EP0000397B1 - Procédé de préparation de polyamides - Google Patents

Procédé de préparation de polyamides Download PDF

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Publication number
EP0000397B1
EP0000397B1 EP78100385A EP78100385A EP0000397B1 EP 0000397 B1 EP0000397 B1 EP 0000397B1 EP 78100385 A EP78100385 A EP 78100385A EP 78100385 A EP78100385 A EP 78100385A EP 0000397 B1 EP0000397 B1 EP 0000397B1
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EP
European Patent Office
Prior art keywords
heat exchanger
weight
polymerization
extract
caprolactam
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.)
Expired
Application number
EP78100385A
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German (de)
English (en)
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EP0000397A1 (fr
Inventor
Claus Dr Cordes
Wolfgang-Dieter Dr. Jeserich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
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BASF SE
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Classifications

    • 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

Definitions

  • the invention relates to a process for the preparation of polyamides by polymerizing caprolactam, extracting the polymer with water, concentrating the extract and returning the concentrate to the polymerization.
  • the polyamides formed in the polymerization of E- caprolactam contain low-molecular components which consist of caprolactam and oligomers. In practice, these low molecular weight components are removed by extraction with hot water. The caprolactam content can be recovered from these extraction waters, purified and, if necessary, reintroduced into the polymerization. It is also possible, by adding cleaving reagents, to convert the oligomers contained in the extract waters to caprolactam, also to isolate, purify and reuse them.
  • German patent application DE-A-25 01 348 relates to a process for the preparation of polyamides by polymerizing ⁇ -caprolactam, extracting the polymer with water and concentrating the extract containing water, monomers and oligomers with the exclusion of atmospheric oxygen, the surfaces in materials being in contact with the extract are carried out, which are inert under the conditions of concentration, and the concentrate is polymerized alone or together with other polyamide-forming starting materials without further purification or separation.
  • the concentrate is preferably returned together with the monomers to the continuous caprolactam polymerization.
  • the concentration is carried out in several stages, the solids content of more than 90% being achieved in the last stage in a thin-film evaporator.
  • the process is used in the continuous polymerization of E- caprolactam.
  • other polyamide-forming monomers such as aminocarboxylic acid, lactams, dicarboxylic acids and diamines and their salts can also be used in minor amounts.
  • the usual catalysts, regulators and other additives can also be present during the polymerization.
  • Polymerization in VK tubes (according to H. Klare, Synthetic Fibers made of Polyamides, Akademie-Verlag Berlin 1963, p. 109 ff.) Is particularly preferred, which is depressurized or with a negative pressure of up to 0.5 bar or an excess pressure of up to 5 bar.
  • a VK pipe according to DE-B-14 95 198 is used.
  • the generally granulated crude polymer obtained after the polymerization step is extracted batchwise or continuously with hot water.
  • the extraction can be carried out in one stage or preferably in several stages and, if appropriate, also under superatmospheric pressure.
  • a multi-stage continuous countercurrent extraction is used.
  • the extraction water obtained after the extraction generally at a temperature of 80 to 110 ° C., normally contains 0.5 to 15% by weight of solids.
  • the extraction waters are then concentrated to a maximum solids content of 60% by weight. The concentration can take place in one stage or preferably in several stages.
  • Tube evaporators with or without forced circulation are suitable as evaporators. such as. Robert evaporators, downflow evaporators, plate evaporators or flash evaporators.
  • the concentration takes place in 3 to 4 stages after the direct current switching with initial temperatures of 150 to 180 ° C and pressures of 4 to 10 bar in such a way that end temperatures of 95 to 120 ° C at pressures of 0.5 to 2 bar and concentrations of 45 to 55% by weight are obtained.
  • the measures prescribed in DE-A-25 01 348 such as strict exclusion of atmospheric oxygen and only contact with inert materials, must be observed.
  • the concentrates obtained can be diluted with E- caprolactam.
  • the concentrate is briefly heated to temperatures above 140 ° C., preferably between 180 ° C. and 280 ° C., in a heat exchanger before the polymerization.
  • Conventional heat exchangers with adequately dimensioned heat transfer can be used.
  • Simple tube bundle heat exchangers with devices for uniformly distributing the product task to the individual tubes which are flowed through from top to bottom are preferred. It has proven to be particularly advantageous to squeeze the heat exchanger tubes over their entire length in sections up to gaps of 1 to 3 mm.
  • the lower end of a heat designed in this way advantageously opens out exchangers directly on the VK tube head, which is the first stage of the polymerization.
  • a vaporous mixture of diphenyl and diphenyl oxide or liquid heat transfer media such as oils.
  • the inlet temperature of the heat transfer medium in the heat exchanger should preferably be 190 to 350 ° C, in particular 210 to 300 ° C. It can be assumed that the high temperature differences produced in this way partially break down the oligomers. Residence times of less than 10 minutes, in particular less than 3 minutes, are preferably used. Mainly normal pressure is maintained in the heat exchanger; when using high temperatures it may be advantageous to maintain slightly elevated pressures, for example up to 6 bar.
  • the concentrates treated according to the invention are then added to the stirred upper part of the VK tube for continuous polymerization.
  • water vapor forms. This water vapor is preferably separated off in the VK tube head using the devices customary there.
  • the monomers used are completely converted into polymer, with no extract waters being obtained which reduce the yield and pollute the environment.
  • the process is characterized by its simplicity and operational reliability, since no apparatus with moving parts is required.
  • a very important and surprising advantage of the process according to the invention is that the concentrates added to the polymerization catalyze the polymerization of caprolactam.
  • the throughput in the continuous polymerization of caprolactam can be increased considerably, depending on the selected conditions by between 10 and 60%. It is particularly favorable that the extract waters to be treated are always homogeneously single-phase under the conditions according to the invention and do not tend to form deposits and blockages.
  • Another advantage of the method according to the invention over the method according to DE-A-25 01 348 is that complex and expensive devices for separating and recovering lactam vapors only once, namely in the condensation process itself and not again in the concentration of extract waters to high Solid concentrations are required.
  • the VK tube head was provided with a packed column in order to retain lactam vapors by partial condensation.
  • the column pressure was maintained at 100 mm water column.
  • the feed consisted of 100 parts by weight / unit time of E- caprolactam melt at 90 ° C., which contained 0.5 part by weight of water and 0.3 part by weight of benzoic acid as catalyst.
  • the discharged end product was granulated, extracted with hot water and dried.
  • the K value (according to Fikentscher, Cellulosechemie 13, 58 (1932) 1% in 96% sulfuric acid) was 69.
  • the yield of polymer, based on the caprolactam feed, was 89.5%.
  • Example 2 The same conditions as in Example 1 were chosen. The feed and thus the throughput was increased to 150 parts by weight / unit of time. The K value after extraction dropped to aif 67. The yield of polymer, based on the caprolactam feed, was 86.5%.
  • Example 2 The same conditions as in Example 1 were chosen.
  • the feed to the VK pipe was 135 parts by weight / unit of time.
  • the extract water obtained from the extraction of the crude polymer with hot water had a solids content of 5%.
  • These waters were fed to a circulation evaporator with the strict exclusion of atmospheric oxygen through nitrogen blanketing. All parts in contact with extracts were made of V2A.
  • the circulation evaporator was heated with steam. The heating was dimensioned such that a solids concentration of 50 to 55% and a temperature of approx. 100 to 105 ° C. were established at an excess pressure of 200 mm water column.
  • This concentrate was fed at a temperature of 100 ° C. from the circulation evaporator continuously from above to a tube bundle evaporator placed on the VK tube head.
  • the amount of concentrate was between 25 and 30 parts by weight / unit of time.
  • the stirred bundle heat exchanger was heated with a vaporous mixture of diphenyl and diphenyl oxide.
  • the inlet temperature of the steam in the heat exchanger was 260 ° C, the temperature of the running condensate was 250 ° C.
  • the residence time was about 1 min. 12 to 15 parts by weight of water per unit of time were discharged via the column at the VK tube head.
  • the poly- E -caprolactam thus produced had the same light intrinsic color as that produced according to example 1. There was no difference in the melt viscosity and the properties of the moldings produced from these polyamides. In comparison, the products according to Example 2 showed a lower melt viscosity and finished parts produced therefrom had a lower toughness.

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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)

Claims (5)

1.Procédé de préparation de polyamides par polymérisation continue de la Ⓟ-caprolactame, extraction du polymère à l'aide d'eau, concentration de l'extrait aqueux, contenant du monomère et des oligomères, dans un appareillage, dont les surfaces venant en contact avec l'extrait sont réalisées en des matériaux qui se comportent comme des matériaux inertes dans les conditions opératoires de cette concentration, le concentrat étant recyclé sans autre purification ou séparation dans la phase de polymérisation, caractérisé en ce que l'extrait, concentré jusqu'à une teneur en matières solides d'au plus 60% en poids, est chauffé pendant une courte durée, dans un échangeur de chaleur, à une température supérieure à 140°C, mais ne dépassant pas 280°C, avant d'être immédiatement introduit dans le premier stade de polymérisation.
2. Procédé suivant la revendication 1, caractérisé en ce que l'extrait avec une teneur en matières solides comprise entre 0,5 et 15% en poids est transformé en un concentrat d'une teneur en matières solides de 45 à 55% en poids à une température comprise entre 95 et 120°C.
3. Procédé suivant la revendication 1, caractérisé en ce que la durée de séjour de l'extrait dans l'échangeur de chaleur est inférieure à 10 mn et de préférence inférieure à 3 mn.
4. Procédé suivant la revendication 1, caractérisé en ce que l'échangeur de chaleur est constitué d'un faisceau de tubes parallèles, dans lequel le fluide caloporteur est introduit à une température comprise entre 190 et 350°C et de préférence entre 210 et 300°C.
5. Procédé suivant la revendication 1, caractérisé en ce que la polymérisation est essentiellement réalisée dans un tube "VK", dans lequel règne une pression normale et qui est alimenté en concentrat par sa partie supérieure ou tête.
EP78100385A 1977-07-16 1978-07-12 Procédé de préparation de polyamides Expired EP0000397B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2732328 1977-07-16
DE19772732328 DE2732328A1 (de) 1977-07-16 1977-07-16 Verfahren zur herstellung von polycaprolactam

Publications (2)

Publication Number Publication Date
EP0000397A1 EP0000397A1 (fr) 1979-01-24
EP0000397B1 true EP0000397B1 (fr) 1980-08-20

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100385A Expired EP0000397B1 (fr) 1977-07-16 1978-07-12 Procédé de préparation de polyamides

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EP (1) EP0000397B1 (fr)
DE (2) DE2732328A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2156933A1 (fr) 2008-08-19 2010-02-24 Lurgi Zimmer GmbH Procédé continu d'extraction de polyamide 6

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3134717A1 (de) * 1981-09-02 1983-03-10 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von polycaprolactam
DE3134716A1 (de) * 1981-09-02 1983-03-10 Basf Ag, 6700 Ludwigshafen Verfahren zur kontinuierlichen herstellung von polycaprolactam
DE3311260A1 (de) * 1983-03-28 1984-10-04 Basf Ag, 6700 Ludwigshafen Verfahren zum kontinuierlichen eindampfen von caprolactam und dessen oligomere enthaltenden waessrigen loesungen
DE4324616A1 (de) * 1993-07-22 1995-01-26 Bayer Ag Extraktion von Polyamid 6
DE19519819A1 (de) * 1995-05-31 1996-12-05 Bayer Ag Verfahren zur Wiederverwertung von wäßrigen Extraktlösungen, die bei der Herstellung von PA 6 oder Copolyamiden anfallen
DE19531990A1 (de) * 1995-08-30 1997-05-15 Polymer Eng Gmbh Verfahren zur kontinuierlichen Herstellung von Polyamid 6 unter Verwendung von Rücklactam
DE19531989A1 (de) * 1995-08-30 1997-05-15 Polymer Eng Gmbh Verfahren zur kontinuierlichen Herstellung eines dimerarmen Polyamid 6
JPH09188758A (ja) * 1995-11-06 1997-07-22 Mitsubishi Chem Corp カプロラクタムよりポリアミド樹脂を製造する方法
NL1007032C2 (nl) 1997-09-12 1999-03-15 Koppens Bv Paneerinrichting.
DE19752182A1 (de) 1997-11-25 1999-05-27 Basf Ag Verfahren zur kontinuierlichen Extraktion von Polyamid
DE19752183A1 (de) 1997-11-25 1999-05-27 Basf Ag Verfahren zur kontinuierlichen Extraktion von Polyamid
DE19753377B4 (de) * 1997-12-02 2008-07-10 Lurgi Zimmer Gmbh Verfahren zur Herstellung von ε-Caprolactam aus Extraktwasser der PA-6-Synthese
DE19901013A1 (de) * 1999-01-13 2000-07-20 Basf Ag Verwendung von Heterogenkatalysatoren in Verfahren zur Herstellung von Polyamiden
DE102007057189A1 (de) 2007-11-28 2009-06-04 Automatik Plastics Machinery Gmbh Verfahren und Vorrichtung zur Herstellung von Polyamid
ES2577612T3 (es) * 2011-06-08 2016-07-15 Uhde Inventa-Fischer Gmbh Procedimiento y dispositivo para la modificación directa, continua de masas fundidas poliméricas
ES2582302T3 (es) 2011-07-11 2016-09-12 Uhde Inventa-Fischer Gmbh Procedimiento para la producción de una solución acuosa de sales
WO2013076037A1 (fr) 2011-11-21 2013-05-30 Basf Se Procédé pour la production simplifiée de polyamide 6
US8629237B2 (en) 2011-11-21 2014-01-14 Basf Se Simplified production of nylon-6
EP2671902B1 (fr) 2012-06-05 2018-01-03 Polymetrix AG Conditionnement de polyamide
WO2014177603A1 (fr) 2013-05-02 2014-11-06 Basf Se Procédé de production de polyamides à viscosité élevée
JP2016518501A (ja) 2013-05-17 2016-06-23 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ケイ素含有ポリアミド複合材料の製造法
DE102013107238A1 (de) 2013-07-09 2015-01-15 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Rückgewinnung von Epsilon-Caprolactam aus Extraktwasser

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2501348C3 (de) * 1975-01-15 1988-02-11 Basf Ag, 6700 Ludwigshafen Kontinuierliches Verfahren zur Herstellung von Polyamiden aus epsilon-Caprolactam

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2156933A1 (fr) 2008-08-19 2010-02-24 Lurgi Zimmer GmbH Procédé continu d'extraction de polyamide 6
DE102008044452A1 (de) 2008-08-19 2010-02-25 Lurgi Zimmer Gmbh Kontinuierliches Verfahren zur Extraktion von Polyamid-6

Also Published As

Publication number Publication date
DE2860230D1 (en) 1980-12-04
DE2732328A1 (de) 1979-02-01
EP0000397A1 (fr) 1979-01-24

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