EP2992043A1

EP2992043A1 - Measuring molten polymer throughput using heat transfer balance

Info

Publication number: EP2992043A1
Application number: EP14724954.4A
Authority: EP
Inventors: Leen Monster; Donald J. Foster
Original assignee: Invista Technologies SARL Switzerland; Invista North America LLC
Current assignee: Invista Technologies SARL Switzerland; Invista North America LLC
Priority date: 2013-05-01
Filing date: 2014-04-15
Publication date: 2016-03-09
Also published as: TW201501901A; CN104129023A; CN104129023B; WO2014179063A1

Abstract

The present disclosure provides methods and apparatuses estimating casting throughput during casting process to provide polyamide pellets. The method of estimating casting throughput of an extruded polyamide polymer comprises measuring an amount of casting water flowing in to a casting apparatus typically from two or more locations, measuring the temperature of the casting water flowing in, and measuring the temperature of the casting water flowing out. Additional steps include calculating a heat transfer between the casting water flowing in and the casting water flowing out using the measured amount, and correlating the heat transfer to the casting throughput.

Description

MEASURING MOLTEN POLYMER THROUGHPUT

USING HEAT TRANSFER BALANCE

TECHNICAL FIELD The present disclosure relates to a method of measuring or estimating casting throughput of an extruded polyamide polymer on a casting apparatus for manufacturing polyamide pellets.

BACKGROUND

A particular class aliphatic polyamides having at least 85 percent aliphatic linkages between repeating amide units describes nylon polyamides. These aliphatic polyamides are known to be derivable from dibasic carboxylic acids and other amide-forming derivatives of dibasic carboxylic acids, such as anhydrides, amides, acid halides, half esters, and diesters, and are typically reacted with a primary or secondary amine. More specifically, the formation of aliphatic polyamide polymers from monomers such as dicarboxylic acids and diamines, is known to be accomplished by reaction of a primary or secondary diamine (diamines having at least one hydrogen attached to each nitrogen) and either a dicarboxylic acid or an amide-forming derivative of a dibasic carboxylic acid. An example reaction scheme is shown below:

HOOC-R-COOH + H₂N-R'-NH₂→

-[NH-R'-NH-CO-R-CO]-_n- + nH₂0 where R and R' represent divalent hydrocarbon radicals, and n represents the number of repeating units and the number of molecules of water. The "structural unit" of the polymer derived from one molecule each of diacid and diamine is named for the number of carbon atoms in the respective radicals, R and R'. Thus, a polyamide from hexamethylene-1 ,6-diamine and adipic acid is "nylon 6,6" (polyhexamethylene adipamide).

The fiber-forming polyamides can be prepared by heating substantially equimolecular amounts of diamine and dicarboxylic acid or an amide forming derivative of a dibasic carboxylic acid under condensation polymerization conditions, generally 180 °C to 300 °C. This product exhibits fiber-forming properties wherein sufficiently high molecular weight can be achieved.

The properties of a given polyamide can vary over a considerable range and can depend upon molecular weight. In part, the polyamide properties are influenced by the nature of its terminal groups, which in turn is dependent upon which reactant is used in excess, diamine or diacid.

Two characteristics of fiber-forming polyamides relate to their high melting points and low solubility. Those derived from the simpler types of amines and acids are almost invariably opaque solids melting or become transparent at a fairly definite temperature. Below their melting points the fiber-forming

polyamides when examined by X-ray generally furnish sharp X-ray crystalline powder diffraction patterns, clear evidence of their crystalline structure in the massive state. Densities of these polyamides generally lie between 1 .0 and 1 .2, and more particularly, the density of nylon 6,6 is recognized today as 1 .14 grams per cubic centimeter.

In common with other condensation polymerization products, polyamides generally include individual units of closely similar structures. The average size of these individual units, the average molecular weight of the polymer, is subject to deliberate control within certain limits. The further the polymerization reaction has progressed, the higher the average molecular weight (and intrinsic viscosity) will be.

If the reactants are used in exactly equimolecular amounts, polymerization and heating is continued for a long time under conditions which permit the escape of the volatile products, and polyamides of very high molecular weight can be obtained. However, if either reactant is used in excess, the polymerization proceeds to a certain point and then essentially stops. The point in time at which polymerization ceases can be dependent upon the amount of diamine or dibasic acid (or derivative) that is used in excess.

A convenient method of preparing polyamides includes making a salt by mixing approximately chemical equivalent amounts of the diamine and the dicarboxylic acid in a liquid, which may be by choice a poor solvent for the resultant salt. The salt which separates from the liquid can then be purified, if desired, by crystallization from a suitable solvent. These diamine-dicarboxylic acid salts are crystalline and have definite melting points. They are soluble in water and may conveniently be crystallized from certain alcohols and alcohol- water mixtures.

The preparation of fiber-forming polyamides from the diamine-dicarboxylic acid salts can be carried out in a number of ways. The salt may be heated in the absence of a solvent or diluent to a reaction temperature (180 °C to 300 °C) under conditions which permit the removal of the water formed in the reaction. It may become desirable to subject a polyamide to reduced pressure, e. g., an absolute pressure equivalent to 50 to 300 mm of mercury (67 to 400 millibar), before using it in making filaments and other shaped-objects. This is conveniently done by evacuating the reaction vessel in which the polyamide is prepared before allowing the polymer to solidify.

In general, no added catalysts are necessarily required in the above described processes of polyamide formation. However, certain phosphorus containing materials, e.g. metal phosphonates, and phosphates, are known to exert a certain degree of catalytic function. The use of added catalysts sometimes confers additional advantages for making high molecular weight materials.

The commercial preparation of most linear condensation polymers, polyamides, typically involves heating monomeric starting materials to cause progressive condensation of the polymers. This process is usually carried out in several stages, with the intermediate formation of low-molecular weight, low viscosity polymeric liquid by the removal of volatiles. The low-molecular weight, low-viscosity polymeric liquid is processed at various vacuum and residence times and temperatures to allow the polymer to reach the desired final molecular weight and viscosity. While a desired final molecular weight and viscosity can be achieved generally, obtaining accurate process parameters, and therefore consistent uniformity of the polymeric material during casting can be problematic. Thus, it would be an advancement in the art to discover and utilize various techniques for manufacturing polymeric materials using highly accurate process parameters.

SUMMARY

The present disclosure relates to methods and devices for producing polyamide pellets. In one embodiment, a method of estimating casting throughput of an extruded polyamide polymer can comprise measuring an amount of casting water flowing in to a casting apparatus (typically from two locations or more, e.g., the water slide and the cutter), measuring the temperature of the casting water flowing in, and measuring the temperature of the casting water flowing out.

Additional steps can include calculating a heat transfer between the casting water flowing in and the casting water flowing out, and correlating the heat transfer to the casting throughput.

In another embodiment, a method of producing pellets of a polyamide polymer can comprise cutting a strand of an extruded polyamide polymer at a cutting speed substantially proportional to throughput of the polyamide polymer. An additional step can include adjusting a first process parameter selected from the group consisting of cutting speed, extrusion valve opening, and vessel pressure in response to a change in an alternative second process parameter selected from the group consisting of cutting speed, extrusion valve opening, and vessel pressure to maintain a uniformity of the polyamide pellets. In this example, the throughput is calculated by the techniques described herein related to casting throughput.

In still another example, an apparatus for manufacturing polyamide pellets can comprise and autoclave vessel, a cutter, and a process controller. The autoclave vessel can include a pressure controller (e.g., provided by inlets, heating components, and/or vent valves, for example) and an extrusion valve. The cutter can be adapted to cut polyamide polymer extruded from the autoclave vessel to form polyamide pellets. The process controller can include a pressure control module for controlling the pressure controller, a cutting speed module for controlling cutter speed, an extrusion valve module for controlling the extrusion valve, and a throughput module for calculating the casting throughput. BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 A is a schematic cross-sectional view of an autoclave vessel that is usable in accordance with examples of the present disclosure;

FIG. 1 B is a schematic cross-sectional view of another autoclave vessel that is usable in accordance with examples of the present disclosure;

FIG. 2 is a diagram of a system in which the apparatus of the present disclosure is usable in accordance with examples of the present disclosure;

FIG. 3 is a sample casting plot of a polyamide in accordance with one embodiment of the present disclosure; and

FIG. 4 is a plot of time against batch weight polyamide in accordance with one embodiment of the present disclosure.

It should be noted that the figures are merely exemplary of embodiments of the present invention and no limitations on the scope of the present disclosure are intended thereby.

DETAILED DESCRIPTION

Although the following detailed description contains many specifics for the purpose of illustration, a person of ordinary skill in the art will appreciate that many variations and alterations to the following details are within the scope of the herein disclosed embodiments.

Accordingly, the following embodiments are set forth without any loss of generality to, and without imposing limitations upon any claimed invention. Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular embodiments described, as this may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

As used in this specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a polyamide" includes a plurality of polyamides.

In this disclosure, "comprises," "comprising," "containing" and "having" and the like can have the meaning ascribed to them in U.S. Patent law and can mean "includes," "including," and the like, and are generally interpreted to be open ended terms. The term "consisting of" is a closed term, and includes only the devices, methods, compositions, components, structures, steps, or the like specifically listed, and that which is in accordance with U.S. Patent law.

"Consisting essentially of or "consists essentially" or the like, when applied to devices, methods, compositions, components, structures, steps, or the like encompassed by the present disclosure, refers to elements like those disclosed herein, but which may contain additional structural groups, composition components, method steps, etc. Such additional devices, methods, compositions, components, structures, steps, or the like, etc., however, do not materially affect the basic and novel characteristic(s) of the devices, compositions, methods, etc., compared to those of the corresponding devices, compositions, methods, etc., disclosed herein. In further detail, "consisting essentially of or "consists essentially" or the like, when applied to devices, methods, compositions, components, structures, steps, or the like encompassed by the present disclosure have the meaning ascribed in U.S. Patent law and the term is open- ended, allowing for the presence of more than that which is recited so long as basic or novel characteristics of that which is recited is not changed by the presence of more than that which is recited, but excludes prior art embodiments. When using an open ended term, like "comprising" or "including," it is understood that direct support should be afforded also to "consisting essentially of language as well as "consisting of language as if stated explicitly.

The term "polymerizable composition" or "polymerizable solution" refers to the solution that is added to the agitated autoclave in accordance with examples of the present disclosure, that upon processing within the autoclave under certain heat and pressure profiles, a polyamide polymer is formed that can be extruded or otherwise harvested for further use.

The term "polyamide salt" refers to the salt that is included in the polymerizable composition (along with other additives) that provides the basic polymerizable material for forming the polyamide polymer. If the polyamide polymer is nylon 6,6, for example, then the salt can be prepared from adipic acid and hexamethylenediamine. Other additives can also be present in the polyamide solution, either introduced prior the reactor vessel, or introduced in the reactor vessel. Titanium dioxide, for example, is typically introduced directly into the vessel, whereas other additives, such as catalysts, optical brighteners, anti- foaming additives, etc. are introduced prior to introducing the polymerizable composition into the vessel, though this sequence or even the presence of these additives is not required.

The term "cycle" refers to the stages of a batch polymerization process as defined primarily by the pressure profile within the vessel. A first cycle (Cycle 1 ) occurs at the beginning of the batch process while the pressure is being increased from a relative low press to a relative high pressure. A second cycle (Cycle 2) occurs as the relative high pressure is maintained for a period of time. A third cycle (Cycle 3) occurs as the relative high pressure is reduced back to a relative low pressure. A fourth cycle (Cycle 4) occurs as the relative low pressure is maintained for a period of time. A fifth cycle (Cycle 5) occurs as the prepared polymer is being extruded from the vessel. The present disclosure uses the terms "fourth cycle", "Cycle 4" and "pre-casting cycle" interchangeably.

Phrases such as "suitable to provide," "sufficient to cause," or "sufficient to yield," or the like, in the context of methods of synthesis, refers to reaction conditions related to time, temperature, solvent, reactant concentrations, and the like, that are within ordinary skill for an experimenter to vary to provide a useful quantity or yield of a reaction product. It is not necessary that the desired reaction product be the only reaction product or that the starting materials be entirely consumed, provided the desired reaction product can be isolated or otherwise further used. It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range includes "about 'x' to about 'y'". To illustrate, a concentration range of "about 0.1 % to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also include individual concentrations (e.g., 1 %, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1 %, 2.2%, 3.3%, and 4.4%) within the indicated range. In an

embodiment, the term "about" can include traditional rounding according to significant figures of the numerical value. In addition, the phrase "about 'x' to 'y " includes "about 'x' to about 'y'".

The term "about" as used herein, when referring to a numerical value or range, allows for a degree of variability in the value or range, for example, within 10%, or, in one aspect within 5%, of a stated value or of a stated limit of a range.

In addition, where features or aspects of the disclosure are described in terms of a list or a Markush group, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group. For example, if X is described as selected from the group consisting of bromine, chlorine, and iodine, claims for X being bromine and claims for X being bromine and chlorine are fully described as if listed individually. For example, where features or aspects of the disclosure are described in terms of such lists, those skilled in the art will recognize that the disclosure is also thereby described in terms of any combination of individual members or subgroups of members of list or Markush group. Thus, if X is described as selected from the group consisting of bromine, chlorine, and iodine, and Y is described as selected from the group consisting of methyl, ethyl, and propyl, claims for X being bromine and Y being methyl are fully described and supported.

As used herein, all percent compositions are given as weight-percentages, unless otherwise stated. When solutions of components are referred to, percentages refer to weight-percentages of the composition including solvent (e.g., water) unless otherwise indicated.

As used herein, all molecular weights (Mw) of polymers are weight- average molecular weights, unless otherwise specified.

All publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the present disclosure is not entitled to antedate such publication by virtue of prior disclosure. Further, the dates of publication provided could be different from the actual publication dates that may need to be independently confirmed.

As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features that may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.

Generally, a method of estimating casting throughput of an extruded polyamide polymer can comprise measuring an amount of casting water flowing in to a casting apparatus typically from two or more locations, measuring the temperature of the casting water flowing in, measuring the temperature of the casting water flowing out, calculating a heat transfer between the casting water flowing in and the casting water flowing out, and correlating the heat transfer to the casting throughput.

Additionally, a method of producing pellets of a polyamide polymer can comprise cutting a strand of an extruded polyamide polymer at a cutting speed substantially proportional to throughput of the polyamide polymer, and adjusting a first process parameter. The first process parameter can be selected from the group consisting of cutting speed, extrusion valve opening, and vessel pressure and can be adjusted in response to a change in an alternative second process parameter selected from the group consisting of cutting speed, extrusion valve opening, and vessel pressure to maintain a uniformity of the polyamide pellets, where the throughput is calculated as the casting throughput as described herein.

Further, an apparatus for manufacturing polyamide pellets can comprise and autoclave vessel, a cutter, and a process controller. The autoclave vessel can include a pressure controller (e.g., inlets, heating components, vent valves, for example) and an extrusion valve. The cutter can be adapted to cut polyamide polymer extruded from the autoclave vessel to form polyamide pellets. The process controller can include a pressure control module for controlling the pressure controller, a cutting speed module for controlling cutter speed, an extrusion valve module for controlling the extrusion valve, and a throughput module for calculating the casting throughput.

It is noted that when discussing the present apparatuses and methods, each of these discussions can be considered applicable to each of these examples, whether or not they are explicitly discussed in the context of that example. Thus, for example, in discussing a polyamide polymer with respect to the apparatus, that discussion is also applicable to the methods, and vice versa.

Returning now to the apparatuses and methods of the present disclosure generally, the present manufacturing processes, casting processes, apparatuses, etc., can be used with polymer systems comprising polyamides. In one

embodiment, the polyamide polymer can comprise, consist essentially of, or consist of nylon 6,6. The nylon 6,6 can be neat polymer, or can be modified by any of a number of additives, including optical brighteners, dyes, etc. Generally, the manufacturing processes referred to herein can include continuous and batch processes unless otherwise specified. Such processes are generally performed in reactor vessels, e.g., an autoclave. In one embodiment, the manufacturing process can be a batch process. Without specific limitation, such a batch process is typically a 5 cycle process, as described herein.

With reference to nylon 6,6 in particular, a typical batch size in accordance with examples of the present disclosure can be from about 1000 Kg to about 2600 Kg, or from 1000 Kg to 1500 Kg, or from 1300 to 2600 Kg, in various examples, and can be cycled during the batch within the autoclave at from about 90 to 150 minutes, or from 100 to 120 minutes. Batch sizes and timing outside of these ranges can also be used, depending on equipment and polymer choices, or other considerations within the knowledge of one skilled in the relevant arts. Generally, the nylon of the polyamide can be added as a salt. In one

embodiment, the nylon can be a nylon 6,6 salt and can be present in the polyamide in an amount ranging from about 50 wt% to 95 wt%.

Various processing parameters can be used in the polymerization of the present polyamides including temperature and pressure. In one embodiment, the temperature can range from about 190°C to about 290°C and the autogenous or other pressure during certain cycles can range from about 250 pounds per square inch absolute (psia) to about 300 pounds per square inch absolute (psia). Additionally, in another embodiment, during certain cycles, heating can be performed under vacuum at a pressure of less than 10 torr.

Generally, the present process for producing polyamide pellets may be made by an autoclave and extrusion/casting process. In one embodiment, the process may start with a concentrated slurry or polyamide solution prepared from an aqueous solution of a polyamide salt, e.g. a nylon 6,6 salt, that is provided to an autoclave vessel. Optionally, the slurry may be dilute and become more concentrated by means of an evaporation step. In one embodiment, the slurry may be prepared from an aqueous solution of the monomers hexamethylene diamine and adipic acid, in the manner known in the art. In another specific embodiment, the slurry may contain a minor amount of nylon 6 monomer with the aqueous solution of the nylon 6,6 monomers in the form of an aqueous caprolactam solution. The autoclave vessel may then be heated to about 230°C (or some other functional temperature) allowing the internal autogenous pressure to rise, in one example. A delusterant, titanium dioxide (Ti0₂) may optionally be injected into the autoclave and monomer mixture as an aqueous dispersion.

The polyamide solution or thickening slurry mixture may then be heated in the autoclave to about 245 C (or some other functional temperature). While at this temperature, the autoclave pressure may be reduced to atmospheric pressure and further reduced in pressure by application of a vacuum in the known manner, to form the polyamide composition. The autoclave, containing the polyamide composition, would be maintained at this temperature and/or pressure for about 30 minutes. This step may be followed by further heating of the polyamide polymer composition in the autoclave to about 285°C, for example, and introducing dry nitrogen to the autoclave vessel and pressurizing the autoclave by introducing dry nitrogen to about 4 to about 5 Bar absolute pressure.

After polymerization, the polyamide polymer can be extruded by a casting process to produce polyamide pellets. In general, the casting throughput is a parameter for such a casing process, and can used to adjust other casting process parameters in the production of the polyamide pellets. As discussed herein, the present disclosure provides a method of estimating the casting throughput in real time. This estimate of the casting throughput can be used to adjust other pelletizing process parameters to provide pellet uniformity that was previously difficult to achieve for the polyamide autoclave casting process.

Generally, the instantaneous casting throughput is calculated using a heat transfer model that uses measured temperatures and flow rates of the casting water. In the examples herein, various heat transfer models are shown and described, but it is understood that in each form (Formulas l-ll l, for example), the same balancing can be used. Constants can be adjusted with positive or negative values. With that understanding, in one embodiment, the casting throughput (TP) can be calculated using heat transfer model as shown in Formula I: TP = TP Model + TP Bias (I) wherein TP Bias is vessel dependent and TP Model is calculated from Formula II:

TP Model = (Temp In - Temp Out - a - (b*Flow 1 ) - (c*Flow 2)) / d (II) wherein:

Temp In = measured temperature of the incoming casting water;

Temp Out = measured temperature of the outgoing casting water;

Flowl = the measured flow rate of the casting water entering a first location (e.g., the water-slide); and

Flow 2 = the measured temperature of the water entering a second location (e.g., the cutter), and wherein a, b, c, and d are independently constants which are bank dependent. Temp In generally corresponds to the temperature of the water flowing into the casting process before contacting the extruded polymer. The Temp Out generally corresponds to the temperature of the water leaving the casting operation after contacting the extruded polymer. As such, these casting water temperatures can be used to calculate the heat transfer of the extruded polymer to the casting water. Generally, a, b, c, and d can be experimentally derived for a specific casting apparatus. The temperature of the casting water flowing in can be controlled within a range within 5 °C, 2 °C, 1 °C, or 0.5 °C. The temperature of the casting water flowing out is raised as a result of contact with the extruded polymer. The TP Model uses this temperature difference to calculate throughput, as described herein. Such a TP Model can allow for precise and consistent estimates of the casting throughput.

In an alternative but related example, the casting throughput can be calculated during peptizing, using a similar energy balance model. The model described herein can use two measured water flows, two temperatures (incoming water temperature and the water temperature downstream the drier), and a series of constants. In this example, the casting throughput (TP) model is shown in Formula III: TP = (P1 - P2 - C4*P3 - C2*P4)/C3 + P5 (II I) wherein:

P1 = Measured temperature casting water downstream the drier;

P2 = Measured temperature casting water incoming;

P3 = Measured casting water Flow 1 ;

P4 = Measured casting water flow 2;

P5 = constant; and

C1 -C4 = Coefficients for water flows and/or other processes.

To provide one example for one specific system, the constants/coefficients might be P5 = -0.76213, C1 = -0.6105, C2 = -0.88531 , C3 = 3.63958, and C4 = 27.7428. These are given by way of example for a specific piece of equipment, and should in no way be considered limiting. One skilled in the art will be able to derive these for a specific situation or equipment. In another example, in order to get the exact relations between throughput and the process variables, experiments can be conducted where a set of process settings for Flowl , Flow2, and throughput are determined and then the measured the temperature difference between incoming and outgoing cooling water for all these predefined settings are also determined. This gave a model with the Tp as X and the temperature increase as Y, leading to the relation (T_out - T_n) = C4 + C3*Throughput + C1 *Flow1 * C2*Flow2. Since the throughput in this relation is one of the X variables, the formula can be reshuffled to get the throughput as Y. Thus, in another example, TP = -7.6225 + 0.27476 * (T_out-Ti_n) + 0.1677 * Flowl + 0.24325 * Flow2. It is noted that this is an alternative version of Formula I.

In further detail regarding Formula I, TP Bias can be calculated as would be appreciated by one skilled in the art. However, in one example, tuning of the throughput model can be carried out done by adjusting a bias which is calculated from the difference between Raw Materials batch weight and the integrated throughput batch weight using the following calculation, for example:

Bias TPModei New = Bias TPModei old* 0.8 +(Batch Weight 1 -Batch Weight 2) * 0.2

Casting Time (IV)

The polyamide polymers described herein can be prepared as well using a catalyst. In one embodiment, the catalyst can be present in the polyamide in an amount ranging from 10 ppm to 1 ,000 ppm by weight. In another aspect, the catalyst can be present in an amount ranging from 10 ppm to 100 ppm by weight. The catalyst can include, without limitation, phosphoric acid, phosphorous acid, hypophosphoric acid arylphosphonic acids, arylphosphinic acids, salts thereof, and mixtures thereof. In one embodiment, the catalyst can be sodium

hypophosphite, manganese hypophosphite sodium phenylphosphinate, sodium phenylphosphonate, potassium phenylphosphinate, potassium

phenylphosphonate, hexamethylenediammonium bis-phenylphosphinate, potassium tolylphosphinate, or mixtures thereof. In one aspect, the catalyst can be sodium hypophosphite. The polyamides and polyamide compositions in accordance with embodiments disclosed herein can be improved in whiteness appearance through the addition of an optical brightener. Such polyamides can exhibit a permanent whiteness improvement and can retain this whiteness improvement through operations such as heat setting. In one embodiment, the optical brightener can be present in the polyamide in an amount ranging from 0.01 wt% to 1 wt%. In one aspect, the optical brightener can be titanium dioxide.

In addition, these polyamide polymers can be prepared with antioxidant stabilizers, antimicrobial additives, etc. Additionally, the polyamide polymers may be prepared using anti-foaming additives. In one embodiment, the anti-foaming additive can be present in the polyamide in an amount ranging from 1 ppm to 500 ppm by weight.

The polyamide polymers in accordance with embodiments disclosed herein are inherently acid dyeable, but may also be rendered into a basic dyeing form by modifying these polymers or copolymers with a cationic dye

copolymerized in the polymer. This modification makes compositions particularly receptive to coloration with base dyes.

Turning now to FIGS. 1 A and 1 B, schematic cross-sectional views of two exemplary agitated autoclaves are shown. These FIGS, are not necessarily drawn to scale, and do not show each and every detail that is typically present in an agitated autoclave, opting instead to show schematic representations of features particularly relevant to the present disclosure. Thus, an agitated autoclave 10 can include an autoclave vessel 20 and an agitator or auger 22 in this example. Although shown, the agitator or auger is not required. The vessel includes a vessel wall 24, which is typically a cladded vessel wall, and the vessel wall and/or other structures are adapted to support one or more type of heating components 26a, 26b. In this example, external jacket heating components are shown at 26a and internal heating components are shown at 26b. It is noted that the heating component in FIG. 1 A is positioned relatively close to the agitator, which can be typical, whereas the heating component FIG 1 .B is positioned closer to the vessel wall, which may be more typical of non-agitated autoclaves. However, this being stated, positioning of the heating elements can be carried out by one skilled in the art after considering the present disclosure. In still further examples, there may be heating elements in both locations, i.e. near the vessel wall and near the agitator.

The external jacket heating components 26a can be used to raise the temperature of the polymerizable composition or polymer contained within the vessel, and the internal heating components 26b in particular can be used to prevent polymer from becoming adhered to an interior surface of the vessel wall and/or to the agitator. As shown in FIG. 1 A, in addition to the internal heating component shown, there is also a pair of refresher bars 1 8 that work with the central agitator or auger 22 to refresh the polymer. The agitator works to move the polymer upward along a center portion, and the pair of refresher bars are used to refresh the molten polymer by removing the polymer from the side wall surfaces as the molten polymer is churned. This arrangement can improve the heat transfer within the system, and can reduce the height of the vortex caused by the agitation. In either case, it is noted that the interior heating components are shown schematically in cross-section, but it is understood that any shape or configuration of interior heating components could be used. It is also noted that the heating components can be configured or adapted to carry any fluid known in the art for providing heat to autoclaves, including gases and/or liquids. An inlet valve 28 and an autoclave vent 30 are also shown and can be used to together or alone as the pressure controller (along with the heating components 26a, 26b, which also control pressure). A pressurizing device or pressure source is not shown, but is understood to be present when pressure is to be added externally. Alternatively, pressure can be increased by the addition of heat and reduced by venting, as is understood in the art. Furthermore, at the bottom end of the autoclave vessel is a valve opening 32. The extrusion valve is not shown in this FIG., but this is the location where polymer prepared in the autoclave is extruded for further processing. It is noted that irrespective of the description and shown location of these inlets, valves, vents, etc., these or other ports can be used differently than shown for any purpose designed by the user, as would be appreciated by one skilled in the art. It is also noted that this exemplary autoclave vessel and methods of forming the polyamide polymer within the autoclave are provided for exemplary purposes only, as any of a number of other process procedures, autoclaves, and additives may be used to generate the polyamide polymer. That being described generally, it is at this point in the process, regardless of how the polymer was prepared in the autoclave vessel that is the primary subject of the present disclosure, i.e. casting of the polymer from the polymerization vessel and estimating casting throughput.

As discussed herein, the present disclosure provides apparatuses and methods for forming pellets of polyamide polymers by cutting an extruded polyamide polymer and adjusting various processing parameters. Particularly, the present method of producing polyamide pellets allows for the adjusting of a first process parameter including cutting speed, extrusion valve opening, and vessel pressure in response to a change of one of the other aforementioned process parameters. Additionally, in one aspect, two of the process parameters can be adjusted in response to the third process parameter. Although any process parameter or dual process parameters can be adjusted, in one embodiment, the adjusted process parameter can be or include vessel pressure. In another aspect, the adjusted process parameter can be or include extrusion valve opening. In another aspect, the adjusted parameter can be or include cutting speed. Such process parameters can be adjusted to maintain a uniformity of the polyamide pellets based on a casting throughput, where the casting throughput can be estimated according to the present disclosure.

Turning now to FIG. 2, an apparatus for manufacturing polyamide pellets can comprise a vessel 20, such as an autoclave similar to that shown in FIG. 1 , including a pressure controller (which can be in the form of an inlet line/valve 28, vent line/valve 30, and/or heating component(s) 26). It is noted that the heating component is shown as an external jacket, but could alternatively or additionally be an internal heating component. Also shown is an extrusion valve 34 for extruding polymer through a die plate or other extrusion configuration. The apparatus can also include a cutter 36 adapted to have a cutting speed suitable for cutting polyamide pellets. The cutter can be a circular cutter adapted to cut very quickly as the extruded polymer is passed thereby, for example. The apparatus can also include a process controller 60, which can include a pressure control module 70, a cutting speed module 80, and an extrusion valve module 90. The apparatus can also include trays 38, slurry collection devices 40, a slurry pipe 42, and a drier/spinner 44. In further detail regarding the process controller 60 of the apparatus, the various modules 70, 80, 90, 100 can be used to automatically carry out the general functions or process steps of the automated apparatus. For example, the pressure valve 28, autoclave vent 30, and a heating component 26 can be controlled by a pressure control module 70 allowing for adjustment of pressure. The cutter 36 can be controlled by the cutting speed module 80. The extrusion valve 34 can be controlled by the extrusion valve module 90. The estimated casting throughput can be calculated using a throughput module 100. Other modules (not shown) can be present including without limitation an agitation module, a drier module, a heating component module, etc. The modules can work together to provide an automated system in a manner to cause uniform polyamide pellets.

FIG. 3 is sets forth a plot that illustrates an example where such modules work together to achieve exceptional uniformity in accordance with examples of the present disclosure. Specifically, FIG. 3 depicts a casting plot of processing parameters of an apparatus in accordance with an embodiment of the present disclosure. Specifically, the plot provides autoclave pressure through a single batch casting process, throughput of the polyamide polymer from the autoclave, a linearized extrusion valve plot, and cutting speed as a function of time during casting. As shown, the various process parameters are adjusted to provide substantially constant throughput at a high cutting speed thereby providing an automated process that can maintain uniformity of the pellets while also maintaining high production rates.

It is also noted in the graph of FIG. 3 that the cutting speed is modified and is substantially proportional to the throughput, i.e. when the throughput moves upward or downward (as shown graphically), the cutting speed likewise moves upward and downward, respectively. The term "substantially" as it relates to the proportionality or relative matching of the throughput to the cutting speed can be defined as any degree of matching where the uniformity of a batch of pellets have an average mass with at least 95% of the individual pellets having an individual mass within 10% of the average mass. It is by substantially matching the relative movements of the cutting speed to the throughput, the uniformity can be maintained. As a result, it is the use of the pressure controller and the extrusion valve that keeps the throughput within a reasonable range for achieving an efficient cutting profile. For example, in an efficient system with high throughput provided by an appropriate pressure and linearized valve opening, cutting speed can be relatively matched with respect to the throughput. Note that when the throughput increases, so does the cutting speed.

Returning now to FIG. 2, as discussed herein, the vessel 20 pressure can be autogenous or can be generated from an outside pressure source.

Additionally, the pressure can be adjusted using a pressure source (not shown) and the pressure valve 28 and/or the vent 30. The extrusion valve 34 generally controls the opening from which the polyamide polymer is extruded. In some aspects, the extrusion valve opening can be referred to as a linearized opening of the extrusion valve. As used herein, "linearized" refers to a mathematical manipulation that equates the opening of the valve, i.e., unblocked area, to the percent of the material that is extruded through the opening. As such, a

"linearized" opening of 50% refers to 50% material extruding from the opening from a total amount of 100% (100% referring to the maximum capacity when the valve is completely open), even though the valve opening (i.e., unblocked area) may not be 50% of the total available opening. It is noted that there is much more control of throughput of the polyamide polymer when the valve is not set near 100% open. As the valve approaches 70% or 80% opening, the control throughput is significantly reduced. For example, modifying the opening of the valve from 40% to 50% has a relatively significant effect on throughput, whereas opening a valve from 80% to 90% has minimal effect on throughput. As a result, it can be desirable to keep the valve, to the extent possible within a range of about 30% to 70% open, and more typically from 35% to 60% open during the polymer casting process. To accomplish this, pressure and/or cutting speed may be changed to keep the valve opening within a desirable range. That being described, this is not strictly required. This merely provides a mechanism to retain maximum flexibility with respect to the extrusion valve opening.

Returning to the various adjustments to process parameters that can be carried out in response to changes in other process parameters, it is noted that adjustments to the process parameters can be performed sequentially or simultaneously (or in an overlapping time sequence). In one embodiment, more than one process parameter can be adjusted in response to a third process parameter change. To provide an example of why such process parameters may benefit from modification, it is noted that once the extrusion process is begun from an autoclave vessel, often, the polyamide polymer contained therein has not completely finished with its polymerization process. Thus, the polyamide polymer may continue to thicken further during the extrusion process. It has been discovered that throughput, and more significantly, pellet uniformity cannot simply be maintained under these conditions by increasing pressure alone. Likewise, merely opening the extrusion valve 34 up further will not always adequately compensate for the thickening polymer. Further, even by controlling both of these parameters together, if the cutting speed is not modulated based on throughput changes, uniformity of polyamide pellets may suffer.

Thus, the present apparatuses and methods include controlling

throughput, and thus, pellet uniformity using varying pressure, varying valve opening, and varying cutting speed to achieve uniform pellets in an efficient manner. Thus, in one specific example, exemplary throughputs can range from 2 to 10 tons per hour, or from 5 to 9 tons per hour, or more particularly, from 6 to 8 tons per hour. Exemplary pressures during extrusion can range from 0 to 12 Bar, from 1 to 10 Bar, or from 5 to 10 Bar. Exemplary valve opening levels can range from 30% to 70%, or from 45% to 65%. Exemplary cutting speeds using a helical cutter or other similar rotational cutter can range from 100 to 2000 RPM, from 400 to 1800 RPM, or from 600 to 1500 RPM. Typically, these process

parameters are kept within these ranges during the casting process, and by adjusting the parameters within these ranges, uniformity of polyamide pellets can be achieved. That being stated, process parameters outside of these ranges can also be used, provided the pellet uniformity can be maintained as described herein.

The throughput can be controlled, at least in part, by the extrusion valve 34 opening, the cutting speed can be controlled by the cutter 36, and the pressure can be controlled by one or more pressure controller 26, 28, 30. While more than one process parameter can be adjusted to provide the polyamide pellets, in one specific embodiment, the pressure and/or cutting speed can allow for the extrusion valve to operate with a linearized opening at from 30% to 70%, from 35% to 65%, or from 40% to 60%. Additionally, to provide desirable efficiency, in one embodiment, the throughput can be at least 5 ton/hour, or at least 7 ton/hour in large systems, and the adjusting of the process parameters can maintain the target throughput varying no more than 10% by weight.

The process controller 60 is generally networked to the cutter 36 and the vessel via a computer, other computing device, or other networked device. The present apparatus can be automated using various modules. In one embodiment, the pressure control module 70 can modulate the pressure controller 26, 28, and/or 30 in response to a change in the cutting speed or an opening of the extrusion valve 34. In one aspect, the pressure control module can modulate the pressure controller in response to changes in the cutting speed and an opening of the extrusion valve. In another embodiment, the cutting speed module 80 can modulate the cutting speed of the cutter 36 in response to a change in pressure or an opening of the extrusion valve. In one aspect, the cutting speed module can modulate the cutting speed in response to changes in pressure and an opening of the extrusion valve. In still another embodiment, the extrusion valve module 90 can modulate the extrusion valve 34 in response to a change in the cutting speed or pressure. In one aspect, the extrusion valve module can modulate the extrusion valve in response to changes in the cutting speed and pressure. In yet another embodiment, the throughput module 100 can calculate the casting throughput based on flow rates and temperature of the casting water. As such, the present modules can work in concert via the process controller to adjust the processing parameters during casting in a manner sufficient to provide polyamide pellets, and specifically consistent and uniform polyamide pellets.

As a further note, some of the functional units described in this

specification have been labeled as "modules," in order to more particularly emphasize their implementation independence. For example, a "module" may be implemented as a hardware circuit comprising custom VLSI circuits or gate arrays, off-the-shelf semiconductors such as logic chips, transistors, or other discrete components. A module may also be implemented in programmable hardware devices such as field programmable gate arrays, programmable array logic, programmable logic devices or the like. Modules may also be implemented in software for execution by various types of processors. An identified module of executable code may, for instance, comprise one or more blocks of computer instructions, which may be organized as an object, procedure, or function.

Nevertheless, the executables of an identified module need not be physically located together, but may comprise disparate instructions stored in different locations which comprise the module and achieve the stated purpose for the module when joined logically together.

Indeed, a module of executable code may be a single instruction, or many instructions, and may even be distributed over several different code segments, among different programs, and across several memory devices. Similarly, operational data may be identified and illustrated herein within modules, and may be embodied in any suitable form and organized within any suitable type of data structure. The operational data may be collected as a single data set, or may be distributed over different locations including over different storage devices. The modules may be passive or active, including agents operable to perform desired functions.

EXAMPLES

Example 1 - Tuning of Throughput Model

Tuning of the throughput model is done using the following variables:

Batch Weight 1 = The calculated expected batch weight from all added raw materials for that batch.

= The integrated throughput, calculated as follows:

Tuning of the throughput model is done by adjusting a bias which is calculated from the difference between Raw Materials batch weight and the integrated throughput batch weight using the following calculation:

Bias TPModei New = Bias TPModei old * 0.8 + (Batch Weight 1 - Batch Weight 2) * 0.2

Casting Time Example 2 - Time vs. Batch Weight

FIG. 4 shows the trend of time against batch weights from the integrated throughput for one specific clave for a series of batches of a specific polymer- type. Each vertical dotted line represents the start of a new run for that polymer- type. Notably, for this autoclave-polymer type combination, each new run often starts with a "too high" throughput batch weight which triggers the DCS to update the TP-bias to correct the error. This error in throughput batch weight may be caused by polymer specifics. Although the subject matter has been described in language specific to structural features and/or operations, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features and operations described above. Rather, the specific features and acts described above are disclosed as example forms of implementing the claims. Numerous modifications and alternative arrangements can be devised without departing from the spirit and scope of the described technology.

Claims

CLAIMS What Is Claimed Is:

1 . A method of estimating casting throughput of an extruded polyamide polymer, comprising:

measuring an amount of casting water flowing in to a casting apparatus at two or more locations;

measuring the temperature of the casting water flowing in;

measuring the temperature of the casting water flowing out;

calculating a heat transfer between the casting water flowing in and the casting water flowing out based on amount of casting water flowing in, temperature of the casting water flowing in, and temperature of the casting water flowing out; and

correlating the heat transfer to the casting throughput.

2. The method of claim 1 , wherein the step of correlating the heat transfer and the casting throughput includes correcting for autoclave vessel bias in accordance with the following formula:

TP = TP Model + TP Bias where TP is casting throughput, TP Model is calculated at least in part from measured temperatures and flow amounts, and TP Bias is vessel dependent.

3. The method of claim 2, the TP Model is calculated using the following formula:

TP Model = (Temp In - Temp Out - a - (b*Flow 1 ) - (c*Flow 2)) / d where Temp In is the temperature of the casting water flowing in to the casting apparatus, Temp Out is the temperature of the casting water flowing out of the casting apparatus, Flow 1 is the casting water flowing into a waterslide, Flow 2 is the casting water flowing into a cutter, and a, b, c, and d are constant and/or bank dependent, wherein a, b, c, and d are experimentally derived for specific casting apparatus.

4. The method of claim 1 , wherein the step of correlating the heat transfer and the casting throughput includes correlating from the following formula:

TP = (P1 - P2 - C4*P3 - C2*P4)/C3 + P5 where P1 is a measured temperature casting water downstream the drier; P2 is a measured temperature casting water incoming; P3 is a measured casting water Flow 1 ; P4 is a measured casting water flow 2; P5 is a constant; and C1 -C4 are independently constant and/or bank dependent as derived for specific casting apparatus.

5. The method of claim 1 , wherein the temperature of the casting water flowing in is controlled within 5 °C.

6. The method of claim 1 , wherein all of the measuring steps are performed continuously.

7. The method of claim 1 , wherein at least one of the measuring steps is performed at least once a second.

8. The method of claim 1 , wherein the vessel is an autoclave.

9. The method of claim 1 , wherein the extruded polyamide is nylon

6,6.

10. A method of producing pellets of a polyamide polymer, comprising: cutting a strand of an extruded polyamide polymer at a cutting speed substantially proportional to throughput of the polyamide polymer; and adjusting a first process parameter selected from the group consisting of cutting speed, extrusion valve opening, and vessel pressure in response to a change in an alternative second process parameter selected from the group consisting of cutting speed, extrusion valve opening, and vessel pressure to maintain a uniformity of the polyamide pellets;

wherein the throughput is calculated as the casting throughput of claim 1 .

1 1 . The method of claim 10, wherein the method provides uniform polyamide pellets, the uniformity measured as a batch of pellets having an average mass with at least 95% of the individual pellets having an individual mass within 10% of the average mass.

12. The method of claim 1 1 , wherein the uniformity is measured as a batch of pellets having an average mass with at least 99% of the individual pellets having an individual mass within 5% of the average mass.

13. The method of claim 1 1 , wherein the uniformity is maintained as the relative viscosity of the polyamide polymer increases over time during a batch extrusion process.

14. The method of claim 10, wherein the throughput is controlled at least partially by the extrusion valve opening.

15. The method of claim 10, wherein the adjusting is in response to a third process parameter.

16. The method of claim 10, further comprising adjusting a third process parameter in response to the change in the second process parameter.

17. The method of claim 16, wherein the adjusting of the first process parameter and the third process parameter are performed simultaneously or in overlapping time frames.

18. The method of claim 10, wherein the vessel is pressurized such that the extrusion valve operates with a linearized opening from 30% to 70%.

19. The method of claim 18, wherein the linearized opening is from 5 45% to 65%.

20. The method of claim 10, wherein the throughput is at a rate of at least 5 ton/hr and the adjusting of the extrusion valve opening or the vessel pressure maintain the throughput varying no more than 10% by average mass. o

21 . The method of claim 10, wherein the throughput is at a rate of from 2 ton/hr to 10 ton/hr.

22. The method of claim 10, wherein the first process parameter is5 vessel pressure which is adjusted in response to a change in one or both of

cutting speed or extrusion valve opening.

23. The method of claim 22, wherein the vessel pressure is adjusted within the range of 0 to 12 Bar.

0

24. The method of claim 22, wherein the vessel pressure is adjusted within the range of 5 to 10 Bar.

25. The method of claim 10, wherein the first process parameter is5 extrusion valve opening which is adjusted in response to a change in one or both of vessel pressure or cutting speed.

26. The method of claim 25, wherein the extrusion valve opening is adjusted within a range of a linearized opening of from 45% to 65%.

0

27. The method of claim 10, wherein the first process parameter is cutting speed which is adjusted in response to a change in one or both of vessel pressure or extrusion valve opening. 5 28. The method of claim 27, wherein the cutting speed is adjusted

within a range of 100 to 2000 RPM using a rotational cutter.

29. The method of claim 10, wherein the polyamide polymer is nylon

6,6.

30. A casting apparatus for manufacturing polyamide pellets at a casting throughput, comprising:

a vessel, the vessel including:

a pressure controller, and

an extrusion valve;

a cutter having a cutting speed; and

a process controller; the process controller including:

a pressure control module for controlling the pressure controller, an extrusion valve module for controlling the extrusion valve, a cutting speed module for controlling the cutting speed, and a throughput module for determining the casting throughput, wherein the throughput module (i) calculates a heat transfer between casting water flowing in to the casting apparatus and casting water flowing out of the apparatus based on amount of casting water flowing in, temperature of the casting water flowing in, and temperature of the casting water flowing out, and (ii) correlates the heat transfer to the casting throughput.

31 . The casting apparatus of claim 30, wherein the throughput module correlates the heat transfer and the casting throughput, correcting for autoclave vessel bias, in accordance with the following formula:

32. The casting apparatus of claim 31 , the TP Model is calculated using the following formula: TP Model = (Temp In - Temp Out - a - (b*Flow 1 ) - (c*Flow 2)) / d where Temp In is the temperature of the casting water flowing in to the casting apparatus, Temp Out is the temperature of the casting water flowing out of the casting apparatus, Flow 1 is the casting water flowing into a waterslide, Flow 2 is the casting water flowing into a cutter, and a, b, c, and d are independently constant and/or bank dependent, wherein a, b, c, and d as derived for specific casting apparatus.

33. The casting apparatus of claim 30, wherein the throughput module correlates the heat transfer and the casting throughput in accordance with the following formula:

TP = (P1 - P2 - C4*P3 - C2*P4) / C3 + P5 where P1 is a measured temperature casting water downstream the drier; P2 is a measured temperature casting water incoming; P3 is a measured casting water Flow 1 ; P4 is a measured casting water flow 2; P5 is a constant; and C1 -C4 are independently constant and/or bank dependent as derived for specific casting apparatus.

34. The casting apparatus of claim 30, wherein the apparatus is configured to manufacture a batch of uniform pellets of nylon 6,6 by cutting a strand of an extruded nylon 6,6, wherein the uniformity is measured as the batch of pellets having an average mass with at least 99% of the individual pellets having an individual mass within 10% of the average mass.

35. The casting apparatus of claim 30, wherein the casting throughput is at least 5 ton/hr.

36. The casting apparatus of claim 30, wherein the extrusion valve module adjusts an opening of the extrusion valve to maintain the casting throughput.

37. The casting apparatus of claim 30, wherein the cutting speed module adjusts the cutting speed substantially proportional to the casting throughput.

38. The casting apparatus of claim 30, wherein the pressure control module adjusts the pressure such that a linearized opening of the extrusion valve is maintained within a range of a linearized opening of from 30% to 70%.

39. The casting apparatus of claim 30, wherein the process controller adjusts at least one process parameter selected from the group consisting of cutting speed, extrusion valve opening, vessel pressure, and combinations thereof, to maintain uniformity of the polyamide pellets, wherein the uniformity is measured as a batch of pellets having an average mass with at least 95% of the individual pellets having an individual mass within 10% of the average mass.

40. The casting apparatus of claim 30, wherein the vessel is a non- agitated autoclave.

41 . The casting apparatus of claim 30, wherein the vessel is an agitated autoclave.

42. The casting apparatus of claim 30, wherein the process controller is networked to the cutter and the vessel via a computer.

43. The casing apparatus of claim 30, wherein the pressure controller includes one or more of a vent valve, an inlet valve, or a heating component.