WO2018041642A1 - Procédé pour la préparation d'un polyamide à l'aide de lactamate de potassium - Google Patents

Procédé pour la préparation d'un polyamide à l'aide de lactamate de potassium Download PDF

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Publication number
WO2018041642A1
WO2018041642A1 PCT/EP2017/070857 EP2017070857W WO2018041642A1 WO 2018041642 A1 WO2018041642 A1 WO 2018041642A1 EP 2017070857 W EP2017070857 W EP 2017070857W WO 2018041642 A1 WO2018041642 A1 WO 2018041642A1
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WIPO (PCT)
Prior art keywords
range
catalyst solution
component
weight
activator
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PCT/EP2017/070857
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German (de)
English (en)
Inventor
Jordan Thomas KOPPING
Philippe Desbois
Rainer Ostermann
Dirk Meckelnburg
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Basf Se
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Publication of WO2018041642A1 publication Critical patent/WO2018041642A1/fr

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    • 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
    • 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
    • C08G69/20—Anionic polymerisation characterised by the catalysts used

Definitions

  • the present invention relates to a process for producing a polyamide (P) by polymerizing a polymerizable mixture (pM).
  • the polymerizable mixture (pM) is prepared by mixing a catalyst solution containing at least one lactam and potassium lactamate prepared by reacting potassium with at least one lactam and an activator solution containing at least one lactam and at least one activator.
  • the catalyst solution contains in the range of 10 to 1000 ppm by weight of water, based on the total weight of the catalyst solution.
  • the present invention relates to a polyamide (P) obtainable by the process according to the invention and the use of potassium lactamate prepared by reacting potassium with at least one lactam in a polymerizable mixture (pM) to increase the polymerization rate of the polymerizable mixture (pM).
  • Polyamides are generally semicrystalline polymers, which are industrially of particular importance, since they are characterized by very good mechanical properties. In particular, they have a high strength, rigidity and toughness, good chemical resistance and a high abrasion resistance and tracking resistance. These properties are particularly important for the production of injection molded parts. High toughness is particularly important for the use of polyamides as packaging films. Due to their properties, polyamides are used industrially for the production of textiles, fishing lines, climbing ropes and carpets. In addition, polyamides find use for the production of dowels, screws and cable ties.
  • polyamides are used as paints, adhesives and coating materials.
  • the production of moldings of the polyamides is advantageously carried out by polymerization of the corresponding monomers directly in the mold, starting from monomer powder, wherein the polymerization is started in situ. In general, only heating to a temperature above the melting point of the monomer is required, not above the melting point of the polymer, which is usually higher than the melting point of the monomer.
  • WO 2014/005791 describes catalysts for and a process for the preparation of cast polyamides.
  • a lactamate, a salt and / or esters of a heteroatom-substituted organic acid and a lactam are reacted together.
  • the lactamate is an alkali and / or alkaline earth lactamate.
  • the mixture may contain activators.
  • a disadvantage of the process described in the prior art for the preparation of polyamides is that the catalysts used often have only a low storage stability and also sensitive to moisture, so that even after storage of a few hours, the catalysts are often no longer suitable for the Initiate polymerization of a lactam.
  • the object underlying the present invention is therefore to provide a process for the preparation of a polyamide, which does not have the disadvantages of the processes as described in the prior art, or only to a reduced extent.
  • step a) potassium lactamate, prepared by reacting potassium with the at least one lactam, b) providing an activator solution containing the components (A) at least one lactam, (C) at least one activator, c) mixing the catalyst solution provided in step a) with the in step b) provided activator solution to obtain a polymerizable mixture (pM), d) polymerization of the polymerizable mixture (pM) obtained in step c) to obtain the polyamide (P), characterized in that the catalyst solution provided in step a) contains in the range from 10 to 1000 ppm by weight of water, based on the total weight of the catalyst solution.
  • a catalyst solution containing at least one lactam and potassium lactam prepared by reacting potassium with the at least one lactam even after storage for several hours, for example in the range of 4 to 72 hours, a good stability and high reactivity has. In addition, it is stable to moisture.
  • the catalyst solution according to the invention has a higher reactivity both directly after its preparation and after storage of, for example, at least 4 hours, which results in a faster increase in temperature in the polymerisation of the polymerisable mixture (pM) in step d), and thereby also leads to a faster reaching the maximum temperature (T max ).
  • the polyamides (P) prepared according to the invention also have a lower residual monomer content than polyamides prepared using catalysts described in the prior art.
  • step a) a catalyst solution is provided.
  • the catalyst solution contains as component (A) at least one lactam and as component (B) potassium lactamate.
  • component (A) at least one lactam
  • component (B) potassium lactamate
  • component (B) and “potassium lactamate”. These terms are also used synonymously in the context of the present invention and therefore have the same meaning.
  • the potassium lactamate contained in the catalyst solution is prepared according to the invention by reacting potassium with the at least one lactam.
  • “potassium” is understood as meaning elemental potassium, ie potassium metal.
  • the provision of the catalyst solution is therefore preferably carried out by adding potassium to the component (A) and reacting the component (A) with potassium to obtain the catalyst solution.
  • the present invention therefore also provides a process in which the catalyst solution is provided in step a) by reacting the component (A) with potassium to obtain the catalyst solution
  • potassium is added in the range of 93 to 10 98% by weight of component (A), preferably in the range of 3 to 6% by weight of potassium to 94 to 97% by weight.
  • the catalyst solution is initially melted component (A) and then potassium slowly, for example over a period of 1 to 8 hours (h), preferably in the range of 2 to 6 hours and more preferably in the range of 3 to 5 hours, to which 20 molten component (A) is added.
  • melted is understood to mean that component (A) is above its melting point (T M (A)), for example at a temperature in the range from 70 to 140 ° C., preferably in the range from 75 to 25 120 ° C, and more preferably in the range of 80 to 100 ° C.
  • the addition of potassium to the component (A) to provide the catalyst solution in step a) is therefore carried out at a temperature in the range of 70 to 100 ° C, preferably in the range of 75 to 85 ° C and particularly preferably in the range of 30 78th up to 82 ° C.
  • the present invention therefore also provides a process wherein the component (B) is prepared by adding potassium to the component (A) at a temperature in the range of 70 to 100 ° C and reacting potassium with the component (A ).
  • potassium to the component (A) 40 take place under a dry atmosphere and / or an inert gas atmosphere, more preferably under an inert gas atmosphere.
  • inert gases are known in the art and, for example, selected from the group consisting of nitrogen and argon.
  • a dry atmosphere consists of dry air.
  • the catalyst solution provided in step a) contains, for example, in the range from 8 to 28% by weight of component (B), preferably in the range from 10 to 25% by weight and particularly preferably in the range from 15 to 20% by weight, in each case based on the total weight of the catalyst solution.
  • the present invention therefore also provides a process in which the catalyst solution provided in step a) contains in the range from 8 to 28% by weight of component (B), based on the total weight of the catalyst solution.
  • the catalyst solution provided in step a) thus contains, for example, in the range from 72 to 92% by weight of component (A) and in the range from 8 to 28% by weight of component (B), in each case based on the sum of the percentages by weight in the catalyst solution contained components (A) and (B), preferably based on the total weight of the catalyst solution.
  • the catalyst solution provided in step a) preferably contains in the range from 75 to 90% by weight of component (A) and in the range from 10 to 25% by weight of component (B), in each case based on the sum of the percentages by weight of the catalyst solution contained components (A) and (B), preferably based on the total weight of the catalyst solution.
  • the catalyst solution provided in step a) contains in the range from 80 to 85% by weight of component (A) and in the range from 15 to 20% by weight of component (B), in each case based on the sum of the percentages by weight in the catalyst solution contained components (A) and (B), preferably based on the total weight of the catalyst solution.
  • the present invention therefore also provides a process in which the catalyst solution provided in step a) is in the range from 72 to 92% by weight of component (A) and in the range from 8 to 28% by weight of component (B). contains, in each case based on the total weight of the catalyst solution.
  • the catalyst solution provided in step a) may additionally contain further components.
  • Such other components are known in the art and, for example, alkylene glycols such as poly-C 2 -C 4 alkylene glycols and / or lactones.
  • the catalyst provided in step a) contains in the range from 0.01 to 5 wt.% Further components, preferably in the range from 0.05 to 1 wt.% And particularly preferably in the range from 0.1 to 0.5 Wt .-%, each based on the total weight of the catalyst solution.
  • the catalyst solution provided in step a) contains water in the range from 10 to 1000 ppm by weight, preferably in the range from 50 to 1000 ppm by weight, and more preferably in the range from 500 to 900 ppm by weight, based in each case on the Total weight of the catalyst solution.
  • the catalyst solution provided in step a) contains no further components. Further preferably, the catalyst solution provided in step a) contains no water.
  • the catalyst solution provided in step a) consists of components (A) of (B). Then, the sum of the weight percentages of the components (A) and (B) gives 100 wt%.
  • the catalyst solution contains at least one lactam as component (A).
  • At least one lactam in the context of the present invention means both exactly one lactam and a mixture of two or more lactams.
  • lactam is meant according to the invention cyclic amides having in the ring 4 to 12 carbon atoms, preferably 6 to 12 carbon atoms.
  • component (A) contains at least one lactam having 4 to 12 carbon atoms.
  • Suitable lactams are, for example, selected from the group consisting of 4-aminobutanoic acid lactam ( ⁇ -lactam; ⁇ -butyrolactam; pyrrolidone), 5-aminopentanoic acid lactam ( ⁇ -lactam, ⁇ -valerolactam, piperidone), 6-aminohexanoic acid lactam ( ⁇ -lactam; ⁇ -caprolactam), 7-aminoheptanoic acid lactam ( ⁇ -lactam; ⁇ -heptanolactam; Enanthlactam), 8-aminooctanoic acid lactam ( ⁇ -lactam, ⁇ -octanolactam, capryllactam), 9-nonanoic acid lactam ( ⁇ -lactam, ⁇ -nonanolactam), 10-decanoic acid lactam ( ⁇ -decano-lactam, caprin lactam), 1-undecanoic acid
  • the present invention thus also provides a process in which component (A) is selected from the group consisting of pyrrolidone, piperidone, ⁇ -caprolactam, enanthlactam, capryllactam, caprinlactam and laurolactam.
  • the lactams may be unsubstituted or at least monosubstituted. In the event that at least monosubstituted lactams are used, they may carry one, two or more substituents on the carbon atoms of the ring, which are selected independently of one another from the group consisting of C to C 10 -alkyl, C 5 to C 6 - Cycloalkyl and C 5 - to C 10 -aryl.
  • component (A) is unsubstituted.
  • Suitable C 1 to C 10 -alkyl substituents are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.
  • a suitable C 5 to C 6 cycloalkyl substituent is, for example, cyclohexyl.
  • Preferred C 5 to C 10 aryl substituents are phenyl and anthranyl.
  • Unsubstituted lactams are particularly preferably used, preference being given to 12-dodecanoic acid lactam (.omega.-dodecanolactam) and .beta.-lactam (.epsilon.-caprolactam). Most preferred is ⁇ -lactam ( ⁇ -caprolactam). ⁇ -caprolactam is the cyclic amide of caproic acid. It is also referred to as 6-aminohexanoic acid lactam, 6-hexanlactam or caprolactam. Its lUPAC name is "Acepan-2-one.” Caprolactam has CAS number 105-60-2 and the general formula CeHnNO. Methods for producing caprolactam are known to those skilled in the art.
  • Step b) In step b) an activator solution is provided.
  • the activator solution contains at least one lactam as component (A) and at least one activator as component (C).
  • component (C) and “at least one activator” are used synonymously and therefore have the same meaning.
  • the component (A) contained in the activator solution the embodiments and preferences described above for the component (A) contained in the catalyst solution apply accordingly.
  • the component (A) contained in the activator solution may be the same as or different from the component (A) contained in the catalyst solution.
  • the component (A) contained in the activator solution is the same as the component (A) contained in the catalyst solution.
  • the component (C) contained in the activator solution will be described in detail below.
  • the activator solution contains, for example, in the range of 5 to 30 wt .-% of component (C), preferably in the range of 10 to 25 wt .-% of component (C) and particularly preferably in the range of 15 to 20 wt .-% of Component (C), based on the sum of the percentages by weight of the components (A) and (C) contained in the activator solution, preferably based on the total weight of the activator solution.
  • the present invention therefore also provides a process in which the activator solution provided in step b) contains in the range from 5.0 to 30% by weight of component (C), based on the total weight of the activator solution.
  • the activator solution thus contains, for example, in the range from 70 to 95% by weight of component (A) and in the range from 5 to 30% by weight of component (C), in each case based on the sum of the percentages by weight of the components contained in the activator solution (A) and (C), preferably based on the total weight of the activator solution.
  • the activator solution provided in step b) preferably contains in the range from 75 to 90% by weight of component (A) and in the range from 10 to 25% by weight of component (C), in each case based on the sum of the percentages by weight of the activator solution contained components (A) and (C), preferably based on the total weight of the activator solution.
  • the activator solution provided in step b) contains in the range from 80 to 85% by weight of component (A) and in the range from 15 to 20% by weight of component (C), in each case based on the sum of the percentages by weight in the activator solution contained components (A) and (C), preferably based on the total weight of the activator solution.
  • the present invention therefore also provides a process in which the activator solution provided in step b) is in the range from 70 to 95% by weight of component (A) and in the range from 5 to 30% by weight of component (C). contains, based on the total weight of the activator solution.
  • the activator solution may also contain other components.
  • the further components optionally contained in the activator solution the embodiments and preferences described above for the other components optionally contained in the catalyst solution apply correspondingly.
  • the activator solution may contain in the range from 0.01 to 5 wt .-% of the further components, preferably in the range of 0.05 to 1 wt .-% and particularly preferably in the range of 0, 1 to 0.5 wt. %, in each case based on the total weight of the activator solution.
  • the activator solution preferably contains no further components.
  • the activator solution provided in step b) may additionally contain water.
  • the activator solution in the range of 10 to 1000 ppm by weight of water, preferably in the range of 50 to 1000 ppm by weight of water and more preferably in the range of 500 to 900 ppm by weight of water, each based on the total weight of activator solution.
  • the present invention therefore also provides a process in which the activator solution provided in step b) contains in the range from 10 to 1000 ppm by weight of water, based on the total weight of the activator solution.
  • the activator solution can be provided in step b) by all methods known to those skilled in the art.
  • the activator solution is preferably provided at a temperature (T b ) above the melting temperature (T M (A)) of the component (A) contained in the activator solution.
  • the activator solution in step b) is provided at a temperature (T b ) in the range of 70 to 140 ° C, preferably in the range of 75 to 120 ° C and more preferably in the range of 80 to 100 ° C.
  • the activator solution can be provided in all containers known to those skilled in the art.
  • the activator solution may be provided in a kettle, in an extruder, or in a tank.
  • component (C) is usually mixed with component (A).
  • the mixing can be carried out by all methods known to the person skilled in the art, for example with a static or a dynamic mixer. Suitable static and dynamic mixers are known to those skilled in the art.
  • component (A) is preferably melted, component (C) is added to component (A) and then component (A) is mixed with component (C).
  • Component (C) may be in solid or liquid form when added to component (A).
  • the activator solution contains according to the invention as component (C) at least one activator.
  • component (C) at least one activator.
  • At least one activator in the context of the present invention means both exactly one activator and a mixture of two or more activators.
  • the at least one activator is any activator known in the art, which is suitable for activating the anionic polymerization of the at least one lactam (component (A)).
  • the at least one activator is selected from the group consisting of allophanates, carbodiimides, isocyanates, acid anhydrides, acid halides and their reaction products with the component (A).
  • the present invention therefore also provides a process in which the component (C) contained in the activator solution provided in step b) is selected from the group consisting of allophanates, carbodiimides, isocyanates, acid anhydrides, acid halides and their reaction products with the component (A ).
  • Suitable allophanates are known to the person skilled in the art.
  • An exemplary allophanate is ethyl allophanate.
  • Suitable isocyanates are, for example, aliphatic diisocyanates such as butylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate,
  • suitable aromatic diisocyanates such as tolylene diisocyanate, 4,4'-methylenebis (phenyl) isocyanate and also polyisocyanates such as, for example, isocyanates of hexamethylene diisocyanate which are also known under the name "Basonat HI 100" from BASF SE as acid halides are, for example, butylene dicurate, Butylendisaurebromid, Hexamethylendiklarechlorid, Hexamethylendiklamid, Octamethylene diacid chloride, octamethylene diacid bromide, decamethylene diacid chloride, decamethylene dicarboxylic acid, dodecamethylene diacid, dodecamethylene dicarboxylic acid, 4,4
  • component (C) is selected from the group consisting of
  • component (C) is hexamethylene diisocyanate.
  • component (A) which contains at least one lactam, forms an activated lactam in situ. This forms activated N-substituted lactams, such as acyl lactam.
  • the person skilled in the corresponding reactions are known.
  • the at least one activator is present in the activator solution usually dissolved in the component (A).
  • Geiegnet as the at least one activator is therefore in particular Brüggolen C20, 80% caprolactamblockêts 1, 6-Hexamethylendiisocyant in caprolactam from Brüggemann DE.
  • step c) the catalyst solution provided in step a) is mixed with the activator solution provided in step b) to obtain a polymerisable mixture (pM).
  • the catalyst solution and the activator solution may be mixed together while being injected into a mold.
  • the catalyst solution and the activator solution may be mixed directly in the mold to give the polymerizable mixture (pM).
  • the catalyst solution and the activator solution are mixed in a suitable mixing device to obtain the polymerizable mixture (pM), which is then subsequently introduced into a mold.
  • the polymerizable mixture (pM) is prepared and subsequently introduced into a mold.
  • Such mixing devices are known in the art as such and for example static and / or dynamic mixer.
  • the temperature when mixing the catalyst solution with the activator solution in step e) may be in any range.
  • the temperature is in the range of 80 to 180 ° C, more preferably in the range of 100 to 150 ° C and particularly preferably in the range of 120 to 140 ° C.
  • the present invention therefore also provides a process in which the mixing of the catalyst solution with the activator solution in step c) takes place at a temperature in the range from 80 to 180 ° C.
  • the process step c) can be carried out at any pressure.
  • the polymerisable mixture (pM) obtained in step c) is preferably in liquid form.
  • step c) in the range of 30 to 70 wt .-% of the catalyst solution with 30 to 70 wt .-% of the activator mixed, in each case based on the sum of the weight percent of the catalyst solution and the activator solution.
  • step c) in the range of 40 to 60 wt .-% of the catalyst solution and in the range of 40 to 60 wt .-% of the activator mixed, in each case based on the sum of the weight percent of the catalyst solution and the activator solution.
  • the polymerizable mixture (pM) obtained in step c) contains, for example, in the range of 60 to 97 wt .-% of component (A), in the range of 2.5 to 20 wt .-% of component (B) and in the range from 0.5 to 20 wt .-% of component (C), each based on the sum of the weight percent of components (A), (B) and (C), preferably based on the total weight of the polymerizable mixture (pM).
  • the polymerisable mixture (pM) obtained in step c) particularly preferably contains in the range of 75 to 94% by weight of component (A), in the range of 4 to 15% by weight of component (B) and in the range of 2 to 10% by weight of component (C), in each case based on the sum of the percentages by weight of components (A), (B) and (C), preferably based on the total weight of the polymerisable mixture (pM).
  • the present invention therefore also provides a process in which the polymerisable mixture (pM) obtained in step c) is in the range from 60 to 97% by weight of component (A), in the range from 2.5 to 20% by weight. % of component (B) and in the range of 0.5 to 20 wt .-% of component (C), in each case based on the total weight of the polymerizable mixture (pM).
  • the catalyst solution and / or the activator solution contain the other components and / or water
  • the polymerisable mixture (pM) obtained in step c) also contains the further components and / or water.
  • composition of the polymerizable mixture (pM) before the start of the polymerization refers to the composition of the polymerizable mixture (pM) before the start of the polymerization.
  • Composition of the polymerizable mixture (pM) before the start of the polymerization refers to the composition of the polymerisable mixture (pM) before the components (A), (B) and (C.) Contained in the polymerisable mixture (pM)
  • the components (A), (B) and (C) contained in the polymerisable mixture (pM) are therefore still present in unreacted form in that, during the polymerization of the polymerisable mixture (pM), the components (A), (B) and (C) contained in the polymerisable mixture (pM) at least partially react with each other and therefore the proportions of the components (A), (B) and (C) to one another in the polymerizable mixture (pM).
  • Those skilled in the art are familiar with these
  • step d) the polymerizable mixture (pM) obtained in step c) is polymerized to obtain the polyamide (P).
  • the polymerizable mixture (pM) may be polymerized in the same container in which it has been obtained by mixing the catalyst solution with the activator solution. It is likewise possible to transfer the polymerisable mixture (pM) after process step c) and before process step d) into a container in which the polymerisable mixture (pM) is then polymerized. It is furthermore preferred that the polymerizable mixture (pM) after process step c) and before step d) is cooled to a temperature in the range from -20 to 70 ° C, preferably in the range from 20 to 40 ° C.
  • the present invention therefore also provides a process in which the polymerisable mixture (pM) obtained in step c) is cooled to a temperature in the range from -20 to 70 ° C. after step c) and before step d).
  • the polymerizable mixture (pM) thus cooled can be transported and stored, for example, and then used at a later time in process step d).
  • the polymerization in step d) is usually carried out at a temperature in the range of 80 to 180 ° C, preferably in the range of 100 to 160 ° C and particularly preferably in the range of 120 to 140 ° C.
  • the present invention therefore also provides a process in which the temperature during the polymerization of the polymerisable mixture (pM) in step d) is in the range from 80 to 180.degree.
  • step d) when the polymerizable mixture (pM) has been cooled after step c) and before step d), the polymerizable mixture (pM) is then reheated for polymerization in step d) becomes. Processes for this are known to the person skilled in the art.
  • Step d) can be carried out at any pressure.
  • the steps c) and d) can also be carried out simultaneously.
  • the steps c) and d) are preferably carried out successively.
  • the polymerization of the polymerisable mixture (pM) in step d) is known to those skilled in the art. It is clear to the person skilled in the art that the polymerization is usually exothermic and therefore the polymerisable mixture (pM) during the polymerization usually heats up to a maximum temperature (T max ). After reaching the maximum temperature (T max ), the polymerizable mixture (pM) and / or the polyamide (P) obtained in the polymerization cools again.
  • step a1) storage of the catalyst solution provided in step a) is carried out at a temperature in the range of 75 to 150 ° C for a period of at least 4 hours. It goes without saying itself, that in this case in step c) the catalyst solution stored in step a1) is mixed with the activator solution provided in step b).
  • the present invention therefore also provides a process in which, prior to step c), an additional step a1) of the catalyst solution provided in step a) is carried out at a temperature in the range of 75 to 150 ° C for a period of at least four hours and in step c) the catalyst solution stored in step a1) is mixed with the activator solution provided in step b) to obtain a polymerisable mixture (pM).
  • the storage in step a1) can be carried out by all methods known to the person skilled in the art.
  • the storage in step a1) can be carried out, for example, in the same container in which the catalyst solution is provided in step a). It is also possible and preferred according to the invention that the catalyst solution is stored in step a1) in a storage container.
  • the storage is carried out at a temperature in the range of 90 to 120 ° C. Further preferably, the storage is carried out for a period of 4 to 72 hours, and more preferably for a period in the range of 4 to 24 hours.
  • the present invention therefore also provides a process in which the catalyst solution is stored in step a1) for a period in the range of 4 to 72 hours at a temperature in the range of 75 to 150 ° C.
  • the present invention therefore further provides a process for preparing a polyamide (P) comprising the steps of a) providing a catalyst solution containing the components
  • step a) potassium lactamate prepared by reacting potassium with the at least one lactam, a1) storing the catalyst solution provided in step a) at a temperature in the range of 75 to 150 ° C for a period of at least 4 hours, b) providing an activator solution containing the components (A) at least one lactam,
  • step 5 mixing the catalyst solution stored in step a1) with the activator solution provided in step b) to obtain a polymerisable mixture (pM), d) polymerizing the polymerisable mixture (pM) 10 obtained in step c) to obtain the polyamide (P) , characterized in that the catalyst solution provided in step a) contains in the range from 10 to 1000 ppm by weight of water, based on the total weight of the catalyst solution.
  • step d) the polyamide (P) is obtained.
  • the crystallinity of the polyamide (P) is usually in the range of 10% to 70%, preferably in the range of 20% to 60%, and more preferably in the range of 25 25% to 40%, determined by differential scanning calorimetry (DSC) ). Methods for determining the crystallinity of the polyamide (P) by means of DSC are known to the person skilled in the art.
  • the melting temperature (T M (P)) of the obtained polyamide (P) is, for example, in the range of> 160 to 280 ° C, preferably in the range of 180 to 250 ° C and particularly preferably in the range of 200 to 230 ° C determined using differential scanning calorimetry (DSC).
  • the glass transition temperature (T G (P)) of the resulting polyamide (P) is, for example, in the range of 20 to 150 ° C, preferably in the range of 30 to 1 10 ° C and particularly preferably in the range of 40 to 80 ° C determined using differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the proportion of unreacted component (A) in the obtained polyamide (P) is usually in the range from 0.01 to 6% by weight, preferably in the range from 0.1 to 3% by weight and particularly preferably in the range from 1 to 2 wt .-%, each based on the total weight of the resulting polyamide (P).
  • the viscosity number of the resulting polyamide (P) is usually in the range of 50 to 1,000, preferably in the range of 200 to 800, and more preferably in the range of 400 to 750, determined with 96 wt .-% sulfuric acid as a solvent at a temperature of 25 ° C with a DIN Ubbelohde II capillary.
  • the present invention therefore also provides a polyamide (P) obtainable by the process according to the invention. It has surprisingly been found that the rate of polymerization of the polymerizable mixture (pM) is increased by the use of a potassium lactamate prepared by reacting potassium with at least one lactam in a polymerisable mixture (pM). The present invention therefore also provides the use of a potassium lactamate prepared by reacting potassium with at least one lactam in a polymerizable mixture (pM) containing the components
  • (C) at least one activator, for increasing the polymerization rate of the polymerizable mixture (pM).
  • the polymerization of the polymerizable mixture (pM) usually proceeds exothermically, so that the polymerizable mixture (pM) during polymerization usually heated to a maximum temperature (T max).
  • T max a maximum temperature
  • the polymerization of the polymerizable mixture (pM) is preferably carried out in a reactor equipped with a stirrer.
  • the polyamide (P) forms, which has a higher viscosity than the polymerizable mixture (pM).
  • the viscosity exceeds a certain value, the resistance for the stirrer is too high and it stops. This time is that at which the polymerization of the polymerizable mixture (pM) is considered to be complete.
  • This stoppage time of the stirrer (t stop ) is achieved more quickly by the use of a potassium lactamate by reacting potassium with at least one lactam in a polymerizable mixture (pM) due to the increased rate of polymerization.
  • the time course of the temperature during polymerization of the polymerizable mixture (pM) was measured with an Almemo 2690 with a thermocouple positioned in the polymerizable mixture (pM) and reached during polymerization maximum temperature (T max ) and the time (t max ) in seconds (s) to reach the maximum temperature (T max ).
  • the time (t stop ) was determined in seconds (s) until the stirrer stopped.
  • VZ viscosity number 0.1% of the polyamide obtained was dissolved in 96% strength by weight sulfuric acid and the viscosity number (VZ) was determined using a DIN Ubbelohde Type II viscometer, capillary constant 0.09995, with a solvent throughput time of 106.68 seconds (seconds) at a temperature of 25 ° C.
  • the water content of the caprolactam used was determined by Karl Fischer titration.
  • Potassium caprolactamate used in the following examples was prepared as follows:
  • caprolactam 277 g (2.45 mol) of caprolactam were weighed out under dry air and heated to 80 ° C. under nitrogen, so that the caprolactam melted. Over a period of 3 h (hours) was then added 56.33 g (2.45 mol) of sodium metal, 10 wherein the temperature did not exceed 90 ° C. Subsequently, the heat source was removed, the solution was cooled, stirred overnight and then heated again to 80 ° C. The resulting melt was then recooled and used in the examples.
  • a catalyst solution consisting of 9.4 g (83.2 mmol) of caprolactam (water content 20 45 ppm by weight) and 0.4 g (0.504 mmol) Brüggolen CI O (17 wt .-% sodium caprolactam in caprolactam) under argon gas on heated to a temperature of 140 ° C.
  • An activator solution consisting of 0.2 g (0.403 mmol) of Brüggolen C20 (80% caprolactam blocked. 1, 6-hexamethylene diisocyanate in caprolactam) was added in the solid state to the catalyst solution to give the polymerizable mixture (pM).
  • the polymerizable mixture (pM) was polymerized and its temperature recorded during the reaction. Ten minutes after the addition of the activator solution to the catalyst solution, the heat source was removed and the polymerizable mixture (pM) cooled.
  • a catalyst solution consisting of 9.55 g (84.4 mmol) of caprolactam (water content 45 ppm by weight) and 0.25 g (0.315 mmol) of Brüggolen CI O (17% by weight of sodium caprolactam in caprolactam) was dissolved under argon gas heated to a temperature of 140 ° C.
  • An activator solution consisting of 0.2 g (0.403 mmol) Brüggolen C20 (80% caprolactamblockiert.es 1, 6-hexamethylene diisocyanate in
  • a catalyst solution consisting of 9.78 g (86.4 mmol) of caprolactam (water content 10 45 ppm by weight) and 0.15 g (0.189 mmol) of Brüggolen CI O (17% by weight of sodium caprolactam in caprolactam) was added Argon gas heated to a temperature of 140 ° C.
  • An activator solution consisting of 0.075 g (0.151 mmol) of Brüggolen C20 (80% caprolactam blocked. 1 1,6-hexamethylene diisocyanate in caprolactam) was added in the solid state to the catalyst solution to give the polymerizable mixture (pM).
  • the polymerizable mixture (pM) was polymerized and its temperature recorded during the reaction.
  • Example B4 5 A catalyst solution consisting of 9.4 g (83.2 mmol) of caprolactam (water content 45 ppm by weight) and 0.4 g (0.490 mmol) of potassium caprolactamate (18.5% by weight of potassium caprolactamate in caprolactam) was added Argon gas heated to a temperature of 140 ° C. An activator solution consisting of 0.2 g (0.403 mmol) Brüggolen C20 (80% caprolactamblockiert.es 1, 6-hexamethylene diisocyanate in
  • a catalyst solution consisting of 9.55 g (84.4 mmol) of caprolactam (water content 45 ppm by weight) and 0.25 g (0.306 mmol) of potassium caprolactamate (18.5% by weight). Potassium caprolactamate in caprolactam) was heated to a temperature of 140 ° C under argon gas.
  • An activator solution consisting of 0.2 g (0.403 mmol) of Brüggolen C20 (80% caprolactam blocked. 1 1,6-hexamethylene diisocyanate in caprolactam) was added in the solid state to the catalyst solution to give the polymerizable mixture (pM).
  • the polymerizable mixture (pM) was polymerized and its temperature recorded during the reaction.
  • Example B6 A catalyst solution consisting of 9.78 g (86.4 mmol) of caprolactam (water content 45 ppm by weight) and 0.15 g (0.182 mmol) of potassium caprolactamate (18.5% by weight of potassium caprolactamate in caprolactam) was added under argon gas heated to a temperature of 140 ° C.
  • An activator solution consisting of 0.075 g (0.151 mmol) of Brüggolen C20 (80% caprolactam blocked.1,6-hexamethylene diisocyanate in caprolactam) was added in the solid state to the catalyst solution to give the polymerizable mixture (pM).
  • the polymerizable mixture (pM) was polymerized and its temperature recorded during the reaction. Ten minutes after the addition of the activator solution to the catalyst solution, the heat source was removed and the polymerizable mixture (pM) cooled.
  • a catalyst solution consisting of 9.4 g (83.2 mmol) of caprolactam (water content 45 ppm by weight) and 0.4 g (0.504 mmol) of Brüggolen CI O (17% by weight).
  • the polymerizable mixture (pM) was polymerized and its temperature recorded during the reaction. Ten minutes after the addition of the activator solution to the catalyst solution, the heat source was removed and the polymerizable mixture (pM) cooled.
  • a catalyst solution consisting of 9.4 g (83.2 mmol) of caprolactam (water content 45 ppm by weight) and 0.4 g (0.490 mmol) of potassium caprolactamate (18.5% by weight of potassium caprolactamate in caprolactam) under argon gas to a Temperature of 140 ° C heated.
  • An activator solution consisting of 0.2 g (0.403 mmol) of Brüggolen C20 (80% caprolactam-blocked 1,6-hexamethylene diisocyanate in caprolactam) was added in the solid state to the catalyst solution to obtain the polymerizable mixture (pM).
  • the polymerizable mixture (pM) was polymerized and its temperature recorded during the reaction.
  • Example B10 A catalyst solution consisting of 9.4 g (83.2 mmol) of caprolactam (water content 45 ppm by weight) and 0.4 g (0.490 mmol) of potassium caprolactamate (18.5% by weight of potassium caprolactamate in caprolactam) was dissolved under argon gas heated to a temperature of 120 ° C and held for 24 h (hours) at this temperature.
  • An activator solution consisting of 0.2 g (0.403 mmol) of Brüggolen C20 (80% caprolactam-blocked 1,6-hexamethylene diisocyanate in caprolactam) was added in the solid state to the catalyst solution to obtain the polymerizable mixture (pM).
  • the polymerizable mixture (pM) was polymerized and its temperature recorded during the reaction. Ten minutes after the addition of the activator solution to the catalyst solution, the heat source was removed and the polymerizable mixture (pM) cooled.
  • a catalyst solution consisting of 9.4 g (83.2 mmol) of caprolactam (water content 45 ppm by weight) and 0.4 g (0.504 mmol) Brüggolen CI O (17 wt .-% sodium caprolactam in caprolactam) under argon gas to a Temperature of 140 ° C heated.
  • An activator solution consisting of 0.2 g (0.403 mmol)
  • Table 3 shows the maximum temperature (T max ), time (t max ) and time (t stop ) until the stirrer stopped.
  • a catalyst solution consisting of 9.4 g (83.2 mmol) of caprolactam (water content 300 ppm by weight) and 0.4 g (0.504 mmol) Brüggolen CI O (17 wt .-% sodium caprolactam in caprolactam) under argon gas to a Temperature of
  • Table 3 shows the maximum temperature (T max ), the time (t max ) and the time (t stop ) to stop the stirrer.
  • An activator solution consisting of 0.2 g (0.403 mmol) of Brüggolen C20 (80% caprolactam blocked. 1 1,6-hexamethylene diisocyanate in caprolactam) was added in the solid state to the catalyst solution to give the polymerizable mixture (pM).
  • the polymerizable mixture (pM) was polymerized and recorded its temperature during the reaction. Ten minutes after the addition of the activator solution to the catalyst solution, the heat source was removed and the polymerizable mixture (pM) cooled.
  • Table 3 shows the maximum temperature (T max ), the time (t max ), and the time (t stop ) to stop the stirrer.
  • the polymerizable mixture (pM) was polymerized and its temperature recorded during the reaction. Ten minutes after the addition of the activator solution to the catalyst solution, the heat source was removed and the polymerizable mixture (pM) cooled.
  • Table 3 shows the maximum temperature (T max ), time (t max ) and time (t stop ) until the stirrer stopped.
  • a catalyst solution consisting of 9.4 g (83.2 mmol) of caprolactam (water content 45 ppm by weight) and 0.4 g (0.504 mmol) of sodium caprolactamate (16.8% by weight of sodium caprolactamate in caprolactam) under argon gas to a Temperature of 140 ° C heated.
  • An activator solution consisting of 0.2 g (0.403 mmol)
  • a catalyst solution consisting of 9.4 g (83.2 mmol) of caprolactam (water content 300 ppm by weight) and 0.4 g (0.504 mmol) of sodium caprolactamate (16.8% by weight of sodium caprolactamate in caprolactam) under argon gas to a Temperature of 120 ° C heated and held for 24 h (hours) at this temperature.
  • An activator solution consisting of 0.2 g (0.403 mmol) of Brüggolen C20 (80% caprolactam blocked. 1 1,6-hexamethylene diisocyanate in caprolactam) was added in the solid state to the catalyst solution to give the polymerizable mixture (pM).
  • the polymerizable mixture (pM) was polymerized and its temperature recorded during the reaction. Ten minutes after the addition of the activator solution to the catalyst solution, the heat source was removed and the polymerizable mixture (pM) cooled.
  • Table 3 shows the maximum temperature (T max ), time (t max ) and time (t stop ) until the stirrer stopped.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne un procédé pour la préparation d'un polyamide (P) par polymérisation d'un mélange polymérisable (pM). Le mélange polymérisable (pM) est préparé par mélange d'une solution de catalyseur, qui contient au moins un lactame ainsi que du lactamate de potassium, préparé par transformation de potassium avec au moins un lactame, et une solution d'activateur, qui contient au moins un lactame et au moins un activateur. La solution de catalyseur contient de 10 à 1000 ppm en poids d'eau, par rapport au poids total de la solution de catalyseur. De plus, la présente invention concerne un polyamide (P) pouvant être obtenu selon le procédé selon l'invention ainsi que l'utilisation de lactamate de potassium préparé par transformation de potassium avec au moins un lactame dans un mélange polymérisable (pM) pour augmenter la vitesse de polymérisation du mélange polymérisable (pM).
PCT/EP2017/070857 2016-09-05 2017-08-17 Procédé pour la préparation d'un polyamide à l'aide de lactamate de potassium WO2018041642A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3670574A1 (fr) 2018-12-20 2020-06-24 L. Brüggemann GmbH & Co. KG Procédé de fabrication d'un système catalyseur, système catalyseur et son utilisation pour la production de polyamide coulé
US11434587B2 (en) 2016-12-13 2022-09-06 Basf Se Filaments for use as a support material in fused deposition modeling
US11964449B2 (en) 2017-03-20 2024-04-23 Basf Se Laminates containing a metal and a polyamide composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2251519A (en) 1939-02-07 1941-08-05 Du Pont Process for making polymeric materials
WO2013045319A1 (fr) * 2011-09-28 2013-04-04 Basf Se Procédé de production de polyamides par polymérisation anionique
WO2014005791A1 (fr) 2012-07-06 2014-01-09 Rhein Chemie Rheinau Gmbh Catalyseurs de production de polyamide coulé, procédé pour les préparer et leur utilisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2251519A (en) 1939-02-07 1941-08-05 Du Pont Process for making polymeric materials
WO2013045319A1 (fr) * 2011-09-28 2013-04-04 Basf Se Procédé de production de polyamides par polymérisation anionique
WO2014005791A1 (fr) 2012-07-06 2014-01-09 Rhein Chemie Rheinau Gmbh Catalyseurs de production de polyamide coulé, procédé pour les préparer et leur utilisation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11434587B2 (en) 2016-12-13 2022-09-06 Basf Se Filaments for use as a support material in fused deposition modeling
US11964449B2 (en) 2017-03-20 2024-04-23 Basf Se Laminates containing a metal and a polyamide composition
EP3670574A1 (fr) 2018-12-20 2020-06-24 L. Brüggemann GmbH & Co. KG Procédé de fabrication d'un système catalyseur, système catalyseur et son utilisation pour la production de polyamide coulé
EP3670575A1 (fr) 2018-12-20 2020-06-24 L. Brüggemann GmbH & Co. KG Procédé de fabrication d'un système catalyseur, système catalyseur et son utilisation pour la fabrication de polyamide coulé

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