CN101437870A - Method for the continuous production of polyamide granules - Google Patents
Method for the continuous production of polyamide granules Download PDFInfo
- Publication number
- CN101437870A CN101437870A CNA2007800160244A CN200780016024A CN101437870A CN 101437870 A CN101437870 A CN 101437870A CN A2007800160244 A CNA2007800160244 A CN A2007800160244A CN 200780016024 A CN200780016024 A CN 200780016024A CN 101437870 A CN101437870 A CN 101437870A
- Authority
- CN
- China
- Prior art keywords
- pressure
- melt
- under
- viscosity
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/46—Post-polymerisation treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
- B29B2009/165—Crystallizing granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyamides (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention relates to a continuous method for production of polyamide granules, comprising a hydrolytic polymerisation of a mixture of at least one lactam and water to give a low-viscosity polyamide melt at a pressure of at least 5 bar and granulation of the low-viscosity polyamide melt by direct droplet formation with maintenance of a pressure which corresponds to at least the vapour pressure of the water retained in the polyamide melt. The low-viscosity granules thus obtained can be condensed in a single-stage subsequent step by treatment with super-heated steam to give a higher viscosity and unreacted monomers and cyclic oligomers extracted and then dried. The invention is characterised by gentle conditions with reduced residence time and temperatures.
Description
Technical field
The invention relates to a kind of method of continuous production polyamide granules, this method comprises the following steps:
-to the mixture that contains water and at least a lactan polymerization that is hydrolyzed, with form polymeric amide melt (polyamide melt) and
-with polymeric amide melt granulating.
Prior art
The production of polymeric amide is known, referring to " Polyamides " as L.Bottenbruch and R.Binsack, and Carl Hanser Press, Munich, 1998.In order to obtain the suitable polymerization degree and almost not have the polymkeric substance of free monomer, ordinary method comprises the certain methods step.
Fig. 1 shows the method steps of the ordinary method that is used for polyamide 6, and this method uses hexanolactam as monomer, has following typical method key element:
-in vertical fixed reaction tubes (so-called VK pipe), under 240-270 ℃, hexanolactam and water are carried out a step or two one-step hydrolysis polymerizations, wherein, the top of described reaction tubes is open, unnecessary water evaporates from here.
-in one-step polymerization, pressure is 1.0-1.2 bars absolute (bar absolute), the residence time is 18-22 hour.
-in two-stage polymerization, the pressure of the first step is the 2-4 crust, and the pressure in second step is the 0.5-1.2 crust, and the residence time of the first step is 3-5 hour, and the residence time in second step is 6-10 hour.In the first step, only generate low viscosity, low-molecular-weight prepolymer.The polymerization degree of required corresponding higher molecular weight reached in second step.
-be that the polymeric amide melt of 2.3-3.0 (measuring in 1 weight % sulphuric acid soln) carries out granulating to the relative viscosity that obtains, for example, be by granulation underwater (underwatergranulation) under 1 crust at pressure.
-be 80-110 ℃ in temperature, pressure is 1 crust, the residence time is that 16-24 hour following water extracts the cyclic oligomer of unreacted monomer and generation from particle.
-concentrate extracting water, for example,, and the extract circulation entered paradigmatic system by evaporation.It is economical especially directly the extract circulation to be entered paradigmatic system, that is to say, extract is not carried out further purifying step, as distillation.Yet if the quality of round-robin extract is had special requirement, for example, the application in film or spinning may need extra purifying step.And, in practice, on other production line to through or be not known through the utilization again of the extract of additional purification step.
-be that 100-140 ℃, pressure are 1 crust, the residence time to be under 10-25 hour the condition in temperature, in nitrogen, particle is carried out drying.Under higher temperature, and generation solid-state post condensation when increasing molecular weight (solid phase postcondensation, SSPC).Yet described solid-state post condensation is not all to need under each situation, because use for great majority, polymkeric substance has just had suitable molecular weight after granulating.By the mode of the solid-state post condensation usually implemented under the 140-180 ℃ following residence time is 12-36 hour condition, relative viscosity can be increased to 4.7 (for example, referring to DE19510698) usually.
-40 ℃, 1 the crust pressure under, in nitrogen, particle is cooled off.
In general, the disadvantageous aspect of established method is that the residence time of growing in the hydrolytic polymerization and the high temperature that experiences subsequently can cause thermal damage and other side reaction to polymkeric substance.
According to prior art, by rotating paddle, be based on another shortcoming of the granular method that the cut mechanically of polymer melts is implemented, can cause safeguarding and the cost that weares and teares very high.Their example comprises linear granulation (strand granulation) and thermal cutting under water.
WO 95/01389A1 discloses and had a kind ofly passed through for two steps to the methods of caprolactam polymerization, and wherein, in the first step, under the residence time of the pressure of 5-30 crust, 2-4 hour, the conversion of hexanolactam has reached 85%.In second step, adiabatic step-down and further polymerization take place.In this step, may cause the foaming of polymkeric substance.By hot water extraction and solid-state post condensation subsequently, perhaps the solid-state post condensation of carrying out when extracting by superheated steam, is handled thereby realization is further in the EP0284968B1 disclosed method as also.
In EP1007582B1, under pressure, in the tubular reactor of sealing, be to realize prepolymerization below 60 minutes in the presence of gas phase with in the residence time.After pressure was reduced to normal atmosphere, the gas phase of volatile component that wherein also contains reaction product was separated.
In DE10037030A1, the polymeric amide melt at least 3 the crust pressure under from pressure reactor, be discharged in the cooling fluid, and therein by above-mentioned granulation underwater by granulating.The relative viscosity of the granulating requirement polymer materials of this form can not be low excessively, is at least 1.6.
On the contrary, low viscous polymeric amide can pass through the method for vibration drippage by granulating.Be understandable that directly Di Luo method can directly form from the fused product and drip, and that is to say, does not need to use cutting or impact tool.This dropping method that is used for polyester has description at WO 01/81450A1 and DE10019508A1, and this method is implemented by the drippage equipment of the Rieter Automatik GmbH D-63762Grossostheim of company.These drippage equipment are known " DROPPO " type equipment.In DE10050463A1, the similar approach that at room temperature is applicable to liquid polyamide resin is disclosed.
Summary of the invention
The objective of the invention is to, a kind of method of continuous production polyamide granules is provided, the residence time that this method utilization is relatively shorter, and can under lower temperature, operate.
This purpose can realize by the following method that this method comprises:
-to the polymerization that under the pressure that are at least 5 crust, is hydrolyzed of the mixture that contains water and at least a lactan, form low viscous polymeric amide melt,
-keep at least with the polymeric amide melt in the corresponding pressure of vapour pressure of contained water, realize the granulating of low-viscosity polyamides melt by direct drippage.
The method according to this invention is compared with ordinary method, by applying the pressure of at least 5 crust, makes that the residence time in the hydrolytic polymerization is substantially reduced.By increasing pressure, be accelerated as the lactan open loop of the initial action of polyreaction.On the other hand, by increasing pressure, prevent that further reaction forms polymkeric substance (polycondensation).Preferably, in the hydrolytic polymerization stage, only produce low viscosity, low-molecular-weight polymkeric substance, this polymkeric substance also can be known as prepolymer.Yet, also can after granulating, increase molecular weight by solid-state condensation, it is adjusted into the value that needs.
The intensity restriction of the pressurized vessel that the maximum pressure that applies in hydrolytic polymerization is used, but can reach 20 crust.In the prior art, the pressurized vessel of Shi Heing is known as the VK pipe.
The precondition of operator scheme of the present invention is, can be to the preferred low-viscosity polyamides melt granulation that produces by hydrolytic polymerization under pressure.As mentioned above, precondition is, prilling process, and as granulation underwater, melt has specific minimal viscosity, and this minimal viscosity can not the method according to this invention realize.Therefore, traditional prilling process can not use within the scope of the invention.On the contrary, foregoing drop method fundamentally is more suitable in low melt viscosity.Yet, so far, develop these method and apparatus that for them and only under environmental stress, move or operation.But under situation of the present invention, the pressure of melt is at least 5 crust.Therefore, as low viscosity, lower molecular weight melt, and compare in lower pressure, it contains more substantial water.When pressure was reduced to environmental stress, corresponding results was exactly the foaming problem of polymkeric substance, and this can make drippage not realize conversely.According to another feature of the present invention, in fact, the granular method of the preferred low-viscosity polyamides melt of the present invention is implemented by drippage, keep simultaneously at least with the polymeric amide melt in the corresponding pressure of vapour pressure of contained water.Therefore, foaming is prevented effectively.
Preferred implementation of the present invention and development limit in the dependent claims.
The minimum pressure that in drippage, requires, corresponding with the vapour pressure of water contained in the polymeric amide melt, depend on service temperature.In the practice, should not be lower than 3 crust.And, also should be than in low 2 Palestine and Israels of the pressure of implementing hydrolytic polymerization.For security, should select the pressure higher, even be set at higher as far as possible than the pressure of implementing hydrolytic polymerization than the minimum pressure of needs.
Described lactan can use, for example ε-Ji Neixianan and/or laurylamide (laurinlactam).
Preferably, the described mixture that contains water and at least a lactan can contain the composition of other formation polymeric amide, di-carboxylic acid particularly, for example hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, terephthalic acid or m-phthalic acid, and diamine, as hexanediamine, decamethylene diamine, dodecane diamines or mphenylenediamine.
Preferably, described mixture also contains chain regulator, as monobasic or di-carboxylic acid.
Water-content in the lactan/water mixture that provides for polymerization should be corresponding with the saturation pressure of polymerizing condition at least, for example, under the pressure of 240 ℃ temperature, 15 crust, when using hexanolactam, should be more than 10%.
Under the situation of hexanolactam, the residence time is 0.5-5 hour, and particularly 1-3 hour, the pressure that satisfies hydrolytic polymerization was in 5 Palestine and Israels.
The hydrolytic polymerization of hexanolactam can be implemented under 200-250 ℃ temperature.The hydrolytic polymerization temperature of above-mentioned ordinary method under any circumstance all is higher than 240 ℃, and in contrast to this, the method according to this invention therefore can be lower in the temperature in this stage.
If by hydrolytic polymerization, it is 0.2-2.0Pas, particularly 0.5-1.5Pas that the polymeric amide melt reaches melt viscosity, just meets the demands.Under PA6 particulate situation, this is 1.3-1.5 corresponding to relative viscosity.
Be suitable for the tubular reactor of superpressure, in so-called VK pipe, hydrolytic polymerization can only be realized by a stage effectively.
From the method for above-mentioned drippage itself as can be known, can pass through drippage equipment, be used for realizing drippage by vibration in gas atmosphere.For example, nitrogen is the gas that is fit to.About known dropping method, melt pushes and makes its vibration by nozzle or dumping mouth (pouring head).Thereby can obtain shape by drippage be the particle that spherical melt drips substantially, and the method that provides with known dropping method through after the stretching, extension (falling stretch) of falling, is collected in cooling fluid in gas atmosphere similarly then.Falling to stretching can be sufficiently long, has time enough partly solidified at least thereby melt is dripped.Especially, suitable cooling fluid comprises water, hexanolactam or their mixture.Opposite with known dropping method, must be maintained to the pressure of few 3 crust, so also be necessary to use special pressurized vessel to be used for drippage.
Particle and cooling fluid are discharged from the pressure span of drippage together, under the preferable case, also have partial pressure reduction at least, separate with cooling fluid then.The separation of cooling fluid can be passed through whizzer, sieve or hydrocyclone and realize.
For all known application, be necessary further to increase particulate viscosity or molecular weight.This can handle by follow-up solid-state condensation and realize, as known more solid-state post condensation of high viscosity scope that is used for itself.
By this subsequent disposal, the relative viscosity of PA6 preferably is increased to 2.4-4.2.
For the subsequent disposal of low viscosity PA6, preferably, further be 140-180 ℃ superheated steam enforcement, for example from WO 95/01389A1 or the known method that is used for other initial viscosity of EP0284968B1 by temperature.For this purpose, the temperature of steam itself should be 170-210 ℃.
For example, the temperature that is higher than 240 ℃ with the subordinate phase of the hydrolytic polymerization of described ordinary method is compared, subsequent disposal in the stage particulate temperature be below the particulate fusing point, therefore, for PA6, under any circumstance temperature is substantially all below 220 ℃.
By with the subsequent disposal of superheated steam to PA6, known similar with WO 95/01389A1 or EP0284968B1, special advantage also extracts unreacted monomer and cyclic dimer simultaneously except being to have increased molecular weight from particle.Therefore, the content of these compositions can be lowered to 0.1-1.0 weight %.In addition, the content of water is lowered in the particle, therefore, compares with the ordinary method of initial description, and follow-up exsiccant complexity is considerably reduced (for example: the water of 10-12% in the ordinary method, the water of the method according to this invention 0.4-1%).In the scope of the method according to this invention, can be to the particulate subsequent disposal to implement in extractor with the mode of superheated steam adverse current.
According to the present invention, for subsequent disposal and solid-state condensation, extraction and the drying simultaneously of PA6, the suitable residence time is elected 5-50 hour as.The method according to this invention, the result who adds the residence time in the hydrolytic polymerization are that total residence time is 25-54 hour, and the total residence time of the initial ordinary method of describing is at least 60 hours.
Preferably, containing of discharging from subsequent disposal reclaimed monomer and made this monomer circulation enter polymerization stage in the monomeric steam, that is to say, as enter above-mentioned tubular reactor.Isolating mode by unconverted hexanolactam has produced special advantage: by the hot water extraction of routine, lactan is separated under liquid state, with under the situation of steam extraction, then separates occurring in gaseous state.It has comprised the purifying step to the extract that utilizes again, and does not need extra cost of equipment.Therefore, be known that water-soluble composition in the inorganic additives as matting agent, also together is extracted out, and the enrichment along with the time of polymerization and extraction under the situation of using hot water extraction.This enrichment to by product has brought problem, shows with the relatively poor dispersiveness of actual additive, shows as unfavorable coating on the equipment unit of transmission product.Prevented the unfavorable effect of this mode in the gasiform extraction.
Except the hexanolactam in the above-mentioned cooling fluid, the preextraction of certain cyclic dimer can realize in drippage equipment earlier.To such an extent as to when the too high levels of those cyclic dimers can be brought destructive influences to further step, do like this and have advantage.
For example, the particle that occurs in subsequent disposal also can further be cooled to 40-50 ℃ with nitrogen in silo (silo).4-6 hour the residence time is enough to realize this purpose.By nitrogen, particle is by after drying, and remaining steam is shifted from the hole of grain bed once more.Thereby, obtain the residual moisture content of 0.04-0.06 weight %.
Description of drawings
Fig. 1 explanation be the use hexanolactam that illustrated method steps as the ordinary method of monomeric preparation polyamide 6; With
What Fig. 2 illustrated is use hexanolactam according to the present invention prepares the method for polyamide 6 as monomer method steps;
Fig. 3 explanation according to the method steps that also comprises the method for preparing polyamide 6 of other step with MONOMER RECOVERY and circulation inlet pipe shape reactor of the present invention.
Embodiment
According to Fig. 2, the method according to this invention, the use hexanolactam prepares polyamide 6 as monomer and comprises that the typical traditional method key element of use is carried out subsequent disposal and the refrigerative method steps is as follows:
-hexanolactam and water carry out an one-step hydrolysis polymerization under the pressure of 200-260 ℃ temperature, 5-25 crust, condition that the residence time is 1-3 hour.Generate lower molecular weight, low viscous prepolymer.
-with the method granulating of polymeric amide melt that obtains by under the pressure of 3-25 crust, directly dripping.
-be 1 crust, the residence time to be by superheated steam the particulate drying to be combined under 20-45 hour the condition with solid state condensation, to the extraction from particle of unreacted monomer and gained cyclic dimer, at 160-190 ℃, pressure.
-be by nitrogen particle to be cooled off under 4-6 hour the condition at 40 ℃, 1 crust pressure and retention time.
What show among Fig. 3 is same step, has also shown recovery and circulation to the material of monomer in the tubular reactor and possible formation polymeric amide at this in addition.
Embodiment 1
By tubular heat exchange,, and place tubular reactor (VK pipe) with the mixture heating up to 150 that contains 85% hexanolactam and 15% water of 30kg/h ℃.In this tubular reactor, design temperature is 242 ℃, and pressure is 6.8 crust.In about 2.5 hours residence time, generated therein and recorded in sulfuric acid that relative viscosity is 1.3, melt viscosity is the polymeric amide melt of 0.5Pas.
The low-viscosity polyamides melt is transferred in the container that main pressure is 10 crust by toothed gear pump, and in nitrogen, dripped, and solidify to form particle through vibration.In the bottom of container, collecting granules and be cooled to 65 ℃ in water.Take out the mixture of pellets/water from container, by the volumetric pump fixed supply to whizzer, in this whizzer, particle and liquid separation.Pressure is carried by waterpower and is reduced to than low 3 crust of whizzer.After centrifugal, main pressure is 1 crust.
Particle is transferred to extractor from whizzer.Particle is directed therein, and with 190 ℃, the superheated steam adverse current of 88kg/h, temperature is promoted to 170 ℃.The residence time of particle in extractor is about 32 hours.By solid-state condensation, the particulate relative viscosity is increased to 2.8.Simultaneously, the content of hexanolactam in particle is reduced to 7.9-0.2 weight %, and the content of cyclic dimer is 0.5-0.05 weight %.The content of water is reduced to 0.3 weight %.
Particle enters silo from extractor through the Spiralism type feeder, and is cooled to 50 ℃ with the nitrogen adverse current.Thereby make water-content be reduced to 0.05 weight %.
Embodiment 2 (counter-example)
Repeat embodiment 1, but the pressure that drips equipment is set to 3 crust.Polymer formation can not be by granular foams (foam mass).
Embodiment 3 (counter-example)
Repeat embodiment 1, but extractor there is different adjustment.The temperature of the steam that provides is 160 ℃, and particle is heated to 140 ℃.After the extraction, residual caprolactam content is 0.6 weight % in the particle, and the content of cyclic dimer is 0.1 weight %.Water-content reaches the numerical value of 1.2 weight %.Because these numerical value, polyamide granules can not satisfy the general requirement about further processing (preparation pressing, film, fiber or silk).
Embodiment 4
Repeat embodiment 1, still, in the drippage process, use the aqueous solution that contains 30 weight % hexanolactams rather than water as refrigerant.Correspondingly, after extracting, the content of the cyclic dimer in the particle can be reduced to 0.02 weight %.Caprolactam content in the particle is 0.3 weight % after extracting, and water-content is 0.3 weight %.In the effluent of cooling silo, water-content still only is adjusted to 0.04 weight %.
Claims (22)
1, a kind of method of continuous production polyamide granules, this method comprises:
-to the mixture that contains water and at least a lactan polymerization that is hydrolyzed, form the polymeric amide melt and
-with polymeric amide melt granulating,
It is characterized in that,
-under the pressure of at least 5 crust, described mixture is implemented described hydrolytic polymerization, with form the low-viscosity polyamides melt and
The described granulating of-described low-viscosity polyamides melt keep at least with the polymeric amide melt in implement by direct drippage in the corresponding pressure of vapour pressure of contained water.
2, method according to claim 1 is characterized in that, described being dropped under at least 3 pressure that cling to implemented.
3, method according to claim 1 and 2 is characterized in that, the pressure of implementing drippage is unlike in low 2 Palestine and Israels of the pressure of implementing hydrolytic polymerization.
4, according to any described method among the claim 1-3, it is characterized in that, use hexanolactam and/or laurylamide as lactan.
5, according to any described method among the claim 1-4, it is characterized in that, described mixture also contains the composition of other formation polymeric amide, particularly di-carboxylic acid such as hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, terephthalic acid or m-phthalic acid and diamine such as hexanediamine, decamethylene diamine, dodecane diamines or mphenylenediamine.
6, according to any described method among the claim 1-5, it is characterized in that described mixture also contains chain regulator, particularly monobasic or di-carboxylic acid.
7, according to any described method among the claim 1-6, it is characterized in that the content of the water in the mixture that provides is corresponding with the saturation pressure under the polymerization temperature at least.
According to any described method among the claim 1-7, it is characterized in that 8, when using hexanolactam as monomer, the residence time of implementing hydrolytic polymerization is 0.5-5 hour, particularly 1-3 hour.
According to any described method among the claim 1-8, it is characterized in that 9, when using hexanolactam as monomer, the temperature of implementing hydrolytic polymerization is 200-250 ℃.
10, according to any described method among the claim 1-9, it is characterized in that the melt viscosity of described low-viscosity polyamides melt is 0.2-2.0Pas, particularly 0.5-1.5Pas.
According to any described method among the claim 1-10, it is characterized in that 11, described hydrolytic polymerization is only implemented by a step in tubular reactor.
12, according to any described method among the claim 1-11, it is characterized in that, described be dropped in the gas atmosphere by vibration be used for realize.
13, method according to claim 12 is characterized in that, the particle that obtains by the drippage melt form of dripping through after falling to stretching, particularly is collected in the mixture of water, hexanolactam or water and caprolactam in cooling fluid in gas atmosphere.
14, method according to claim 13 is characterized in that, described particle and cooling fluid are discharged from the pressure span of drippage together, and separate with described cooling fluid.
15, according to any described method among the claim 1-14, it is characterized in that, in order to improve relative viscosity or molecular weight and/or to extract unconverted monomer and cyclic oligomer and/or drying, described particle is had the subsequent disposal of solid-state condensation.
16, method according to claim 15 is characterized in that, under PA6 particulate situation, described particulate relative viscosity reaches 2.4 value at least by described solid-state condensation.
According to claim 15 or 16 described methods, it is characterized in that 17, under PA6 particulate situation, described particle carries out subsequent disposal by superheated steam under 170-210 ℃ vapor temperature.
According to any described method among the claim 15-17, it is characterized in that 18, under PA6 particulate situation, described subsequent disposal is to implement under 5-50 hour the condition in the residence time.
19, according to claim 17 or 18 described methods, it is characterized in that, described particulate subsequent disposal in extractor to implement with the mode of superheated steam adverse current.
According to any described method among the claim 15-19, it is characterized in that 20, being cooled to temperature through the particle of subsequent disposal by nitrogen is 40-50 ℃.
21, method according to claim 20 is characterized in that, through the cooling of the particulate of subsequent disposal in silo to implement with the mode of nitrogen adverse current.
According to any described method among the claim 17-19, it is characterized in that 22, extract or the steam that contains extract are imported in the polymerization reactor of same or another production line.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH00723/06 | 2006-05-04 | ||
| CH7232006 | 2006-05-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101437870A true CN101437870A (en) | 2009-05-20 |
Family
ID=37478883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800160244A Pending CN101437870A (en) | 2006-05-04 | 2007-05-04 | Method for the continuous production of polyamide granules |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2046863A2 (en) |
| JP (1) | JP2009535468A (en) |
| KR (1) | KR20090009231A (en) |
| CN (1) | CN101437870A (en) |
| WO (1) | WO2007128521A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127221A (en) * | 2010-12-24 | 2011-07-20 | 肖文华 | Production method of caprolactam polymer with low cyclic oligomer content |
| CN103080189A (en) * | 2010-09-10 | 2013-05-01 | 巴斯夫欧洲公司 | Method for producing processing-stable polyamide |
| CN105669969A (en) * | 2016-02-01 | 2016-06-15 | 东华大学 | Nylon 6 polymerization method and direct spinning method of melt of polymer obtained with nylon 6 polymerization method |
| CN106661158A (en) * | 2014-04-30 | 2017-05-10 | 阿朗新科新加坡私人有限公司 | Copolymer having low cyclic oligomer content |
| CN110561642A (en) * | 2011-10-25 | 2019-12-13 | 罗地亚经营管理公司 | Process for producing polyamide granules |
| CN114702699A (en) * | 2022-04-07 | 2022-07-05 | 江门市德众泰尼龙有限公司 | Method for producing polyamide powder and polyamide powder |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008004692A1 (en) * | 2008-01-16 | 2009-07-23 | Automatik Plastics Machinery Gmbh | Dropping device and method for its operation |
| FR2930251A1 (en) * | 2008-08-11 | 2009-10-23 | Arkema France | Reducing content of caprolactam and oligomers of copolyamide based on epsilon-caprolactam, comprises first washing of copolyamide with aqueous solution comprising epsilon-caprolactam and second washing of copolyamide with aqueous solution |
| EP2532698B1 (en) * | 2011-06-08 | 2016-04-20 | Uhde Inventa-Fischer GmbH | Method and device for direct, continuous modification of polymer melts |
| ES2664894T3 (en) * | 2012-06-05 | 2018-04-23 | Polymetrix Ag | Polyamide Conditioning |
| PL2784102T3 (en) * | 2013-03-26 | 2016-06-30 | Uhde Inventa Fischer Gmbh | Method and device for the continuous return of extract water in the polyamide production process |
| DE202016006519U1 (en) * | 2016-10-21 | 2016-11-09 | Maag Automatik Gmbh | Dropping device with collecting device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3306906A1 (en) * | 1983-02-26 | 1984-08-30 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE CONTINUOUS PRODUCTION OF POLYLACTAMES |
| DE10037030A1 (en) * | 2000-07-27 | 2002-02-07 | Basf Ag | Production of polyamide with a low dirt content, e.g. for production of mouldings, film or fibres, involves polymerization with a higher water vapor pressure and granulation at higher hydraulic pressure |
| DE10042476A1 (en) * | 2000-08-29 | 2002-03-28 | Tessag Ind Anlagen Gmbh | Spherical PET or PBT pellet production from polymer melt, involves production of droplets in a vibrating nozzle plate and part crystallization in a precipitation tower with opposing gas flow |
-
2007
- 2007-05-04 JP JP2009508220A patent/JP2009535468A/en active Pending
- 2007-05-04 KR KR1020087027445A patent/KR20090009231A/en not_active Application Discontinuation
- 2007-05-04 CN CNA2007800160244A patent/CN101437870A/en active Pending
- 2007-05-04 WO PCT/EP2007/003960 patent/WO2007128521A2/en active Application Filing
- 2007-05-04 EP EP07724885A patent/EP2046863A2/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103080189A (en) * | 2010-09-10 | 2013-05-01 | 巴斯夫欧洲公司 | Method for producing processing-stable polyamide |
| CN102127221A (en) * | 2010-12-24 | 2011-07-20 | 肖文华 | Production method of caprolactam polymer with low cyclic oligomer content |
| CN110561642A (en) * | 2011-10-25 | 2019-12-13 | 罗地亚经营管理公司 | Process for producing polyamide granules |
| CN106661158A (en) * | 2014-04-30 | 2017-05-10 | 阿朗新科新加坡私人有限公司 | Copolymer having low cyclic oligomer content |
| US11066498B2 (en) | 2014-04-30 | 2021-07-20 | Arlanxeo Singapore Pte. Ltd. | Copolymer having low cyclic oligomer content |
| CN105669969A (en) * | 2016-02-01 | 2016-06-15 | 东华大学 | Nylon 6 polymerization method and direct spinning method of melt of polymer obtained with nylon 6 polymerization method |
| CN105669969B (en) * | 2016-02-01 | 2018-02-09 | 东华大学 | A kind of nylon 6/poly closes method and its fused mass directly spinning method |
| CN114702699A (en) * | 2022-04-07 | 2022-07-05 | 江门市德众泰尼龙有限公司 | Method for producing polyamide powder and polyamide powder |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007128521A3 (en) | 2008-03-13 |
| KR20090009231A (en) | 2009-01-22 |
| WO2007128521A2 (en) | 2007-11-15 |
| JP2009535468A (en) | 2009-10-01 |
| EP2046863A2 (en) | 2009-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101437870A (en) | Method for the continuous production of polyamide granules | |
| CA1216993A (en) | Continuous preparation of nylons | |
| CA1222590A (en) | Continuous preparation of nylons | |
| CN102317351B (en) | Process for continuously preparing copolyamides from lactams and salts of diamines and dicarboxylic acids | |
| JP5542667B2 (en) | Method for producing polyamide | |
| CN1065239C (en) | Method for preparation of melamine | |
| CA1211889A (en) | Continuous preparation of polylactams | |
| KR20150126017A (en) | Preparation of polyamides by hydrolytic polymerization, postpolymerization and subsequent extraction | |
| CN102002160A (en) | Production process for preparing nylon slices for new membranes by using caprolactam | |
| JPS598729A (en) | Polyamide continuous manufacture | |
| US20170081472A1 (en) | Production of polyamides by hydrolytic polymerization and subsequent treatment in a kneader | |
| SK286576B6 (en) | Process for producing polyamide | |
| JP2001514281A (en) | Preparation method of polyamide | |
| US20030176625A1 (en) | Polyamide composition and method for producing the same | |
| US7615606B2 (en) | Method and device for continuously producing copolyamides with melting points greater than 265° C. | |
| KR20160010393A (en) | Method and apparatus for the continuous recycling of extraction waters in the polyamide production process | |
| CN1130353C (en) | Method for preparing melamine | |
| US20140256905A1 (en) | Preparation of polyamides by hydrolytic polymerization and subsequent devolatilization | |
| SK17412001A3 (en) | Method for preparing polyamides from lactams and polyamide extracts | |
| US6258926B1 (en) | Process and device for producing high-viscosity or highly stabilized reaction-stable polyamides, and for continuously demonomerizing polyamides | |
| KR20150129791A (en) | Production of polyamides by hydrolytic polymerization and multiple extraction | |
| US20050209436A1 (en) | Method and device for the continuous production of polyamide 6, 6 and copolyamides thereof | |
| US20140256887A1 (en) | Preparation of polyamides by hydrolytic polymierization and multiple extraction | |
| CA2362510A1 (en) | Method for producing polyamide 6 of a low extract content, high viscosity stability and low remonomerization rate | |
| US5696227A (en) | Process for the batchwise preparation of polylaurolactam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090520 |