DE1232348B - Process for the production of polyesters - Google Patents

Process for the production of polyesters

Info

Publication number
DE1232348B
DE1232348B DEI17179A DEI0017179A DE1232348B DE 1232348 B DE1232348 B DE 1232348B DE I17179 A DEI17179 A DE I17179A DE I0017179 A DEI0017179 A DE I0017179A DE 1232348 B DE1232348 B DE 1232348B
Authority
DE
Germany
Prior art keywords
polyesters
parts
bis
production
phosphinic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
DEI17179A
Other languages
German (de)
Inventor
Anthony Arthur Briarly Browne
John Mather
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.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
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 Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of DE1232348B publication Critical patent/DE1232348B/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/22—Polyalkenes, e.g. polystyrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/30—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant
    • B05D2401/32—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant applied as powders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

Description

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Deutsche Kl-: 39 c -16German Kl-: 39 c -16

Nummer: 1232 348Number: 1232 348

Aktenzeichen: 117179IV d/39 cFile number: 117179IV d / 39 c

Amneldetag: 3. November 1959Registration date: November 3, 1959

Auslegetagr 12. Januar 1967Auslegetagr January 12, 1967

Es war bisher nicht möglich, Polyester und Mischpolyester aus den freien bis-carboxy-substituierten Phosphinsäuren nach üblichen Kondensationsverfahren herzustellen, da diese Säuren trifunktionell sind und daher Vernetzung und Gelbildung verursachen. Ä
liehen Schwierigkeiten begegnete man mit den biscarboxy-substituierten Phosphinaten, wo zwischen den Phosphinsäure- und Carbonsäuregruppen eine Disproportionierung des Kations erfolgen kann, so daß wiederum trifunktionelle Verbindungen vorhanden sind. Die bisher bei der Herstellung dieser Polyester eingeschlagenen Wege waren daher umständlich, beispielsweise durch Veresterung beider Carbonsäure- und Phosphinsäuregruppen, gefolgt von der Umwandlung des Phosphinsäureesters in das Phosphinsäuresalz.Up to now it has not been possible to produce polyesters and mixed polyesters from the free bis-carboxy-substituted phosphinic acids by customary condensation processes, since these acids are trifunctional and therefore cause crosslinking and gel formation. Ä
Borrowed difficulties were encountered with the biscarboxy-substituted phosphinates, where a disproportionation of the cation can take place between the phosphinic acid and carboxylic acid groups, so that trifunctional compounds are again present. The routes previously taken in the production of these polyesters were therefore cumbersome, for example by esterifying both carboxylic acid and phosphinic acid groups, followed by the conversion of the phosphinic acid ester into the phosphinic acid salt.

Die Erfindung betrifft nun ein Verfahren zur Herstellung von Polyestern, das dadurch gekennzeichnet ist, daß man die Bis-(p-carboxyphenyl)-phosphinsäure der FormelThe invention now relates to a method for the production of polyesters, which is characterized is that the bis (p-carboxyphenyl) phosphinic acid of the formula

HOOCHOOC

COOHCOOH

OHOH

in der ersten Stufe mit einem Diol in Gegenwart eines Alkalihalogenide, -cyanids oder -cyanats umsetzt und die erhaltenen Diolester in der zweiten Stufe mit einem Bis-(/?-hydroxyalkyl)-terephthalat polykondensiert.in the first stage with a diol in the presence of a Reacts alkali halides, cyanide or cyanate and the diol esters obtained are polycondensed with a bis (/? - hydroxyalkyl) terephthalate in the second stage.

Erfindungsgemäß ist es möglich, die Carbonsäuregruppen gleichzeitig mit der Bildung des Salzes der Phosphinsäure zu verestern.According to the invention it is possible to simultaneously with the formation of the salt of the carboxylic acid groups To esterify phosphinic acid.

Von den Alkalihalogeniden wurden insbesondere die Jodide als besonders wirksam gefunden.Of the alkali halides, the iodides in particular have been found to be particularly effective.

Das erfindungsgemäße Verfahren ist besonders brauchbar zur Herstellung von Polyestern mit einem niedrigen Phosphinatgehalt von weniger als 10 MoI-prozent im endgültigen Polyester. Auf diese Weise wurde ein modifiziertesPoly-(äthylenglykolterephthalat) hergestellt, das ein wertvolles Ausgangsmaterial für Fasern mit guter Affinität für basische und dispergierte Farbstoffe darstellt.The inventive method is particularly useful for making polyesters with a low phosphinate content of less than 10 mol percent in the final polyester. In this way a modified poly (ethylene glycol terephthalate) was produced, which is a valuable starting material for Represents fibers with good affinity for basic and dispersed dyes.

Die Polykondensation wird in an sich bekannter Weise bei vermindertem Druck und erhöhten Temperaturen in Gegenwart eines Katalysators durchgeführt. Metallische Stoffe, wie Antimonverbindungen, sind gute Katalysatoren.The polycondensation is carried out in a manner known per se at reduced pressure and elevated temperatures carried out in the presence of a catalyst. Metallic substances such as antimony compounds are good catalysts.

Das folgende Beispiel erläutert die Erfindung.The following example illustrates the invention.

Beispielexample

Eine klare Schmelze wurde erhalten, indem man 7,3 Teile Dimethylterephthalat, 5,2 Teile Äthylengly-Verfahren zur Herstellung von PolyesternA clear melt was obtained by using 7.3 parts of dimethyl terephthalate, 5.2 parts of ethylene glycol process for the production of polyesters

Anmelder:Applicant:

Imperial Chemical Industries Limited, LondonImperial Chemical Industries Limited, London

Vertreter:Representative:

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr
und Dipl.-Ing. S. Staeger, Patentanwälte,
München 5, Müllerstr. 31Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr
and Dipl.-Ing. S. Staeger, patent attorneys,
Munich 5, Müllerstr. 31

Als Erfinder benannt:Named as inventor:

Anthony Arthur Briarly Browne,Anthony Arthur Briarly Browne,

John Mather,John Mather,

Harrogate, Yorkshire (Großbritannien)Harrogate, Yorkshire (UK)

Beanspruchte Priorität:
Großbritannien vom 5. November 1958
(35 498, 35 501)Claimed priority:
Great Britain 5 November 1958
(35 498, 35 501)

kol und 0,001 Teile Zinkacetat unter Verwendung eines kurzen Fraktionieraufsatzes erwärmte, so daß Methanol aus der Reaktionsmischung kontinuierlich abdestillierte. Auf ähnliche Weise wurden 0,60 Teile Bis-(p-carboxyphenyl)-phosphinsäure, 0,115 Teile Natriumchlorid und 10 Teile Äthylenglykol 2 Stunden unter Rückfluß bis zur klaren Schmelze erwärmt. Die beiden Schmelzen wurden vereinigt, 0,002 Teile Antimonoxyd zugefügt und überschüssiges Glykol abdestilliert. Die Reaktionspartner wurden schließlich 55 Minuten bei 28O0C und 0,1mm gehalten. Ein klarer Polyester mit einem kristallinen Schmelzpunkt von 230 bis 2350C, aus welchem sich Fasern spinnen und ziehen ließen, wurde erhalten.kol and 0.001 part of zinc acetate were heated using a short fractionator so that methanol continuously distilled off from the reaction mixture. In a similar manner, 0.60 part of bis (p-carboxyphenyl) phosphinic acid, 0.115 part of sodium chloride and 10 parts of ethylene glycol were heated under reflux for 2 hours until a clear melt. The two melts were combined, 0.002 part of antimony oxide was added and excess glycol was distilled off. The reactants were held finally for 55 minutes at 28O 0 C and 0.1 mm. A clear polyester with a crystalline melting point of 230 to 235 ° C., from which fibers could be spun and drawn, was obtained.

Diese Fasern zeigen eine gute Affinität für Dispersionsfarbstoffe, beispielsweise wurden beim Färben mit Dispersol Echt Scharlach B (Colour Index 11110) und mit Duranol Blau G (Colour Index 63305) auf den Fasern tiefe Farbtöne erhalten.These fibers show a good affinity for disperse dyes, For example, when dyeing with Dispersol Real Scarlet B (Color Index 11110) and use Duranol Blue G (Color Index 63305) to obtain deep shades of color on the fibers.

Vergleichsversuch AComparative experiment A

52,7 Teile Terephthalsäure, 5,1 Teile _ Bis-(p-carboxyphenyl)-phosphinsäure und 70 Teile Äthylenglykol wurden unter Verwendung eines kurzen Fraktionieraufsatzes erwärmt, so daß Wasser aus der Reaktionsmischung kontinuierlich abdestillierte. 0,015 Teile 52.7 parts of terephthalic acid, 5.1 parts of bis (p-carboxyphenyl) phosphinic acid and 70 parts of ethylene glycol were added using a short fractionator heated so that water continuously distilled off from the reaction mixture. 0.015 parts

·■ ■-■"; ■ · ■■; 609 757/414· ■ ■ - ■ "; ■ · ■■; 609 757/414

Antimonoxyd wurden zugefügt, überschüssiges Glykol abdestilliert und die Reaktionspartner 55 Minuten bei 2800C und 0,1mm gehalten. Man erhielt ein Gel, welches unterhalb 2800C nicht schmolz und sich bei weiterem Erhitzen zersetzte.Antimony was added, distilled off excess glycol and the reactants maintained for 55 minutes at 280 0 C and 0.1 mm. A gel was obtained which did not melt below 280 ° C. and decomposed on further heating.

Vergleichsversuch BComparative experiment B

Eine Schmelze wurde hergestellt, indem man 9,2 Teile Dimethylterephthalat, 6,5 Teile Äthylenglykol und 0,0014 Teile Zinkacetat unter Verwendung eines kurzen Fraktionieraufsatzes erwärmte, so daß Methanol aus der Reaktionsmischung kontinuierlich abdestillierte. Eine ähnliche Schmelze wurde hergestellt durch Erhitzen von 0,765 Teilen Bis-(p-carboxyphenyl)-phosphinsäure, 0,265 Teilen Natriumcarbonat und 10 Teilen Äthylenglykol unter Rückfluß während 2 Stunden. Die zwei Schmelzen wurden vereinigt, 0,002 Teile Antimonoxyd zugegeben und überschüssiges Glykol abdestilliert. Auf dieser Stufe trat weitgehende Ausfällung ein, und ein normaler Polyester konnte nicht erhalten werden.A melt was prepared by adding 9.2 parts of dimethyl terephthalate, 6.5 parts of ethylene glycol and 0.0014 parts of zinc acetate heated using a short fractionator so that the methanol was removed the reaction mixture distilled off continuously. A similar melt was made by heating of 0.765 parts of bis (p-carboxyphenyl) phosphinic acid, 0.265 parts of sodium carbonate and 10 parts Ethylene glycol under reflux for 2 hours. The two melts were combined, 0.002 parts Added antimony oxide and distilled off excess glycol. Substantial precipitation occurred at this stage and a normal polyester could not be obtained.

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung von Polyestern, d adurch gekennzeichnet, daß man die Bis-(p-carboxyphenyl)-phosphinsäure der FormelProcess for the production of polyesters, characterized in that the Bis (p-carboxyphenyl) phosphinic acid of the formula HOOC-HOOC- V- P—/. V- COOHV- P- /. V- COOH OHOH in der ersten Stufe mit einem Diol in Gegenwart eines Alkalihalogenids, -cyanids oder -cyanats umsetzt und die erhaltenen Diolester in der zweiten Stufe mit einem Bis-(/9-hydroxyalkyl)-terephthalat polykondensiert.in the first stage with a diol in the presence of an alkali halide, cyanide or cyanate and the diol esters obtained in the second stage with a bis (/ 9-hydroxyalkyl) terephthalate polycondensed. In Betracht gezogene Druckschriften:
Journal of Polymer Science, Bd. 31, Nr. 123 (1958), S. 319 bis 326.Considered publications:
Journal of Polymer Science, Vol. 31, No. 123 (1958), pp. 319 to 326. 609 757/414 1.67 © Bundesdruckerei Berlin609 757/414 1.67 © Bundesdruckerei Berlin
DEI17179A 1958-11-05 1959-11-03 Process for the production of polyesters Pending DE1232348B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB3550158 1958-11-05
GB3549858A GB869964A (en) 1958-11-05 1958-11-05 Manufacture of copolyesters

Publications (1)

Publication Number Publication Date
DE1232348B true DE1232348B (en) 1967-01-12

Family

ID=47430170

Family Applications (1)

Application Number Title Priority Date Filing Date
DEI17179A Pending DE1232348B (en) 1958-11-05 1959-11-03 Process for the production of polyesters

Country Status (2)

Country Link
DE (1) DE1232348B (en)
GB (1) GB869964A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE30783E (en) 1973-09-17 1981-10-27 Hoechst Aktiengesellschaft Flame retarding linear polyesters and shaped articles thereof
US5859173A (en) * 1997-09-11 1999-01-12 Lurgi Zimmer Aktiengesellschaft Process for the production of flame-resistant polyesters

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4579676A (en) * 1984-12-17 1986-04-01 Economics Laboratory, Inc. Low-phosphate liquid cleaning composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE30783E (en) 1973-09-17 1981-10-27 Hoechst Aktiengesellschaft Flame retarding linear polyesters and shaped articles thereof
US5859173A (en) * 1997-09-11 1999-01-12 Lurgi Zimmer Aktiengesellschaft Process for the production of flame-resistant polyesters

Also Published As

Publication number Publication date
GB869964A (en) 1961-06-07

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