EP0000158B1 - Verfahren zur kontinuierlichen Herstellung wässriger Lösungen von Salzen aus Alkandicarbonsäuren und Alkandiaminen - Google Patents

Verfahren zur kontinuierlichen Herstellung wässriger Lösungen von Salzen aus Alkandicarbonsäuren und Alkandiaminen Download PDF

Info

Publication number
EP0000158B1
EP0000158B1 EP78100176A EP78100176A EP0000158B1 EP 0000158 B1 EP0000158 B1 EP 0000158B1 EP 78100176 A EP78100176 A EP 78100176A EP 78100176 A EP78100176 A EP 78100176A EP 0000158 B1 EP0000158 B1 EP 0000158B1
Authority
EP
European Patent Office
Prior art keywords
mixing zone
alkanediamine
alkane
aqueous
solution
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
EP78100176A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0000158A1 (de
Inventor
Rudi-Heinz Dr. Rotzoll
Paul Dr. Duffner
Ernst Dr. Dietl
Georg Pilz
Gerhard Thiel
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
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0000158A1 publication Critical patent/EP0000158A1/de
Application granted granted Critical
Publication of EP0000158B1 publication Critical patent/EP0000158B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part

Definitions

  • the invention relates to a process for the continuous preparation of aqueous solutions of salts from alkanedicarboxylic acids with 6 to 12 carbon atoms and alkanediamines with 6 to 12 carbon atoms by reacting the corresponding alkanedicarboxylic acids with the respective alkanediamines in an aqueous solution of the salt to be prepared.
  • salts of dicarboxylic acids and diamines are produced by reacting dicarboxylic acids and diamines in an alcoholic medium, for example methanol.
  • the corresponding salt precipitates out of the solution and is isolated by centrifugation. Since the work with volatile, flammable solvents is undesirable in technology, it has also started to produce such salts from aqueous solutions.
  • DE-OS 24 03 178 describes a process for the preparation of solid salts from alkanedicarboxylic acids and alkanediamines.
  • solid dicarboxylic acid is dissolved in an aqueous solution from the salt to be produced and this solution is neutralized in a mixing container with the corresponding solution in a mixing container with the corresponding alkanediamine, solid salt separating out due to oversaturation.
  • Solid salt crystallization begins before neutralization is complete.
  • the temperature should not exceed 80 ° during neutralization.
  • an aqueous solution of hexamethylenediamine is first mixed with adipic acid, preferably in solid form, in the preparation of AH salt (hexamethylene diammonium adipate).
  • adipic acid preferably in solid form
  • AH salt hexamethylene diammonium adipate
  • the diamine is used in the deficit.
  • the solution thus obtained is then adjusted to the required pH in a second large mixing vessel and at least twice the amount of the feed is returned to the first mixing vessel.
  • temperatures above 70 ° C must not be used here, since otherwise contaminants will form which cause discoloration of the polymer and can no longer be removed even by treatment with activated carbon. It is noteworthy that the aqueous solution obtained must in any case be cleaned with activated carbon.
  • the technical task was therefore to produce aqueous solutions of salts from dicarboxylic acids and diamines in a continuous manner in such a way that equivalent ratios are maintained and aftertreatment is not necessary.
  • This object is achieved in a process for the continuous preparation of 45 to 56% by weight aqueous solutions of salts from alkanedicarboxylic acids with 6 to 12 carbon atoms and alkanediamines with 6 to 12 carbon atoms by reacting the corresponding alkanedicarboxylic acids with the respective alkanediamines in an aqueous solution of the salt to be prepared in each case, in which the aqueous salt solution is circulated, first reacting dicarboxylic acid with alkane diamine in a deficit and then adding the remaining amount of alkane diamine, and the aqueous salt solution being transferred from a first mixing zone at a temperature of 90 to 102 ° C a conveying zone and a second mixing zone leads back into the first mixing zone, between which feeds liquid alkane diamine and an aqueous solution of alkane dicarboxylic acid to the first and second mixing zones, with the proviso that less than the equivalent amount of alkane diamine is added, after the second mixing zone adds the
  • the new method has the advantage that there are no mother liquors that require treatment.
  • the new process is also very flexible and easy to control. It is therefore ideally suited for exercise on a technical scale.
  • the new process enables the continuous production of large quantities with little expenditure on equipment.
  • the reaction is carried out in a mixing circuit with a buffer container.
  • the raw materials are introduced into the mixed circuit line.
  • the claimed method of operation allows the reaction to be carried out even at temperatures above 70 ° C. without the disadvantages described in Japanese Patent Application 25119172 occurring. It was by no means to be expected that the claimed method of working would prevent the formation of contaminants at temperatures above 70 ° C. and that post-treatment would no longer be necessary. In view of the difficulties described in the Japanese patent application, it was a not inconsiderable risk to take the path claimed.
  • the process claimed makes it possible to produce substantially more concentrated solutions, for example up to 65% by weight, which subsequently do not require any complex concentration.
  • Alkane dicarboxylic acids with 6 to 12 carbon atoms are used as starting materials. It is preferred to start from straight-chain ⁇ , w-alkanedicarboxylic acids of the carbon number mentioned.
  • Suitable dicarboxylic acids are, for example, adipic acid, azelaic acid, suberic acid, sebacic acid, decanedioic acid or dodecanedioic acid. Adipic acid and sebacic acid have acquired particular technical importance.
  • Alkanediamines having 6 to 12 carbon atoms are also used as starting materials. It is preferred to start from straight-chain a, w-alkanediamines with the stated carbon number. Suitable alkane diamines are, for example, hexamethylene diamine, octamethylene diamine, decamethylene diamine or dodecane methylene diamine. Hexamethylenediamine has gained particular technical importance.
  • the preferred salts are hexamethylene diamonium adipate and hexamethylene diammonium sebacate.
  • concentration of the aqueous solution on the salts prepared is 45 to 65, in particular 55 to 65 percent by weight.
  • the alkane dicarboxylic acid to be used in each case is reacted with a corresponding alkane diamine in an aqueous solution of the salt to be prepared in each case. It is understood that the concentration of the aqueous solution of the salt used corresponds to that of the product.
  • the aqueous salt solution is returned from a first mixing zone via a conveying zone and a second mixing zone to the first mixing zone.
  • the amount of salt solution in the first mixing zone is advantageously 2 to 3 times the amount of salt solution in all other zones and lines.
  • the first mixing zone on the shelf is a stirred tank or an adequate device with mixing elements, e.g. Circulation pumps, it being important to ensure that the first mixing zone has sufficient buffer capacity compared to the other zones. Continuously pumping pumps such as e.g. Centrifugal pumps.
  • the second mixing zone is advantageously designed as a mixing section, i.e. deflections and / or internals ensure rapid, effective mixing of the medium flowing through.
  • 40 to 80 times the amount of the content of the first mixing zone is circulated every hour.
  • alkanediamine in liquid form and alkanedicarboxylic acid are fed in as an aqueous solution.
  • the alkane diamines are advantageously used in molten form.
  • alkane diamines by adding small amounts of water, e.g. liquefy up to 20 percent by weight.
  • Alkanedicarboxylic acids are advantageously added in 48 to 55 percent by weight aqueous solution. It goes without saying that the total amount of water added must be such that, after combining, a solution of salts of alkanedicarboxylic acids and alkanediamines corresponding to the desired concentration results.
  • the amount of alkanediamines fed in is chosen so that it is below the necessary equivalent amount, based on the amount of dicarboxylic acid. It is advantageous to add 95 to 99 mole percent of the amount of diamine required for equivalence.
  • alkane diamines are first introduced, in particular on the suction side of the delivery zone, and then the aqueous solution of alkane dicarboxylic acids, preferably on the pressure side of the delivery zone.
  • the reaction mixture which now contains a small amount of excess alkanedicarboxylic acid, is passed through a second mixing zone directed to ensure salt formation. Subsequent to the second mixing zone, the remaining amount of liquid alkane diamine is fed in, which is necessary to reach the equivalence point.
  • the equivalence point can easily be determined for the individual salts on the basis of the pH value. It is 7.65 for hexamethylene diammonium adipate (measured as a 10% aqueous solution at 25 ° C.) and 7.60 for hexamethylene diammonium sebacate.
  • alkane diamine for example up to 0.5 mol percent
  • the addition of the remaining amount of alkanediamine advantageously is followed by a further mixing zone, the structure of which corresponds to that of the second mixing zone.
  • the aqueous solution of salts obtained from alkanedicarboxylic acids and alkanediamines is returned to the first mixing zone.
  • the aqueous solution is advantageously passed through a cooler beforehand. A temperature of 90 to 102 ° C. is maintained during the reaction.
  • the addition of the remaining amount of alkane diamines is controlled on the basis of the pH of the aqueous salt solution which is circulated. This is done e.g. so that after the addition of the aforementioned starting materials, a small amount of saline solution is continuously taken, diluted to 10%, the pH is measured and the amount of alkane diamine added is controlled after the second mixing zone on the basis of the measured pH. It is advantageous if a dilute alkane diamine solution, e.g. uses up to 25%.
  • the reaction is usually carried out at atmospheric pressure or slightly elevated pressure.
  • An inert gas atmosphere e.g. Nitrogen atmosphere, upright.
  • the aqueous salt solution is removed from the first mixing zone to the extent that it is formed, e.g. through an overflow.
  • FIG. 1 The method according to the invention is explained for example in FIG. 1.
  • a circulation system consisting of a stirred tank 1 with a stirrer 2, a circuit 3, a feed pump 4, a mixing section 7 and a cooler 11
  • liquid alkane diamine is fed on the suction side of the pump 4 via line 5, while on the pressure side of the pump feeds an aqueous solution of the alkanedicarboxylic acid via line 6.
  • the remaining amount of liquid alkanediamine is fed via line 8.
  • a small part of the aqueous salt solution is continuously removed via line 9 and diluted to 10% and the pH is measured.
  • the values determined are transmitted as a pulse via the measuring line 10 to the feed line 8 and the feed quantity is thus regulated.
  • the resulting salt solution is removed from the system by the overflow line 12 to the extent that the solution forms.
  • Aqueous solutions of salts from alkanedicarboxylic acids and alkanediamines are used for the production of polyamides.
  • a circulation system consisting of a 5 m 3 stirred tank with stirrer, a circulation pump, a mixing section formed by deflection elements, a cooler and a pH control, 3.8 m '52.5% adipic acid solution and 1.65 t molten hexamethylenediamine are fed per hour . Only so much heat of neutralization is dissipated to keep the system at 98 ° C.
  • a circulation pump 250 m 3 / h AH salt solution are pumped around in a circuit. 10 kg / h of AH salt solution are removed every hour and diluted to 10% AH salt content with water.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyamides (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP78100176A 1977-06-27 1978-06-16 Verfahren zur kontinuierlichen Herstellung wässriger Lösungen von Salzen aus Alkandicarbonsäuren und Alkandiaminen Expired EP0000158B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2728818A DE2728818C3 (de) 1977-06-27 1977-06-27 Verfahren zur kontinuierlichen Herstellung wäßriger Lösungen von Salzen aus Alkandicarbonsäuren und Alkandiaminen
DE2728818 1977-06-27

Publications (2)

Publication Number Publication Date
EP0000158A1 EP0000158A1 (de) 1979-01-10
EP0000158B1 true EP0000158B1 (de) 1981-10-14

Family

ID=6012416

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100176A Expired EP0000158B1 (de) 1977-06-27 1978-06-16 Verfahren zur kontinuierlichen Herstellung wässriger Lösungen von Salzen aus Alkandicarbonsäuren und Alkandiaminen

Country Status (5)

Country Link
US (1) US4233234A (enrdf_load_stackoverflow)
EP (1) EP0000158B1 (enrdf_load_stackoverflow)
JP (1) JPS5412317A (enrdf_load_stackoverflow)
DE (2) DE2728818C3 (enrdf_load_stackoverflow)
IT (1) IT1096589B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2546227A1 (de) 2011-07-11 2013-01-16 Uhde Inventa-Fischer GmbH Verfahren zur Herstellung einer wässrigen Lösung von Salzen

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4627940A (en) * 1982-09-29 1986-12-09 Monsanto Company Process for preparing a polyamide
US4442260A (en) * 1983-03-14 1984-04-10 E. I. Du Pont De Nemours & Company Preparation of salt solution useful for making nylon
IT1291919B1 (it) 1997-05-30 1999-01-21 Sigma Tau Ind Farmaceuti Sali idrosolubili dell'acido dodecandioico e composizioni farmaceutiche e nutrizionali contenenti tali sali
FR2916756B1 (fr) * 2007-06-04 2009-07-17 Rhodia Recherches & Tech Procede de fabrication d'une solution de sels de diacides/diamines
CN104130131B (zh) 2013-05-01 2018-05-29 英威达纺织（英国）有限公司 从部分平衡酸溶液来进行的尼龙盐溶液的制备
TW201446812A (zh) * 2013-05-01 2014-12-16 Invista Tech Sarl 用於尼龍鹽溶液製備方法中之前饋程序控制
CN104130134B (zh) * 2013-05-01 2017-12-08 英威达纺织（英国）有限公司 用于尼龙盐溶液制备方法的前馈工序控制和pH值后馈
CN104130132B (zh) 2013-05-01 2017-10-03 英威达科技公司 用于尼龙盐溶液制备方法的前馈工序控制和在线pH值反馈
TW201444792A (zh) * 2013-05-01 2014-12-01 Invista Tech Sarl 用於計量供製造尼龍鹽溶液之二羧酸粉末之方法
TW201446729A (zh) 2013-05-01 2014-12-16 Invista Tech Sarl 使用調節二胺之尼龍鹽溶液製備方法
TW201500405A (zh) 2013-05-01 2015-01-01 Invista Tech Sarl 用於尼龍鹽溶液製備方法的前饋及反饋程序控制
TW201446836A (zh) 2013-05-01 2014-12-16 Invista Tech Sarl 用於製備部分平衡之酸性溶液之方法
TW201446730A (zh) * 2013-05-01 2014-12-16 Invista Tech Sarl 使用調節二胺混合之尼龍鹽溶液製備方法
CN104710317B (zh) 2013-12-17 2019-01-25 英威达纺织（英国）有限公司 用有分散头的容器生产pba溶液的尼龙盐溶液生产方法
CN104555163B (zh) * 2014-12-26 2017-08-15 河南神马尼龙化工有限责任公司 一种尼龙66盐水溶液储存装置及储存方法
TWI787251B (zh) 2017-04-13 2022-12-21 英商英威達紡織（英國）有限公司 製備用於聚醯胺化製程之前體之單體平衡控制

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2130947A (en) * 1935-01-02 1938-09-20 Du Pont Diamine-dicarboxylic acid salts and process of preparing same
NL296609A (enrdf_load_stackoverflow) * 1962-08-14
US3294759A (en) * 1963-08-26 1966-12-27 Grace W R & Co Linear copolyamides resistant to boiling water
GB1034307A (en) 1964-06-12 1966-06-29 Ici Ltd Production of diamine salts of dicarboxylic acids
US3952051A (en) * 1971-05-08 1976-04-20 Asahi Kasei Kogyo Kabushiki Kaisha Method for crystallization of diamine dicarboxylate
DE2139642A1 (de) * 1971-08-07 1973-02-15 Davy Ashmore Ag Verfahren zur kontinuierlichen herstellung des salzes eines diamins und einer dicarbonsaeure
DE2403178A1 (de) * 1973-01-25 1974-08-01 Ici Ltd Verfahren zur herstellung von aminsalzen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2546227A1 (de) 2011-07-11 2013-01-16 Uhde Inventa-Fischer GmbH Verfahren zur Herstellung einer wässrigen Lösung von Salzen
WO2013007451A1 (de) 2011-07-11 2013-01-17 Uhde Inventa-Fischer Gmbh Verfahren zur herstellung einer wässrigen lösung von salzen

Also Published As

Publication number Publication date
DE2728818C3 (de) 1980-05-08
DE2861152D1 (en) 1981-12-24
IT1096589B (it) 1985-08-26
US4233234A (en) 1980-11-11
DE2728818A1 (de) 1979-01-04
IT7824770A0 (it) 1978-06-20
JPS5412317A (en) 1979-01-30
JPS6223736B2 (enrdf_load_stackoverflow) 1987-05-25
EP0000158A1 (de) 1979-01-10
DE2728818B2 (de) 1979-08-30

Similar Documents

Publication Publication Date Title
EP0000158B1 (de) Verfahren zur kontinuierlichen Herstellung wässriger Lösungen von Salzen aus Alkandicarbonsäuren und Alkandiaminen
DE69323140T2 (de) Verfahren zur Herstellung von Phenol, Aceton und alpha-Methylstyrol
EP0765855B1 (de) Verfahren zur Herstellung von Copolyamiden
DE2936759C2 (de) Transparente Copolyamide
DE2263125C2 (de) Verfahren zur kontinuierlichen Herstellung von Harnstoff-Formaldehyd-Kondensaten
DE4337353B4 (de) Verfahren zur Synthese von Polyamiden
CH509359A (de) Verfahren zur Herstellung von faserbildendem Polyester
EP0000157B1 (de) Verfahren zur Herstellung von hochkonzentrierten wässrigen Lösungen von Dicarbonsäurediaminsalzen und Polyamidpräkondensaten und deren Verwendung
DE3212510C2 (enrdf_load_stackoverflow)
EP0000142B1 (de) Verfahren zur Herstellung von Polyamiden
DE69626738T2 (de) Verfahren zur Herstellung von Polyamiden aus Caprolactam
DE2119118B2 (de) Verfahren zur katalytischen Oxydation von Pseudocumol in flüssiger Phase zu Trimellithsäure unter stufenweiser Katalysatorzugabe
DE1938384A1 (de) Verfahren zur Verringerung der sauren,Chlor enthaltenden Verunreinigungen von Methylen-Diphenyl-Diisocyanat
DE2364088B2 (de) Kontinuierliches Verfahren zur Herstellung von Phenol-Harnstoff- oder Melaminharzen
DE2035733A1 (de) Verfahren zur anionischen Polymerisation von Lactamen
EP0074025B1 (de) Verfahren zur kontinuierlichen Herstellung von Polycaprolactam
DE1445372A1 (de) Verfahren zur Erzeugung von veraetherten Aminharzen
DE69215817T2 (de) Verfahren zur Herstellung von Polytetramethylenadipamide
EP0520276A2 (de) Verfahren zur Herstellung von Polycarbonat
DE2633110C3 (de) Salze aus α,ω-Alkandicarbonsäuren und α,ω-Diaminen mit verbesserter Farbzahl und deren Verwendung
DE2547025A1 (de) Verfahren zur herstellung von epsilon-caprolactam
DE2638824B2 (de) Verfahren zur Herstellung von Salzen aus Dicarbonsäuren und Diaminen
DE1910458C3 (de) Verfahren zur Herstellung von Tris-OiydroxymethyD-nitromethan
DE2331082B2 (de) Verfahren zur kontinuierlichen oxydation von substituierten benzolen oder benzolderivaten mit salpetersaeure
DE1493480A1 (de) Verfahren zur kontinuierlichen Herstellung von Alkalisalzen von Diamin-Polyessigsaeuren

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB NL

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB NL

Designated state(s): BE DE FR GB NL

REF Corresponds to:

Ref document number: 2861152

Country of ref document: DE

Date of ref document: 19811224

KL Correction list

Free format text: 82/02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970520

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970527

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19970612

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970616

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970624

Year of fee payment: 20

BE20 Be: patent expired

Free format text: 980616 *BASF A.G.

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19980615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19980616

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Effective date: 19980615

NLV7 Nl: ceased due to reaching the maximum lifetime of a patent

Effective date: 19980616

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT