CN104129010A - Vacuum pre-casting of polyamide polymers - Google Patents

Abstract

The present disclosure provides methods and apparatuses for providing uniform polyamide pellets. In one embodiment, a method can include maintaining a vacuum during a pre-casting polymerization cycle of the cyclic process such that the pre-casting polymerization cycle produces a reactive polyamide polymer with decreased pre-casting polymerization cycle time, extruding the reactive polyamide polymer during a casting cycle by adjusting process parameters including vessel pressure and extrusion valve opening to generate a throughput of extruded polymer, and cutting the extruded polymer at a cutting speed substantially proportional to the throughput to provide polyamide pellets.

Description

The vacuum pre-cast of polyamide polymer

Technical field

The disclosure relates to a kind of for utilizing vacuum pre-cast to manufacture the method and apparatus of polyamide granules and the method for cast polyamides particle.

Background technology

The fatty polyamide between the amide units repeating with the Special Category of at least 85% aliphatic key is called as nylon polyamide.Known these fatty polyamides are derived from dicarboxylic acids and other and form the derivative of the dicarboxylic acids of acid amides, as acid anhydrides, acid amides, carboxylic acid halides, half ester, diester, and conventionally and primary amine or secondary amine carry out chemical reaction.More specifically, known by the fatty polyamide polymer forming with the monomer diamines such as dicarboxylic acids be by uncle or secondary diamine (diamines that each nitrogen-atoms is at least connected with a hydrogen) and dicarboxylic acids or form the dicarboxylic acids of acid amides derivative react obtain.The example of reacting flow chart is as follows:

$\mathrm{HOOC}-R-\mathrm{COOH}+H_{2}N-R^{\′}-N{H}_2\↔$

-[NH-R'-NH-CO-R-CO]- _n-+nH ₂O

Wherein R and R' represent bivalent hydrocarbon radical, and n represents the number of repetitive and the number of hydrone.

" construction unit " that is derived from each diacid of a part and the polymer of diamines is all with group separately, and in R and R', the number of carbon atom is named.Therefore, be derived from hexa-methylene-1, the polyamide of 6-diamines and adipic acid is " nylon 6,6 " (polyhexamethylene adipamide).

Fibre-forming polyamide can be by the preparing of derivative that (generally at 180 DEG C to 300 DEG C) heat the diamines of equimolar amounts and the formation acid amides of dicarboxylic acids or dicarboxylic acids substantially under condensation polymerization reaction condition.This product has the fibroblast characteristic that can reach sufficiently high molecular weight.

A kind of characteristic of given polyamide can change in sizable scope, and can depend on molecular weight.To a certain extent, the characteristic of this polyamide is subject to the impact of the character of its end group, and this end group depends on reactant, diamines or the diacid of excessive use conversely.

Two features of fibre-forming polyamide relate to its high-melting-point and low solubility.By the amine of simple types and prepared those the opaque molten solids or become transparent at a quite definite temperature always almost of acid.At the temperature lower than its fusing point, fibre-forming polyamide generally provides sharp-pointed X-ray crystal powder diffraction pattern while detection with X ray, the positive evidence of crystal structure under extensive state.The density of these polyamide is conventionally between 1.0 and 1.2, and more specifically, the density of nylon 6,6 is considered to 1.14 gram per centimeters at present ³.

The same with other polycondensation products, polyamide generally comprises the separate unit with closely similar structure.The average grain diameter of these separate units, the mean molecule quantity of polymer, is deliberately controlled within the specific limits.Polymerisation is after further carrying out, and the mean molecule quantity (and inherent viscosity) of acquisition can be higher.

Use if reactant is equimolar amounts completely, polymerisation and heating all continue a very long time under the condition that allows volatile products to overflow, and can obtain the polyamide with ultra high molecular weight.But excessive if arbitrary reactant uses, polymerisation proceeds to that certain is a bit upper and substantially stop so.The time point that polymerisation stops can depend on the amount of diamines or the binary acid (or derivative) of excessive use.

The easy method of preparing polyamide comprises: prepare a salt by the diamines and the dicarboxylic acids that mix about chemical equivalent in liquid, this liquid can be chosen as the poor solvent of product salt.If needed, can be by the salt purifying separating from liquid by crystallization from suitable solvent.These diamines-dicarboxylates be crystallization and have a definite melting point.Their water solubles, and crystallization from some alcohol and alcohol-aqueous mixtures easily.

Preparing fibre-forming polyamide from diamines-dicarboxylate can carry out in many ways.This salt can not use solvent or diluent, allow to be heated to reaction temperature (180 DEG C to 300 DEG C) under the condition except the water generating in dereaction.

Before the object for making silk and other shape, may need polyamide to be placed under decompression, for example, be equivalent under the absolute pressure of 50 to 300 millimetress of mercury (67 to 400 millibars).This can accomplish easily, making before polymer cure, by the emptying reaction vessel of preparing polyamide.

Generally speaking it is essential, in above-mentioned polyamide forming process, not adding catalyst.But, known some phosphorous material, for example metal phosphinate hydrochlorate and phosphate, can play catalytic action to a certain extent.Use extra catalyst sometimes for the material of preparing HMW brings extra advantage.

Most of linear condensation polymers, the commercialization preparation of polyamide, relates generally to heat raw material monomer to cause progressively condensation of polymer.The method divides several stages to carry out conventionally, evaporates into the intermediate of assigning to form low-molecular-weight, low viscosity polymer liquid by removing simultaneously.At various vacuum and the time of staying and temperature, process this low-molecular-weight, low viscosity polymer liquid to make polymer reach desired final molecular weight and viscosity.

Although desired final molecular weight and viscosity generally can both realize, in casting cycle, the consistent polymeric material uniformly of Reaction time shorten acquisition may go wrong.Thereby, to develop and utilize various technology to carry out to manufacture more efficiently polymeric material and there is the homogeneity of improvement, this will be progress in this area.

Summary of the invention

The disclosure relates to the method and apparatus that uses cyclic process to prepare polyamide granules.In one embodiment, the method for cast polyamides polymer can be included in the step that keeps vacuum in pre-cast polymerization cycle, extrudes the polymer that active polyamide polymer and cutting be extruded in casting cycle.More specifically, the method can be included in the pre-cast polymerization cycle of cyclic process and keep vacuum to make pre-cast polymerization cycle produce active polyamide polymer, shortens the pre-cast polymerization cycle time simultaneously.The method is also included in casting cycle the mode that the technological parameter that is comprised container pressure and extruded valve opening by adjusting produces the handling capacity of extruded polymer and extrudes described active polyamide polymer.Can cut the polymer of being extruded to provide polyamide granules to obtain homogeneity with the cutting speed being substantially directly proportional to handling capacity.

In another embodiment, can comprise autoclave vessel, cutter and process controller for the production of the device of polyamide granules.Autoclave vessel can comprise extrude valve and pressure controller (for example, intake valve, air bleeding valve, heating element heater, or can be used for except extruding valve regulate any other device of the pressure in autoclave).Cutter can be suitable for cutting the polyamide polymer of extruding from autoclave vessel to form polyamide granules.Process controller can comprise for the pressure control module of controlled pressure controller, for controlling the cutting speed module of cutter speed and for controlling the valve module of extruding of extruding valve.This device can be set in the pre-cast polymerization cycle of cyclic process and keep vacuum to produce active polyamide polymer, shortens the pre-cast polymerization cycle time simultaneously.

In the embodiment of disclosed method, the problem of elongating pre-cast polymerization cycle can be solved by operate the pre-cast cycle under at least part of vacuum.

Brief description of the drawings

Figure 1A is can be for the schematic cross sectional views of a kind of autoclave vessel of embodiment of the present disclosure;

Figure 1B is can be for the schematic cross sectional views of the another kind of autoclave vessel of embodiment of the present disclosure;

Fig. 2 is can be for of the device of the present disclosure of an embodiment of the present disclosure system schematic;

Fig. 3 is the exemplary plot of describing according to several pressure distribution of the 5 cycle autoclave methods of embodiment of the present disclosure; With

Fig. 4 is the casting master drawing according to the polyamide of an embodiment of the present disclosure.

It is pointed out that these accompanying drawings are only exemplary embodiments of the present invention, and be not intended to therefore limit the scope of the present disclosure.

Detailed description of the invention

Although following detailed Description Of The Invention comprises many particular contents for illustration purpose, will be understood by those skilled in the art that, below particular content many variations and change all within the scope of embodiment disclosed herein.

Therefore, below the embodiment that provides without loss of generality, and not to claimed invention any restriction in addition.Before the disclosure is described in detail, should understand, the disclosure is not limited to described detailed description of the invention, because this can change.It is also understood that, term used herein is only for the object of describing specific implementations, and be not intended to be limited, because the scope of the present disclosure is only subject to the restriction of appended claims, unless otherwise defined, all technology used herein and scientific words all have common the understood identical implication of disclosure those of ordinary skill in the field.

Unless separately have clearly regulation in context, singulative " " and " being somebody's turn to do " of using in this description and appending claims also comprise plural form.Therefore, for example, mention that " a kind of polyamide " comprises multiple polyamide.

In the disclosure, " comprise ", " comprising ", " containing " and " having " etc. can have the implication of giving them in united states patent law, and can represent " comprising ", the meaning of " including " and so on, and be that general solution is interpreted as open language.Term " by ... composition " be a kind of closed term, and only comprise equipment concrete listed and that meet united states patent law, method, composition, composition, structure, step etc." mainly by ... composition " or " mainly containing " etc., in the time being applied to device that the disclosure contains, method, composition, composition, structure, step etc., refer to picture those elements disclosed herein, but may comprise additional construction package, composition components, method step etc.But, these additional equipment, method, composition, composition, structure, step etc., compared with these corresponding devices disclosed herein, composition, method etc., the new characteristic of the fundamental sum of those devices, composition, method etc. is not had to substantial impact.In more detail, " mainly by ... composition " or " mainly containing " etc., in the time being applied to device that the disclosure contains, method, composition, composition, structure, step etc., there is the implication of giving in united states patent law, and these terms are open, allow to exceed its cited content, as long as its basic or new feature of enumerating does not change because exceeding its cited content, but do not comprise prior art embodiment.When use open language, as " comprising " or " comprising ", should understand, also should give " mainly by ... composition " expression way and " by ... composition " expression way directly to support that just looking like is to clearly state.

Term " polymerisable composition " or " polymerisable solution " refer to and are added into according in the agitating type autoclave of embodiment of the present disclosure, in the time processing within certain temperature and pressure divides the autoclave planting, the polyamide polymer forming can be extruded or otherwise obtain solution for further use.

Term " polyamide salt " refers to the salt being included in the polymerisable compound (together with other additive) that is provided for the basic polymerizable material that forms described polyamide polymer.For example, if polyamide polymer is nylon 6,6, this salt can be prepared by adipic acid and hexamethylene diamine.In polyamide solution, also can there is other additive, both can before reactor, add, also can add in reactor.For example, titanium dioxide, normally directly adds in container, and other additive, such as catalyst, fluorescent whitening agent, defoamer etc. adds before polymerisable compound adds container, although the existence of this operation and even these additives is all not necessarily.

Term " cycle " refers to each stage of an intermittent polyreaction process that is mainly distributed to define by container inner pressure.Period 1 (cycle 1) is the beginning in batch process, and in this process, pressure is increased to a relatively high pressure from environment low pressure.Be to keep a period of time under relatively high pressure second round (cycle 2).Period 3 (cycle 3) is that relatively high pressure is reduced back to a relatively low pressure.The 4th cycle (cycle 4) is to keep a period of time under relatively low pressure, is in this example under vacuum.The 5th cycle (cycle 5) is that prepared polymer is extruded from container.The disclosure can be exchanged term " the 4th cycle ", " cycle 4 " and " pre-cast cycle " of using.

Such as the phrase of " being suitable for providing ", " being enough to cause " or " being enough to produce " etc., under the context environmental of synthetic method, refer to relate to the time, the reaction condition of temperature, solvent, reactant concentration etc., can be for providing in the scope of the ordinary skill that the product of a large amount of or large productive rate changes for experimenter.If when desired product can further be used separated or in other respects, product is that unique product or initiation material consumed not necessarily completely.

It should be noted, ratio, concentration, amount and other numeric data can represent in scope mode in this article.But should understand, the mode that uses this scope is for convenience and simplicity, and therefore, should be interpreted as not only comprising in mode flexibly the numerical value of the boundary of the scope of clearly recording, but also comprise that all indivedual numerical value of that encompasses or subrange comprise " approximately ' X' to approximately ' y' " as each numerical value and subrange.In order to describe, the concentration range of " approximately 0.1% to approximately 5% " should be interpreted as not only comprising the extremely concentration of approximately 5 % by weight of approximately 0.1 % by weight of clearly recording, but also (for example comprise indivedual concentration, 1%, 2%, 3% and 4%) subrange and in this specified scope (for example, 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%).In one embodiment, term " approximately " can comprise according to the routine of the significant digits of numerical value and rounding off.In addition, " approximately ' X' to ' y' " word comprises " approximately ' X' to approximately ' y' ".

" approximately " word is for herein time, and in the time relating to numerical value or scope, permissible level or scope have changeability to a certain degree, for example, the boundary value of scope 10% in, or in a certain respect in 5%.

In addition, feature of the present disclosure or viewpoint are to describe with the form of list or Ma Kushi group, person of skill in the art will appreciate that, the disclosure also can be described with the member's of Ma Kushi group any single member or the form of subgroup thus.For example, if X is described to select the collection group of free bromine, chlorine and iodine composition, the claim that X is bromine and X are that the claim of bromine and chlorine is absolutely proved just as exemplified separately.For example, feature of the present disclosure or viewpoint are described in the mode of list, those skilled in the art will recognize that, the disclosure also can be described with the member's of Ma Kushi group any single member or the form of subgroup thus.Therefore, if X is described to select the collection group of free bromine, chlorine and iodine composition, Y is described to select the collection group of free methyl, ethyl and propyl group composition, and X is that the claim that bromine and Y are methyl is absolutely proved also supported.

As used herein, all percentage compositions all provide in the mode of percetage by weight, except as otherwise noted.In the time being regarded as solution composition, percentage refers to the percetage by weight that comprises solvent (for example water) composition, except as otherwise noted.

As used herein, the molecular weight (Mw) of polymer is weight average molecular weight, unless otherwise prescribed.

This is showing to reading those skilled in the art of the present disclosure, describe herein and each independent embodiment of illustrating have can be easily with the character separation of all other several embodiment or in conjunction with and can not depart from independent element and the feature of the scope of the present disclosure or spirit.Any method exemplifying can with the item order that exemplified or with any other in logic possible order carry out.

Conventionally, the method for cast polyamides polymer can be included in the step that keeps vacuum in pre-cast polymerization cycle, extrudes the polymer that active polyamide polymer and cutting be extruded in casting cycle.More specifically, the method can be included in the pre-cast polymerization cycle of cyclic process and keep vacuum to make pre-cast polymerization cycle produce active polyamide polymer, shortens the pre-cast polymerization cycle time simultaneously.Can also be included in casting cycle and comprise that by adjustment the handling capacity that container pressure and the technological parameter of extruding valve opening form the polymer of extruding extrudes active polyamide polymer, and with other steps of the basic polymer of being extruded to the cutting speed that provides the handling capacity of polyamide granules to be directly proportional cutting.

Similarly, can comprise autoclave, cutter and process controller for the manufacture of the device of polyamide granules.Autoclave can comprise extrudes valve and pressure controller (for example, intake valve, air bleeding valve, heating element heater or except extruding valve, can be used for regulating any miscellaneous equipment of autoclave internal pressure).Cutter can be suitable for cutting the polyamide polymer of extruding from autoclave to form polyamide granules.Process controller can comprise for the pressure control module of controlled pressure controller, for controlling the cutting speed module of cutter speed and for controlling the valve module of extruding of extruding valve.This device can be configured to keep vacuum in the pre-cast polymerization cycle of cyclic process, makes pre-cast polymerization cycle produce active polyamide polymer, shortens the pre-cast polymerization cycle time simultaneously.

It should be noted that in the time that apparatus of the present invention and method are discussed, in these discussion, each all can be considered to be applicable to each in these examples, and no matter whether they clearly discussed in the context of that example.Therefore, for example, in the time that discussion relates to the polyamide polymer of described device, this discussion is also applicable to this method, and vice versa.

Get back to now apparatus and method of the present disclosure, generally speaking, manufacturing process of the present invention, casting process, device etc. all can be used for comprising the polymeric system of polyamide.In one embodiment, described polyamide polymer can comprise, mainly by or by nylon 6,6 composition.Nylon 6,6 can be pure polymer, or can pass through any amount of additive, comprises that fluorescent whitening agent, dyestuff etc. carry out modification.Conventionally, related manufacturing process can comprise continuously and batch process herein, unless otherwise prescribed.These techniques conventionally at reactor, for example, are carried out in autoclave.In one embodiment, manufacturing process can be batch process.Have no particular limits, such batch process is generally 5 periodic processes, as described herein.

Particularly, for nylon 6,6, can be about 1000 kilograms to about 1500 kilograms according to embodiment of the present disclosure typical batch, and circulate in the batch process of autoclave with approximately 100 to 120 minutes.Can also use except these extraneous batch and timing, this depends on the selection of equipment and polymer, or otherwise consideration in the ken of various equivalent modifications.Conventionally, the nylon of polyamide can add with salt form.In one embodiment, nylon can be nylon 6,6 salt, can be present in polyamide with the content range of approximately 50 % by weight to 95 % by weight.

Can comprise temperature and pressure for the kinds of processes parameter of polymerizing polyamide reaction of the present invention.In one embodiment, temperature can be in the scope of approximately 190 DEG C to approximately 290 DEG C, and within some cycle self or other pressure can be at approximately 250 pounds/inch ²(psia, definitely) to approximately 300 pounds/inch ²(psia, in scope definitely).In addition, in another embodiment, in some cycle, heating can be less than under the pressure of 10 holders under vacuum condition to be carried out.

The term " RV " using herein and " formic acid RV " are with reference to ASTM D789-07e1 " for measuring the standard test method of solution viscosity of polyamide (PA) ".

According to the present invention, we have found that, the pressure in pre-cast stage has solved in long problem of the undesired time of staying in pre-cast stage lower than atmospheric pressure.For the nylon-6 with higher RV, 6 preparation effects seem more remarkable.For example, when the nylon-6 of this technique to preparation RV from approximately 20 to approximately 60, the 6th, when useful, they are for preparation RV more than 30, and for example, higher than 40 or 50 nylon-6,6 polymer are especially favourable.In one embodiment, can to produce RV be 40 to 250 for example approximately 50 to approximately 60 nylon 6,6 polymer to this technique.

This technique is included in slightly or is starkly lower than implements pre-cast step under atmospheric condition.According to the present invention, the pressure in pre-cast step can reduce with the gradient of about 1psi, and for example 1.2,1.4,1.6,1.7,1.8,1.9 or 2psi.The pressure decreased producing cycle time in required pre-cast is for the nylon-6 of higher RV, and 6 preparations are more remarkable, and in reactant mixture no matter be contain inertia substantially or polymerisation inhibitory action additive also all can be more obvious.

Usually, can carry out by by autoclave and extrude/cutting technique for the preparation of the technique of the present invention of polyamide granules.In one embodiment, this technique can concentrate slurry or by polyamide salt, and for example aqueous solution of nylon 6,6 salt makes polyamide solution and feeds in autoclave as raw material.Optionally, can be diluted and to pass through evaporation step further concentrated for described slurry.In one embodiment, described slurry can be made by the aqueous solution of hexamethylene diamine and adipic acid monomer in a manner known in the art.In another detailed description of the invention, described slurry can comprise nylon 6,6 monomers of the aqueous solution of nylon 6,6 monomers that containing of small amount exist with the aqueous solution form of caprolactam.In one embodiment, can then autoclave vessel be heated to approximately 230 DEG C (or some other function temperature) rises inner self-generated pressure.Delustering agent, titanium dioxide (TiO ₂) be optionally injected in autoclave and monomer mixture as water dispersant.

Polyamide solution or multiviscosisty slurry mix can then be heated to approximately 245 DEG C (or some other function temperature) in autoclave.And at this temperature, the pressure in autoclave can be lowered to atmospheric pressure, and further in known manner application of reduced pressure method reduce pressure form daiamid composition.The autoclave that contains daiamid composition will keep approximately 30 minutes under this temperature and/or pressure.After this step, for example, further extremely approximately 285 DEG C of the polyamide polymer composition in heating high-pressure still, and drying nitrogen is introduced in autoclave vessel, and by introducing dry nitrogen, this autoclave is pressurized to approximately 4 absolute pressures to approximately 5 bar.

According to conventional heating discussed herein and pressures cycle, usually, the inventive method is included in immediately and uses pre-cast polymerization cycle before casting cycle.The pre-cast cycle implements under vacuum, has shortened cycle time like this in forming living polymer.Therefore, term " pre-cast cycle " is defined as in this article and comprises the immediately cycle before casting cycle.Therefore, for example, in the polymerization cycle in 5 cycles, the polymerization cycle in 5 cycles as described herein, the pre-cast cycle can be the cycle 4, and casting cycle can be the cycle 5.Cycle 1-3 in this example is not considered to " pre-cast cycle ", because they are not immediately before casting cycle.

Further in fact, the pre-cast cycle is characterised in that to have one " cycle time of shortening ".Thus, be recently to determine mutually with adopt the identical cycle that identical equipment is implemented under identical condition the cycle time of shortening, at room temperature except the cycle of enforcement.Therefore, determining in the pre-cast cycle while in fact whether there is " cycle time of shortening ", can implement two kinds of polymer preparation process, one of them adopts decompression method and another not adopt.If polymerization reaction time can be because adopting vacuum that the unique variable of environmental pressure is changed and shortened, the pre-cast cycle can be described as and has " the circulation timei of shortening.In one embodiment, the pre-cast polymerization cycle time of shortening, for example, shortened at least 10%, 20%, 40% or 50%.With regard to actual time, with under identical condition, adopt identical equipment to carry out the identical cycle to compare the incremental time of cycle time that (except the pre-cast polymerization cycle carrying out) shortens under environmental pressure, for example, can be at least 1 minute, 2 minutes, 4 minutes, 6 minutes, 8 minutes or 10 minutes.This time quantum may seem seldom, but substantially in the process of 2 hours, carries out again and again, and this time shorten amount can add up fast, improves the whole efficiency of system.

Polyamide polymer of the present invention can be active polyamide polymer.In another embodiment, active polyamide polymer can be proceeded polymerization after extruding.Therefore, can produce various polymer by method and apparatus of the present invention.It should be noted that this class living polymer may be difficult in casting cycle, process and keep homogeneity.Therefore, method and apparatus of the present invention can further provide uniform casting.

With regard to even casting, the inventive method can comprise regulate comprise container pressure, the technological parameter of extruding valve opening and cutting speed to be to keep homogeneity in casting cycle.Conventionally, each technological parameter can control separately so that the handling capacity of active polyamide polymer and cutting speed are proportional, thereby uniform polyamide granules is provided.Under normal circumstances, the measurement of homogeneity based on granular mass.With regard to being directly proportional, cutting speed of the present invention can match with handling capacity, and when this handling capacity is reduced, cutting speed also reduces, or this handling capacity while increasing cutting speed also increase.Being directly proportional can be to be substantially directly proportional, so that the homogeneity of polyamide granules can weigh with the average quality of measuring a collection of particle, it is described average quality in 10% that described a collection of particle has the Individual Quality of at least 95% individual particles.Aspect certain, it is described average quality in 5% that described a collection of particle has the Individual Quality of at least 99% individual particles.

Polyamide polymer as herein described can also be prepared with catalyst.In one embodiment, the amount of the catalyst that can exist in polyamide is at 10ppm to 1,000ppm(weight) in scope.In yet another aspect, the amount of existing catalyst can be within the scope of 10ppm to 100 ppm by weight.This catalyst can include, but not limited to phosphoric acid, phosphorous acid, hypophosphoric acid, arylphosphonic acid (arylphosphonic acids), aryl hypophosphorous acid and salt and their mixture.In one embodiment, catalyst can be sodium hypophosphite, manganese hypophosphite, sodium phenylphosphinate, phenyl-phosphonic acid sodium, phenyl phosphinic acid potassium, phenyl-phosphonic acid potassium, cyclohexyl diammonium hydrogen phosphate, diphenyl phosphonic acid salt, tolyl potassium phosphite or their mixture.Aspect certain, catalyst can be sodium hypophosphite.

According to embodiment disclosed herein, polyamide and daiamid composition can be by adding fluorescent whitening agent being improved aspect whiteness outward appearance.Such polyamide can show permanent whiteness and improve, and can keep this whiteness to improve by the operation such as heat setting.The amount of the fluorescent whitening agent that can exist in polyamide in one embodiment, is within the scope of 0.01 % by weight-1 % by weight.In aspect certain, fluorescent whitening agent can be titanium dioxide.

In addition, these polyamide polymers can be prepared with antioxidative stabilizer, microbicidal additives etc.In addition, this polyamide polymer can be prepared with defoamer.The amount of the defoamer that can exist in polyamide in one embodiment, is in 1-10ppm to 500ppm(weight) in scope.

According to embodiment disclosed herein, polyamide polymer is acid-dyeable type in essence, is translated into basic-dyeable fibre and can dyes type but also can modify these polymer or copolymer by the dye of positive ion in polymer.This modification makes the acceptant especially basic dyeing of composition.

Forward now Figure 1A and 1B to, it shows the schematic cross sectional views of two exemplary stirred autoclave.This figure not necessarily draws in proportion, and does not show and be generally present in each details in stirred autoclave, but selects to show the schematic diagram relevant especially to feature of the present disclosure.Therefore, in the present embodiment, stirred autoclave 10 can comprise high-pressure bottle 20 and agitator or auger 22.Although there is demonstration, agitator or auger are not essential.This container comprises chamber wall 24, and it is lining type chamber wall normally, and chamber wall and/or other structures are adjusted to the heating element heater 26a, the 26b that support one or more types.In this embodiment, external jacket heating element heater is shown in 26a and internal heating element is shown in 26b.Heating element heater that it should be noted that Figure 1A is positioned the position nearer apart from agitator, and it can be preferred, and the heating element heater of Figure 1B is positioned the position nearer apart from chamber wall, and this can be more preferred non-stirred autoclave.But this just illustrates, the location of heating element heater can be carried out by those skilled in the art after considering the disclosure.In another embodiment, can there is heating element heater in these two positions, namely near chamber wall and near agitator.

External jacket formula heating element heater 26a can be used for improving polymerisable compound contained in container or the temperature of polymer, particularly internal heating element 26b can be used for preventing polymer on the inner surface of chamber wall and or agitator on form bonding.As shown in Figure 1A, except shown internal heating element, also have a pair of multiple new rod 18, it works together with central agitator or auger 22, with multiple novel polymer.Agitator work so that polymer move up along core, and that to new rod again in the time stirring molten polymer by remove the new molten polymer of polymer reflex from sidewall surfaces.The heat transmission of this set in can improved system, and can reduce the height that stirs the eddy current causing.In both cases, it should be noted that internal heating element is schematically illustrated in the mode of cross section, but should be understood that the internal heating element that can adopt any shape or structure.Shall also be noted that this heating element heater can be set or adjust be suitable for loading as known in the art for heat being supplied with to any fluid that comprises gas and/or liquid of autoclave.Also have intake valve 28 and autoclave steam vent 30, can be jointly or use as pressure controller (together with heating element heater 26a, 26b, it also can controlled pressure) separately.Pressue device or pressure source are also not shown, exist but can be regarded as when from external pressurized.Selectively, pressure can increase by heating and reduce exhaust, as known in the art.In addition be valve opening 32 in the bottom of autoclave.In this figure and the not shown valve of extruding, but to be polymer prepared in autoclave be extruded so that the further position of processing for this.It should be noted that, no matter how are the explanation of these entrances, valve, steam vent etc. and shown position, these or other port can use from shown different mode with any purpose of design because of user, as the skilled personnel can understand.It shall yet further be noted that the method that this exemplary autoclave is provided and forms polyamide polymer in autoclave is only for exemplary object, because many other technological processes, autoclave and additive all can be for the production of polyamide polymers.This is described conventionally in this point of the method, no matter how polymer is prepared in the autoclave as main theme of the present disclosure, polymer is cast from polymerization container.

As discussed herein, the disclosure provides the polyamide polymer for extruding by cutting and has adjusted the apparatus and method that various technological parameters are prepared polymerizing polyamide composition granule.Especially, the inventive method allows to regulate the technological parameter that comprises container pressure and extrude valve opening, to produce the handling capacity of extruded polymer.In addition, cutting speed can be conditioned and match with handling capacity so that quality can be in a predetermined narrow range, as described herein.Usually, handling capacity can be controlled at least in part by the aperture of extruding valve.It should be noted that these technological parameters can adjust in casting cycle, to keep homogeneity.Therefore, in one embodiment, the inventive method can comprise the homogeneity that maintains polyamide granules corresponding to the variation adjusting cutting speed of extruding valve opening and/or container pressure.In another embodiment, cutting speed can substantially be directly proportional in handling capacity or match to provide uniform polyamide granules.

Forward now Fig. 2 to, device for the manufacture of polyamide granules can comprise container 20, for example, with the similar autoclave shown in Figure 1A and 1B, it comprises pressure controller (it can be the form of admission line/valve 28, exhaust line/valve 30 and/or heating element heater 26).It should be noted that described heating element heater is represented as external jacket, but selectively can also be maybe internal heating element.Also show and extrude valve 34 for what extrude configuration body extruded polymer by Die and mould plate or other.This device can also comprise and is suitable for having the cutter 36 that is suitable for the cutting speed of cutting uniform polyamide granules.This cutter can be for example, to be suitable for cutting very fast the disc cutter of the polymer of extruding passing through thus.This device can also comprise process controller 60, and it can comprise pressure control module 70, cutting speed module 80 and extrude valve module 90.This device can also comprise pallet 38, slurry gathering-device 40, slurry pipe 42 and drier/circulator 44.

For the process controller 60 of this device, to say in further detail, each module 70,80,90 all can be used for automatically performing conventional func or the processing step of automation equipment.For example, intake valve 28, autoclave steam vent 30 and heating element heater 26 can control to realize pressure adjusting by pressure control module 70.Cutter 36 can be controlled by cutting speed module 80.Extruding valve 34 can control by extruding valve module 90.Can also have other module (not shown), it includes but not limited to stir module, drier module, heating element heater module etc.Each module can work to provide a kind of automated system that makes to a certain extent polyamide granules homogenising together.

Fig. 3 is used for showing the independent embodiment of 5 periodic processes that limited by the pressure distribution of each circulation.Particularly, the period 1 (cycle 1) is the beginning in batch process, and in this process, pressure is increased to a relatively high pressure 120 from environment low pressure 110a.Be to keep a period of time under relatively high pressure second round (cycle 2).Period 3 (cycle 3) is that relatively high pressure is lowered the pressure 110b lower than (pressure) of initial existence, and it can be to reduce pressure lower than the example of initial environment pressure according to disclosure utilization decompression method.The 4th cycle (cycle 4) is to keep a period of time under relatively low pressure.In this concrete example, the cycle 4 is " pre-cast cycles ".Period 5 (cycle 5) is the order for extruded polymer from stirred autoclave, and pressure is improved again.In this concrete example, the cycle 5 is " casting cycles ".

It should be noted that many other pressure distribution that can be used for preparation and cast polymerization thing, and the example shown in Fig. 3 is only exemplary.Shall also be noted that and can also use miscellaneous equipment to realize this pressure distribution, as exhaust distributes, adds heat distribution, agitator distribution (in the time using agitator) etc., as understood by those skilled in the art.For example, heating can be used for improving the pressure in autoclave.Similarly, exhaust can be for during second round remaining on relatively high pressure a relatively constant level.In addition, decompression method can be used in period 4 process, pressure decreased be arrived lower than environmental pressure, as described herein.

Fig. 4 has provided and has illustrated that these module cooperative work realize according to the diagram of the example of the homogeneity of brilliance of the present invention.Particularly, Fig. 4 has described according to the casting section of the device technique parameter of an embodiment of the present disclosure, for example, and the cycle 5.Particularly, this figure provided the high-pressure bottle pressure of whole single batch of casting cycle, from the handling capacity of the polyamide polymer of autoclave, section that linearity is extruded valve and in casting cycle as the cutting speed of the function of time.As shown in the figure, various technological parameters are adjusted with a kind of higher cutting speed substantially invariable handling capacity is provided, thereby a kind of homogeneity that keeps particle is provided, also keep large-duty automation process simultaneously.

It should further be appreciated that the curve of Fig. 4, its cutting speed, through revising, is proportional to handling capacity substantially, and, when handling capacity moves up or moves down (curve as shown in the figure), cutting speed moves respectively too up and down.Term " substantially ", be directly proportional with cutting speed or comparatively mate because relating to handling capacity, can be defined as the coupling of any degree, the homogeneity of the particle of one of them batch be have at least 95% the independent quality of individual particle and the difference of average quality average quality 10% in.Utilize cutting speed substantially to mate with the relative motion of handling capacity, homogeneity is kept.Consequently, utilize pressure controller and extrude valve, handling capacity is remained in rational scope and distributed to realize high efficiency cutting.For example, in the efficient system of a high-throughput providing by suitable pressure and linear valve aperture, cutting speed can be mated relatively with handling capacity.Note that in the time that handling capacity increases, cutting speed also increases thereupon.

Get back to now Fig. 2, as discussed herein, the pressure of container 20 can be spontaneous, or can be produced by external pressure source.In addition, this pressure can regulate with heating, pressure source (not shown) and/or air bleeding valve 30.Extrude valve 34 and conventionally control the opening being extruded from polyamide polymer.In some aspects, the aperture of extruding valve can be called as the linearizing aperture of extruding valve.Herein use " linearisation " to refer to a kind of mathematical measure that is equivalent to this valve opening, that is, and unblocked area, the percentage of the material of extruding by opening.Like this, the opening that refers to 50% the material total amount (100% refers to when the heap(ed) capacity of valve in complete open state) from 100% of " linearisation " aperture of 50% is extruded, even if the aperture of valve (, unblocked area) is not total may be 50% of available aperture.It should be noted that in the time that valve is not set to approach 100% aperture to have the control of more polyamide polymer handling capacity.Because valve approaches 70% or 80% aperture, control handling capacity and significantly reduce.For example, the aperture of valve is changed to 50% from 40% to be had and comparatively significantly affects use handling capacity, and the aperture of valve changes to 90% minimum on the impact of handling capacity from 80%.Consequently, in polymer casting cycle, as much as possible valve is maintained at about within the scope of 30% to 70% aperture, and more preferably remains within the scope of 35% to 60% aperture.Accomplish this point, can change pressure and/or cutting speed, so that valve opening is remained in desirable scope.This just illustrates, this is not strict with.This has been to provide a kind of mechanism, to keep with respect to the maximum flexibility of aperture of extruding valve.

The various adjustment that can carry out technological parameter corresponding to the variation of other technological parameters again, should be noted that the adjustment of technological parameter can be carried out successively or simultaneously the mode of overlapping sequential (or with).In one embodiment, more than one technological parameter can be adjusted corresponding to the variation of the 3rd technological parameter.The example that can benefit from change for being provided as what such technological parameter, it should be noted, if extrusion is since an autoclave, many times, wherein the polymerization process of contained polyamide polymer does not also finish completely.Therefore, this polyamide polymer can continue further multiviscosisty in extrusion.Have been found that handling capacity, more significant, particle homogeneity can not keep under these conditions by increasing pressure merely simply.Equally, only further decontrol and extrude the loss that valve 34 can't always be enough to compensate thickening polymer.In addition,, even control together by these two parameters, not adjusted if cutting speed changes based on handling capacity, the homogeneity of polyamide granules may be impaired.It should be noted that and keep the homogeneity of living polymer can be more challenging because of its characteristic.

Therefore, apparatus of the present invention and method comprise utilizing to change pressure, change valve opening and change cutting speed controls handling capacity, and controls thus particle homogeneity, obtains uniform particle in an efficient way.Therefore, in a concrete example, preferred handling capacity scope can be 2 to 10 tons per hour, or 5 to 9 tons per hour, or more preferably, 6 to 8 tons per hour.In extrusion, preferred pressure limit can be 0 to 12 bar, 1 to 10 bar, or 5 to 10 bar.Preferred valve opening level can be in 30% to 70% or 45% to 65% scope.Use the preferred cutting speed of helical cutter or other similar rotary cutter can be 100 to 2000RPM, or 400 to 1800RPM, or 600 to 1500RPM.Conventionally, these technological parameters remain within the scope of these in casting cycle, and pass through these parameter adjustments, in above-mentioned scope, can obtain the polyamide granules with homogeneity.As described, can also use the technological parameter outside these scopes, as long as the homogeneity of particle can keep as described herein.

Handling capacity is passable, controls at least in part by extruding valve 34 apertures, and cutting speed can be controlled by cutter 36, and pressure can be controlled by one or more pressure controllers 26,28,30.In a concrete embodiment, in the time that more than one technological parameter can adjust to keep the homogeneity of polyamide granules, it is 30% to 70%, 35% to 65% or 40% to 60% time operation at linearity degree of melting that pressure and/or cutting speed can allow to extrude valve.In addition, in one embodiment, for desired efficiency is provided, handling capacity can be at least 5 tons/hours, or in large scale system, is at least 7 tons/hour, and the adjustment of this technological parameter can keep target throughput variation to be no more than 10 % by weight.

Process controller 60 is networked to cutter 36 and container by computer, other computer equipments or other network equipments conventionally.Apparatus of the present invention can utilize various modules to realize automation.In one embodiment, pressure control module 70 can corresponding to described cutting speed or extrude valve 34 apertures variation regulate pressure controller 26,28,30.Aspect certain, pressure control module can corresponding to cutting speed or extrude valve opening variation regulate pressure controller.In another embodiment, cutting speed module 80 can regulate the cutting speed of cutter 36 corresponding to pressure or the variation of extruding valve opening.Aspect certain, cutting speed module can corresponding to pressure or extrude valve opening variation regulate cutting speed.In another embodiment, extruding valve module 90 can regulate and extrude valve 34 corresponding to the variation of cutting speed or pressure.Aspect certain, extruding valve module can regulate and extrude valve corresponding to the variation of cutting speed or pressure.Therefore, module of the present invention can work to be enough to provide mode consistent and uniform polyamide granules to carry out adjusting process parameter in casting cycle by process controller simultaneously.

As further instruction, for helping to determine the dynamic proper level of technological parameter, for example, pressure, valve opening and cutter speed, handling capacity can estimate based on any amount of technology, comprises utilizing optics estimation, utilizing weight and/or volume (in this container and/or after extruding) to estimate, estimate etc. based on energy transmission technology with respect to the casting water around extruded polymer.For referring explicitly to energy transmission technology, this casting cycle can comprise the estimation of casting handling capacity or dynamic value distribution applications adjusting process parameter in the production of polyamide granules.For example, estimation casting handling capacity can comprise temperature and the flow velocity of measuring casting water, and described heat transmission can be calculated, then interrelated with casting handling capacity.

As further instruction, some functional units described in this description are called as " module " and carry out independence more particularly to emphasize it.For example, one " module " can be used as and comprise that hardware circuit, finished product semiconductor such as logic chip, transistor or other discrete components of customization VLSI circuit or gate array carry out.Module can also be carried out in the programmable hardware device such as such as field programmable gate array, programmable logic array, PLD.Module also can be carried out in the mode of software by various types of processors.The identification module of executable code can, for example, comprise one or more computer instruction plates, it can be organized as target, program or function.But, the executable code of identification module needn't physical location together, but can comprise the diverse instruction that realizes the appointment object of this module while being stored in the comprising this module and logically link together of diverse location.

In fact, the module of executable code can be single instrction or MIMD, and even can be distributed between some different code segments, distinct program and cross over multiple memory devices.Similarly, operating data can be identified and be illustrated in this in module, and can embody with any suitable form, and in the data structure inner tissue of any suitable type.Operating data can be collected as individual data collection, maybe can be distributed in the diverse location that is included in different memory devices.This module can be passive or active, comprises and can operate the agency who carries out required function.

Embodiment

The conventional cycle of embodiment 1 autoclave

Be to produce the aqueous solution that adds adipic acid and hexamethylene diamine in plant-scale autoclave of 1200 kg nylon 6,6 each cycle to production capacity.Temperature is risen to 280 DEG C from 150 DEG C.Plant-scale autoclave is furnished with the pressure-control valve that is emptied to exhaust line.In the time that the pressure of autoclave reaches 300psia, control valve is opened to is enough to pressure to maintain 300psia.Water in solution and the water of being emitted by adipic acid and hexamethylene diamine condensation reaction these two all by control valve controllably from autoclave discharge enter exhaust line.

Embodiment 2 compared with the cycle time that target RV is 38.5

Repeating embodiment 1, to produce RV be 38.5 nylon-6,6.In the pre-cast cycle, absolute pressure is reduced to 12psia from 16psia.Relatively, for the time in pre-cast cycle, under reduced pressure desired RV has realized fast 4 minutes.

Embodiment 3 compared with the cycle time that is 40 containing the target RV of non-inhibity additive

Repeat embodiment 1 produce RV be 40 containing non-inhibity additive, as the nylon-6 of catalyst, fluorescent whitening agent and defoamer, 6.Term " non-inhibity additive " refers to that this additive is not that those those of ordinary skill will be selected the additive of the object for suppressing polymerization.In the pre-cast cycle, absolute pressure is reduced to 7psia from 13psia.Relatively, for the time in pre-cast cycle, under reduced pressure realize desired RV fast 6 minutes.Embodiment 4 compared with the cycle time that is 45 containing the target RV of Inhibition of polymerization additive

Repeat embodiment 1 produce RV be 45 containing the nylon-6 of Inhibition of polymerization additive, 6.The example of these additives comprises following: quinhydrones, p methoxy phenol, cresols, tert-butyl catechol, 3,5-bis--tertiary butyl-4-hydroxy toluene, 2,2'-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butyl phenol), 4,9'-thiobis (3 methy 6 tert butyl phenol); Thioether class, as phenthazine, distearyl ester; Amine type, as p-phenylenediamine (PPD), 4-ADPA, N, N'-diphenyl-p-phenylenediamine (PPD), N-isopropyl-N'-phenyl-p-phenylenediamine (PPD), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (PPD), N, N'-bis--2-naphthyl-p-phenylenediamine (PPD), diphenylamines, N-PBNA, 4,4'-dicumyl diphenylamines, 4,4'-dioctyl diphenylamine; Nitroso compound, as N nitrosodiphenyl amine, N-nitroso phenyl naphthylamine, N-nitroso dinaphthylamine, p-Nitrosophenol, nitrosobenzene, NDPA, alpha-nitroso-beta-naphthol; Nitrite, as ammonium nilrite, natrium nitrosum, potassium nitrite, cupric nitrite, nitrous acid iron, nitrous acid trimethyl ammonium (trimethylammonium nitrite), the just own ester of nitrous acid (n-hexyl nitrite), 1-octyl group nitrous acid (1-octyl nitrite) and ester thereof; Nitrogen oxide, as piperidines-1-oxygen base, pyrrolidines-1-oxygen base, 2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxygen base, 2,2,6,6-tetramethyl piperidine-1-oxygen base; Mantoquita, as dimethylamino two bamic acid copper, Diethylamina Dithiomothyle acid copper, dibutylamino two bamic acid copper, Schweinfurt green, Cupric salicylate, cupric thiocyanate, copper sulphate and copper chloride; Chromium compound, for example chromium acetate and chromium oxide; Thiourea compound, as thiocarbamide, 1,3-dimethyl sulfourea, 1,3-diethyl thiourea, 1,3-di-isopropyl thiourea, 1,3-dibutyl thiourea and dimethanol thiocarbamide; Iodine, iodide, as lithium iodide, sodium iodide, KI, cesium iodide, calcium iodide and titanium iodide; Bromide, as lithium bromide, sodium bromide, KBr and cesium bromide etc.Term " Inhibition of polymerization additive " refer to that those of ordinary skill will select for suppressing those additives of polymerization object.In the pre-cast cycle, absolute pressure is reduced to 5psia from 8psia.Relatively, for the time in pre-cast cycle, under reduced pressure realize desired RV fast 7 minutes.

Although described theme, to be described specific to the expression way of architectural feature and/or operation, should be appreciated that the theme defined in appended claims might not be limited to special characteristic as above and operation.On the contrary, above-mentioned specific features and operation are published as the exemplary form that realizes claim.A large amount of amendments and replacement are adjusted in the spirit and scope that do not depart from described technology all can be expected.

Claims (33)

1. a method for cast polyamides polymer from container in cyclic process, comprising:

In the pre-cast cycle of cyclic process, maintain vacuum to make pre-cast polymerization cycle produce active polyamide polymer, shorten the pre-cast polymerization cycle time simultaneously;

The technological parameter that is comprised container pressure and extruded valve opening by adjustment is extruded active polyamide polymer with the handling capacity that produces extruded polymer in casting cycle; And

The polymer of being extruded with the cutting speed cutting being substantially directly proportional to handling capacity is to provide polyamide granules.

2. method according to claim 1, is characterized in that: described active polyamide polymer is nylon 6,6.

3. method according to claim 1, it is characterized in that: the pre-cast polymerization cycle time of described shortening is to compare and reduced at least 1 minute with the pre-cast polymerization cycle carrying out with identical equipment under the same conditions, under environmental pressure, carries out except pre-cast polymerization cycle.

4. method according to claim 3, is characterized in that: the pre-cast polymerization cycle time of described shortening is at least having shortened 4 minutes.

5. method according to claim 1, is characterized in that: described active polyamide polymer is proceeded polymerization after extruding.

6. method according to claim 1, it is characterized in that, described cutting speed is substantially directly proportional the polyamide granules with homogeneity can be provided to handling capacity, described homogeneity is that the average quality of measuring a collection of particle is weighed, and it is described average quality in 10% that described a collection of particle has the Individual Quality of at least 95% individual particles.

7. method according to claim 1, further comprises corresponding to extruding the aperture of valve and/or the variation of vessel pressure and regulates described cutting speed to maintain the homogeneity of polyamide granules.

8. method according to claim 1, is characterized in that, described container container pressurization is made to extrude valve and under 30% to 70% linear aperture, turn round.

9. method according to claim 1, is characterized in that, described linear aperture is 45% to 65%.

10. method according to claim 1, is characterized in that, the speed that described handling capacity is at least 5 tons/hours, and regulate aperture or the container pressure of extruding valve to keep handling capacity variation to be no more than 10% of average quality.

11. methods according to claim 1, is characterized in that, described handling capacity is the speed of 2 tons/hour to 10 tons/hour.

12. methods according to claim 1, is characterized in that, corresponding to cutting speed or extrude in valve opening one or both variations and adjust container pressure.

13. methods according to claim 12, is characterized in that, described container vessel pressure regulates in the scope of 0-12 bar.

14. methods according to claim 12, is characterized in that, described container container pressure regulates in the scope of 5-10 bar.

15. methods according to claim 1, is characterized in that, described cutting speed is with corresponding to container pressure or extrude in valve opening one or both variations and regulate.

16. methods according to claim 15, is characterized in that, described cutting speed is adjusted within the scope of 100 to 2000RPM by rotary cutter.

17. methods according to claim 1, is characterized in that, described in to extrude valve be to regulate corresponding to one in container pressure or cutting speed or both variations.

18. 1 kinds of devices for the manufacture of polyamide granules, comprising:

Autoclave, it comprises:

Pressure controller, and

Extrude valve;

Be adjusted to and be suitable for cutting the active polyamide polymer of extruding to form the cutter of polyamide granules from autoclave; With

Process controller, it comprises:

For controlling the pressure control module of described pressure controller,

For controlling the cutting speed module of cutter speed; With

For controlling the valve module of extruding of extruding valve,

Wherein said device is set in the pre-cast polymerization cycle in described cyclic process and keeps vacuum, makes pre-cast polymerization cycle produce active polyamide polymer, shortens the pre-cast polymerization cycle time simultaneously.

19. devices according to claim 18, it is characterized in that: described device is set to extrude one active polyamide polymer and cut this strand of polymer with certain cutting speed and manufacture a collection of uniform polyamide granules with certain handling capacity by extruding valve, wherein said homogeneity is that the average quality of measuring a collection of particle is weighed, and it is described average quality in 10% that described a collection of particle has the Individual Quality of at least 95% individual particles.

20. devices according to claim 18, is characterized in that: described container is non-stirred autoclave.

21. devices according to claim 18, is characterized in that: described container is stirred autoclave.

22. devices according to claim 18, is characterized in that: described process controller is networked to described cutter and described container by computer.

23. devices according to claim 18, is characterized in that: described pressure control module regulates pressure controller corresponding to the variation of described cutting speed or the variation of extruding valve opening.

24. devices according to claim 18, is characterized in that: described pressure control module regulates pressure controller corresponding to the variation of described cutting speed or the variation of extruding valve opening.

25. devices according to claim 18, is characterized in that: described pressure controller comprises one or more air bleeding valves, intake valve or heating element heater.

26. devices according to claim 18, is characterized in that: described cutting speed module regulates cutting speed corresponding to pressure or the variation of extruding valve opening.

27. devices according to claim 18, is characterized in that: described cutting speed module regulates cutting speed corresponding to pressure or the variation of extruding valve opening.

28. devices according to claim 18, is characterized in that: described in extrude valve module and regulate and extrude valve opening corresponding to the variation of cutting speed or pressure.

29. devices according to claim 18, is characterized in that: described in extrude valve module and regulate and extrude valve opening corresponding to the variation of cutting speed or pressure.

30. devices according to claim 18, is characterized in that: described process controller will be extruded the linear aperture of valve and remain on 45% to 65%.

31. devices according to claim 18, is characterized in that: described active polyamide polymer is nylon 6,6.

32. devices according to claim 18, is characterized in that: described homogeneity is that the average quality of measuring a collection of particle is weighed, and it is described average quality in 5% that described a collection of particle has the Individual Quality of at least 99% individual particles.

33. devices according to claim 18, is characterized in that: described device is suitable for before cutting or in cutting process with cold casting shrend deactivation polyamide polymer.