CN104128125A

CN104128125A - Agitated autoclave with water pressurized mechanical seal

Info

Publication number: CN104128125A
Application number: CN201410142516.XA
Authority: CN
Inventors: 利恩·曼斯特; 莱昂纳德斯·J·米伦迪杰克
Original assignee: Scientific & Technical Corp Of English Weida
Current assignee: Invista Textiles UK Ltd
Priority date: 2013-05-01
Filing date: 2014-04-10
Publication date: 2014-11-05
Anticipated expiration: 2034-04-10
Also published as: CN104128125B; TW201505709A; WO2014179052A1; EP2992036A1

Abstract

An agitated autoclave comprises an autoclave vessel, an agitator, and a mechanical seal. The autoclave vessel can be adapted to receive and polymerize a polyamide salt composition to form a polyamide polymer. The agitator includes a shaft, an auger portion, and a drive portion. The mechanical seal forms a pressure boundary about the shaft at or adjacent to a wall of the autoclave vessel. The mechanical seal includes a pressurized water chamber pressurized with seal water and is held at a seal pressure greater than a vessel pressure within the autoclave vessel. The seal water in the pressurized water chamber has a calcium content of less than 3 ppm and an iron content of less than 0.3 ppm.

Description

There is the stirred autoclave of the mechanical sealing member of water pressurization

Technical field

The disclosure relates to stirred autoclave container and correlation technique thereof, and this autoclave vessel occurs during polymerization is processed to utilize mechanical seal piece of stirrer in container, to keep the content of low interference mineral in inside.

Background technology

Can use complicated chemical industry to process such as the polyamide polymer of nylon 6,6 synthesizes with relatively large scale.These chemical industry processing can comprise the steps, such as: salt impacts step, wherein prepares the salting liquid of polyamide (such as nylon 6,6); Evaporation step wherein evaporates some water from salting liquid, and optionally comprises certain additive; Autoclave polymerization procedure, is wherein placed on salting liquid under HTHP to carry out polymerization; And extruding/cutting step, wherein substantially form final polymerization raw material.Understand according to those skilled in the art's routine, also can draw together other steps.

Specifically, for the autoclave polymerization procedure in batch process, it should be noted that many kinds of autoclaves can be used for obtaining acceptable result.The autoclave of one type is stirred autoclave, and it conventionally comprises and can bore from the rotary spiral of autoclave vessel external control in autoclave vessel.In order to keep the pressure in container, can enter at agitator the position use mechanical sealing member of autoclave vessel.But, owing to preparing the very sensitivity of chemical property of polyamide polymer, therefore can implement concrete design parameter to mechanical sealing member, to keep the integrality of polymerization processing.

Summary of the invention

The disclosure relates to and a kind ofly has the stirred autoclave of pressurization mechanical sealing member, the method for sealing stirred autoclave, and in stirred autoclave, prepares the method for polyamide polymer.Described stirred autoclave can comprise autoclave vessel, agitator and mechanical sealing member.Described autoclave vessel can be suitable for holding and making the composition polymerization of polyamide salt, to form polyamide polymer.Described agitator can comprise axle, auger part (for example, being positioned at described internal tank) and drive part (being positioned at external container).Described mechanical sealing member can be at the wall place of described autoclave vessel or with the adjacent place of the wall of described autoclave vessel around described axle and mineralization pressure border.Described mechanical sealing member comprises by the pressurization water cavity of sealing water pressurization, described sealing water also with described be coupling tactile.Sealing load can be greater than the container pressure in described autoclave vessel.Sealing water in described pressurization water cavity can have the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm.In an example, in an automation stirred autoclave, can comprise above-mentioned agitated autoclave and process controller.Described process controller can comprise modular pressure for controlling the pressure in described autoclave vessel, for controlling the stirring module of described agitator, and for controlling the seal modules of the sealing water pressure in described pressurization water cavity.

In another example, the method that seals stirred autoclave sealing around stirrer shaft can comprise: the agitator of the chamber wall that is arranged through autoclave vessel is assemblied in described autoclave vessel, mechanical sealing member is attached on the described axle between auger part and drive part, and by sealing water, water cavity is pressurizeed.Described agitator can comprise axle, be arranged in the auger part in described autoclave vessel, and is positioned at the drive part that engage with driving mechanism the outside of described autoclave vessel.Described mechanical sealing member can be suitable for adjacent place at chamber wall place or chamber wall around described axle and mineralization pressure border.Described sealing water can contact with described axle (described axle from the outside of described autoclave vessel the position to the inner transition of described autoclave vessel), and can remain on than under the larger sealing load of the container pressure in described autoclave vessel.Described sealing water can have the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm.In one example, described mechanical sealing member can further comprise can operate to form the cooling water cavity around the cooling jacket of described axle, but different from described sealing water, cooling water conventionally not with described be coupling tactile.In this example, described method can further comprise the step that cooling water is entered or pass cooling water cavity.

In another example, the method of preparing polyamide polymer in stirred autoclave can comprise feeds to described stirred autoclave with the composition that is suitable for the polyamide salt of preparing polyamide polymer, and uses the various pressure that is suitable for forming described polyamide polymer to pressurize to described stirred autoclave.Additional step stirs the composition of described polyamide salt when can being included in the described polyamide polymer of preparation.Described agitator can comprise axle, be arranged in the auger part in described autoclave vessel, and the drive part that is positioned at the outside of described autoclave vessel and engages with driving mechanism.Described axle from the outside of described autoclave vessel to autoclave vessel in the adjacent position of transition position, be provided with by described sealing water and carry out pressure-tight mechanical sealing member.And, described sealing water can remain on the pressure that is greater than described stirred autoclave internal pressure around described axle (entering the position of described autoclave vessel through chamber wall at described axle), prevents that thus the pressure in described autoclave vessel from missing by described mechanical sealing member.Additionally, described sealing water can have the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm.

Other features and advantages of the present invention will become intuitively according to following detailed description, and feature of the present invention is wherein shown by way of example.

Brief description of the drawings

Fig. 1 is the schematic cross sectional views having according to the automatic agitating type autoclave of the available mechanical sealing member of disclosure embodiment;

Fig. 2 shows according to disclosure embodiment and prepares the pressure in batch cycle of polyamide polymer and stir the example illustration of the correlogram of action;

Fig. 3 is according to the cutaway view of the mechanical sealing member that can be used in conjunction with the autoclave of Fig. 1 of disclosure embodiment; With

Fig. 4 is according to the cutaway view of another mechanical sealing member that can be used in conjunction with the autoclave of Fig. 1 of disclosure embodiment.

It should be pointed out that accompanying drawing is only the example of certain embodiments of the invention, is not intended to, with this, scope of the present invention is formed to any restriction.

Detailed description of the invention

For purpose of explanation, although following specific embodiment comprises many details, this area routine techniques personnel will understand, and all belong in the scope of disclosure disclosed embodiment for multiple amendment and the modification of following details.

Therefore,, making protected invention not lose any generality and not form under the prerequisite of limitation ot it, embodiment is set forth as follows.Before the disclosure is described in more detail, should be appreciated that in view of these and all may change, therefore the disclosure is not limited to described specific embodiment.Also should be appreciated that and will only be limited by claims in view of the scope of present disclosure, therefore term as used herein is only for describing the object of specific embodiment, and is not intended to limit.Unless otherwise defined, all technical and scientific term using herein have with the disclosure under routine techniques personnel's the routine in field understand identical implication.

Unless context separately has clearly regulation, otherwise include plural number and refer to thing as the singulative being adopted in this specification and the appended claims " one ", " one " and " being somebody's turn to do ".Therefore, for example, the appellation of " a kind of polyamide " comprises multiple polyamide.

Term " polymerism solution " or " polymerizable composition, polymerizable composition " refer to and add to according to the solution in the stirred autoclave of disclosure embodiment or composition, and based on the processing to composition in autoclave under uniform temperature and pressure configuration, can form polymer, it is squeezed out or otherwise collects for further use.But, it should be noted that said composition will start retrogradation and become polymer along with polymerism solution or composition start polymerization in autoclave.Therefore,, with just compared with the polymer of retrogradation, be difficult to delimit that it is no longer polymerism solution or composition on which point.Consequently, for simplicity, term " polymerism solution " or " polymerizable composition, polymerizable composition " can be used for describing the composition in autoclave in this article, and irrelevant with its polymerization state.In addition, term " solution " is not intended to describe the each component in composition, because in fact some materials of for example titanium dioxide or additive can be scattered in liquid.Term " solution " or " composition " are only for the abbreviation of some materials in solution at the very start.

Term " polyamide salt " refers to the salt being included in the polymerizable composition, polymerizable composition (optionally together with other additives) that can be provided for the basic polymeric materials that forms polyamide polymer.If polyamide polymer is nylon 6,6, this salt for example can be prepared by the condensation reaction between adipic acid and hexamethylene diamine so.No matter in daiamid composition, also can comprise other additives, be the mode that joins in advance stirred autoclave, or all can in the mode that directly joins stirred autoclave.Titanium dioxide for example can optionally directly join in autoclave in the second pressure cycle, but, before polymerizable composition, polymerizable composition joins stirred autoclave or in other pressure cycle of autoclave, can be more suitable for mixing with polymerism salt such as other additives such as catalyst, antifoaming agent, but this order or and even the existence of these or other additive all optional.

Term " cycle " referred to as the main stage by the defined batch polymerization processing of the pressure configuration in stirred autoclave.Period 1 (cycle 1) occurs in the starting point of batch process, and pressure is just increased to relatively high force from low-pressure simultaneously.Occur as second round (cycle 2) and make this relatively high pressure force retaining a period of time, this conventionally by heat is regulated and simultaneously the mode of discharge pressure complete.Period 3 (cycle 3) occurs as and makes this relatively high force fall back low-pressure (according to using vacuum, this low-pressure is optionally even lower than initial pressure pressure).The 4th cycle (cycle 4) occurs as and makes (vacuum) low-pressure keep a period of time.The pressure that the 5th cycle (cycle 5) occurs as by increasing squeezes out the polymer of preparing in autoclave from stirred autoclave container.Agitator uses conventionally during cycle 1-4 as described herein, and can use with various rotating speeds (RPM) speed or under different timing configuration in during these cycles.

Term " relatively high force " refers to the pressure in batch process, and wherein this pressure is in fact in its highest level.Therefore, this pressure is " height " with respect to other stress levels during batch period treatment.For example, during the cycle 2, initial low-pressure can be increased to relatively high force.In the time of the pressure configuration of considering under 5 periodic batches, when pressure in or approximately when the maximum pressure in batch process configuration, reached this " relatively high force ".In examples more shown in this article, show about relatively high force of 16 to 20Bar, but other pressure configuration can provide the relatively high force outside this scope.Therefore, mechanical sealing member generally includes the pressurization water cavity with sealing water, thereby this pressurization water cavity can the pressurized relatively high force at least adapting in autoclave vessel, for example, even adapts to the pressure slightly higher than the relatively high force of autoclave.

" stirring " this word refers to the agitator state in the time that agitator operates in the grade that is enough to bring out at least some polymerizable composition, polymerizable compositions or reactive polymeric thing generation mixing.In one example, agitator can be the auger to rotate up to 100RPM in autoclave, but its scope for example can be from 5RPM to 90RPM.

Term " sealing water " and " cooling water " all refer to water.But, because cooling water is not participated in the stirrer seal that autoclave vessel surface (water may occur to be leaked) is located directly herein, therefore sealing water can be any obtainable water that is suitable for cooling mechanical seal part, for example, and running water, recirculated water, deionized water etc.But, with regard to " sealing water ", because this water can comprise the water can (wherein preparing polymer) from mechanical sealing member internal leakage to autoclave vessel by design, therefore this water should be the water of low ion concentration, particularly the water of low iron and calcium ion content.For example, sealing water can have the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm.

In the disclosure, " comprising ", " comprising ", " containing " and " having " etc. can have the implication that united states patent law is given, and can refer to " comprising ", " comprising " etc., and are that ordinary solution is interpreted as open-ended term.Term " by ... composition " be closed term, and only comprise the device, method, formation, parts, structure, step etc. of particular illustrated example, and united states patent law followed in this term.The terms such as " substantially by ... composition " or " substantially composition " when being applied to the device, the method that are contained by the disclosure, form, when parts, structure, step etc., except referring to as disclosed herein this type of key element, can also comprise additional structural combination, component parts, method step etc.But compared with related device disclosed herein, formation, method etc., this type of additional device, method, formation, parts, structure, step etc. do not affect in fact fundamental characteristics and the novel characteristics of device, formation, method etc.In more detail, the terms such as " substantially by ... composition " or " substantially composition " when being applied to the device, the method that are contained by the disclosure, form, have when parts, structure, step etc. the implication that united states patent law is given, and this term is open, but do not comprise the embodiment of prior art, therefore as long as the fundamental characteristics of the part of recording or novel characteristics are not exceeded the content of record part to be changed, just allow to exist the content that exceedes record part.Should be appreciated that when the saying that uses as when the open-ended term of " comprising " or " comprising ", also should give " substantially by ... composition " and " by ... composition " is directly to support, as explicit state.

In the content about synthetic method, refer to the reaction condition relevant with time, temperature, solvent, reactant concentration etc. phrases such as " being suitable for providing ", " being enough to bring out " or " being enough to output ", these are all the product amount that changes to provide for experimenter or the routine techniques of output.Following situation is optional, and the product of expecting is that unique product or raw material are consumed completely, makes it possible to isolate the product of expectation or further uses this product again.

It should be pointed out that ratio, concentration, consumption and other numeric datas can represent with the form of scope in this article.Be appreciated that, this range format is to use with succinct order for convenience, therefore should be interpreted as not only comprising in mode flexibly the numerical value of the bound that is clearly recited as scope, but also comprise all single numerical value or the subrange within the scope of this, contained, such as, each numerical value and comprise the subrange of " approximately ' X ' to approximately ' Y ' ".In order to illustrate, the concentration range of " approximately 0.1% to approximately 5% " should be interpreted as not only comprising that the concentration of the approximately 0.1wt% clearly recording is to the concentration of about 5wt%, but also comprise that monodrome concentration in specified scope (for example, 1%, 2%, 3% and 4%) and subrange (for example, 0.5%, 1.1%, 2.2%, 3.3% and 4.4%).In one embodiment, term " about " can comprise that the tradition of the significant digits based on numerical value rounds up.In addition, phrase " approximately ' X ' is to ' Y ' " comprises " approximately ' X ' extremely approximately ' Y ' ".

Term as used herein " approximately ", in the time referring to numerical value or scope, allows this numerical value or scope to a certain degree to change, and for example, in 10% or monolateral 5% scope of the limits value of setting or prescribed limit, changes.

Wherein, according to the mode of enumerating or Ma Kushi combines, feature of the present disclosure and aspect are described, those skilled in the art will recognize that, the disclosure is also described according to any single member or member's subset of Ma Kushi combination thus.For example, if X is described as being selected from bromine, chlorine and iodine, the protection that to require so X be bromine and require to X be bromine and chlorine protection can as enumerate separately fully recorded.For example, feature of the present disclosure or aspect enumerate in the part that mode describes according to this, those skilled in the art will recognize that, the disclosure also thus according to exemplify or Ma Kushi combination in single member's any combination or member's subset be described.Therefore, if X is described as selecting the combination of free bromine, chlorine and iodine composition, and Y is described as being selected from the combination of methyl, ethyl and propyl group composition, requiring so X is that the protection that bromine and Y are methyl can fully be recorded and support.

Except as otherwise noted, otherwise as used herein, all percentage formations provide with percentage by weight.In the time relating to component solution, except as otherwise noted, otherwise percentage refers to the percentage by weight of the component that includes solvent (for example, water).

Unless otherwise prescribed, otherwise as used herein, the weight average that the molecular weight of all polymer (Mw) is molecular weight.

Those skilled in the art it is evident that by reading the disclosure, described herein and each independent embodiment that illustrate all has discreet component and feature, do not deviating under the prerequisite of the scope of the present disclosure or spirit, this feature can separate easily or combine with the feature of any other some embodiment.The order that any recorded method can event occurs or in logic feasible any other order are implemented.

In view of this point, there are several dissimilar autoclaves for the preparation of polymer raw material.A kind of autoclave of particular type is the autoclave comprising for the agitating member (such as auger) of auxiliary polymerization processing.This agitator by controlling in use foaming, in autoclave, provide salt flowage to mix and the continuous mixing (there is no layered effect) of content, Heat Transfer Control, minimizing eddy current, by polymer sucking-off autoclave, realize autoclave vessel more high production rate, provide viscosimeter to measure the modes such as relative viscosity (RV) to carry out aid in treatment.In one example, stirred autoclave comprises agitator as follows, there is the auger part or the working end that are positioned at autoclave vessel inside, and the drive end that for example, carries out interface connection with the stirrer drive (, motor) that is positioned at autoclave vessel outside.Therefore, enter the position of autoclave at the axle of agitator, can use seal to keep the pressure in autoclave vessel, meanwhile make shaft rotation.More specifically, seal can be the mechanical sealing member that comprises water-stop characteristic, and this characteristic utilizes pressure differential to keep the pressure in autoclave vessel.But under this pressure differential, water can inevitably enter in autoclave vessel.Therefore, along with water from mechanical seal leakage to autoclave vessel, be particularly accompanied by polymerizing polyamide processing many times, the finite concentration calcium carbonate being conventionally present in water may become problem.For example, because calcium carbonate and the phosphate catalyst conventionally using interact, make the active variation of this catalyst in the polymeric system of polyamide.And, if leaking in autoclave vessel, the amount of the ferrous components in conventional water also may become problem, because polyamide polymer may be excessively crosslinked in less desirable mode.

According to this point, content herein relates to a kind of a kind of stirred autoclave, method that seals stirred autoclave with pressurization mechanical sealing member, and a kind of method of preparing polyamide polymer in stirred autoclave.Stirred autoclave can comprise autoclave vessel, agitator, and mechanical sealing member.Autoclave vessel can be suitable for holding and making the composition polymerization of polyamide salt, to form polyamide polymer.Agitator can comprise axle, auger part (for example, at internal tank), and drive part (at outside of containers).Mechanical sealing member can be at autoclave vessel wall place or with the adjacent place of autoclave vessel wall around axle and mineralization pressure border.Mechanical sealing member comprises that one by the pressurization water cavity of sealing water pressurization, its also be coupling tactile.Sealing load can be greater than the container pressure in autoclave vessel.Sealing water in pressurization water cavity can have the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm.In one example, an automatic agitating type autoclave can comprise above-mentioned stirred autoclave and process controller.Process controller can comprise the modular pressure of the pressure for controlling autoclave vessel, for controlling the stirring module of agitator, and for controlling the seal modules of the sealing water pressure in pressurization water cavity.

In another example, the method that seals stirred autoclave around stirrer shaft can comprise: the agitator of the chamber wall that is arranged through autoclave vessel is assemblied in autoclave vessel, mechanical sealing member is attached on the axle between auger part and drive part, and by sealing water, water cavity is pressurizeed.Agitator can comprise axle, be arranged in the auger part in autoclave vessel, and is positioned at the drive part that the outside of autoclave vessel engages with driving mechanism.Mechanical sealing member can be suitable at chamber wall place or with the adjacent place of chamber wall around axle and mineralization pressure border.Sealing water can contact with axle, and can remain on than under the larger sealing load of the container pressure in autoclave vessel.Sealing water can have the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm.In one example, mechanical sealing member can further comprise around axle and can operate and form the cooling water cavity of cooling jacket, but different from sealing water, cooling water conventionally not be coupling tactile.In this example, the method can further comprise the step that cooling water is entered or pass cooling water cavity.

In another example, the method of preparing polyamide polymer in stirred autoclave can comprise: stirred autoclave is feeded with the composition that is suitable for the polyamide salt of preparing polyamide polymer, and use the various pressure that is suitable for forming polyamide polymer to pressurize to stirred autoclave.Additional step can be included in the composition that stirs polyamide salt when preparing polyamide polymer.Agitator can comprise axle, is arranged in the auger part in autoclave vessel, and the drive part that is positioned at the outside of autoclave vessel and engages with driving mechanism.Axle from the outside of autoclave vessel to the close position of the inner transition of autoclave vessel, be provided with by sealing water carry out pressure-tight mechanical sealing member.And sealing water can remain under the pressure that is greater than stirred autoclave internal pressure around axle (entering the position of autoclave vessel through chamber wall at this axle), prevents that thus the pressure in autoclave vessel from missing by mechanical sealing member.Additionally, sealing water can have the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm.

By above-mentioned these general examples, should in the disclosure, note, in the time describing automatic agitating type autoclave or method, no matter whether carried out clearly discussing, all think that it is suitable for a volume description or independent description each other in the context of a particular example or embodiment.For example, in the time that specific agitator itself is discussed, because embodiment of the method is relevant to device, therefore the method embodiment is also included in above-mentioned discussion inherently, and vice versa.

With reference now to Fig. 1,, the schematic cross sectional views in the autoclave of automatic agitating type shown in it.This figure does not need to draw in proportion, and the each details being conventionally present in stirred autoclave is not shown, but schematically showing of the feature relevant especially to the disclosure is optionally shown.Therefore, automatic agitating type autoclave 10 can comprise autoclave vessel 20 and agitator 30.This container comprises chamber wall 22, it typically is clad chamber wall, and chamber wall and/or other structures are suitable for supporting the heater block 24,26 of one or more types.In this example, outside chuck heater block illustrates with Reference numeral 24, and inner heater block illustrates with Reference numeral 26.Note any shown in inner heater block can be present in or two positions.In one example, inner heater block is arranged as and more approaches agitator (shown in dotted line), to provide suitable heat near of agitator.In this example, also can have the space for a pair of wall scraper (not shown) near outer vessel walls 22, this wall scraper for removing and the polymer of chamber wall close contact in the time that polymer moves through container.External jacket heater block can be used for improving and is included in polymerizable composition, polymerizable composition in container or the temperature of polymer, and inner heater block can be especially for preventing that polymer from adhering to the inner surface of chamber wall.Note, inner heater block is schematically illustrated by cutaway view, but should be appreciated that inner heater block can use any shape or structure.Shall also be noted that heater block can be configured to or be suitable for carrying and knownly in this area anyly can be autoclave the fluid of heat is provided, and comprises gas and/or liquid.And, be valve openings 28 in the bottom of autoclave vessel.Valve is not shown, but this is that the extruded polymer of preparing in autoclave is gone out to the position of processing for further.

For concrete stir process as herein described, shown in structure in, agitator 30, the auger part 34 that more specifically says agitator drive polymerizable composition, polymerizable composition (or polymer of its telogenesis) upwards towards the central area of autoclave vessel 20 with move towards chamber wall 22 downwards with the flow pattern 32 shown in Fig. 1.Therefore,, in a concrete example, in the time that auger rotates, shown in auger basis, pattern is just to be enough to bring out the RPM horizontal movement of at least a portion polymerizable composition, polymerizable composition or mixed with polymers.For example, the auger part of agitator can be in autoclave with the speed rotation up to 100RPM, but be conventionally set to the speed of for example 5RPM to 90RPM, or from the speed of 70RPM to 90RPM.As the skilled personnel can understand, also can use the RPM level outside this scope.About the further details of agitator, except auger part is positioned at autoclave vessel as shown, drive part 36 is depicted as the outside that is positioned at autoclave vessel, is connected with stirrer-driven device 38 by interface, causes thus agitator rotation.

Conventionally, pressure in autoclave is provided by heater block and heating module, but also can additionally be incorporated in container by injection pipeline or valve 44, this injection pipeline or valve 44 are for being incorporated into autoclave by polymerizable composition, polymerizable composition or other additives from evaporimeter (not shown).And, inject and the pressure of rising in temperature or fluid for control response, autoclave air bleeding valve 46 also can be set, for emitting gas from autoclave vessel to reduce pressure.Other input ports or outlet 48 also can be set, such as with input port for injecting polymeric compositions or injection pipeline be separated for injecting the input port of additive.Conventionally be set to only illustrate with exemplary purpose in the layout being provided with the injection pipeline shown in Reference numeral 44,46 and/or 48, exhaust outlet, input port, valve etc., if those skilled in the art are by understanding, can use any layout or suitable construction for these devices.

Autoclave vessel 20 and agitator 30 are configured to make the interface of mechanical sealing member 36 between external container and internal tank conventionally.Therefore, mechanical sealing member is usually located at or enters a little more than stirrer shaft on the chamber wall 22 at position of autoclave vessel, and is adjacent to stirrer shaft and enters the chamber wall at the position of autoclave vessel.As above, as described in concise and to the point, in the second round of the polymerization processing in autoclave,, during the basic cycle 2 that keeps constant pressure, pressure reaches a relatively high force.For example, the pressure in second round can remain on 16 to 20Bar during whole second round, but also can use the pressure configuration outside this scope in some examples.Because this is the highest container pressure during periodic as herein described is processed, in one example, the pressure remaining in mechanical sealing member can keep or temporarily reach the level even higher than this stress level, to avoid fluid or gas to spray from the autoclave vessel of pressurization and to pass seal.Alternatively, can in mechanical sealing member, regulate pressure, to be kept above the stress level in autoclave vessel, but in some instances, the pressure in mechanical sealing member does not need to remain on its maximum pressure level (as long as it is kept above the pressure in container) always.Will be understood that, if the pressure differential between the sealing water in mechanical sealing member and autoclave vessel is excessive, so a large amount of sealing water can enter in autoclave vessel.Therefore, the pressure configuration of the sealing water in mechanical sealing member can reach the level that is greater than the pressure in autoclave vessel, does not allow too much to seal water and enters the level in autoclave vessel but can remain on.

About further details, the autoclave in Fig. 1 can be suitable for the automation control of use procedure controller 50, and this process controller 50 comprises the various modules 60,79,80,90 that can carry out general function or treatment step.For example, heater block 24,26, intake pipeline or valve 44, and exhaust outlet 46 can be controlled by pressure control module 60.Agitator 30, such as RPM and the drive unit 42 of agitator, can control by stirring module 70.Comprising the mechanical sealing member 36 that seals water pressure can be controlled by seal modules 80.Other modules 90 also can be set, such as extruding module or according to disclosure example and other favourable modules.These modules can cooperate jointly, thereby carry out the circulatory system in the mode of the batch polymerization that brings out predictable polymerism solution or composition.

For illustrating the relation between pressure cycle and the use of agitator, Fig. 2 illustrates as next embodiment, and wherein the agitator cycle is depicted as relevant with the pressure configuration in several typical pressure cycle.More specifically, 5 pressure cycle shown in this figure.Particularly, the period 1 (cycle 1) occurs in the starting point of batch process, and pressure is just increased to relatively high force 94 from low-pressure 92a simultaneously.Occur as second round (cycle 2) and make this relatively high pressure force retaining a period of time.Period 3 (cycle 3) occurs as and makes this relatively high force be down to even lower than initial pressure low-pressure 92b, and this reduces by vacuum in some instances.The 4th cycle (cycle 4) occurs as and makes this lower (vacuum) pressure keep a period of time.The 5th cycle (cycle 5) occurs as, and for the object that polymer is squeezed out from stirred autoclave container, pressure increased again.About the configuration of agitator in Fig. 2, in the example shown, agitator is for example switched to the horizontal 96(of relatively high RMP in the starting point of period 1, and 70 to 90RMP), and remain on this level, until again decline with step-wise manner during the cycle 4.The first ladder decline 98a can be carried out to save energy, and the second ladder decline 98b can be carried out to test the viscosity that is formed at the polymer in autoclave vessel with auger.Note, this configuration is optional, and it can stop and starting as required, and RPM configuration can regulate equally as required.

Figure 3 shows that the mechanical sealing member 100 according to an embodiment of the present disclosure.Mechanical sealing member can the wall of container 102 (it is upper wall in this example) locate or with the wall adjacent of container 102 around stirrer shaft 101 mineralization pressure borders.Axle is extensible through the opening 103 in chamber wall and through mechanical sealing member, thereby the stirrer-driven mechanism of external container is carried out to mechanical connection with the agitator auger being arranged in container.In one aspect, driving mechanism can rotate around the longitudinal axis of axle 104.The size of vessel port can be made as and allow axle motion without restriction in opening.Mechanical sealing member can be connected with container 102 by one or more securing member 105a, 105b.Seal 106 such as O shape ring can be arranged between chamber wall and mechanical sealing member, to reduce or to prevent Leakage Gas and/or the pressure loss in container as far as possible.Alternatively, seal can be only hard material/hard material seal, for example metal/metal seal, it is arranged on two place's hard materials junction point that very flatly (for example, the flatness of optical measurement and/or checking) combines in the very strict margin of tolerance.Alternatively, also can use double mechanical seal part or there is the seal of lap joint.In essence, can use any seal that can fully prevent fluid loss.

Mechanical sealing member 100 can comprise the interior axle collar 110 of arranging around axle 101, makes to exist gap 107 between the interior axle collar and axle.Mechanical sealing member also can comprise the sleeve 120 of arranging and can directly contacting with axle around axle 101.On the one hand, sleeve can be configured to be convenient to the relative motion between axle and sleeve, such as sliding-contact.On the other hand, sleeve can be configured to rotate together with the axis such as logical interference fit.Seal 130,131 can be associated with sleeve and arrange around axle, to prevent or to try one's best and reduce gas or the fluid passage between sleeve and axle.

Sleeve 120 can be connected with outer collar 140 by bearing 150, and sleeve can be moved with respect to outer collar, the interior axle collar 110 and container 102.Bearing can comprise ball bearing, roller bearing, axle bush, or the bearing of any other adequate types or swivel joint.In one aspect, bearing can comprise spherical bearing, misalignment or the skew of axle 101 while rotation around axis 104 along with axle to hold.Seal 132 can be arranged between sleeve and outer collar, to prevent or to reduce gas or the fluid passage between sleeve pipe and outer collar as far as possible, also allows the relative motion between sleeve and outer collar simultaneously.

Mechanical sealing member 100 can comprise the pressurization water cavity 160 being formed by the interior axle collar 110 at least in part.Pressurization water cavity can fluidly be connected with water source 161 by entrance 162.Water source can provide sealing water to pressurization water cavity, makes to seal water and contacts with axle, and remain under the sealing load that container pressure in container 102 is larger.Therefore, by with the combination of one or more seals 130,131,132, pressurization water can reduce as far as possible or prevent that gas from overflowing from container, and/or keeps the pressure in container.Seal 130,131,132 disclosed herein can comprise O shape ring or any other suitable seal, for example, can reduce the very smooth surface, double mechanical seal part, lap joint of leakage etc. as far as possible.In one aspect, the sealing water in pressurization water cavity can also play the effect of all parts of cooling mechanical seal, such as the cooling interior axle collar and sleeve 120, and axle 101.

In some manufacture processes, the pressure in container 102 can change in whole processing procedure.In one aspect, along with the variation of container inner pressure, can comprise the pressure differential constant or that other are default that pump or the water source 161 that can cooperate with pump can keep pressurizeing between the sealing load of water cavity 160 and container pressure.Therefore, for example during the cycle 2 of polymerization cycle the pressure in required pressure seal by larger pressure required during than the cycle 4.Therefore, during the cycle 4, remain on lower by than during the cycle 2 of the pressure of pressurization in water cavity.In one example, in the situation that sealing load is greater than container pressure, the pressure differential (taking Bar as unit) between container pressure and sealing load can be at least 2%, at least 5%, at least 10%, at least 25% or at least 50%.In mechanical sealing member slightly high hydraulic pressure needn't follow in autoclave vessel upwards and downward pressure change, or proportional with it, but this is an alternative aspect of the present disclosure.In a word, in this case, pressure seal can be configured to provide the water pressure with following function: the composition of polyamide polymer and associated gas pressure thereof are remained in autoclave vessel, but meanwhile, for the operation of given batch more practical or make ideally from pressure seal to autoclave vessel leakage minimum, for example, it is desirable to, only have few water to leak into autoclave vessel from substantially autoclave vessel not being existed to leak into.For example, at given batch run duration (for example, use the cycle 1-4 of agitator), the weight of the water using in water cavity according to pressurization can be there is no or be less than 1%, be less than 5%, be less than 10%, be less than 20% or be less than 50% from the leakage of the pressurization water cavity of mechanical sealing member to the leakage of pressurization autoclave vessel.

As mentioned, in use, some sealing water from pressurization water cavity 160 may such as with between the interior axle collar 110 and axle 101 through and leak and enter container 102 along the mode flowing in container axial.In one aspect, the sealing water being provided to pressurization water cavity by water source 161 can have the calcium content that is less than 3ppm and/or the iron content that is less than 0.3ppm.In another example, calcium content can be less than 1ppm and/or iron content can be less than 0.1ppm.And, sealing water can comprise there is at least 1M Ω, at least 5M Ω, at least 10M Ω, at least 15M Ω or the demineralised water of the resistivity of 18M Ω at least.In this case, once deionized water from the canonical system for the preparation of water out, water will be exposed in atmosphere at once, along with water becomes ionic state again fast, it can very fastly lose resistivity.Therefore,, although resistivity is commonly used to determine demineralization or the deionizing degree of water, it should be noted that this also not exclusive Consideration.For example, due to the formation for polyamide polymer, the existence meeting of iron ion more easily causes problem than multiple other mineral or the ion that are present in equally in water, if therefore the water of 1M Ω has substantially carried out deionization to many ions but also had the iron that is greater than 0.3ppm, so this water in use remains undesirable.Therefore, special concern is substantially removed iron ion and calcium ion from the sealing water of pressurization water cavity 160.In a word, should be noted that and in the time that light water is incorporated in chemical treatment as herein described, there will be problem.But the low-down calcium and/or the iron content that seal as described herein in water can minimize or reduce problems, even in the case of enter from mechanical sealing member the leakage of autoclave relatively high too.

In this case, be not that all leakage parts have problem.In one aspect, when axle is in the time that axis 104 rotates, the gap 107 between the interior axle collar 110 and axle 101 can prevent or try one's best and reduce contacting between the interior axle collar and axle.But due to the defect of axle or unbalance, along with axle rotation, it can contact or rub with the interior axle collar.In this case, the sealing water leaking from pressurization water cavity 160 can provide some lubricated for the friction of rotating shaft and the interior axle collar.In one aspect, can carry out balance to agitator, to prevent or to reduce the vibration that can cause the rotating shaft leaking as far as possible, but lubricated and a small amount of additional benefits of leaking is desirable in some cases, particularly in the time getting on except calcium and/or iron for water base.

Mechanical sealing member 100 also can comprise cooling water cavity 170, and it can operate to form the cooling jacket around axle 101, but not be coupling tactile.As shown in the figure, cooling water cavity can be included in outer collar 140, with all parts of cooling mechanical seal part.Cooling water cavity can receive water entrance 172 from cooling water source 171.Because cooling water cavity not be coupling tactilely, the water using in cooling water cavity can be the water of any adequate types, and is not limited to as herein described for sealing the purer water of water.But, in one aspect in, cooling water source can with sealing water source identical.In another aspect, cooling water is capable of circulation by cooling water cavity, and discharges via outlet 173.In aspect another, cooling water can reflux or be recycled to entrance from the outlet of cooling water cavity.Heat exchanger 174 is used in recirculation water and is transported to entrance before to carrying out cooling from the water of outlet.

Fig. 4 illustrates the mechanical sealing member 200 according to another embodiment of the disclosure.The present embodiment is similar with the mechanical sealing member 100 of Fig. 3 in many aspects, has many same characteristic features.Because some features and Fig. 3 are wherein described same or similar, therefore except pointing out that the discussion of Fig. 3 is applicable to, the embodiment shown in Fig. 4, repeat no more in many aspects here.But in the present embodiment, owing to lacking bearing, axle 201 is configured to along with axle can slide with respect to outer collar 240 in the time that the longitudinal axis 204 of axle rotates.The depression 208 that is formed on outer collar can reduce the obtainable contact surface area between axle and outer collar, reduces thus friction.Depression also can be convenient to the assembling of axle and outer collar.Depression can also reduce the cost of manufacturing outer collar by the length reducing for keeping strict tolerance.

Especially for nylon 6,6, can be from about 1000Kg to about 1500Kg according to the typical batch size of example of the present disclosure, and can be from ground circulation in approximately 100 to 120 minutes during the batch jobs in autoclave.Also can use batch size outside these scopes and timing, this depends on the selection of equipment and polymer, or other factors in various equivalent modifications ken.

As mentioned, the polyamide polymer of preparing according to disclosure example can be nylon type polyamide, as nylon 6,6 or nylon 6.For example, the polymerizable composition, polymerizable composition that is used to form nylon 6,6 polymer can be prepared by the salt shock treatment of being reacted by adipic acid and hexamethylene diamine at first.No matter be the water of introducing to carry reactant as solvent, or the water that produced by the condensation reaction of adipic acid and hexamethylene diamine, be present in water in said composition all can be before being incorporated into stirred autoclave as described herein salting liquid is removed by the mode of remove portion water in being first incorporated into evaporimeter.This solution is referred to herein as polymerizable composition, polymerizable composition, it can comprise nylon 6,6 salt, and other additives, all antifoaming agents as generally known in the art, catalyst, antioxidative stabilizer, microbicidal additives, fluorescent whitening agent, acid dyeing polymer, acid dyes or other dyestuffs etc.If target is that product is brightened, also can comprises titanium dioxide, but normally directly join in autoclave to avoid caking.When prepare polymerization in autoclave time, polyamic acid salt (such as the salt of nylon 6,6) can for example be present in polymerizable composition, polymerizable composition from the content range of about 50wt% to 95wt%.

If add catalyst, catalyst can weight on from 10ppm to 1, the content range of 000ppm is present in polymerism daiamid composition.In another aspect, catalyst can exist by the content range from 10ppm to 100ppm in weight.Catalyst can include but not limited to phosphoric acid, phosphorous acid, low phosphoric acid arylphosphonic acid, alkyl phosphonic acid, alkyl phosphonate and their mixture.In one embodiment, catalyst can be sodium hypophosphite, manganese phosphate, sodium benzene phosphinate, polyphosphate sodium, phenyl potassium hypophosphite, PA 800K, hexamethylene diamine cresyl diphenyl phosphate, tolyl PA 800K or their mixture.In one aspect, catalyst can be sodium hypophosphite.

The daiamid composition prepared according to embodiment disclosed herein can improve whiteness outward appearance by adding such as the Optical Bleaching Agent of titanium dioxide.This polyamide can show permanent improved whiteness, and can be by retaining this improved whiteness such as the operation of heat setting.In one embodiment, optical brightener can be present in polymerism polyamide from the content range of 0.01wt% to 1wt%.

In addition, these polymerism polyamide can contain antioxidant stabilizer known in the art or microbicidal additives.In addition, polymerizable composition, polymerizable composition can contain antifoaming agent.In one embodiment, antifoaming agent can be present in polymerizable composition, polymerizable composition from 1ppm to 500ppm content range in weight.

Can be intrinsic acid dyes according to the polymerizable composition, polymerizable composition of the embodiment of the present invention, but also can provide basic dyeing form by the mode that the dye of positive ion in polymer is transformed these polymer or copolymer with copolymerization.It is painted that this transformation makes composition especially easily receive basic-dyeable fibre.

Further point out, some functional units described in this description are called as " module ", thereby more particularly emphasize their enforcement independence.For example, " module " can be embodied as the hardware circuit that comprises customization VLSI circuit or gate array, ready-made semiconductor (such as logic chip, transistor or other discrete parts).Module can also be implemented in programmable hardware device, such as field programmable gate array, programmable logic array, PLD etc.Module also may be embodied as the software of being carried out by various types of processors.The identification module of executable code formula can for example comprise one or more blocks of computer instructions that are organized as object, process or function.But the identification module of executable code formula needn't physically be arranged together, but can comprise the complete different instruction that is stored in a difference position that comprises this module, and in the time linking together in logic, realize the appointment effect of module.

In fact, the module of executable code formula can be perhaps many instructions of individual instructions, and even can be distributed between several different code segments, different program and cross over multiple memory devices.Similarly, operating data can be identified and illustrate here in module, and can be presented as any suitable form and be arranged in the data structure of any adequate types.Operating data can be used as individual data set and collects, or can be distributed on different positions, comprises and being distributed on different memory devices.Module can be passive or active, comprises the medicament that can operate to carry out required function.

Although theme is to be described with the tone of concrete architectural feature and/or operation, should be appreciated that the theme defining is not necessarily limited to above-mentioned specific features and operation in claims.On the contrary, above-mentioned specific features and action are as the description of the exemplifying embodiment form to claim.Under the prerequisite of spirit and scope that does not depart from described technology, can design multiple amendment and modified arrangement.

Claims

1. a stirred autoclave, comprising:

Autoclave vessel, it is suitable for holding polyamide salt composition and makes the polymerization of polyamide salt composition, to form polyamide polymer;

Agitator, it comprises axle, for mix the auger part of described polyamide salt composition in described autoclave vessel, and the drive part that is located at the outside of described autoclave vessel and engages with stirrer-driven mechanism; With

Mechanical sealing member, its described axle on the wall of described autoclave vessel enters the described position of vicinity part on the position of described autoclave or the wall of described autoclave vessel around described axle and mineralization pressure border, wherein said mechanical sealing member comprises the pressurization water cavity pressurizeing by sealing water, described sealing water is contacted with described axle and described wall, and remain under the sealing load that is greater than the container pressure in described autoclave vessel, the sealing glassware for drinking water in wherein said pressurization water cavity has the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm.

2. stirred autoclave as claimed in claim 1, wherein, also comprises and can operate the cooling water cavity forming around the cooling jacket of described axle, but described cooling water cavity not with described be coupling tactile.

3. stirred autoclave as claimed in claim 2, wherein, described cooling water cavity comprises the cooling water of circulation through described cooling water cavity.

4. stirred autoclave as claimed in claim 3, wherein, described cooling water is not deionized water.

5. stirred autoclave as claimed in claim 1, wherein, described sealing glassware for drinking water has the calcium content that is less than 1ppm.

6. stirred autoclave as claimed in claim 1, wherein, described sealing glassware for drinking water has the iron content that is less than 0.1ppm.

7. stirred autoclave as claimed in claim 1, wherein, described sealing water in the time of the rotation of described axle for described axle provides lubricated.

8. stirred autoclave as claimed in claim 1, wherein, described pressurization water cavity is suitable for allowing the sealing water that is less than 20% weight that described pressurization water cavity uses to enter described container in batch polymerization is processed.

9. stirred autoclave as claimed in claim 1, wherein, described container pressure in the polymerisation cycle rises to the level of scope from 16 to 20Bar, and described pressurization water cavity at least remains on than the level of the described container pressure in the described cycle large at least 5% in the described cycle.

10. stirred autoclave as claimed in claim 1, wherein, during the cycle 1-4 preparing at the batch of described polyamide polymer, described pressurization water cavity remains under the pressure that is greater than autoclave vessel internal pressure.

11. stirred autoclave as claimed in claim 1, wherein, described agitator is auger type agitator, it rotates to the scope of 90RPM approximately 70 in being suitable under the described pressurization water cavity of maintenance is in than the larger pressure of described container pressure.

12. stirred autoclave as claimed in claim 1, wherein, described polyamide polymer comprises being conventionally present in the calcium sensitive phosphorus catalyst of carbonic acid in water, and described sealing water has been removed calcium carbonate substantially.

13. stirred autoclave as claimed in claim 1, wherein, described polyamide polymer is cross-linked under the existence of iron.

14. stirred autoclave as claimed in claim 1, wherein, the composition of described polyamide salt is nylon 6,6 salt.

15. 1 kinds of automatic agitating type autoclaves, comprising:

Stirred autoclave as claimed in claim 1; With

Process controller, it comprises:

For controlling the modular pressure of the pressure in described autoclave vessel;

For controlling the stirring module of described agitator; With

For controlling the seal modules of the sealing water pressure in described pressurization water cavity.

16. automatic agitating type autoclaves as claimed in claim 15, wherein, described modular pressure carrys out controlled pressure by handling one or more heater blocks, suction line valve or drain tap.

17. automatic agitating type autoclaves as claimed in claim 15, wherein, the RPM level of described stirring module controls agitator.

18. automatic agitating type autoclaves as claimed in claim 15, wherein, described seal modules and the communication connection of described modular pressure, be greater than described autoclave vessel pressure to guarantee that described sealing water pressure remains.

19. 1 kinds seal the method for stirred autoclave sealing, comprising around stirrer shaft:

The agitator of the chamber wall that is arranged through autoclave vessel is assemblied in to described autoclave vessel, described agitator comprises axle, is arranged in the auger part in described autoclave vessel, and is positioned at the drive part that the outside of described autoclave vessel engages with driving mechanism;

Mechanical sealing member is attached on described axle and is between described auger part and described drive part and adjacent with described chamber wall, described mechanical sealing member is suitable for being adjacent to mineralization pressure border around described axle and with described chamber wall,

With sealing water, water cavity is pressurizeed, making to seal water contacts with described axle and chamber wall, wherein, described sealing water is under the larger pressure of the container pressure than in described autoclave vessel, and described sealing glassware for drinking water has the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm

20. methods as claimed in claim 19, wherein, described mechanical sealing member also comprises can operate the cooling water cavity forming around the cooling jacket of described axle, but described cooling water cavity is not coupling tactilely with described, and wherein said method also comprises enters cooling water or through the step of described cooling water cavity.

In stirred autoclave, prepare the method for polyamide polymer, comprising for 21. 1 kinds:

With the polyamide salt composition that is suitable for preparing polyamide polymer, described stirred autoclave is feeded;

Use the various pressure that is suitable for forming described polyamide polymer to pressurize to described stirred autoclave;

In the described polyamide polymer of preparation, use agitator to stir described polyamide salt composition, described agitator comprises axle, is arranged in the auger part in autoclave vessel, and the drive part that is positioned at the outside of described autoclave vessel and engages with driving mechanism

Wherein, be provided with to the adjacent position of the inner transition of autoclave vessel from the outside of described autoclave vessel at described axle by sealing water and carry out pressure-tight mechanical sealing member, wherein said sealing water is around described axle and under described chamber wall place remains on than the larger pressure of the pressure in described stirred autoclave, and wherein said sealing glassware for drinking water has the calcium content that is less than 3ppm and the iron content that is less than 0.3ppm.

22. methods as claimed in claim 21, wherein, the composition of described polyamic acid salt comprises the catalyst of loss of activity because calcium carbonate exists.

23. methods as claimed in claim 22, wherein, described polyamide salt composition is cross-linked under the existence of iron.

24. methods as claimed in claim 22, wherein, seal water described at least a portion and leak in described autoclave vessel, thereby provide lubricated for the described axle that is positioned at described chamber wall place.