference in its entirety in its entirety in the the the the the the the the the In the extrusion process of ethylene, the pressure of the extrusion plate is lowered, as is the case with other polyolefins. In addition, the use of such additives can significantly increase the extrusion rate without causing solution cracking.

Kamiya and Inui, in the copending patent application K〇k〇ku 45-30574, list the use of crystalline fluorocarbon polymers to eliminate scale deposits at temperatures below the melting point' but it does not reveal other The extrusion improvement of the aspect.

An injection molding composition comprising a polystyrene olefin copolymer having a melt flow rate (MFR) of 0.2 to 200 g/10 min and a density of 0.850 is disclosed in Japanese Patent Application Laid-Open No. Hei. No. 62-64847. A mixture of fluorocarbon polymers having a ratio of fluorine to carbon of from 0.945 g/cm 3 to 5% by weight of fluorinated hydrocarbon polymer of at least 1:2.

A blend having improved extrusion properties comprising a linear polymer of ethylene in which a small amount of a fluorocarbon polymer and a polyoxoxime is incorporated is disclosed in U.S. Patent No. 4,74,341. The fluorocarbon polymer has a ratio of carbon to carbon of at least 1: 2' and is at 12 Torr. Up to 30 (TC is a fluid.

Larsen, U.S. Patent No. 3,334,157, the disclosure of which is incorporated herein by reference in its entire entire entire entire entire entire entire entire entire entire entire entire entire disclosure Optical properties. Recently, 'US Patent Nos. 4,855,360, 5,587,429 and -5-i paper scales apply to Chinese National Standards (cNS) 7iii:_(210 X 297 mm)---------1251003 A7 B7 V. DESCRIPTION OF THE INVENTION (3) An improved fluoropolymer processing aid composition is disclosed in 5,7 0 7,5 6 9 . In the fluoropolymer processing aid composition, a second additive such as a poly(alkylene oxide) or an ionic bond copolymer resin is introduced to improve the extrusion processability of the non-fluorinated polymer. In order to optimize processability improvements, the prior art states that it is desirable that the fluoropolymer processing aid composition be sufficiently dispersed in the non-fluorinated polymer to be extruded 'and that the particle size of the fluoropolymer is desired to be small, The dispersibility is better, so that the processability is better. For example, "DynamarTM Polymer Processing Additive Optical Microscopy Method for Dispersion Analysis in Polyolefins'' (Dyneon 1997), it is recommended to uniformly disperse and process fluoropolymers having a particle size of 2 microns or less in the extrusion. nDynamarTM Polymer Processing Additive Direct Addition During Resin Manufacture" (Dyneon 12/2000), recommended for uniform dispersions and fluoropolymer processing aids having a particle size of 3 microns or less in the extrudable composition The same recommendations are also made in U.S. Patent Nos. 3,125,547; 5,010,130 and 6,048,939. Because the extrusion processability is taught to improve the dispersion of the fluoropolymer processing aid in the melt processed polymer, And by improving the plasticization processability by reducing the particle size of the fluoropolymer, many art research in this field has focused on improving the quality of the dispersion and minimizing the particle size of the fluoropolymer. There is still room for improvement in extrusion processability. SUMMARY OF THE INVENTION It has been unexpectedly discovered that fluoropolymers are used with the highest performance and use of the prior art specifications. Compared with the dispersive composition, it contains the large particle size of -6 - the paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1251003

The fluoropolymer extrudable composition is actually more processable and has fewer solution defects' and has a faster processing time. "Gas-containing polymer based on large particle size" means that the weight average particle diameter (defined below) is greater than 2 μm but less than 1 μm when measured at a point just before the extrusion plate. The extrudable composition having a large particle (iv) main gas-containing polymer can be achieved in several ways. The present invention is an extrudable composition for passing through an extrusion plate, the composition comprising: A) a non-fluorinated melt processable polymer; and B) The total weight of the &plastic composition is from 25 to 2 parts per million by weight of the fluoropolymer, the fluoropolymer having greater than 2 microns when measured at a position just prior to the extrusion plate And less than the weight average particle size of the working rice; and wherein the composition is substantially free of surfactant. Another sorrow of the present invention is an extrudable composition for passing through an extrusion plate, the composition comprising: A) a non-fluorinated melt-processable polymer; B) The total weight of the plastic composition is from 25 to 2 parts by weight of the fluoropolymer, the fluoropolymer having a diameter greater than 2 microns when measured just prior to the extrusion plate a weight average particle size of less than 1 micron; and C) at least an effective amount of a surfactant such that the fluoropolymer has a diameter greater than 2 microns and less than 10 meters when measured at a location just prior to the extrusion plate. The average particle size is repeated, but the weight ratio of the surfactant to the fluoropolymer is not more than 5:1. Another aspect of the present invention is a processing aid masterbatch comprising: the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1251003 A7 B7 5. Invention Description (5)" ' " A) a non-fluorinated melt-processable polymer; B) a fluoropolymer having a weight percentage of u5G based on the total weight of the masterbatch; and C) an effective amount of a surfactant which at least improves workability, but The ratio of the surfactant II to the fluoropolymer is not more than 5:1, and the limitation is that if the surfactant is a poly(alkylene oxide) polymer, the poly(epoxy) polymer is relative to The weight ratio of the fluoropolymer is less than 1: work. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for improving the extrusion processability of a non-fluorinated melt processable polymer composition containing a fluoropolymer as a processing aid. The term "extrusion processability" as used in the present invention means the treatment time (i.e., after the extruder is started, and the extruded article has a high melt crack, and is obtained with a smooth surface, without melting The time elapsed before the extrusion of the body crack). In order to minimize waste and reduce costs, it is clearly desirable to have a very short time. Examples of non-fluorinated melt processible polymers include, but are not limited to, hydrocarbon resins, polyamines, fluorinated polyethylenes, polyethylenes, and polyesters. "Non-fluorinated," means that the ratio of fluorine atoms to carbon atoms contained in the polymer is less than 1 · 1. The non-fluorinated melt processable polymer of the present invention may be selected from various polymer types. The polymer system comprises a melt index (measured according to ASTM D1238 at 19 ° C, using 2160 grams of missing code) of 5.0 g/10 min or less of a hydrocarbon polymer, 2.0 g/10 min or less. Smaller. The hydrocarbon polymer may be an elastomeric copolymer of ethylene, propylene, and optionally a non-conjugated diene monomer such as ruthenium, tetrahexadiene. The hydrocarbon polymer usually also includes any Having the formula -8 - 1251003 A7 B7 V. Inventive Note (6) CH2=CHR ' wherein R is a hydrazine or an alkyl group, usually not more than eight carbon atoms, is homopolymerized or copolymerized. Thermoplastic hydrocarbon polymer. The invention is particularly applicable to polyethylene, including both high density and low density, for example, polyethylene having a density ranging from 0.85 to 97·97 g/cm 3 ; polypropylene, polybutene -1 ; poly(3-mercaptobutene); poly(methylpentene); and ethylene and α olefin a copolymer of propylene, butene 4, hexene <, octene oxime, decene 4, and octadecene. The hydrocarbon polymer may also include a vinyl aromatic polymer such as polystyrene. The polymer has a variable melt characteristic, so the present invention has a greater degree of application to certain hydrocarbon polymers. Therefore, hydrocarbon polymers having no high molecular weight, such as polypropylene and branched chain polyethylene, even At low temperatures, it still has better melt flow characteristics, so surface roughness and other surface defects can be avoided by adjusting the extrusion conditions. These hydrocarbon X-members may be under unusually severe extrusion conditions. The fluorocarbon polymer extrusion aids and methods of the present invention are used. However, other polymers such as the same knife, two-density polyethylene, linear low-density polyethylene copolymer, inter-knife polypropylene, and propylene and other olefins Copolymers, especially those having a narrow molecular weight distribution, are not capable of permitting such a degree of variation under various extrusion conditions. The surface quality of the extruded product is particularly obtained by using the compositions and methods of the present invention. Improved Resins Other non-fluorinated melt processible polymers which may be used as a component of the compositions of the present invention include polyamines and polyesters. The special case of the polyamines which can be used in the present invention is resistant (nyl〇n). 6, nylon 6/6, nylon 6/10, resistance theory and financial theory 12. Appropriate polyester vinegar including polyethylene terephthalate and polybutylene terephthalate-9- 1251003 A7 _________ B7 V. INSTRUCTIONS (7~V~~' - fluoropolymer-coated (tetra) gas-containing polymer (ie, fluoroelastomer or amorphous fluoropolymer) and thermoplastic which can be used in the composition of the present invention Fluoropolymer (ie, semi-crystalline fluoropolymer). τ used in the gas-containing elastomer of the present invention is a fluoropolymer which is generally in a fluid state at room temperature and higher, ie, & Fluoropolymer which is almost temperatureless and has no crystallinity at room temperature. Preferably, but not necessarily, the ratio of fluorine to hydrogen is at least 3 fluoroquinones. Gasification monomers which can be copolymerized to produce a suitable fluoroelastomer include diamethylene hexahydrate, hexafluoropropylene, trifluoroethylene, tetrafluoroethylene and perfluoroalkyl perfluorovinyl ether. Specific examples of fluoroelastomers which may be used include copolymers of vinylidene fluoride and a comonomer selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, hydrogen pentafluoropropene, and 2-hydropentafluoropropene; Copolymers of ethylene, tetrafluoroethylene, and hexafluoropropylene or diterpene hydrogen pentafluoropropylene; and copolymers of tetrafluoroethylene, propylene, and optionally vinylidene fluoride are known to the art. In some cases, such copolymers may also include bromine-containing comonomers as taught by U.S. Patent No. 4, pp. 35,565 to Apotheker and Krusic, or terminal iodine as taught in U.S. Patent No. 4,243,77. base. The latter patent also discloses the use of fluoroolefin comonomers containing iodine groups. When the copolymer contains a specific molar ratio of fluorinated monomer, the glass transition temperature of the polymer is close to or lower than that of the copolymer, and the composition is a useful elastic material for commercially available articles that can be easily obtained. . Semi-crystalline fluoropolymers useful in the present invention include, but are not limited to, poly(vinylidene fluoride), homopolymers and copolymers of tetrafluoroethylene (such as Tefl〇n® FEP fluorocarbon). Resin, and tetrafluoroethylene, propylene and, as the case may be, a copolymer of partial air and fine gas). This paper scale is applicable to the National Standard (CNS) A4 specification (210 X 2973⁄4^ 1251003 A7 B7 5. Inventive Note (8) — Multimodal fluoropolymers, such as disclosed in International Patent Publications w〇〇〇/69967 It can also be used as the fluoropolymer in the composition of the present invention. "Multimodal" means that the fluoropolymer has at least two components having a discontinuous and different molecular weight. Both components may be amorphous or semi-. The crystal form may be one component amorphous and the other component semicrystalline. If a single fluoropolymer is used in the composition of the present invention, the processing temperature of the fluoropolymer in the non-fluorinated main polymer Substantial melting is required. If a fluoropolymer blend is used, at least one of the blend components is required to meet this standard. In order to effectively serve as a processing aid at weight average particle sizes as low as about 2 microns, The viscosity of the molten component of the processing aid has an upper limit. If the melting component of the processing aid is a fluoroelastomer, the Montessori viscosity (measured according to ASTM_D1646 at 121 jC, large rotor condition Μ: ι + ι〇 min) Need to be 80 or lower, It is preferably from 60 to 80. If the melting component of the processing aid is semi-crystalline, the melt index (ASTM D-1238, 265 ° C, 5 gong = weight) needs to be greater than 0.5 dg/min to 〇·5 to 3 dg/min is preferred. Because of the increased viscosity of fluoropolymers, fluoropolymers become more difficult to distribute on the inner surface of processing equipment. Therefore, beyond these viscosity limits, 'unless The weight average particle size delivered to the extrusion plate is extremely large, greater than about 1 〇 micro$, otherwise the processing aid performance is reduced. Fluoride particles having such a size are sufficient to form surface deformation or internal defects in the extrusion. Therefore, it is desirable to limit the weight average particle diameter of the fluoropolymer to less than 1 μm. In the present invention, when the composition to be extruded reaches the position just before the extrusion in the procedure (ie, at the inlet of the extrusion plate) When it is desired to control the weight average particle diameter of the fluorine-containing processing aid in the composition to be greater than 2 μm, but less than (7) 1251003 A7 --------- 5, invention description (9) — - Micron. Measure the gentleman in the month of the month before the pressure plate. The weight average particle diameter of the fluoropolymer is preferably greater than 4 μm (optimally greater than 6 μm). The weight average particle diameter (diameter) is defined by the following formula: Σ = (Σ, where A is the weight average particle diameter (diameter); % is the fluoropolymer weight fraction of the particle size within the range defined by Xi in the specific sample; and is specified as the particle size range in the sample divided by the _ interval, and is designated as the (10) The average particle size of the particle size range included in the interval. Wi can be determined in several ways, including a) using an optical microscope, a digital camera, and a hot stage for dissolving the carrier resin to detect the fluoropolymer dispersion' b) three-dimensional imaging of the fluoroelastomer particles using a Confocal Laser microscope, followed by size analysis using appropriate software, c) analysis of photomicrographs of the polymer dispersion, or d) dissolving the fluoroelastomer The matrix resin separates the fluoropolymer particles from the matrix polymer resin, followed by astigmatism or other known techniques to measure the particle size distribution. When the Wi system is calculated from a microphotograph, the particle can be assumed to be substantially spherical in the absence of other contradictory experience. Although the statistical distribution of distribution has been widely used in polymer science, these tools are still not used in the field of fluoropolymer processing aids. For example, in The Elements of P〇lymer science and Engineering (Academic Press, 1982) by Alfred Rudin, the number average molecular weight of a polymer is defined as the ratio of the first fraction of the molecular weight distribution to the zeroth fraction, and The weight average molecular weight is defined as the ratio of the second fraction of the molecular weight distribution to the first fraction. The quantity and weight average correspond to the arithmetic mean of the number 1 or weight distribution. Use weight average instead of number -12- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1 --- 1251003 V. Description of invention (1 〇 average to the particle size distribution of the fluoropolymer Qualitatively suitable for the present invention as described by J. Rheol (45), March/April 2, the polymer processing aid is deposited on the inner surface of the extrusion plate. Fluorine: human, coating works. Because the present invention is based on the same fluorine-containing poly:: wave, larger particles of smaller particles move the gas-containing polymer to the surface of the waste plate faster, so the processing aid The significant quality of the particle distribution is a measure of the particle size distribution of most of the compounds. Furthermore, since the statistical methods of particle size analysis have not been used in this field, the previous reference generally describes the fluoropolymer dispersion. Particle size range. Unfortunately, the particle size range does not provide the weight average particle size of the distribution γ ' does not show that the weight average needs to be within a certain range. Contains a small amount of particle size j of 2 micron containing particles , but most of the prior art of fluorine-containing particles less than 2 microns The extrudable composition cannot be modified as in the composition of the invention. ϋ ^ In terms of ease of handling, the inclusion of a compounding aid in the non-gasified melt-processable polymer is formed When the composition is to be extruded, it is often in the form of a masterbatch, rather than a pure form. The masterbatch is a dispersion (mixture) of a gas-containing polymer in a diluent polymer. The diluent polymer; The non-fluorinated refractory polymer, or which may be a second non-fluorine that does not adversely affect the extrusion properties of the first non-vaporizable melt processable polymer/processing aid composition. The melt processable polymer. The masterbatch generally contains U50 by weight (preferably U3 〇 weight percent) of the gas-containing polymer processing aid (based on the total weight of the masterbatch). The masterbatch can be, for example, at high At the temperature of the melting point of the non-fluorinated melt-processable polymer, the Chinese National Standard (CNS) Α4 specification (210X297 DON) is applied to the paper scale of the mixer. -13 - 1251003 V. Description of the invention (11 such as Banbury Banbury ® mixed crying ^ ^ ^ ^ , σ The fluoropolymer of the appropriate type 1 is mixed with the diluted ΐ ΐ ♦ compound to form the tannin and / or the mother 枓, depending on the concentration, composition and the conditions of the masterbatch. The weight average particles of the fluoropolymer may be only less than or more than 2 micrometers. Preparation of a masterbatch which can be used in the extrudable composition of the present invention, with emphasis on the fact that the W-containing (four) is exposed to high shear forces. To a minimum, especially a low fluoropolymer concentration masterbatch (ie, containing less than about 5 weight percent fluoropolymer). Otherwise, the weight average particle size of the fluoropolymer may be in the masterbatch Shrinking to less than 2 microns. The rate at which the fluoropolymer auxiliaries masterbatch is fed to the extruder is controlled 'so that the fluoropolymer concentration in the extrudable composition formed is the total of the extrudable composition The recalculation is between 25 and then the parts by weight (25 to 1 part by weight is preferred). There are several types of fluoropolymers that achieve a desired fluoropolymer weight greater than 2 microns but less than 1 micron: an average particle size - a crescent method in the extrudable composition at a location near the extrusion plate. One of the methods - one aspect of the invention - is a novel extrudable mono-compound comprising a non-gasified (four) processable polymer; and based on the total weight of the extrudable composition 25 to 2 ounces by weight of a pure fluoropolymer, wherein the a-containing polymer is measured at a position just before the extrusion plate (ie, the inlet of the extrusion plate), having a diameter greater than 2 microns (to be greater than Preferably 4 microns, more than 6 microns optimal, but less than 1 〇 microns by weight average particle size. Such an extrudable composition is substantially free of surfactants (as defined below). "Only without" means a surfactant of from 0 to about 10 parts by mole of the total weight of the extrudable composition. The extrudable composition of the present invention can be prepared by a method , wherein the fluoropolymer is introduced (pure-14-1251003 A7 ______ B7 V, invention description (12) a '~'-material form or masterbatch form) (the weight average particle size before introduction into the extruder is greater than 2 microns, Preferably, greater than 4 microns, more preferably greater than 6 microns, mixed with the non-fluorinated melt processible polymer to form an extrudable composition comprising from 25 to 2000 parts per million of fluoropolymer. The non-fluorinated polymer and the fluoropolymer, pumping the formed composition to the extrusion plate, minimizes the time during which the fluoropolymer is exposed to high shear, and thus, when the extrudable combination The weight average particle size of the fluoropolymer is still greater than 2 microns when the material reaches the inlet of the extrusion plate. Care must be taken not to over-process the fluoropolymer-containing extrudable composition to the inlet of the extrusion plate. Otherwise, it may appear large when it is fed to the extruder. The weight average particle size fluoropolymer may have a size of 1 micron (or less) when it reaches the extrusion plate. Overprocessing includes any process in which the fluoropolymer processing aid is exposed to dispersive mixing conditions for too long. Over-processing can occur in some types of polymer mixing devices such as fully-feeding twin-screw extruders, Buss Kneaders®, and devices with built-in mixing devices (such as Midas (Madd) a single screw extruder of a screw of 〇 elements elements), a sheath mixer, a ring element, a reverse squeegee, and a fine mesh bag that generates a high pressure (ie > 2 MPa) at the exit of the extruder or A single-screw extruder for limiting the extrusion plate. The processing is preferably carried out in a single-screw extruder with or without the mixing elements of the screw. In the best case, there should be no mixing elements mounted on the screw and Downstream mixing unit. Since all extrusion methods may reduce the particle size of the fluoropolymer, it is desirable to have particularly coarse particles such as pellets, coarsely ground powder, or fluoropolymer particles having a weight average particle size of much larger than 2 microns. The conductivity in the fluoropolymer masterbatch state -15-

Ϊ251003 V. Description of the invention (13 ^ in the extruder). In order to minimize the dispersion and improve the processing speed, β, the viscosity of the mouse polymer under extrusion processing conditions should be equal to or greater than the f 2 to be meltable The viscosity of the processed thermoplastic polymer. For example, the coarsely ground content can be dried in two to two portions with a polyethylene resin at 25 to 2 parts per million and fed to a single screw extruder. The machine screw should have a low compression ratio (3:1 or lower) and no mixing elements. The polymer flow path downstream of the screw should have a minimum limit, rather than the extrusion plate itself. 疋S Fluoride ♦ & A preferred method for the vehicle having a weight average particle diameter of more than 2 μm when the sheet is extruded is to introduce a surfactant into the master batch or the extrudable composition, and the surfactant can stabilize the particle size of the fluoropolymer slightly. , such that the fluoropolymer particles are less sensitive to a high shear environment such as a mixed surfactant" means a thermoplastic polymer having the following characteristics: 1) being liquid (or molten) at extrusion = temperature, 2) having Lower than non-gasification can process the polymer and fluorine-containing polymerization a solution viscosity of the processing aid, and 3) optionally rinsing the surface of the gas-containing polymer particles in the erasable composition. Examples of the surfactant include, but are not limited to, 0 stone paint (tetra) copolymer; π) aliphatic poly- vinegar such as (single-acid vinegar), poly(lactic acid) and poly-caprolactone vinegar (the vinegar is a copolymer of non-(tetra) and poly(epoxy) polymers For Jiaguang (1)) aromatic polyester vinegar such as diisobutyl acetonate; sangha polyol (preferably non-polyoxyalkylene) such as poly(tetramethylene sterene diol); lanthanum oxide such as oxidized octyl Dimethyl valence; vi) retinoic acid such as thio-butanic acid; syllabus (4) 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 诸如 及 及 及 及 及 及 及 及 及 及 及 及The term "poly(epoxy compound) polymer" as used in the present invention means a polymer and a derivative thereof as defined in U.S. Patent No. 4,855,36, which is incorporated herein by reference. Standard (CNS) A4 size (210X297 mm) 16- 1251003 V. Description of invention (μ Polyethyl) - alcohol and its derivatives. Preferred aliphatic poly-S interface The agent has a polycaprolactone having a number average molecular weight ranging from 3 to 3, preferably from 1 to 4,000. The surfactant is a relatively low molecular weight component, and the fluorine is processed. Auxiliary and non-Donghua smelting and processing polymer-specific systems are preferentially positioned at the interface between the two polymers. Although not intended to be bound by any specific description, it is believed that the surfactant is in the non-fluorine. The smelting process of the polymer reduces the shear stress on the polymer particles and reduces (4) the ability of the processing equipment to affect the dispersion of the fluoropolymer. The surfactant can reach the final glare forming process. Any point before and including the introduction of the process into the mixture of fluoropolymer and non-fluorinated polymer is such that at the point of introduction, the weight average particle size of the fluoropolymer particles needs to be greater than 2 microns. It is desirable to combine the fluoropolymer and the surfactant in a parent mixing step in which both components are at a high concentration (i.e., greater than or equal to 1 weight percent based on the total weight of the masterbatch), so that the fluoropolymer interface is known. The active agent can be wetted quickly. Therefore, the invention is a masterbatch comprising a) a non-fluorinated melt-processable polymer; b) a fluoropolymer of from i to 50% by weight based on the total weight of the masterbatch; c) A surfactant which is at least effective in improving the processability. At least an effective amount is defined as any amount of the surfactant contained in the masterbatch such that when the masterbatch is mixed with the non-fluorinated melt processable polymer, the resulting extrudable composition is during extrusion. The treatment time required to remove all surface melt cracks is comparable to that of the same composition without surfactants, and the amount of shortening is measurable in the masterbatch. National Standard (CNS) A4 Specification (210X297 mm) 17- l25l〇〇3 V. Invention Description (15) ~" -------~ The concentration of the processing aid is five times more surfactant ( That is, when the weight ratio of the surfactant to the gas-containing polymer in the composition is as high as 5:1), it is apparent that when the extrusion n surfactant is poly(epoxy polymer), the surfactant is relative to The weight ratio of the fluoropolymer to the masterbatch is lower than that of the other aspect of the invention, which comprises a) an IL-containing polymer and b) a polycaprolactone. "Free" is used to produce masterbatch, or as an additive directly introduced into the mouth and mouth. In the composition, the weight ratio of polycaprolactone to the fluoropolymer is preferably not more than 5: 1. In the aspect of the invention, the polycaprolactone has a ratio of from 1 〇〇〇 to 32 〇. The average number of knives within the range is 仫, 2000 to 1〇〇0〇 is better, and 2〇〇〇 to 4〇〇〇 is best. These L-mouths can be made by various methods, including blending. Pellet or powder of fluoropolymer and polycaprolactone, or encapsulated with gas polymer particles using a coating of polyhexene. The other sadness of Maoming is a kind of squeezing through the extrusion plate. a plastic composition comprising a) a non-fluorinated melt processable polymer; 25 to 2 parts by weight, based on the total weight of the extrudable composition, of a fluorine-containing compound泫, 泫 fluoropolymer having a weight average particle size greater than 2 microns (preferably greater than 4 microns, and more preferably greater than 6 microns) but less than 1 〇 micron (measured at a position just below the extrusion plate) And c) at least an effective amount of surfactant to achieve greater than 2 microns but less than 10 when measured just prior to the extrusion plate The weight average particle size of the fluoropolymer. The upper limit of the surfactant contained in the extrudable composition is the weight ratio of the surfactant to the fluoropolymer of 5 ··1, when the surfactant is In the case of poly(alkylene oxide) polymers, the ratio is preferably less than 1:1.

1251003 A7 B7 V. INSTRUCTION DESCRIPTION (16) The compositions of the present invention are particularly useful for extrusion of melt processible polyolefins. The extrusion process is generally used to make blown films and wire and cable coatings. EXAMPLES The following examples illustrate the significant improvement in the processability of the plasticization, which is evidenced by the shortened treatment time and the reduced pressure of the extruded plate. In this case, the weight average particle size of the fluoropolymer processing aid when it reaches the extrusion plate The system is larger than 2 microns. The molecular weights used in this specific example are as follows: The non-fluorinated melt-processable polymer is (a) high molecular weight linear low density polyethylene, ie, a linear low density (d=〇918) copolymer of ethylene and 1-butene. The number of days of melt (ASTM D-1238, condition E) is 1 · 〇 (hereinafter referred to as "llDPE-Γ,) or (b) ethylene-octene linear low-density polymer, melt index of 25 〇 And the density is 0.917 g / cc (LLDPE-2). The fluoropolymer processing aid used is a fluoroelastomer, used alone or in combination with a thermoplastic fluoropolymer. Fluoroelastomers (FEd, FE_2) And FE-3) is a copolymer of vinylidene fluoride and hexafluoropropylene at a weight ratio of 6〇/4〇. The Montessori viscosity of FE-1 (Mooney "%〇他幻为55, fe_2 The viscosity is 40, while the ME-3 viscosity of FE-3 is 75 (all measured according to ASTM D-1646, using a large rotor, condition ML 1 +1 〇 min, 121 ° C).

The melting temperature (ASTMD4894) was 325 °C ± 5 °C.

., Ichikawa 々% is derived from the ring-opening reaction. PCL-1 is a 1000 number average molecular weight polycaprolactone diol. PCL-2 is a 2000 number average molecular weight polycaprolactone diol.

1251003 A7 ________ B7_ V. INSTRUCTIONS (17) PCL-3 is a 4000 number average molecular weight polycaprolactone diol. PCL-4 is a 32,000 number average molecular weight polycaprolactone diol. Another surfactant used in the examples is PEG, which has a number average molecular weight of about 8,000 and is sold under the trademark CarbowaxTM 8000 (Union Carbide Corp.). Example 1 Masterbatch of the invention (code MB· 1 and the control group (encoding MB-A, etc.) were prepared from the compositions listed in Table i (values are by weight) at 200. (The mixture was melt-mixed using a 28 mm co-rotating twin-screw extruder operating at 3 rpm and the extruded cable was cooled and pelletized in a water bath.

Table I Materials MB-A MB-1 MB-2 MB-3 MB-4 MB-B MB-C MB-D MB-5 MB-6 MB-E LLDPE-1 99 98.75 98.5 98 96 96.39 98.5 95 95 95 95 FE-1 0.96 0.96 0.96 0.96 0.96 0 0 0 0 0 0 FE-2 0 0 0 0 0 0 1.5 1.5 1.5 1.5 1.5 FP 0.04 0.04 0.04 0.04 0.04 0 0 0 0 0 0 PCL-1 0 0 0 0 0 0 0 3.5 0 0 0 PCL-2 0 0 0 0 0 0 0 0 3.5 0 0 PCL-3 0 0.25 0.5 1 3 3.61 0 0 0 3.5 0 PCL-4 0 0 0 0 0 0 0 0 0 0 3.5 Extrusion processability The evaluation was performed on a CW Brabender Instruments Inc. Computerized Plasti-Corder with a 19.1 mm (3/4 inch) diameter extruder and a length to diameter ratio of 25/1. Unless otherwise stated, the loom screw has 15 feed scrapers, 5 transfer scrapers, 5 metering scrapers-20- This paper scale applies to China National Standard (CNS) A4 specifications (210X297 mm) ''; 1251003 V. Invention description (18 Fortification ratio 3 · 1, and does not have mixed components. Operating parameters by four separate heating zone, a dust transducer, and - a device has M20 revolutions per minute The % force torque measurement 1 drive unit is controlled. The machine is equipped with a 0.51 mm (0.020 inch) extrusion plate gap and a 1 〇 16 cm (〇·4 inch) landing, land length The 2.54 cm (1 inch) slot produces a continuous strip of polyethylene. This equipment configuration does not contain components that are specifically used for mixing during extrusion. Therefore, the equipment is for feeding to extrusion. The particle size of the fluoropolymer processing aid of the press is highly sensitive because the extruder has a very limited ability to change the size of the fluoropolymer before it reaches the extrusion plate. Set at 2nd generation, and the extruder barrel temperature is set at 16〇t (feeding area), 18(rc (middle), and 2〇〇0〇: (export). The extruder screw speed is kept constant at 45 revolutions per minute. The pressure of the extrusion plate and the torque of the extruder are at one minute intervals during the test. Automatically recorded by the computer. By using pure LLDPE-i feed (ie, no fluoropolymer processing aid or surfactant) to establish a 100% melt cracking baseline condition, the extruder is rotated and extruded The pressure reached a steady state. The feed was switched to the dry blend of the LLDPE-i and the masterbatch in the evaluation, and a digital timer with a second read value was started to measure the treatment time. The sample of the plastic, the percentage of the surface area covered by the melt crack defect was evaluated by visual inspection using a 30-times illuminating magnifying glass. The test was carried out for (9) minutes. The extruded samples were obtained under the mark of 60 minutes. When this state is reached during the test, the time required to reach the percentage of melt cracking (ie, the treatment time) is recorded. In the test, the feed is converted to a percentage in the polyethylene - 21 - the paper Scale applicable National Standard (CNS) A4 Specification (210 X 297 mm) 1251003 A7 B7 __ V. Description of Invention (19) Abrasive cleaning compound for cerium oxide (KC-60, Α·Schulman Inc.) The fluoropolymer processing aid is removed from the casting machine and the extrusion plate. After sufficient cleaning (30 to 45 minutes), pure LLDPE-1 is introduced to establish the pressure, output, and melt crack of the recovered plate. Baseline conditions. In order to determine that the particle size measurement was not obscured by the residual cerium oxide particles in the test extruder, the extruder and the extrusion plate were removed and cleaned. The extruder barrel was scrubbed with a wire brush. Then scrub with a cloth dampened with xylene. The high pressure air containing the particulate spray medium is used to remove the screw and all of the polymer on the extrusion plate. The fluoroelastomer particle size distribution was measured using a Nikon Microphot-SE composite microscope using standard reflected light and a 40x objective for obtaining digital data. The total magnification is 400 times. The illumination is provided by the Nikon Transformer model UN set at position 4. Images were acquired and digitized using a DXC-760 MD model with DXC-750 control, and displayed on the computer screen with Intelrocam 2.0 software using a Matrox Meteor Graphics card. Place the portable hot stage of the Instec Inc. model HS400 on the microscope stage. The hot stage temperature is 220 °C. When measuring the particle size distribution, the sample to be analyzed was sliced (~0.5 mm) perpendicularly to the direction of extrusion using a razor. The sheet is placed on a hot stage to balance it. The fluoroelastomer particles are imaged by moving the focal plane in the thickness direction of the sample. To avoid calculation of dust particles, only the focal plane inside the specimen is analyzed. When analyzing the extrudable composition, there are typically five to fifteen fluoroelastomer particles in any particular focal plane. In some of the samples, the fluoroelastomer particles were not uniformly distributed in the sample, and were examined at a low magnification to determine a region rich in fluoroelastomer particles. Masterbatch composition at a specific focus flat-22- This paper scale applies Chinese National Standard (CNS) A4 specification (21〇X 297 mm) 1251003 A7 B7 V. Description of invention (2〇) The surface contains a large number of particles, Depending on the concentration of the material. The fluoroelastomer particle size is determined by measuring the diameter in a 2 micron increment on a go-to-image of a computer screen relative to a 1 micron scale. The minimum particle size obtained by this technique is 0.5 micron. The particle size closest to an integer micron of more than 0.5 microns was measured. At a particle size of up to about 5 microns, the particle diameter appears uniformly circular on the digitized image. Although many particles larger than 5 microns are round, some large particles are elongated. In these cases, take the long size as the particle size. Angled or irregular particles are often found in the sample. These particles are not analyzed given that they are not fluoroelastomer particles. From 1 to 15 particles were counted in each sample. A fluoroelastomer-free plasticate control sample was taken at the beginning of each extrusion test. Detect as described in Section 4 to determine that there are no contaminants that affect particle size measurements. When the extrusion test is completed (i.e., after the melt crack is completely removed, or after 60 minutes of extrusion), the extruder screw speed is set to zero, and the extrusion plate is removed. The screw speed is set at about 10 revolutions per minute, so that the material of the extrusion plate should be slowly extruded from the material (just upstream of the extrusion plate). About five grams of the extrudate was collected in this manner and allowed to cool without interference, and then used to qualitatively transfer to the extrusion plate for the fluoroelastomer particles used in the extrusion test. The masterbatch ΜΒ-1, ΜΒ-2, ΜΒ-3 and ΜΒ-4 of the present invention are dry blended with LLDPE-1 at a concentration of 2% by weight to produce a fluoropolymer containing 2 parts by weight in total. The composition of the processing aid and the interface surfactant PCL-3 between 5 and 6 parts per million to form the renderable composition (EC-1 to EC-4) of the present invention. The control extrudable composition (EC_A) was prepared in the same manner, and 2 parts by weight of the master batches MB-A and LLDPE-1 were blended to form a

1251003 A7 B7 V. INSTRUCTIONS (21) A composition containing 20,000 parts per million of fluoropolymer processing aid, but no interfacial activator. The second control extrudable composition (EC-B) is obtained by drying the blended masterbatch MB-B and LLDPE-1 at a concentration of 1.33 weight percent to produce a surfactant comprising 480 parts per million. PCL-3, but not containing a composition of a fluoropolymer processing aid. Table II lists the foregoing extrusion test results and particle size measurements for these extrudable compositions.

Table II Weight average particle size of the extrudable composition masterbatch to the extruding plate (micron) Particle size range (micron) delivered to the extruding plate Melt crack % at the completion of the test Processing time (minutes) When the test is completed Extrusion plate pressure (MPa) EC-A MB-A Ϊ.8 0·5 to 3 3 >60 13.2 EC-1 MB-1 2.9 0.5 to 4 0 41 11.5 EC-2 MB-2 3.7 1 to 6 0 44 10.9 EC-3 MB-3 2.7 1 to 4 0 30 10.7 EC-4 MB-4 4.9 1 to 8 0 11 11.2 EC-B MB-B No particles and no particles 100 > 60 19.9 Results listed in Table II Shows the extrudable composition of the present invention (EC-1 to EC-4) (containing both surfactant PCL-3 and fluoropolymer processing aids FE-1 and FP), relative to processing containing only fluoropolymer When the control group EC-A without the surfactant was used, the time required to eliminate the melt crack defect on the extruded tape was shortened, and the pressure of the extrusion plate was lowered. Control group EC-B containing only surfactant PCL-3 and no fluoropolymer processing aid had no effect on melt crack defects, and the pressure of the extruded plate was worse (ie higher) than that of the control group EC-A. . PCL-3 # $文i也予贝尸方| 5^十生斗勿米t 4 #才斗言周酉己& ^ ^ f ^The moon is reduced to a weight average particle size below 2 microns, so improve Fluoroelastic-24 - This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1251003 A7 B7 V. Description of invention (22) Properties of processing aids. In addition, the performance of the processing aid is related to the weight average fluoroelastomer particle size delivered to the extrusion plate during the extrusion test. For example, although EC-A does not contain particles larger than 2 microns, the amount of such particles is not sufficient to increase the weight average particle size above 2 microns, so when the test is completed, the extrudable composition contains The composition of the present invention having a fluoroelastomer particle and having a weight average particle diameter of more than 2 μm, in comparison, exhibits a poor treatment time, > and a higher platen pressure. Example 2 The extrudable compositions (EC-5 and EC-6) of the present invention and the control extrudable composition (EC-C~EC-E) were blended by dry blending with 1.33 weight percent of masterbatch and LLDPE. -1 and prepared from masterbatch ΜΒ·5, MB-6, MB-7, MB-8 and MB-C (individually), all of the extrudable compositions produced contain 200 parts per million FE -2 fluoropolymer processing aids and 0 parts per million (Control C) or 465 parts of PCL surfactants with different molecular weights (EC-5 and EC-6, and EC-D and EC-E) . Table III lists the results of the extrusion test and particle size measurement conducted in accordance with the method described in Example 1.

Table III Weight average particle size of the extrudable composition masterbatch to the extruding plate (micron) % melt crack at the completion of the test Treatment time (minutes) Extrusion plate pressure (MPa) at the completion of the test EC-C MB -C 1.6 50 >60 18.7 EC-D MB-D 1.5 1 >60 13.4 EC-5 MB-5 6.5 0 9 10 EC-6 MB-6 5.1 0 9 11.2 -25- This paper scale applies to Chinese national standards (CNS) A4 size (210 X 297 mm) 1251003 A7 B7 V. Description of invention (23) EC-E MB-E 1.9 30 > 60 16.4 The results listed in Table III show PCL surfactant (with fluoropolymerization) All of the molecular weight ranges tested by the processing aids improve extrusion processability by reducing melt cracking, shortening processing time, and reducing the pressure of the extrusion plate. However, at least in combination with the fluoropolymer FE-2, the polycaprolactone having a number average molecular weight of 2000 (PCL-2) and 4000 (PCL-3) has a number average molecular weight of 100 or 3 2 Compared with the polycaprolactone of 0 0 0, it is more effective to prevent the fluoroelastomer particles from breaking into small sizes. Increased fluoroelastomer particle size (greater than 2.0 micron weight average) in combination with formulations containing PCL-1 or PCL_4 eliminates melt cracking and lowers pressure in PCL-2 or PCL-3 Board pressure. Example 3 The masterbatch shown in Table IV (values expressed by weight percent) was obtained by melt mixing the components using a 28 mm co-rotating twin-screw extruder operated at 300 rpm and 200 °C. The extruded strands are cooled and granulated in a water bath. The size of the fluoroelastomer particles in the masterbatch is increased by increasing the concentration of FE-1 in the masterbatch. When the amount of dispersion in the Brabender 8 extruder is insufficient to reduce the large fluoroelastomer particles in the masterbatch to a weight average diameter of less than 2 microns (at the inlet of the extrusion plate), it contains large particles. The melt crack defects of the masterbatch disappear faster than the masterbatch containing the small fluoroelastomer particles. MB-9 and MB-10 demonstrate that the particle size of the fluoroelastomer in the masterbatch is also increased by maintaining a low fluoroelastomer concentration (same as MB-G and MB-Η), while increasing the polyethylene used in the masterbatch Melt index during blending. The third method for producing large fluoroelastomer particles and transporting them to the extrusion plate is described by MB-11-26- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1251003 A7 B7 V. Inventive Note (24) in which a relatively low concentration (same as MB-G) high viscosity fluoroelastomer (FE_3) is used. Since FE-3 is more difficult to disperse than FE-1, MB-11 masterbatch delivers larger fluoroelastomer particles to the extruding plate, eliminating melt defects faster than MB-G.

Table IV MB-F MB-G ΜΒ-Η ΜΒ-7 ΜΒ-8 ΜΒ-9 ΜΒ-10 ΜΒ-11 LLDPE-1 99.9 99 95 88 75 99 LLDPE-2 99 95 FE-1 0.1 1 5 12 25 1 5 FE-3 1 The present extrudable composition (EC-7 to EC-11) and the control composition (7) 匕F, EC-G, EC-Η, EC-Ι and EC-J) are by the table Prepared by drying the blended masterbatch MB_7 to MB-11 and MB-F to a bismuth ratio at the ratios listed in V, without using a non-fluorinated melt-processable polymer, to obtain 10 extrudable compositions, each having a hundred A uniform concentration of 200 parts of FE-1 or FE-3 processing aid.

Table V EC-F EC-G EC-H EC-7 EC-8 EC-9 EC-10 EC-I EC-J EC-11 LLDPE-1 80 98 99.6 99.83 99.92 98 99.6 96.02 99.22 98 LLDPE-2 1.98 0.38 MB-F 20 MB-G 2 2 ΜΒ-Η 0.4 0.4 ΜΒ-7 0.17 ΜΒ-8 0.08 -27- This paper scale applies to China National Standard (CNS) Α4 specification (210 X 297 mm) 1251003 A7 B7 V. Invention Description (25) MB-9 2 MB-10 0.4 MB-11 2 Table VI shows the results of extrusion tests and particle size measurements using compositions EC-F to EC-J and EC-7 to EC-11, as described above The same procedure as in Example 1 was carried out. To confirm the accuracy of the particle size measuring method described in Example 1, the fluoroelastomer particles in one of the samples (EC-7) were additionally characterized using a Carl Zeiss LSM 5 10 confocal microscope. The 488 nm Ray Ray was used to excite and the Khoros kit software was used to capture and analyze the 3D image of the particles. The minimum resolvable particle size for this type of equipment is 1 micron.

Table VI Extrusion Composition Masterbatch Composition Masterbatch Weight Average Particle Diameter (μm) Weight Average Particle Size Delivered to Extrusion Plate (μm) Melt Crack % at Test Completion Processing Time (minutes) Upon completion of the test Extrusion plate pressure (MPa) EC-F MB-F 2 2 35 > 60 17.3 EC-G MB-G 1.7 1.7 40 > 60 17.8 EC-H MB-H 2.1 2 30 > 60 16.8 EC-7 MB-7 4.1 4.8* 0 25 12 EC-8 MB-8 13.1 6.6 0 22 10.6 EC-9 MB-9 4.6 6 0 20 11.2 EC-10 MB-10 7.3 6.6 0 14 10.5 EC-I MB-G 1.7 nm 20 >60 15.7 EC-J MB-H 2.1 nm 5 >60 14.3 EC-11 MB-11 Nm 2.3 0 45 12.3 nm: Untwisted J -28- This paper scale applies to China National Standard (CNS) A4 Specifications (210X 297 mm) 1251003 A7

*4.56 microns, measured using confocal laser technology, 11 〇〇 particle count. The extrusion test results of the composition of the present invention (EC-7 to EC-11) showed an unexpected improvement in the melt defect and a decrease in the pressure of the platen (relative to the control group ec_f to EC-J). The control groups EC-F, g and η and samples EC-7 to 11 show that these methods are modified because the weight average particle size of the fluoroelastomer processing aid delivered to the extrusion plate increases to greater than 2 microns. Measurement of the particle size of the fluoroelastomer in the master batches MB-F, G and lanthanum and ytterbium-7 and 8 confirmed that the fluoroelastomer dispersion became coarse as the concentration of the fluoroelastomer in the masterbatch increased. With the extruder structure used in Examples 丨 to 3, the weight average particle diameter of the fluoroelastomer in the master batch was increased so that the particle diameter of the fluoroelastomer fed to the nip plate was correspondingly increased. EC-9 and EC-10 demonstrate that thickening of the fluoroelastomer dispersion can also be achieved by increasing the melt index of the polyethylene used in the manufacture of the masterbatch without increasing the concentration of the fluoropolymer processing aid. The use of a high melt index non-fluorinated melt processable polymer as a carrier for the masterbatch is predicted to reduce the dispersive mixing ability of the twin screw extruder used in the manufacture of the masterbatch, and therefore, even if a low solution index is used (for example, 1 · 0 ΜΙ) Resin, a coarser fluoroelastomer dispersion can still be produced. The comparative examples EC-Ι and J show that during the extrusion test, the introduction of the finely dispersed masterbatch (ΜΒ-Ε and MB-F) having the same concentration of the elastomer is introduced, etc. 25:!: volume index LLDPE, it is not possible to quickly eliminate melt defects and significantly reduce the pressure of the extrusion plate as in the EC-9 and EC-10 groups of the present invention. EC-11 demonstrates that even if the concentration of fluoroelastomer in the masterbatch is low, increasing the viscosity of the gas-containing elastomer can still deliver a weight average particle size greater than 2 microns at the extrusion plate. EC-11 also demonstrates that a weight average fluoroelastomer particle size slightly larger than 2 microns is more effective than a weight average particle size of 2 microns or less, but is not as good as the Chinese national standard for the 29-I paper scale shown in Examples 1 to 3. (CNS) Α4 size (210X297 mm) ----------- 1251003 A7 B7 V. INSTRUCTIONS (27) Extremely large fluoroelastomer particles (4 microns and larger) are effective. The particle size analysis of the fluoroelastomer delivered to the extrusion plate in EC-7 shows the manual particle counting technique described in Example 1 and the automated technique of using a laser confocal microscope reasonably. Example 4 The MB-12 composition of the present invention and the control masterbatch MB_I and MB·J are shown in Table VII. Values are expressed in weight percent. The masterbatch MB-12 and MB-J were prepared on a twin-screw extruder as described in Example 1, with different treatment temperatures of 280 ° C instead of 200 ° C, all other blending parameters were maintained. constant. Such higher processing temperatures are generally the temperatures reached by granulating extruders used in the manufacture of industrial polyethylene. The fluoropolymer processing aid is often incorporated into the polyethylene resin by direct addition (i.e., without the use of a masterbatch) to the hopper of the granulation extruder.

Table VII MB-12 MB-I MB-J LLDPE-1 96 96 96.39 FE-1 1 1 0 PEG 3 3 3.61 The extrudable composition shown in Table VIII was prepared by the method described in Example 1. The extrudable composition ECM2 is a composition of the invention, while the other is a control composition. The values in Table VIII are expressed in weight percent. EC-12, EC-K, and EC-Μ contain 200 parts per million of FE-1 and 600 parts per million of PEG. EC-L contains 480 parts per million PEG but does not contain fluoroelastomers. -30- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) l25l〇〇3 A7 ^___B7 V. Invention description (28)

Table VIII EC-12 EC-K EC-L EC-M LLDPE-1 98 96.34 98.67 98 ΜΒ-12 2 MB - G 2 MB-I 2 MB-J 1.66 1.33 The results of the extrusion experiments listed in Table IX are indicated in The effect of increasing the amount of dispersion mixing during compounding and extrusion, and the role of surfactants such as PEG in preventing the rupture of fluoroelastomer particles in the presence of such dispersions. In addition, such tests have shown an extrudable composition comprising a processing aid comprising a fluoroelastomer and PEG, wherein the ratio of pEG to fluoroelastomer in the processing aid is 3.0, and the fluoroelastomer weight average The particle size is 2 microns or less - it is not possible to quickly eliminate melt crack defects as in the composition of the present invention, and to greatly reduce the pressure. In order to vary the amount of dispersion during the extrusion experiment, two different extruder screws were used. The first type of screw, hereinafter referred to as a metering screw, is described in Example 1. A second type of screw, hereinafter referred to as a Maddock screw, has a Maddock mixing element at the end of the discharge. The Maddock screw has 10 feed screeds, 5 transfer screeds, 5 metering screeds, and an L/D of 25: 1, and has a Maddock mixer around the last five diameters of the screw. In order to maintain the output and shear rate of the extruder in the same plate, the extruder screw-31 - the paper size standard (CNS) A4 specifications ((10) χ 297 public) 1251003 A7 B7 V. Description of the invention (29) The speed was set at 52 revolutions per minute for the Maddock screw and 45 revolutions per minute using the metering screw (as described in Example 1). All other extrusion test parameters remained unchanged between experiments with different screws. Objects such as screw I plastics often use a screw comprising a mixing element such as the Maddock tip to determine the good dispersion of additives such as pigments (e.g., Ti02) or anti-blocking agents (e.g., cerium oxide or talc). Because extrusion of such films requires small extrusion plate gaps, the article often uses fluoropolymer processing aids to eliminate melt defects and reduce the pressure of the extrusion plate to increase yield.

Table IX Weight average particle size in the masterbatch of the extrudable composition (micron) Weight average particle size (micron) delivered to the extruding plate Melt crack % at the completion of the test Treatment time (minutes) Extrusion plate at the completion of the test Pressure (MPa) Extruder screw type EC-8 13.1 6.6 0 22 10.6 Metering EC-8 13.1 1.0 2 > 60 12.5 Maddock EC-12 3.0 3.1 0 40 11.2 Metering EC-12 3.0 3.5 0 50 11.9 Maddock EC-K 1.7 1.4 30 > 60 16.6 Metering EC-L No particles and no particles 100 > 60 19.2 Metering EC-M 2.2 1.9 25 > 60 14.5 Maddock As shown in Table IX, EC-8 is displayed in the mother when tested with Maddock screw. The particle size of the large fluoroelastomer entering the extruder in the feed does not necessarily fully determine the performance of the processing aid. In this embodiment, the Maddock screw disperses the fluoroelastomer to a weight average particle diameter of 1 μm, and the composition does not eliminate melt defects within one hour. It should be noted that EC-8 does deliver large fluoroelastomer particles to the extrusion plate when tested using the metering screw of Example 3, and is applicable to the Chinese National Standard (CNS) A4 specification (210 X) at 22 -32- this paper scale. 297 mm) 1251003 A7

Melt cracks are eliminated in minutes. Conversely, EC-12 has excellent performance regardless of the type of screw. MB_12 contains fluoroelastomer particles with a weight average particle size of 3 μm 2 , and pEG in EC-12 acts as a surfactant to limit the rupture of the fluoroelastomer particles during extrusion, so the weight average diameter is greater than 2.0 μm. The fluoroelastomer particles are delivered to the extrusion plate regardless of the type of screw. Although EC-12 represents the extrudable composition of the present invention in Table IX, further increase in dispersion mixing in the extruder may be delivered to the extruding plate; the weight average fluoroelastomer particle size of 〇12 is reduced to Below 2 microns. Both EC_K and EC_M illustrate this situation. EC-K has the same LLDPE, I-containing elastomer, and PEG composition as EC_12, but the fluoroelastomer particles delivered to the extrusion plate are smaller (less than 2 microns weight average). EC_K is prepared by blending a masterbatch known to contain small fluoroelastomer particles with a masterbatch containing peg. As a result, the effect of the surfactant provided by PEG during the masterbatch formulation disappears. The results in Table IX show that PEG did not improve processing aid performance (compared to EC-K and EC_G) when small fluoroelastomers were delivered to the extrusion plate. ° EC-K did not remove melt defects within one hour. The pressure of the extrusion plate was also not greatly reduced because the weight average fluoroelastomer particle size delivered to the extrusion plate was 1/4 μm. The results of EC-Μ in Table IX show that the masterbatch contains a polyethylene glycol surfactant. Failure to ensure that the masterbatch can produce the extrudable composition of the present invention. Although Mb-12 and MB·J contain equal concentrations of fluoropolymer and polyethylene glycol, the MW-J containing polymer particles have a weight average particle size less than MB-12 (2.2 microns vs. 3.0 μm). ). It is believed that the difference in the particle size of the fluoropolymer is due to the increase in the formulation temperature for the production of the masterbatch. Because "6-of 2.2 micron weight average particle size -33- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1251003 A7 B7 V. Invention description (31) Close to critical 2 micron Pro The limit, so that even if the degree of dispersion of the fluoropolymer in the extruder is slightly increased, the weight average particle size of the fluoropolymer is reduced to less than 2.0 microns, and the performance of the processing aid is impaired. EC-Μ in Table IX The data shows that the Maddock screw reduces the weight average fluoropolymer particle size in MB-J from 2.2 microns to 1.9 microns in the EC-Μ delivered to the extrusion plate, so EC-M cannot be extruded as in the present invention. Effectively eliminate melt cracks or reduce the pressure of the extrusion plate. Only the PEG-based control extrusion test (EC-L) determines that PEG cannot eliminate melt defects, reduce the pressure of the extrusion plate, or may cause misunderstanding of fluorine Particles of Elastomers -34- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

1251003 An extrudable composition for extruding a sheet comprising: A) a refractory processable non-fluorinated polymer; and B) based on the total weight of the extrudable composition A 25- to 2-inch heavy-weight fluoropolymer having a weight average particle of greater than 2 microns and less than 10 microns when measured just prior to the extrusion plate! And wherein the composition comprises a surfactant of 〇 to 丨〇 (5). The composition of claim 1, wherein the fluoropolymer is a fluoroelastomer. 3. The composition of claim 2, wherein the fluoroelastomer has a ml (1 + 10) of up to 8 Torr at 121 C. The composition of claim 1, wherein the fluoropolymer is a semi-crystalline fluoropolymer. 5. The composition of claim 4, wherein the semicrystalline fluoropolymer has a melt index (ASTM D1238, 265 ° C, 5 kg weight) greater than 0.5 dg/min. 6. The composition of claim 1, wherein the fluoropolymer is a multimodal fluoropolymer. The composition of claim 1, wherein the fluoropolymer has a weight average particle size of more than 4 micrometers at a position just before the extrusion plate. 8. The composition of claim 7, wherein the fluoropolymer has a weight average particle size greater than 6 microns measured at a position just prior to the extrusion plate. This paper scale applies to China National Standard (CNS) a4 specification (21〇X 297 mm) 1251003 A BCD VI. Patent application scope 9. For example, the composition of the scope of claim 1 of the patent application, wherein the melt processable non-fluorine The polymer is selected from the group consisting of a 0 hydrocarbon resin, ii) polyguanamine, iii) chlorinated polyethylene, iv) polyethylene, and v) polyester. 10. The composition of claim 9, wherein the melt-processable non-fluorinated polymer-based hydrocarbon resin is selected from the group consisting of ruthenium polyethylene, (1) polypropylene, ii 〇 poly-Tene-1, iv) Poly(3-methylbutene), magic poly(decylpentene), and vi) a group of copolymers of ethylene and an alpha-olefin. 11. An extrudable composition for extruding a sheet comprising: a melt-processable non-fluorinated polymer; 曰W based on the total weight of the extrudable composition 25 to 2 parts by weight of the fluoropolymer having a weight loss, the fluoropolymer having a weight average particle of more than 2 μm and less than 1 μm when measured at a position just below the embossed plate And C) at least an effective amount of a surfactant such that the fluoropolymer has a weight average particle size of greater than 2 microns and less than 10 microns when measured at a position prior to the extrusion plate, but interface activity The weight ratio of the agent to the fluoropolymer is not more than 5:1. 12. The composition of claim U, wherein the surfactant is selected from the group consisting of fluorenone-polyether copolymers; (1) aliphatic polyesters; iii) aromatic polyfluorenes; iv) polyfluorene polyols ; v) amine oxide; v (10) acid; ν ϋ) fatty acid vinegar; and viii) a group of poly(alkylene oxide) polymers. U. The composition of claim 12, wherein the surfactant is an aliphatic polymer. The composition of claim 13, wherein the surfactant is -2- 1251003 A8 It is a polycaprolactone having a number average molecular weight of between 1,000 and 32,000. 15. The composition of claim 14, wherein the surfactant is polycaprolactone having a number average molecular weight of between 2,000 and 10,000. The composition of claim 15 wherein the surfactant is polycaprolactone having a number average molecular weight of between 2,000 and 4,000. The composition of claim 12, wherein the surfactant is a poly(alkylene oxide) polymer. The composition of claim 17, wherein the poly(alkylene oxide) polymer is present in a ratio of less than 1: 1 by weight of the poly(alkylene oxide) polymer to the fluoropolymer. 19. The composition of claim 11, wherein the fluoropolymer is an I-containing elastomer. The composition of claim 19, wherein the fluoroelastomer has a ML (1 + 10) of up to 80 at 121 °C. 21. The composition of claim 2, wherein the fluoroelastomer has an ML (1 + 10) of from 65 to 80 at 121 °C. 22. The composition of claim 5, wherein the fluoropolymer is a semi-crystalline fluoropolymer. The composition of claim 22, wherein the semicrystalline fluoropolymer has a melt index (ASTM D1238, 265 ° C, 5 kg weight) greater than 〇·5 dg/min. The composition of claim 11, wherein the fluoropolymer is a multimodal fluoropolymer. 2 5. The composition of the Scope of the Patent Application No. 3, wherein the fluoropolymer is applicable to the Chinese National Standard (CNS) A4 specification (210×297 mm) 1251003, and the weight average particle size of the patent application range The measurement is greater than 4 microns at a location just prior to the extrusion plate. 26. The composition of claim 25, wherein the fluoropolymer has a weight average particle size greater than 6 microns measured at a location just prior to the extrusion plate. 2 The composition of claim 5, wherein the melt processable non-fluorinated polymer is selected from the group consisting of a hydrocarbon resin, a polyamine, a chlorinated polyethylene, and a iv) polyvinyl chloride. , and the group of magic polyester. 28. The composition of claim 27, wherein the melt processable non-disruptive polymer hydrocarbon resin is selected from the group consisting of ruthenium polyethylene, (1) polypropylene, and polybutene-1, iv a group of poly(3-methylbutene), fluorene poly(methylpentene), and vi) a copolymer of ethylene and an α-olefin. 29 processing aid masterbatch compositions comprising: Α) a melt processable non-fluorinated polymer; a fluoropolymer based on the total weight of the masterbatch C) at least an effective amount to improve processability Surfactant, but the weight ratio of the surfactant to the fluoropolymer is not more than 5:], if the surfactant is a poly(epoxy) polymer, the oxopolymer is relatively The weight ratio of the fluoropolymer is lower than □··/long. 30. The processing aid masterbatch composition according to the scope of claim 29 is selected from the group consisting of (4) (4) polypolymers. Polyacetate; iv) poly(alcohol); v) amine oxide; di: vii) fatty acid ester, and viii) a group of poly(alkylene oxide) polymers. , -4- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1251003 31. The processing co-surfactant as claimed in claim 3G is an aliphatic polyester. Master batch composition, wherein the 32. auxiliary masterbatch composition, wherein the amount of between 1000 and 32000, as in the scope of claim 31, the processing surfactant is a number average molecular concentration . 33. The processing aid masterbatch composition of claim 32, wherein the surfactant is a number average molecular weight of from 2 Å to 1 聚 polycaprolactone. 34. The auxiliaries masterbatch composition of claim 33, wherein the surfactant is polycaprolactone having a number average molecular weight of between 2,000 and 4,000. 5. The composition of claim 29, wherein the fluoropolymer is a fluoroelastomer. 36. The composition of claim 35, wherein the gas-containing elastic material has a maximum of 8 〇 at the 121 (:: ^1^1 + 1 (^. 37) as claimed in claim 29 The composition of the present invention, wherein the gas-containing polymer is a semi-crystalline fluoropolymer. The composition of claim 37, wherein the semi-crystalline fluoropolymer has a 〇·5 dg/ Melt index of min (ASTM D1238, 265 ° C, 5 kg weight). 39. The composition of claim 29, wherein the fluoropolymer is a multimodal fluoropolymer. The composition of claim 29, wherein the melt processable non-fluorinated polymer is selected from the group consisting of i) a hydrocarbon resin, (1) polyamine, iii) gasification ______ · 5 - the paper size is applicable to the Chinese country Standard (CNS) Α4 size (210 X 297 public) 1251003 A8 B8 C8 ______ D8 Sixth, the patent range I vinyl 'iV) polyvinyl chloride, and V) polyester group. 41. The composition of claim 4, wherein the melt processable non-fluorinated polymer hydrocarbon resin is selected from the group consisting of ruthenium polyethylene, polypropylene '1 Π) polybutene-1, iv) Poly(3-methylbutene), ν) poly(methylpentene), and vi) a group of copolymers of ethylene and an α-olefin. 42. A fluoropolymer processing aid composition comprising a) a fluoropolymer and b) a number average molecular weight of between 2,000 and 10,000. 43. The composition of claim 42, wherein the composition has a weight ratio of up to 5: i relative to the fluoropolymer. 44. The composition of claim 42, wherein the amount of the average molecular weight of the polyene is between 1 and 32,000. 45. The composition of claim 44, wherein the polyhexene has a number average molecular weight of between 2,000 and 4,000. 46. The composition of claim 42, wherein the fluoropolymer is a fluoroelastomer. < 47. The composition of claim 42, wherein the fluoropolymer is a semi-crystalline fluoropolymer. -6- This paper scale applies to Chinese National Standard (CNS) A4 specification (210X 297 mm)