EP0000158A1 - Procédé pour la production continue de solutions aqueuses de sels d'acides alcanedioiques et de diamines alcoyliques - Google Patents

Procédé pour la production continue de solutions aqueuses de sels d'acides alcanedioiques et de diamines alcoyliques Download PDF

Info

Publication number
EP0000158A1
EP0000158A1 EP78100176A EP78100176A EP0000158A1 EP 0000158 A1 EP0000158 A1 EP 0000158A1 EP 78100176 A EP78100176 A EP 78100176A EP 78100176 A EP78100176 A EP 78100176A EP 0000158 A1 EP0000158 A1 EP 0000158A1
Authority
EP
European Patent Office
Prior art keywords
mixing zone
aqueous
alkane
salts
zone
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.)
Granted
Application number
EP78100176A
Other languages
German (de)
English (en)
Other versions
EP0000158B1 (fr
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/fr
Application granted granted Critical
Publication of EP0000158B1 publication Critical patent/EP0000158B1/fr
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 are produced from dicarboxylic acids and diamines, for example hexamethylene diammonium adipate, 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 operation with volatile flammable solvents is undesirable in technology, it has already started to produce such salts from aqueous solutions.
  • salts of dicarboxylic acids and diamines are obtained by starting from an aqueous solution of the salt to be prepared, which contains the excess dicarboxylic acid in solution and then neutralizing it with the diamine.
  • 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.
  • 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.
  • Alkane dicarboxylic acids with 6 to 12 carbon atoms are used as starting materials. It is preferable to start from straight-chain ⁇ , ⁇ -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 gained particular technical importance.
  • alkane diamines with 6 to 12 carbon atoms are used as starting materials. It is preferred to start from straight-chain ⁇ , ⁇ -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 generally 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 in all other zones and lines of salt solution.
  • the first mixing zone used 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. It is advantageous to circulate 40 to 80 times the amount of the content of the first mixing zone 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.
  • alkanediamines by adding small amounts of water, e.g. B. liquefy up to 20 percent by weight.
  • Alkane disarsonic acids are advantageously added in 48 to 55 weight percent aqueous solution. It goes without saying that the total amount of water supplied must be such that, after combination, a solution of salts of alkanedicarboxylic acids and alkanediamines corresponding to the desired concentration results.
  • the amount of the alkane diamines added 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 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 in order 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. It is also possible to use a small excess of alkane diamine e.g.
  • alkanediamines add up to 0.5 mole percent and compensate for alkane diamine losses in the condensation.
  • 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. It has proven to be useful if the total amount of starting substances supplied per hour, i.e. Alkanediamines, alkanedicarboxylic acids and water correspond to 0.5 to 2 times the amount of aqueous salt solution in the entire circuit.
  • 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. It has proven useful to maintain a temperature of 90 to 102 ° C 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 happens For example, in such a way 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, based on the measured pH, the amount of alkane diamine is controlled after the second mixing zone. It is advantageous to use a dilute alkane diamine solution, for example up to 25%, for control purposes.
  • 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 portion 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.
  • the method according to the invention is illustrated by the following example.
  • 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 3 52.5% adipic acid solution and 1.65 t per hour molten hexamethylenediamine fed. 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyamides (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP78100176A 1977-06-27 1978-06-16 Procédé pour la production continue de solutions aqueuses de sels d'acides alcanedioiques et de diamines alcoyliques Expired EP0000158B1 (fr)

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 true EP0000158A1 (fr) 1979-01-10
EP0000158B1 EP0000158B1 (fr) 1981-10-14

Family

ID=6012416

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100176A Expired EP0000158B1 (fr) 1977-06-27 1978-06-16 Procédé pour la production continue de solutions aqueuses de sels d'acides alcanedioiques et de diamines alcoyliques

Country Status (5)

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998054119A1 (fr) * 1997-05-30 1998-12-03 Sigma-Tau Healthscience S.P.A. Sels d'acide dodecanoique solubles dans l'eau et compositions pharmaceutiques ou nutritives les contenant
EP2546227A1 (fr) * 2011-07-11 2013-01-16 Uhde Inventa-Fischer GmbH Procédé de fabrication d'une solution aqueuse de sels

Families Citing this family (15)

* 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
FR2916756B1 (fr) * 2007-06-04 2009-07-17 Rhodia Recherches & Tech Procede de fabrication d'une solution de sels de diacides/diamines
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
CN104130135B (zh) 2013-05-01 2018-07-03 英威达纺织（英国）有限公司 用于生产部分平衡酸溶液的方法
TW201446728A (zh) 2013-05-01 2014-12-16 Invista Tech Sarl 用於尼龍鹽溶液製備方法之前饋程序控制及線上ｐｈ反饋
CN104130133B (zh) 2013-05-01 2018-01-19 英威达纺织（英国）有限公司 尼龙盐溶液制备方法中的前馈工序控制
CN104130136B (zh) * 2013-05-01 2017-10-24 英威达科技公司 尼龙盐溶液制备方法中的前馈和后馈工序控制
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
CN104130396B (zh) * 2013-05-01 2018-05-29 英威达纺织（英国）有限公司 使用补充二胺的尼龙盐溶液制备方法
TW201443103A (zh) 2013-05-01 2014-11-16 Invista Tech Sarl 自部分平衡之酸性溶液製備尼龍鹽溶液的方法
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
TW201529640A (zh) * 2013-12-17 2015-08-01 Invista Tech Sarl 以具有分散器桿頭之容器製造供生產尼龍鹽之部分平衡酸溶液之方法
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6507519A (fr) * 1964-06-12 1965-12-13
DE2139642A1 (de) * 1971-08-07 1973-02-15 Davy Ashmore Ag Verfahren zur kontinuierlichen herstellung des salzes eines diamins und einer dicarbonsaeure
FR2215411A1 (en) * 1973-01-25 1974-08-23 Ici Ltd Amine salts, esp. nylon-6,6 salts, prodn. - economically and avoiding decompsn. by pptg. the salt from an aq. soln.

Family Cites Families (4)

* 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 (fr) * 1962-08-14
US3294759A (en) * 1963-08-26 1966-12-27 Grace W R & Co Linear copolyamides resistant to boiling water
US3952051A (en) * 1971-05-08 1976-04-20 Asahi Kasei Kogyo Kabushiki Kaisha Method for crystallization of diamine dicarboxylate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6507519A (fr) * 1964-06-12 1965-12-13
DE2139642A1 (de) * 1971-08-07 1973-02-15 Davy Ashmore Ag Verfahren zur kontinuierlichen herstellung des salzes eines diamins und einer dicarbonsaeure
FR2215411A1 (en) * 1973-01-25 1974-08-23 Ici Ltd Amine salts, esp. nylon-6,6 salts, prodn. - economically and avoiding decompsn. by pptg. the salt from an aq. soln.

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998054119A1 (fr) * 1997-05-30 1998-12-03 Sigma-Tau Healthscience S.P.A. Sels d'acide dodecanoique solubles dans l'eau et compositions pharmaceutiques ou nutritives les contenant
US6255503B1 (en) 1997-05-30 2001-07-03 Sigma-Tau Healthscience S.P.A. Water-soluble salts of dodecandioic acid and pharmaceutical and nutritional compositions containing same
EP2546227A1 (fr) * 2011-07-11 2013-01-16 Uhde Inventa-Fischer GmbH Procédé de fabrication d'une solution aqueuse de sels
WO2013007451A1 (fr) * 2011-07-11 2013-01-17 Uhde Inventa-Fischer Gmbh Procédé de production d'une solution aqueuse de sels
RU2602817C2 (ru) * 2011-07-11 2016-11-20 Уде Инвента-Фишер ГмбХ Способ получения водного раствора солей
US9561999B2 (en) 2011-07-11 2017-02-07 Uhde Inventa-Fischer Gmbh Method for the production of an aqueous solution of salts

Also Published As

Publication number Publication date
EP0000158B1 (fr) 1981-10-14
US4233234A (en) 1980-11-11
DE2728818A1 (de) 1979-01-04
JPS6223736B2 (fr) 1987-05-25
JPS5412317A (en) 1979-01-30
DE2861152D1 (en) 1981-12-24
DE2728818B2 (de) 1979-08-30
DE2728818C3 (de) 1980-05-08
IT7824770A0 (it) 1978-06-20
IT1096589B (it) 1985-08-26

Similar Documents

Publication Publication Date Title
EP0000158B1 (fr) Procédé pour la production continue de solutions aqueuses de sels d'acides alcanedioiques et de diamines alcoyliques
EP0129196A2 (fr) Procédé pour la production continue de polyamides
DE2515760A1 (de) Verfahren zur herstellung von stickstoffhaltigen kondensationsprodukten
WO2013007451A1 (fr) Procédé de production d'une solution aqueuse de sels
DE3212510C2 (fr)
EP0000157B1 (fr) Procédé pour la préparation de solutions aqueuses très concentrées de sels d'acides dicarboxyliques avec des diamines et de précondensats de polyamides et leur utilisation
EP0000142B1 (fr) Procédé de préparation de polyamides
DE2364088B2 (de) Kontinuierliches Verfahren zur Herstellung von Phenol-Harnstoff- oder Melaminharzen
DE1938384A1 (de) Verfahren zur Verringerung der sauren,Chlor enthaltenden Verunreinigungen von Methylen-Diphenyl-Diisocyanat
DE3327271C2 (de) Verfahren zur Herstellung von Polyethylenpolyaminen
DE2745783B2 (de) Herstellung von Nitroguanidin aus Guanidinnitrat unter Einwirkung von wäßriger Schwefelsäure
DE1230412B (de) Verfahren und Vorrichtung zur Herstellung von 2, 3-Dibrompropanol
DE2547025A1 (de) Verfahren zur herstellung von epsilon-caprolactam
DE2331082B2 (de) Verfahren zur kontinuierlichen oxydation von substituierten benzolen oder benzolderivaten mit salpetersaeure
DE854701C (de) Verfahren zur Herstellung von Kondensationsprodukten
DE3147533C2 (fr)
DE1910458C3 (de) Verfahren zur Herstellung von Tris-OiydroxymethyD-nitromethan
DE2309544A1 (de) Verfahren und anlage zur kontinuierlichen herstellung von trinitrotoluol
DE2606269B2 (de) Verfahren zur Herstellung von Harnstoff-Formaldehyd-Klebstoffen oder -Harzen
DE851128C (de) Verfahren zur Herstellung von Polyamiden
DE1493480A1 (de) Verfahren zur kontinuierlichen Herstellung von Alkalisalzen von Diamin-Polyessigsaeuren
AT226208B (de) Verfahren zur kontinuierlichen Herstellung von Pentaerythrit
DE1908329C3 (de) Verfahren zur Aufarbeitung von Reaktionsgemischen der Cyclohexanoxydation
DE1168882B (de) Verfahren zum Absorbieren von Formaldehyd aus formaldehydhaltigen Gasen
DE924537C (de) Verfahren zur Herstellung von Polyamiden

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