TW201501901A - Measuring molten polymer throughput using heat transfer balance - Google Patents

Abstract

The present disclosure provides methods and apparatuses estimating casting throughput during casting process to provide polyamide pellets. In one example, 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, 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 using the measured amount, and correlating the heat transfer to the casting throughput.

Description

Measuring the throughput of molten polymer by heat transfer equilibrium

The present invention is directed to a method of measuring or estimating the casting throughput of an extruded polyamine polymer on a casting apparatus for use in preparing a polyamide pellet.

A specific aliphatic polyamine having at least 85% of an aliphatic bond between repeating guanamine units describes nylon polyamine. It is known that such aliphatic polyamines can be derived from diamine-forming derivatives of dicarboxylic acids and dicarboxylic acids, such as anhydrides, guanamines, acid halides, half esters and diesters, and usually with primary or Secondary amine reaction. More specifically, it is known that an aliphatic polyamine polymer is formed from a monomer such as a dicarboxylic acid and a diamine by a primary or secondary diamine (a diamine having at least one hydrogen attached to each nitrogen) and two This is achieved by reacting a carboxylic acid or a carboxylic acid of a dicarboxylic acid to form a derivative. An exemplary reaction scheme is shown below: HOOC-R-COOH+H ₂ N-R'-NH ₂ -[NH-R'-NH-CO-R-CO]- _n -+nH ₂ O

Wherein R and R' represent a divalent hydrocarbon group, and n represents the number of repeating units and the number of water molecules.

The "structural unit" derived from the polymer of each of the diacid and the diamine is named for the number of carbon atoms in the respective groups R and R'. Therefore, the polyamine which is derived from hexamethylene-1,6-diamine and adipic acid is "nylon 6,6" (polyhexamethylene hexamethyleneamine).

Fibrous formation of polyamines can be carried out under condensation polymerization conditions, generally at 180 ° C to 300 ° C It is prepared by heating a diamine of substantially equal molecular weight and a decylamine of a dicarboxylic acid or a dicarboxylic acid to form a derivative. This product exhibits fiber forming properties in which a sufficiently high molecular weight can be achieved.

The properties of a given polyamine can vary over a wide range and can depend on the molecular weight. In part, the properties of polyamines are affected by the nature of the end groups, and the nature of the end groups depends on which reactant (diamine or diacid) is used in excess.

Two characteristics of fiber-forming polyamines relate to their high melting point and low solubility. Polyamines derived from simpler types of amines and acids are solids that are almost always opaque, melting or becoming transparent at fairly well defined temperatures. Below its melting point, the fiber forms polyamine which generally provides a sharp X-ray crystalline powder diffraction pattern when examined by X-rays, with clear evidence that it is in a massive crystalline structure. The density of such polyamines is generally between 1.0 and 1.2, and more specifically, the density of nylon 6,6 is now known to be 1.14 grams per cubic centimeter.

Common to other condensation polymerization products is that polyamines generally comprise individual units of closely similar structure. The average size of the individual units, that is, the average molecular weight of the polymer, is intentionally controlled within certain limits. As the polymerization proceeds further, the average molecular weight (and intrinsic viscosity) will be higher.

If the reactant is used at a precise equal molecular weight, the polymerization and heating are continued for a long period of time under conditions allowing the volatile product to escape, and a polyamine having a very high molecular weight can be obtained. However, if any of the reactants are used in excess, the polymerization proceeds to a certain point and then stops substantially. The point in time at which the polymerization is stopped may depend on the amount of diamine or dibasic acid (or derivative) used in excess.

A suitable method for preparing polyamines comprises forming a salt by mixing an approximate chemical equivalent of a diamine and a dicarboxylic acid in a liquid, which may be selected as a poor solvent for the resulting salt. If necessary, the salt isolated from the liquid can then be purified by crystallization from a suitable solvent. These diamine-dicarboxylates are crystalline and have a defined melting point. The salts are soluble in water and are preferably crystallized from certain alcohols and alcohol-water mixtures.

The preparation of fibers from diamine-dicarboxylates to form polyamines can be carried out in a number of ways. The salt can be heated to the reaction temperature (180 ° C to 300 ° C) in the absence of a solvent or diluent under conditions which permit removal of water formed in the reaction. It may be desirable to subject the polyamide to a reduced pressure, such as an absolute pressure equivalent to 50 to 300 mm mercury (67 to 400 mbar), followed by the use of the polyamide to make filaments and other shaped articles. This is preferably accomplished by evacuating the reaction vessel from which the polyamide is prepared, followed by solidification of the polymer.

In general, it is not necessary to add a catalyst in the polyamine formation process described above. However, certain phosphorus-containing materials, such as metal phosphonates and phosphates, are known to exert a certain degree of catalytic function. The use of the added catalyst sometimes gives other advantages regarding the preparation of high molecular weight materials.

Commercial preparation of the most linear condensation polymer polyamine involves heating the monomer starting material to gradually condense the polymer. This process is typically carried out in several stages in which a low molecular weight, low viscosity polymeric liquid is formed intermediate by the removal of volatiles. The low molecular weight, low viscosity polymeric liquid is treated at various vacuum levels and residence times and temperatures to achieve the desired final molecular weight and viscosity of the polymer.

Although the desired final molecular weight and viscosity are generally achieved, obtaining precise process parameters during casting and thus achieving uniform uniformity of the polymeric material can be problematic. Therefore, it is a great advancement in the art to discover and utilize various techniques for preparing polymeric materials using highly accurate process parameters.

This invention relates to methods and devices for making polyamide pellets. In one embodiment, the method of estimating the casting throughput of the extruded polyamine polymer can include measuring into the casting device (typically from two or more locations, such as water slides and cutters). The amount of water casted, the temperature of the incoming casting water, and the temperature of the molten water flowing out. Other steps may include calculating the heat transfer between the influent casting water and the flowing casting water, and correlating the heat transfer with the casting throughput.

In another embodiment, a method of making a polyamide polymer pellet can comprise cutting an extruded polyamine polymer at a cutting speed substantially proportional to the throughput of the polyamide polymer. Other steps may include adjusting a population selected from the group consisting of cutting speed, squeeze valve opening, and container pressure in response to a change in an alternative second process parameter selected from the group consisting of cutting speed, squeeze valve opening, and vessel pressure. The first process parameter is to maintain the uniformity of the polyamide pellets. In this example, the throughput is calculated by the techniques described herein with respect to casting throughput.

In another example, an apparatus for preparing polyamine pellets can include an autoclave vessel, a cutter, and a process controller. The autoclave vessel can include a pressure controller (eg, provided by an air inlet, a heating assembly, and/or an exhaust valve) and a squeeze valve. The cutter can be adapted to cut the polyamine polymer extruded from the autoclave vessel to form a polyamide pellet. The process controller may include a pressure control module for controlling the pressure controller, a cutting speed module for controlling the speed of the cutting machine, a squeeze valve module for controlling the squeeze valve, and a calculation of the casting throughput. Pass the module.

10‧‧‧Stirring autoclave

18‧‧‧A pair of new poles

20‧‧‧ autoclave container/container

22‧‧‧Agitator or auger

24‧‧‧ container wall

26a‧‧‧Heating assembly/external jacket heating assembly

26b‧‧‧Heating components/internal heating components

26‧‧‧heating components

28‧‧‧Intake valve / intake line / valve / pressure valve

30‧‧‧ Autoclave exhaust / exhaust line / valve

32‧‧‧ valve opening

34‧‧‧Squeezing valve

36‧‧‧Cutting machine

38‧‧‧ bracket

40‧‧‧Slurry collection device

42‧‧‧ slurry tube

44‧‧‧Dryer/rotator

60‧‧‧Process Controller

70‧‧‧ Pressure Control Module

80‧‧‧ Cutting speed module

90‧‧‧Squeezing valve module

100‧‧‧through module

1A is a schematic cross-sectional view of an autoclave container usable in accordance with an example of the present invention; FIG. 1B is a schematic cross-sectional view of another autoclave container usable in accordance with an example of the present invention; and FIG. 2 is an illustration of the present invention according to an embodiment of the present invention. Figure 3 is a graph of a sample casting of polyamine according to one embodiment of the present invention; and Figure 4 is a graph of time versus weight of polyamine according to one embodiment of the present invention. .

It should be noted that the drawings are merely illustrative of the embodiments of the invention and are not intended to limit the scope of the invention.

Although the following [embodiments] contain many details for the purpose of illustration, It will be appreciated by those skilled in the art that many variations and modifications of the details described below are within the scope of the embodiments disclosed herein.

Therefore, the following examples are set forth without any loss of the generality of the claimed invention, and no limitation of any claimed invention. Before the present invention is described in more detail, it is understood that the invention is not limited to the specific embodiments described, as the invention may vary. It is also understood that the terminology used herein is used for the purpose of the description of the particular embodiments of the invention, and the scope of the invention is limited by the scope of the accompanying claims. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art.

The singular forms "a", "the" and "the" are used in the <RTI ID=0.0> </ RTI> </ RTI> <RTIgt; Thus, for example, reference to "a polyamine" includes a plurality of polyamines.

In the present invention, "including", "containing" and "having" and the like may have the meanings assigned to them by the US Patent Law and may mean "include" and the like, and are generally interpreted as Open terminology. The term "consisting of" is a closed term and includes only the specifically listed devices, methods, compositions, components, structures, steps, or the like, and is a term according to U.S. Patent Law. "Consisting essentially of" or a similar term when applied to a device, method, component, component, structure, step or the like, which is encompassed by the present invention, means an element of the elements as disclosed herein, but Contains other structural groups, component components, method steps, and so on. However, such other devices, methods, components, components, structures, steps or the like do not substantially affect the basic and novel aspects of devices, compositions, methods, etc., as compared to the corresponding devices, compositions, methods, etc. disclosed herein. feature. In further detail, "consisting essentially of" or the like, when applied to a device, method, component, component, structure, step, or the like, encompassed by the present invention, has the meaning assigned by U.S. Patent Law. And the term is open, allowing for more than the listed, as long as the presence of the listed person does not change the basic or new The features are optional, but do not include prior art embodiments. When using open-ended terms such as "contains" or "includes", it should be understood that direct support should be provided for the language "consisting essentially of" and the language "consisting of," as expressly stated.

The term "polymerizable composition" or "polymerizable solution" refers to a solution added to a stirred autoclave according to an example of the present invention, which solution forms a poly-polymer when treated in an autoclave under certain heat and pressure profiles. The guanamine polymer can be extruded or otherwise collected for further use.

The term "polyammonium salt" refers to a salt (along with other additives) included in the polymerizable composition that provides a substantially polymerizable material for forming a polyamidamide polymer. For example, if the polyamine polymer is nylon 6,6, the salt can be prepared from adipic acid and hexamethylene diamine. Other additives may also be present in the polyamine solution, either before the reactor vessel or into the reactor vessel. For example, titanium dioxide is typically introduced directly into the vessel, while other additives, such as catalysts, optical brighteners, defoaming additives, etc., are introduced prior to introduction of the polymerizable composition into the vessel, although this order or even the presence of such additives Not required.

The term "cycle" refers to the stage of a batch polymerization process that is primarily defined by the pressure profile within the vessel. The first cycle (Cycle 1) is performed at the beginning of the batch process while the pressure is increased from a relatively low pressure to a relatively high pressure. The second cycle (Cycle 2) is performed while maintaining a relatively high pressure for a certain period of time. The third cycle (Cycle 3) is performed when the relative high pressure drops back to a relatively low pressure. The fourth cycle (Cycle 4) is performed while maintaining a relatively low pressure for a certain period of time. The fifth cycle (Cycle 5) was carried out when the prepared polymer was extruded from the vessel. The terms "fourth cycle", "cycle 4" and "manufacturing cycle" are used interchangeably in the present invention.

In the case of a synthetic method, phrases such as "suitable for providing", "sufficient to cause" or "sufficient to obtain" or similar phrases refer to reactions related to time, temperature, solvent, reactant concentration and the like. Conditions, such reaction conditions vary within the general skill of the experimenter to provide a suitable amount or yield of the reaction product. The desired reaction product does not need to be A reaction product or starting material need not be completely consumed, provided that the desired reaction product can be isolated or otherwise used further.

It should be noted that ratios, concentrations, amounts, and other numerical data may be represented herein in a range format. It is to be understood that the scope of the range is used for convenience and conciseness, and therefore should be interpreted in a flexible manner to include not only the numerical values that are explicitly recited in the scope of the scope, but also all the individual values or sub-ranges As the values and sub-ranges include "about "x" to about "y"". For purposes of explanation, the range of concentrations from "about 0.1% to about 5%" should be interpreted to include not only the concentrations of about 0.1% to about 5% by weight, as well as the individual concentrations within the indicated ranges (eg 1%). , 2%, 3%, and 4%) and sub-ranges (eg, 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%). In one embodiment, the term "about" can include traditional rounding based on a significant number of values. In addition, the phrase "about "x" to "y"" includes "about "x" to about "y"".

The term "about" as used herein, when referring to a value or range, allows the value or range to have a certain degree of variability, such as within 10% of the specified value or within the specified range limits, or within 5% of an aspect.

In addition, where the features or aspects of the present invention are described in the context of a list or a Markush group, those skilled in the art will recognize that the present invention also employs any individual of the Markush group. A member or a subgroup of members to describe. For example, if X is described as being selected from the group consisting of bromine, chlorine, and iodine, the assertion that X is bromine and the claim that X is bromine and chlorine are fully described, as listed individually. For example, in the case of describing the features or aspects of the invention in the list, those skilled in the art will recognize that the invention is also in the form of a list or a subgroup of individual members or members of the Markusi group. Any combination to describe. Thus, if X is described as being selected from the group consisting of bromine, chlorine, and iodine, and Y is described as being selected from the group consisting of methyl, ethyl, and propyl, then fully described and supported that X is bromine and Y is methyl. Advocate.

Unless otherwise specified, all percentage components used herein are by weight The ratio is given. When referring to a solution of a component, percentages are meant by weight of the composition including the solvent (eg, water), unless otherwise indicated.

Unless otherwise specified, all molecular weights (Mw) of the polymers as used herein are weight average molecular weights.

All publications and patents cited in this specification are hereby incorporated by reference in their entirety herein in their entirety in particular in particular The manner in which the present invention is incorporated by reference to the disclosure of the disclosure is to disclose and describe the method and/or substance. The disclosure of any publication is for its disclosure prior to the filing date and is not to be construed as an admission that the invention In addition, the date of publication provided may be different from the actual publication date that may need to be independently confirmed.

Each of the individual embodiments described and illustrated herein has discrete components and features, which can be used without departing from the scope of the invention, as will be apparent to those skilled in the art. Or mentally, it is susceptible to being separated or combined with features of any of several other embodiments. Any of the methods described can be performed in the order of the events or in any other order that is logically possible.

In general, the method of estimating the casting throughput of the extruded polyamine polymer can include measuring the amount of casting water that typically flows into the casting device from two or more locations, and measuring the temperature of the influent casting water, The temperature of the effluent casting water is measured, the heat transfer between the incoming casting water and the effluent casting water is calculated, and the heat transfer is correlated with the casting throughput.

Additionally, the method of making a polyamide polymer pellet can comprise cutting an extruded polyamine polymer at a cutting speed substantially proportional to the throughput of the polyamide polymer, and adjusting the first process parameter. . The first process parameter may be selected from a free cutting speed, a squeeze valve opening, and a container pressure, and may be responsive to a change in an alternative second process parameter selected from the group consisting of a cutting speed, a squeeze valve opening, and a container pressure. Adjusted to maintain polyamide pellets Uniformity, where throughput is calculated as casting throughput as described herein.

Additionally, the apparatus for preparing polyamine pellets can include an autoclave vessel, a cutter, and a process controller. The autoclave vessel can include a pressure controller (eg, an air inlet, a heating assembly, an exhaust valve) and a squeeze valve. The cutter can be adapted to cut the polyamine polymer extruded from the autoclave vessel to form a polyamide pellet. The process controller may include a pressure control module for controlling the pressure controller, a cutting speed module for controlling the speed of the cutting machine, a squeeze valve module for controlling the squeeze valve, and a calculation of the casting throughput. Pass the module.

It should be noted that when discussing the apparatus and method of the present invention, each of these discussions can be considered as being applicable to each of these examples, whether or not they are explicitly discussed in the context of the examples. Thus, for example, when discussing polyamine polymers with respect to devices, the discussion applies to methods as well, and vice versa.

Returning to the apparatus and method of the present invention, in general, the fabrication process, casting process, apparatus, and the like of the present invention can be used with a polymer system comprising polyamine. In one embodiment, the polyamide polymer may comprise nylon 6,6, consist essentially of nylon 6,6, or consist of nylon 6,6. Nylon 6,6 can be a neat polymer or can be modified by any of a number of additives, including optical brighteners, dyes, and the like. In general, the preparation processes referred to herein may include continuous process and batch process unless otherwise specified. These processes are generally carried out in a reactor vessel, such as an autoclave. In one embodiment, the preparation process can be a batch process. Without particular limitation, such batch processes are typically a 5 cycle process as described herein.

In particular, with respect to nylon 6,6, in various instances, typical sub-batches according to examples of the present invention may range from about 1000 Kg to about 2600 Kg, or from 1000 Kg to 1500 Kg, or from 1300 Kg to 2600 Kg, and may be used during batch processing. The autoclave is circulated for about 90 to 150 minutes or 100 to 120 minutes. Depending on the equipment and polymer selection or other considerations within the knowledge of those skilled in the art, sub-lots and times outside of these ranges may also be used. In general, polyamides of polyamine can be added in the form of a salt. In one embodiment, the nylon can be Nylon 6,6 salt, and may be present in the polyamine in an amount ranging from about 50% to about 95% by weight.

A variety of processing parameters can be used in the polymerization of the polyamines of the present invention, including temperature and pressure. In one embodiment, the temperature may range from about 190 ° C to about 290 ° C, and the autogenous pressure or other pressure during certain cycles may range from about 250 absolute pounds per square foot (psia) to about 300 absolute pounds per volume. Within the range of pisa (psia). Additionally, in another embodiment, heating may be performed under vacuum at a pressure of less than 10 Torr during certain cycles.

In general, the process of the invention for making polyamine pellets can be carried out by autoclaving and extrusion/casting processes. In one embodiment, the process can begin with a concentrated slurry or polyamine solution prepared from an aqueous solution of a polyammonium salt (eg, nylon 6,6 salt), which is provided in an autoclave vessel. Optionally, the slurry can be a thin slurry and become more concentrated by means of an evaporation step. In one embodiment, the slurry can be prepared from aqueous solutions of the monomers hexamethylenediamine and adipic acid in a manner known in the art. In another particular embodiment, the slurry may contain a small amount of an aqueous solution of a nylon 6 monomer and a nylon 6,6 monomer in the form of an aqueous solution of caprolactam. In one example, the autoclave vessel can then be heated to about 230 °C (or some other functional temperature) to allow the internal autogenous pressure to rise. The photoresist titanium dioxide (TiO ₂ ) can optionally be injected into the autoclave and the monomer mixture in the form of an aqueous dispersion.

The polyamine solution or thickening slurry mixture can then be heated to about 245 ° C (or some other functional temperature) in an autoclave. When at this temperature, the autoclave pressure can be reduced to atmospheric pressure and the pressure is further reduced by applying a vacuum in a known manner to form a polyamine composition. The autoclave containing the polyamine composition will be maintained at this temperature and/or pressure for about 30 minutes. After this step, the polyamine polymer composition can be further heated in an autoclave to, for example, about 285 ° C, and dry nitrogen is introduced into the autoclave vessel, and the autoclave is pressurized to about 4 bar by introducing dry nitrogen. To about 5 bar absolute pressure.

After the polymerization, the polyamide polymer can be extruded by a casting process to produce a polyamide pellet. In general, the casting throughput is a parameter of such a casting process and can be used in the production process. Adjust the other casting process parameters in the polyamide gun pellets. As discussed herein, the present invention provides a method of estimating casting throughput in real time. This estimate of casting throughput can be used to adjust other pelletizing process parameters to provide pellet uniformity that was previously difficult to achieve for the polyamide melt autoclaving process. In general, the instantaneous casting throughput is calculated using a heat transfer model that uses the measured temperature and flow rate of the cast water. In the examples herein, various heat transfer models are shown and described, but it should be understood that the same balance can be used in various forms (eg, Formulas I-III). Constants can be adjusted with positive or negative values. By way of understanding, in one embodiment, the casting throughput (TP) can be calculated using the heat transfer model as shown in Equation I: TP = TP model + TP bias value (I)

The TP bias value depends on the container and the TP model is calculated from Formula II: TP model = (inflow temperature - outflow temperature - a - (b × flow 1) - (c × flow 2)) / d (II)

Where: inflow temperature = measured temperature of the incoming casting water; outflow temperature = measured temperature of the drawn casting water; flow rate 1 = measured flow rate of the casting water entering the first position (eg water slide); and flow rate 2 = The measured temperature of the water entering the second location (eg, a cutting machine), and wherein a, b, c, and d are independently library dependent constants.

The influent temperature generally corresponds to the temperature of the water flowing into the casting process prior to contacting the extruded polymer. The effluent temperature generally corresponds to the temperature of the water leaving the casting operation after contacting the extruded polymer. Thus, these casting water temperatures can be used to calculate the heat transfer of the extruded polymer to the foundry water. In general, a, b, c and d can be experimentally derived for a particular casting device. The temperature of the inflowing casting water can be controlled within a range of 5 ° C, 2 ° C, 1 ° C or 0.5 ° C. The temperature of the molten casting water rises due to contact with the extruded polymer. As described herein, the TP model uses this temperature difference to calculate throughput. This TP model accurately and consistently estimates the casting throughput.

In an alternative but related example, the casting throughput can be calculated using a similar capacity balance model during peptization. The model described herein can use two measured water flows, two temperatures (introduced water temperature and water temperature downstream of the dryer), and a series of constants. In this example, the casting throughput (TP) model is shown in Equation III: TP = (P1-P2-C4 × P3-C2 × P4) / C3 + P5 (III)

Where: P1 = measured temperature of the casting water downstream of the dryer; P2 = measured temperature of the introduced casting water; P3 = measured casting water flow 1; P4 = measured casting water flow 2; P5 = constant ; and C1-C4 = coefficient of water flow and / or other processes.

To provide an example of a particular system, the constant/coefficient can be P5=-0.76213, C1=-0.6105, C2=-0.88531, C3=3.63958, and C4=27.7428. These constants/coefficients are given by way of example for a particular device and should in no way be considered as limiting. Those skilled in the art should be able to derive such constants/coefficients for a particular situation or device.

In another example, to obtain an exact relationship between throughput and process variables, an experiment can be performed in which flow 1, flow 2, and throughput are set to one set of process settings and then determined for all such predefined settings. The measured temperature difference between the introduction of cooling water and the extraction of cooling water is introduced. This results in a model in which Tp is taken as X and temperature is increased as Y, resulting in a relationship (T _out -T _in ) = C4 + C3 × throughput + C1 × flow rate 1 × C2 × flow rate 2. Since the throughput in this relationship is one of the X variables, the equations can be reconfigured to obtain a throughput as Y. Thus, in another example, TP = -7.6225 + 0.27476 x (T _{out -} T _in ) + 0.1677 x flow 1 + 0.24325 x flow 2. It should be noted that this is an alternative version of Equation I.

In further detail, with respect to Equation I, as will be appreciated by those skilled in the art, the TP bias value can be calculated. However, in one example, the tuning of the throughput model can be performed by adjusting the bias value calculated from the difference between the raw material batch weight and the integrated throughput batch weight using, for example, the following formula:

Catalysts can also be used to prepare the polyamine polymers described herein. In one embodiment, the catalyst may be present in the polyamine 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. Catalysts can include, but are not limited to, phosphoric acid, phosphorous acid, low phosphoric acid, arylphosphonic acid, aryl monophosphonic acid, salts thereof, and mixtures thereof. In one embodiment, the catalyst may be sodium hypophosphite, manganese hypophosphite, sodium phenylphosphinate, sodium phenylphosphonate, potassium phenylphosphinate, potassium phenylphosphonate, bisphenylphosphinic acid Diammonium, potassium tolylphosphinate or a mixture thereof. In one aspect, the catalyst can be sodium hypophosphite.

The polyamine and polyamine compositions according to the embodiments disclosed herein can improve the whiteness appearance via the addition of an optical brightener. The polyamines can exhibit a permanent whiteness improvement and can be maintained by such operations as heat setting. In one embodiment, the optical brightener may be present in the polyamine in an amount ranging from 0.01% to 1% by weight. In one aspect, the optical brightener can be titanium dioxide.

Additionally, such polyamine polymers can be prepared with antioxidant stabilizers, antimicrobial additives, and the like. Additionally, polyamine polymers can be prepared using defoaming additives. In one embodiment, the antifoam additive may be present in the polyamine in an amount ranging from 1 ppm to 500 ppm by weight.

Polyamine polymers according to embodiments disclosed herein are inherently acid dyeable, but may also be modified by the use of cationic dyes copolymerized in a polymer to modify such polymers or copolymers. Become an alkaline dyed form. This modification makes the composition particularly susceptible to alkali dyeing Material coloring.

Turning now to Figures 1A and 1B, schematic cross-sectional views of two exemplary agitated autoclaves are shown. The figures are not necessarily to scale, and not to show every detail that is typically present in the agitated autoclave, but rather to illustrate a schematic representation of features particularly relevant to the present invention. Thus, in this example, the agitated autoclave 10 can include an autoclave vessel 20 and an agitator or auger 22. Agitators or augers are not required, although illustrated. The container includes a container wall 24, which is typically a coated container wall, and the container wall and/or other structure is adapted to support one or more types of heating assemblies 26a, 26b. In this example, the outer jacket heating assembly is shown at 26a and the internal heating assembly is shown at 26b. It should be noted that the heating assembly of Figure 1A is relatively close to the agitator positioning, which may be typical, while the heating assembly of Figure 1B is positioned closer to the vessel wall, which may be more typical for non-stirred autoclaves. However, it is provided herein that the positioning of the heating element can be performed by those skilled in the art after considering the present invention. In other examples, the heating element can be in two locations, that is, near the vessel wall and near the agitator.

The outer jacket heating assembly 26a can be used to raise the temperature of the polymerizable composition or polymer contained within the container, and the inner heating assembly 26b can be particularly useful to prevent the polymer from sticking to the inner surface of the container wall and/or to adhere thereto. Blender. As shown in Figure 1A, in addition to the internal heating assembly shown, there is also a pair of renewed rods 18 that work with a central agitator or auger 22 to renew the polymer. The agitator operates to move the polymer up the central portion and the pair of re-rods are used to renew the molten polymer by removing the polymer from the sidewall surface as the molten polymer is agitated. This configuration improves heat transfer within the system and reduces the height of the vortex caused by the agitation. In either case, it should be noted that the profile of the internal heating assembly is schematically illustrated, but it should be understood that any shape or configuration of the internal heating assembly can be used. It should also be noted that the heating assembly can be configured or adapted to carry any fluid known in the art for supplying heat to the autoclave, including gases and/or liquids. Intake valve 28 and autoclave vent 30 are also shown and can be used together or separately as a pressure controller (along with heating components) Together with 26a, 26b, the heating elements also control the pressure). A pressurized device or pressure source is not shown, but should be understood to be present when external pressure is to be increased. Alternatively, as understood in such techniques, pressure can be increased by heating and pressure can be reduced by venting. Additionally, the valve opening 32 is at the bottom end of the autoclave vessel. The squeeze valve is not shown in this figure, but this is where the polymer prepared in the autoclave is extruded for further processing. It should be noted that those skilled in the art will appreciate that regardless of the description and location of such ports, valves, vents, etc., these or other ports may be used in a manner different from that shown to achieve the user. Any purpose designed. It should also be noted that this exemplary autoclave vessel and method of forming a polyamine polymer in the autoclave are provided for illustrative purposes only, as any of a number of other process procedures, autoclaves, and additives may be used. A polyamine polymer is produced. It is generally described that regardless of how the polymer is prepared in the autoclave vessel, this point in the process is the primary subject of the invention, namely casting the polymer from the polymerization vessel and estimating the casting throughput.

As discussed herein, the present invention provides apparatus and methods for forming polyamine polymer pellets by cutting the extruded polyamide polymer and adjusting various processing parameters. In particular, the method of the present invention for producing polyamine pellets can adjust a first process parameter including cutting speed, squeeze valve opening, and vessel pressure in response to changes in one of the other process parameters described above. Additionally, in one aspect, both of the process parameters can be adjusted in response to the third process parameter. Although any process parameters or dual process parameters can be adjusted, in one embodiment, the adjusted process parameters can be vessel pressure or can include vessel pressure. In another aspect, the adjusted process parameter can be a squeeze valve opening or can include a squeeze valve opening. In another aspect, the adjusted parameter can be a cutting speed or can include a cutting speed. The process parameters can be adjusted based on casting throughput to maintain the uniformity of the polyamide pellets, wherein the casting throughput can be estimated in accordance with the present invention.

Turning now to Figure 2, the apparatus for preparing polyamide pellets can comprise a container 20, such as an autoclave similar to that shown in Figure 1, which includes a pressure controller (which can be in the intake line / valve 28, row In the form of a gas line/valve 30 and/or heating assembly 26). It should be noted that the heating element is The outer jacket is shown in the form, but it may alternatively or additionally be an internal heating component. A squeeze valve 34 for extruding the polymer via a stencil or other extrusion configuration is also shown. The apparatus can also include a cutter 36 that is adapted to have a cutting speed suitable for cutting the polyamide pellets. For example, the cutting machine can be a disc cutter that is adapted to cut very quickly as it passes through the extruded polymer. The apparatus can also include a process controller 60 that can include a pressure control module 70, a cutting speed module 80, and a squeeze valve module 90. The apparatus can also include a cradle 38, a slurry collection device 40, a slurry tube 42 and a dryer/rotator 44.

In further detail, with respect to the process controller 60 of the apparatus, the various modules 70, 80, 90, 100 can be used to automate the general functions or process steps of the automated device. For example, pressure valve 28, autoclave vent 30, and heating assembly 26 may be controlled by pressure control module 70 that allows for pressure adjustment. The cutter 36 can be controlled by a cutting speed module 80. The squeeze valve 34 can be controlled by the squeeze valve module 90. The estimated casting throughput can be calculated using the throughput module 100. Other modules (not shown) may be present, including but not limited to agitation modules, dryer modules, heating assembly modules, and the like. The modules can work together in a manner to provide an automated system to produce uniform polyamine pellets.

Figure 3 illustrates a graph illustrating an example in which the modules work together to achieve excellent uniformity in accordance with examples of the present invention. In particular, Figure 3 depicts a casting graph of processing parameters of a device in accordance with an embodiment of the present invention. In particular, the graph provides autoclave pressure through a single batch casting process, throughput of polyamine polymer from an autoclave, linearized squeeze valve graph, and cutting speed over time during casting . As illustrated, various process parameters are adjusted to provide a substantially constant throughput at high cutting speeds, thereby providing an automated process that maintains pellet uniformity while also maintaining high productivity.

It should also be noted that in the graph of Figure 3, the cutting speed is altered and substantially proportional to the throughput, i.e., when the throughput is moved up or down (as indicated by the graph), the cutting speed is equally upward and Move Downward. The term "substantially" when referring to the ratio or relative match of throughput to cutting speed, can be defined as any degree of matching below, where a batch of pills The uniformity of the granules has an average quality wherein at least 95% of the individual pellets have individual masses within 10% of the average mass. Uniformity can be maintained by substantially matching the relative speed of the cutting speed to the throughput. Therefore, the pressure controller and the squeeze valve are used to maintain the throughput within a reasonable range for achieving an effective cutting pattern. For example, in an efficient system with high throughput provided by appropriate pressure and linearized valve opening, the cutting speed can be relatively matched with respect to throughput. It should be noted that as the throughput increases, the cutting speed also increases.

Returning now to Figure 2, as discussed herein, the pressure of the vessel 20 can be autogenous or can be generated from an external source of pressure. Further, the pressure can be adjusted using a pressure source (not shown) and a pressure valve 28 and/or an exhaust port 30. The squeeze valve 34 generally controls the opening from which the polyamide polymer is extruded. In some aspects, the squeeze valve opening can be referred to as the linearized opening of the squeeze valve. As used herein, "linearization" refers to a mathematical operation that causes the valve opening (i.e., the unblocked area) to be equal to the percentage of material extruded through the opening. Thus, a 50% "linearization" opening means that 50% of the total amount (100% means the maximum capacity when the valve is fully open) is extruded from the opening, even the valve opening (ie, not blocked). Area) may not be 50% of the total available opening. It should be noted that there is more control over the throughput of the polyamide polymer when the valve is not set to approach 100% open. When the valve is close to 70% or 80% opening, the control of throughput is significantly reduced. For example, changing the valve opening from 40% to 50% has a relatively significant effect on throughput, while valve opening from 80% to 90% has minimal impact on throughput. Thus, it may be desirable to maintain the valve within the polymer casting process to a degree that may be in the range of about 30% to 70% open and more typically 35% to 60% open. To achieve this, the pressure and/or cutting speed can be varied to maintain the valve opening within the desired range. What is described is not strictly required. This only provides a mechanism to maintain maximum flexibility with regard to the opening of the squeeze valve.

The return can be adjusted in response to changes in other process parameters. The adjustment of the process parameters can be performed sequentially or simultaneously (or with overlapping timing). In one embodiment, more than one process parameter can be adjusted in response to changes in the third process parameter. In order to provide examples of why such process parameters can benefit from changes, it should be noted that once squeezed The process begins with the autoclave vessel, and the polyamine polymer contained therein often does not end completely with its polymerization process. Thus, the polyamide polymer can continue to thicken further during the extrusion process. It has been found that the throughput and more pronounced pellet uniformity cannot be simply maintained by increasing the pressure alone under these conditions. Likewise, merely increasing the opening of the squeeze valve 34 will not always fully compensate for the thickened polymer. Furthermore, even by controlling both of these parameters together, if the cutting speed is not adjusted based on the change in throughput, the uniformity of the polyamide pellets can be impaired.

Accordingly, the apparatus and method of the present invention involves using different pressures, different valve opening degrees, and different cutting speeds to control throughput and thereby control pellet uniformity to achieve uniform pellets in an efficient manner. Thus, in one particular example, the exemplary throughput can be in the range of 2 to 10 metric tons per hour or 5 to 9 metric tons per hour or more specifically 6 to 8 metric tons per hour. Exemplary pressures during extrusion can range from 0 to 12 bar, 1 to 10 bar, or 5 to 10 bar. Exemplary valve opening can range from 30% to 70% or from 45% to 65%. Exemplary cutting speeds using a spiral cutter or other similar rotary cutter can range from 100 to 2000 RPM, 400 to 1800 RPM, or 600 to 1500 RPM. Typically, such process parameters are maintained within such ranges during the casting process, and by adjusting the parameters within these ranges, the uniformity of the polyamide particles can be achieved. It is provided herein that process parameters outside of these ranges can also be used with the proviso that the pellet uniformity can be maintained as described herein.

The throughput can be controlled, at least in part, by the opening of the squeeze valve 34, which can be controlled by the cutter 36, and the pressure can be controlled by one or more pressure controllers 26, 28, 30. While more than one process parameter can be adjusted to provide polyamine pellets, in one particular embodiment, the pressure and/or cutting speed can be 30% to 70%, 35% to 65%, or 40% to the extrusion valve. 60% linearized opening operation. Additionally, to provide the desired efficiency, in one embodiment, the throughput can be at least 5 metric tons per hour, or at least 7 metric tons per hour in a large system, and the process parameters can be adjusted to maintain a target throughput variation of no more than 10 weights. %.

Process controller 60 is typically connected via a computer, other computing device, or other networked device Net to cutter 36 and container. The device of the present invention can be automated using a variety of modules. In one embodiment, the pressure control module 70 can adjust the pressure controllers 26, 28, and/or 30 in response to changes in the cutting speed or the opening of the squeeze valve 34. In one aspect, the pressure control module can adjust the pressure controller in response to changes in the cutting speed and the opening of the squeeze valve. In another embodiment, the cutting speed module 80 can adjust the cutting speed of the cutter 36 in response to changes in pressure or squeeze valve opening. In one aspect, the cutting speed module adjusts the cutting speed in response to changes in pressure and squeeze valve opening. In another embodiment, the squeeze valve module 90 can adjust the squeeze valve 34 in response to changes in cutting speed or pressure. In one aspect, the squeeze valve module adjusts the squeeze valve in response to changes in cutting speed and pressure. In another embodiment, the throughput module 100 can calculate the casting throughput based on the flow rate and temperature of the cast water. Thus, the modules of the present invention can be coordinated via a process controller to adjust processing parameters during casting sufficient to provide polyamine pellets and, in particular, uniform and uniform polyamine pellets.

It should be further noted that some of the functional units described in this specification have been labeled as "modules" to more specifically emphasize their implementation independence. For example, a "module" can be implemented in a hardware circuit that includes a custom VLSI circuit or gate array, an off-the-shelf semiconductor (such as a logic die), a transistor, or other discrete components. Modules can also be implemented in programmable hardware devices, such as field programmable gate arrays, programmable array logic, programmable logic devices, or the like. Modules can also be implemented in software for execution by multiple types of processors. The identification module of the executable code may, for example, comprise one or more blocks of computer instructions that may be organized as objects, programs or functions. Nevertheless, the executable modules of the identification module need not be physically located together, but may comprise disparate instructions stored at different locations, the locations comprising the modules and the logical purpose of achieving the specified purpose of the modules when connected together .

Of course, the modules of executable code can be single instructions or many instructions, and can even be distributed over several different code segments, in different programs, and across several memory devices. Similarly, the job data can be identified and illustrated in the module herein and can be embodied in any suitable form. And organized within any suitable type of data structure. Job data can be collected in a single data set or distributed across different locations, including different storage devices. The modules can be passive or active modules, including agents that are operable to perform the desired functions.

Instance Example 1 - Tuning of the throughput model

The tuning of the throughput model is performed using the following variables: batch weight 1 = expected batch weight calculated from all added raw materials for the batch.

Batch weight 2 = integrated throughput, calculated as follows:

The tuning of the throughput model is performed by adjusting the bias value calculated from the difference between the raw material batch weight and the integrated throughput batch weight using the following formula:

Example 2 - Time vs. Batch Weight

Figure 4 shows the trend of batch time versus batch gain from a particular autoclave for a series of batches for a particular polymer type. Each vertical dotted line indicates the beginning of a new operation of the polymer type. Significantly, for this autoclave-polymer type combination, each new operation often begins with a "too high" throughput, which triggers the DCS to update the TP bias to correct the error. This error by the batch weight may be caused by polymer details.

Although the subject matter has been described with particular reference to the structural features and/or the operation of the invention, it is understood that the subject matter defined in the appended claims Rather, the specific features and acts described above are disclosed as examples of the scope of the invention. Numerous modifications and alternative configurations can be devised without departing from the spirit and scope of the technology.

20‧‧‧ autoclave container/container

26‧‧‧heating components

28‧‧‧Intake valve / intake line / valve / pressure valve

30‧‧‧ Autoclave exhaust / exhaust line / valve

34‧‧‧Squeezing valve

36‧‧‧Cutting machine

38‧‧‧ bracket

40‧‧‧Slurry collection device

42‧‧‧ slurry tube

44‧‧‧Dryer/rotator

60‧‧‧Process Controller

70‧‧‧ Pressure Control Module

80‧‧‧ Cutting speed module

90‧‧‧Squeezing valve module

100‧‧‧through module

Claims (43)

A method for estimating a casting throughput of an extruded polyamine polymer, comprising: measuring an amount of casting water flowing into a casting device at two or more locations; measuring a temperature of the inflowing casting water; measuring The temperature of the flowing water flowing out; calculating the heat transfer between the inflowing casting water and the flowing casting water based on the amount of the inflowing casting water, the temperature of the inflowing casting water, and the temperature of the flowing water flowing out; and making the heat transfer Associated with the casting throughput. The method of claim 1, wherein the step of correlating the heat transfer with the casting throughput comprises modifying the autoclave container bias value according to the following formula: TP = TP model + TP bias value, wherein TP is casting throughput, TP model system Calculated at least in part from the measured temperature and flow rate, and the TP bias value is dependent on the container. As in the method of claim 2, the TP model is calculated using the following formula: TP model = (inflow temperature - outflow temperature - a - (b × flow 1) - (c × flow 2)) / d where the inflow temperature is inflow The temperature of the casting water in the casting device, the outflow temperature is the temperature of the casting water flowing out of the casting device, the flow rate 1 is the casting water flowing into the water slide, the flow rate 2 is the casting water flowing into the cutting machine, and a, b, c And d is constant and/or dependent on the library, where a, b, c and d are experimentally derived for a particular casting device. The method of claim 1, wherein the step of correlating the heat transfer with the casting throughput comprises associating by the following formula: TP = (P1 - P2 - C4 × P3 - C2 × P4) / C3 + P5 Wherein P1 is the measured temperature of the casting water downstream of the dryer; P2 is the measured temperature of the introduced casting water; P3 is the measured casting water flow rate 1; P4 is the measured casting water flow rate 2; P5 is a constant; And C1-C4 are independently constant and/or dependent on the library as obtained for a particular casting device. The method of claim 1, wherein the temperature of the inflowing foundry water is controlled within 5 °C. The method of claim 1, wherein all of the measuring steps are performed continuously. The method of claim 1, wherein at least one of the measuring steps is performed at least once per second. The method of claim 1, wherein the container is an autoclave. The method of claim 1, wherein the extruded polyamine is nylon 6,6 (nylon 6,6). A method of making a polyamide polymer pellet comprising: cutting an extruded polyamine polymer at a cutting speed substantially proportional to the throughput of the polyamide polymer; and responding to selection A change in the alternative second process parameter of the group of free cutting speed, squeeze valve opening, and container pressure to adjust a first process parameter selected from the group consisting of cutting speed, squeeze valve opening, and vessel pressure to maintain The uniformity of the polyamide pellets; wherein the throughput is calculated as the casting throughput as claimed in claim 1. The method of claim 10, wherein the method provides uniform polyamine pellets, the uniformity being measured in one batch of pellets having an average mass of at least 95% of the individual pellets having 10% of the average mass Individual quality within. The method of claim 11, wherein the uniformity is measured in one batch of pellets having an average mass of at least 99% of the individual pellets having an individual mass within 5% of the average mass. The method of claim 11, wherein the uniformity is maintained as the relative viscosity of the polyamide polymer increases over time during batch extrusion. The method of claim 10, wherein the throughput is controlled at least in part by the squeeze valve opening. The method of claim 10, wherein the adjusting is in response to the third process parameter. The method of claim 10, further comprising adjusting the third process parameter in response to the change in the second process parameter. The method of claim 16, wherein the adjusting of the first process parameter and the third process parameter is performed simultaneously or within overlapping time ranges. The method of claim 10, wherein the container is pressurized such that the squeeze valve operates at a linearized opening of 30% to 70%. The method of claim 18, wherein the linearization opening is from 45% to 65%. The method of claim 10, wherein the throughput is at a rate of at least 5 metric tons per hour, and the adjustment of the squeeze valve opening or the vessel pressure maintains the change in throughput not exceeding 10% of the average mass. The method of claim 10, wherein the throughput is at a rate of from 2 metric tons per hour to 10 metric tons per hour. The method of claim 10, wherein the first process parameter is a vessel pressure, the vessel pressure being adjusted in response to a change in one or both of a cutting speed or a squeeze valve opening. The method of claim 22, wherein the vessel pressure is adjusted in the range of 0 to 12 bar. The method of claim 22, wherein the vessel pressure is adjusted within a range of 5 to 10 bar. The method of claim 10, wherein the first process parameter is a squeeze valve opening, the squeeze valve opening being responsive to one or both of a vessel pressure or a cutting speed To adjust. The method of claim 25, wherein the squeeze valve opening is adjusted within a linearized opening range of 45% to 65%. The method of claim 10, wherein the first process parameter is a cutting speed that is adjusted in response to a change in one or both of a vessel pressure or a squeeze valve opening. The method of claim 27, wherein the cutting speed is adjusted using a rotary cutter in the range of 100 to 2000 RPM. The method of claim 10, wherein the polyamine polymer is nylon 6,6. A casting apparatus for preparing polyamine pellets at a certain casting throughput, comprising: a container comprising: a pressure controller, and a squeeze valve; a cutting machine having a cutting speed; and a process a controller, the process controller includes: a pressure control module for controlling the pressure controller, a squeeze valve module, for controlling the squeeze valve, a cutting speed module, for controlling the cutting speed, and passing a quantity module for determining the casting throughput, wherein the throughput module (i) is calculated to flow into the casting device based on the amount of inflowing casting water, the temperature of the inflowing casting water, and the temperature of the flowing water flowing out Heat transfer between the cast water and the casting water flowing out of the apparatus, and (ii) correlating the heat transfer with the casting throughput. The casting apparatus of claim 30, wherein the throughput module correlates the heat transfer with the casting throughput to correct the autoclave container bias value according to the following formula: TP = TP model + TP bias value where TP is the casting throughput and the TP model is calculated, at least in part, from the measured temperature and flow rate, and the TP bias value is dependent on the vessel. As in the casting apparatus of claim 31, the TP model is calculated using the following formula: TP model = (inflow temperature - outflow temperature - a - (b × flow 1) - (c × flow 2)) / d where the inflow temperature is inflow The temperature of the casting water in the casting device, the outflow temperature is the temperature of the casting water flowing out of the casting device, the flow rate 1 is the casting water flowing into the water slide, the flow rate 2 is the casting water flowing into the cutting machine, and a, b, c and d are independently constant and/or dependent on the library, where a, b, c and d are derived for a particular casting device. The casting apparatus of claim 30, wherein the throughput module associates the heat transfer with the casting throughput according to the following formula: TP = (P1 - P2 - C4 × P3 - C2 × P4) / C3 + P5, wherein P1 The measured temperature of the casting water downstream of the dryer; P2 is the measured temperature of the introduced casting water; P3 is the measured casting water flow rate 1; P4 is the measured casting water flow rate 2; P5 is a constant; The -C4 is independently constant and/or dependent on the library as obtained for a particular casting device. A casting apparatus according to claim 30, wherein the apparatus is configured to prepare a batch of uniform nylon 6,6 pellets by cutting an extruded nylon 6,6, wherein the uniformity is as follows The batch of pellets of average quality is measured wherein at least 99% of the individual pellets have individual masses within 10% of the average mass. The casting apparatus of claim 30, wherein the casting throughput is at least 5 metric tons per hour. The casting apparatus of claim 30, wherein the squeeze valve module adjusts an opening of the squeeze valve to maintain the casting throughput. The casting apparatus of claim 30, wherein the cutting speed module substantially adjusts the cutting speed in proportion to the casting throughput. The casting device of claim 30, wherein the pressure control module adjusts the pressure such that the linearized opening of the squeeze valve is maintained within a linearized opening range of 30% to 70%. The casting apparatus of claim 30, wherein the process controller adjusts at least one process parameter selected from the group consisting of a cutting speed, a squeeze valve opening, a container pressure, and combinations thereof to maintain uniformity of the polyamide pellets Degree, wherein the uniformity is measured in one batch of pellets having an average mass of at least 95% of the individual pellets having an individual mass within 10% of the average mass. The casting apparatus of claim 30, wherein the vessel is a non-stirred autoclave. The casting apparatus of claim 30, wherein the vessel is a stirred autoclave. The casting apparatus of claim 30, wherein the process controller is networked to the cutter and the container via a computer. The casting apparatus of claim 30, wherein the pressure controller comprises one or more of an exhaust valve, an intake valve, or a heating assembly.