WO1996016969A1 - Phosphoric acid triesters - Google Patents

Phosphoric acid triesters Download PDF

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Publication number
WO1996016969A1
WO1996016969A1 PCT/EP1995/004558 EP9504558W WO9616969A1 WO 1996016969 A1 WO1996016969 A1 WO 1996016969A1 EP 9504558 W EP9504558 W EP 9504558W WO 9616969 A1 WO9616969 A1 WO 9616969A1
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Prior art keywords
phosphoric acid
mono
radical
alcohols
primary alcohols
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PCT/EP1995/004558
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German (de)
French (fr)
Inventor
Oriol Ponsati Obiols
Rafael Pi Subirana
Joaquim Bigorra Llosas
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1996016969A1 publication Critical patent/WO1996016969A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/667—Organo-phosphorus compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0418—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing P-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof

Definitions

  • the invention relates to new phosphoric acid triesters which are obtained by preparing phosphoric acid mono- / diester mixtures in a manner known per se and then esterifying the free acid functions with alkylene oxide, a process for their preparation and their use for the production of textile and fiber aids.
  • Phosphoric acid esters which are often also referred to as alkyl phosphates, are important anionic surfactants which, because of their good wetting properties, are used for the production of detergents and cleaning agents, particularly in the field of textile and fiber treatment.
  • Overviews on this topic have been published by RSCooper et al. in J.Am.Oil.Chem.Soc. 41, 337 (1964), H. Oistler et al. in tens. Deterg. JL2, 263 (1975), K. Hennig in Seifen-Ole-Fette-Wchse 102, 221 (1976) and AJO'Lennick et al. in Soap, Cosm.Chem. Spec. T_, 26 (1986).
  • esters of Phosphoric acid with polyethylene glycol as an antistatic agent for fibers report A. Polowinska et al. in Acta Polymeric 38, 5 (1987).
  • phosphoric acid esters For the preparation of phosphoric acid esters, one usually starts from primary alcohols which are esterified with phosphorus pentoxide, more rarely orthophosphoric acid. In the case of P2O5, the reactants are usually used in a ratio of about 3: 1, i.e. the resulting products are technical mixtures of mono- and diesters; the degree of esterification is around 1.5. Although these partial esters are generally well suited for industrial use, there is a need for triesters, that is to say products in which all the ester groups of the phosphoric acid are saturated.
  • the object of the invention was therefore to develop phosphoric acid triesters and a process for their preparation which are free from the disadvantages described.
  • the invention relates to phosphoric acid triesters which are obtained by first primary alcohols or their alkoxylates of the formula (I)
  • the invention further relates to a process for the preparation of phosphoric acid triesters, in which primary alcohols or their alkoxylates of the formula (I)
  • R ⁇ is a linear and / or branched alkyl and / or alkenyl radical having 1 to 22 carbon atoms
  • R 2 is hydrogen or a methyl radical and n is 0 or numbers from 1 to 20, with phosphorus pentoxide or polyphosphoric acid to form one Reacting phosphoric acid mono / diester mixture and then esterifying free acid groups still present in the molecule with alkylene oxides.
  • Lower aliphatic alcohols such as, for example, methanol, ethanol, propanol, butanol and pentanol, are suitable as starting materials for the preparation of the phosphoric acid triesters according to the invention.
  • Linear fatty alcohols or partially branched oxo alcohols having 6 to 22 and in particular 12 to 18 carbon atoms are preferably used.
  • Typical examples are capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleol alcohol, alcoholol alcohol alcohol, petro-selyl alcohol alcohol , Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which, for example in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
  • fatty alcohols having 8 to 18 or 12 to 18 carbon atoms such as, for example, coconut, palm, palm kernel or tallow fatty alcohol, are preferred.
  • the esterification of primary alcohols with phosphorus pentoxide or polyphosphoric acid is known per se.
  • the fatty alcohols and the phosphating agent are preferably used in a molar ratio of 1: 1 to 4: 1, the reaction temperature being in the range from 40 to 100 and preferably 50 to 90 ° C.
  • P2O5 is used as the phosphating agent
  • a molar ratio of 2.5: 1 to 3.5: 1 is particularly recommended.
  • polyphosphoric acid is used, the optimal ratio is 1.4: 1 to 1.7: 1
  • the resulting esters are technical mono / diester mixtures and generally have a degree of esterification in the range from 1.0 to 1.5, ie on average only about every second acid group is esterified.
  • the mixtures can also contain small amounts of phosphoric acid and - depending on the chain length - about 0.5 to 20% by weight of free alcohol. Because of the strongly exothermic reaction of short-chain alcohols or alkylene glycols with phosphorus pentoxide, the use of polyphosphoric acid is particularly recommended in these cases. This also applies if you prefer to receive monoesters. Alkoxylation
  • the alkoxylation of the mono- / diester mixtures obtained in the first process step is possible without the addition of catalysts, since the mixtures have a sufficiently high acid number.
  • the amount of alkylene oxide is to be selected so that, at least in mathematical terms, all acid groups still free are saturated. In practice, of course, a clear excess will be chosen, in particular in order to advantageously influence the hydrophilicity and - in particular when long-chain alcohols are used - the physical appearance of the products.
  • the amount of the alkylene oxide can advantageously also be controlled via the decrease in the acid number.
  • the ester mixtures and the alkylene oxides are usually used in a molar ratio of 1: 1 to 1:20 and in particular 1: 2 to 1:10, based on the phosphorus content
  • the alkoxylation which is preferably the addition of ethylene oxide to the acidic hydroxyl groups, can be carried out at comparatively low temperatures of 90 to 150 ° C.
  • esterification of the acid groups predominates; the insertion in ester bonds, however, is disadvantaged and at most takes place subordinate. It is true that the milder the reaction conditions, the higher the selectivity.
  • the alkylene oxide is generally added in portions so that an autogenous pressure of a few bar is not exceeded.
  • the phosphoric acid triesters according to the invention are light colored, liquid and have a high hydrophilicity. They are therefore suitable for the production of textile and fiber auxiliaries, such as, for example, spin fiber preparations, wetting agents for textile pretreatment, defoamers or antistatic agents, in which they are present in amounts of 0.5 to 30, preferably 1 to 15% by weight, based on the Means - may be included.
  • textile and fiber auxiliaries such as, for example, spin fiber preparations, wetting agents for textile pretreatment, defoamers or antistatic agents, in which they are present in amounts of 0.5 to 30, preferably 1 to 15% by weight, based on the Means - may be included.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)

Abstract

The invention concerns novel phosphoric acid triesters which are obtained firstly by reacting primary alcohols or their alkoxylates with phosphorus pentoxide or polyphosphoric acid to form a phosphoric acid mono/diester mixture and then esterifying free acid groups still present in the molecule with alkylene oxides. The products are suitable for preparing textile and fibre aids, antifoam agents and antistatic agents.

Description

Phosphorsäuretriester Phosphoric acid triesters
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft neue Phosphorsäuretriester, die man erhält, indem man in an sich bekannter Weise Phosphorsäuremo- no-/diester-Gemische herstellt und die freien Säurefunktionen anschließend mit Alkylenoxid verestert, ein Verfahren zu ih¬ rer Herstellung sowie deren Verwendung zur Herstellung von Textil- und Faserhilfsmitteln.The invention relates to new phosphoric acid triesters which are obtained by preparing phosphoric acid mono- / diester mixtures in a manner known per se and then esterifying the free acid functions with alkylene oxide, a process for their preparation and their use for the production of textile and fiber aids.
Stand der TechnikState of the art
Phosphorsäureester, die häufig auch als Alkylphosphate be¬ zeichnet werden, stellen wichtige anionische Tenside dar, die wegen ihren guten Netzeigenschaften zur Herstellung von Wasch- und Reinigungsmitteln, insbesondere im Bereich der Textil- und Faserbehandlung eingesetzt werden. Übersichten zu diesem Thema sind beispielsweise von R.S.Cooper et al. in J.Am.Oil.Chem.Soc. .41, 337 (1964), H.Oistler et al. in Tens. Deterg. JL2, 263 (1975), K.Hennig in Seifen-Öle-Fette-Wchse 102, 221 (1976) und A.J.O'Lennick et al. in Soap,Cosm.Chem. Spec. T_, 26 (1986) zu finden. Über den Einsatz von Estern der Phosphorsäure mit Polyethylenglycol als Antistatikmittel für Fasern berichten A.Polowinska et al. in Acta Polymeric 38., 5 (1987).Phosphoric acid esters, which are often also referred to as alkyl phosphates, are important anionic surfactants which, because of their good wetting properties, are used for the production of detergents and cleaning agents, particularly in the field of textile and fiber treatment. Overviews on this topic have been published by RSCooper et al. in J.Am.Oil.Chem.Soc. 41, 337 (1964), H. Oistler et al. in tens. Deterg. JL2, 263 (1975), K. Hennig in Seifen-Ole-Fette-Wchse 102, 221 (1976) and AJO'Lennick et al. in Soap, Cosm.Chem. Spec. T_, 26 (1986). About the use of esters of Phosphoric acid with polyethylene glycol as an antistatic agent for fibers report A. Polowinska et al. in Acta Polymeric 38, 5 (1987).
Zur Herstellung von Phosphorsäureestern geht man üblicher¬ weise von primären Alkoholen aus, die mit Phosphorpentoxid, seltener ortho-Phosphorsäure, verestert werden. Im Fall von P2O5 setzt man die Reaktionspartner üblicherweise in einem Verhältnis von etwa 3 : 1 ein, d.h., bei den resultierenden Produkten handelt es sich um technische Gemische von Mono- und Diestern; der Veresterungsgrad liegt um 1,5. Für den technischen Einsatz sind diese Partialester zwar in der Regel gut geeignet, es besteht jedoch ein Bedürfnis nach Triestern, also Produkten, bei denen alle Estergruppen der Phosphorsäure abgesättigt sind.For the preparation of phosphoric acid esters, one usually starts from primary alcohols which are esterified with phosphorus pentoxide, more rarely orthophosphoric acid. In the case of P2O5, the reactants are usually used in a ratio of about 3: 1, i.e. the resulting products are technical mixtures of mono- and diesters; the degree of esterification is around 1.5. Although these partial esters are generally well suited for industrial use, there is a need for triesters, that is to say products in which all the ester groups of the phosphoric acid are saturated.
Die Aufgabe der Erfindung hat somit darin bestanden, Phos¬ phorsäuretriester und ein Verfahren zu ihrer Herstellung zu entwickeln, die frei von den geschilderten Nachteilen sind.The object of the invention was therefore to develop phosphoric acid triesters and a process for their preparation which are free from the disadvantages described.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung sind Phosphorsäuretriester, die man erhält, indem man zunächst primäre Alkohole bzw. deren Alk- oxylate der Formel (I)The invention relates to phosphoric acid triesters which are obtained by first primary alcohols or their alkoxylates of the formula (I)
R2R2
I R10(CH2CHO)nH (I) in der R für einen linearen und/oder verzweigten Alkyl- und/ oder Alkenylrest mit 1 bis 22 Kohlenstoffatomen, R2 für Was¬ serstoff oder einen Methylrest und n für 0 oder Zahlen von 1 bis 20 steht, mit Phosphorpentoxid oder Polyphosphorsäure zu einem Phosphorsäuremono-/diester-Gemisch umsetzt und an¬ schließend noch im Molekül vorhandene freie Säuregruppen mit Alkylenoxiden verestert.IR 1 0 (CH 2 CHO) n H (I) in which R represents a linear and / or branched alkyl and / or alkenyl radical having 1 to 22 carbon atoms, R 2 represents hydrogen or a methyl radical and n represents 0 or numbers from 1 to 20, with phosphorus pentoxide or polyphosphoric acid to a phosphoric acid mono - / diester mixture and then esterified free acid groups still present in the molecule with alkylene oxides.
Überraschenderweise wurde gefunden, daß sich auf diese Weise auch die dritte Säuregruppe in den technischen Estergemischen problemlos und vollständig verestern läßt und Triester mit ausgezeichneten anwendungstechnischen Eigenschaften resul¬ tieren.Surprisingly, it was found that the third acid group in the technical ester mixtures can also be completely and easily esterified in this way and result in triesters with excellent performance properties.
Ein weiterer Gegenstand der Erfindung betrifft ein Verfahren zur Herstellung von Phosphorsäuretriestern, bei dem man zu¬ nächst primäre Alkohole bzw. deren Alkoxylate der Formel (I)The invention further relates to a process for the preparation of phosphoric acid triesters, in which primary alcohols or their alkoxylates of the formula (I)
R2R2
I R10(CH2CHO)nH (I)IR 1 0 (CH2CHO) n H (I)
in der R^ für einen linearen und/oder verzweigten Alkyl- und/ oder Alkenylrest mit 1 bis 22 Kohlenstoffatomen, R2 für Was¬ serstoff oder einen Methylrest und n für 0 oder Zahlen von 1 bis 20 steht, mit Phosphorpentoxid oder Polyphosphorsäure zu einem Phosphorsäuremono-/diester-Gemisch umsetzt und an¬ schließend noch im Molekül vorhandene freie Säuregruppen mit Alkylenoxiden verestert. Primäre Alkoholein which R ^ is a linear and / or branched alkyl and / or alkenyl radical having 1 to 22 carbon atoms, R 2 is hydrogen or a methyl radical and n is 0 or numbers from 1 to 20, with phosphorus pentoxide or polyphosphoric acid to form one Reacting phosphoric acid mono / diester mixture and then esterifying free acid groups still present in the molecule with alkylene oxides. Primary alcohols
Als Ausgangsstoffe für die Herstellung der erfindungsgemäßen Phosphorsäuretriester kommen niedere aliphatische Alkohole wie beispielsweise Methanol, Ethanol, Propanol, Butanol und Pentanol in Betracht. Vorzugsweise werden lineare Fettalko¬ hole bzw. teilweise verzweigte Oxoalkohole mit 6 bis 22 und insbesondere 12 bis 18 Kohlenstoffatomen eingesetzt. Typische Beispiele sind Capronalkohol, Caprylalkohol, 2-Ethylhexylal- kohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, My- ristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalko- hol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petro- selinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostea- rylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und ölen oder Aldehyden aus der Roelen'sehen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen.Lower aliphatic alcohols, such as, for example, methanol, ethanol, propanol, butanol and pentanol, are suitable as starting materials for the preparation of the phosphoric acid triesters according to the invention. Linear fatty alcohols or partially branched oxo alcohols having 6 to 22 and in particular 12 to 18 carbon atoms are preferably used. Typical examples are capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleol alcohol, alcoholol alcohol alcohol, petro-selyl alcohol alcohol , Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which, for example in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
Bevorzugt sind technische Fettalkohole mit 8 bis 18 bzw. 12 bis 18 Kohlenstoffatomen wie beispielsweise Kokos-, Palm-, Palmkem- oder Taigfettalkohol.Technical fatty alcohols having 8 to 18 or 12 to 18 carbon atoms, such as, for example, coconut, palm, palm kernel or tallow fatty alcohol, are preferred.
Neben den genannten Alkoholen können auch deren Anlagerungs¬ produkte mit durchschnittlich 1 bis 20, vorzugsweise 3 bis 15 Mol Ethylenoxid und/oder Propylenoxid eingesetzt werden. Be¬ vorzugt sind Anlagerungsprodukte von Ethylenoxid an Fettal¬ kohole mit 1 bis 22 und insbesondere 8 bis 18 Kohlenstoffato¬ men. Als primäre Alkohole kommen schließlich auch Diole vom Typ des Ethylenglycols sowie Polyethylenglycole mit einem durch¬ schnittlichen Molekulargewicht von 50 bis 2000 und vorzugs¬ weise 100 bis 400 in Frage.In addition to the alcohols mentioned, their adducts with an average of 1 to 20, preferably 3 to 15, mol of ethylene oxide and / or propylene oxide can also be used. Addition products of ethylene oxide onto fatty alcohols having 1 to 22 and in particular 8 to 18 carbon atoms are preferred. Finally, diols of the ethylene glycol type and polyethylene glycols with an average molecular weight of 50 to 2000 and preferably 100 to 400 are also suitable as primary alcohols.
Umsetzung mit Phosphorpentoxid bzw. PolyphosphorsäureReaction with phosphorus pentoxide or polyphosphoric acid
Die Veresterung von primären Alkoholen mit Phosphorpentoxid bzw. Polyphosphorsäure ist an sich bekannt. Vorzugsweise wer¬ den die Fettalkohole und das Phosphatierungsmittel im molaren Verhältnis von 1 : 1 bis 4 : 1 eingesetzt, wobei die Reak¬ tionstemperatur im Bereich von 40 bis 100 und vozugsweise 50 bis 90°C liegen sollte. Bei Einsatz von P2O5 als Phosphatie¬ rungsmittel empfiehlt sich insbesondere ein molares Einsatz¬ verhältnis von 2,5 : 1 bis 3,5 : 1, wird Polyphosphorsäure eingesetzt, liegt das optimale Einsatzverhältnis hingegen bei 1,4 : 1 bis 1,7 : 1. Die resultierenden Ester stellen tech¬ nische Mono-/diester-Gemische dar und weisen in der Regel einen Veresterungsgrad im Bereich von 1,0 bis 1,5 auf, d.h., durchschnittlich ist nur etwa jede zweite Säuregruppe ver¬ estert. Die Gemische können ferner geringe Mengen Phosphor¬ säure sowie - abhängig von der Kettenlänge - etwa 0,5 bis 20 Gew.-% freien Alkohol enthalten. Wegen der stark exothermen Reaktion von kurzkettigen Alkoholen bzw. Alkylenglycolen mit Phosphorpentoxid empfiehlt sich vor allem in diesen Fällen der Einsatz von Polyphosphorsäure. Dies gilt auch dann, wenn man vorzugsweise Monoester erhalten möchte. AlkoxylierunαThe esterification of primary alcohols with phosphorus pentoxide or polyphosphoric acid is known per se. The fatty alcohols and the phosphating agent are preferably used in a molar ratio of 1: 1 to 4: 1, the reaction temperature being in the range from 40 to 100 and preferably 50 to 90 ° C. When P2O5 is used as the phosphating agent, a molar ratio of 2.5: 1 to 3.5: 1 is particularly recommended. If polyphosphoric acid is used, the optimal ratio is 1.4: 1 to 1.7: 1 The resulting esters are technical mono / diester mixtures and generally have a degree of esterification in the range from 1.0 to 1.5, ie on average only about every second acid group is esterified. The mixtures can also contain small amounts of phosphoric acid and - depending on the chain length - about 0.5 to 20% by weight of free alcohol. Because of the strongly exothermic reaction of short-chain alcohols or alkylene glycols with phosphorus pentoxide, the use of polyphosphoric acid is particularly recommended in these cases. This also applies if you prefer to receive monoesters. Alkoxylation
Die Alkoxylierung der im ersten Verfahrensschritt erhaltenen Mono-/diester-Gemische gelingt ohne Zugabe von Katalysatoren, da die Gemische eine ausreichend hohe Säurezahl aufweisen. Die Menge an Alkylenoxid ist so zu wählen, daß zumindest rechnerisch eine Absättigung aller noch freien Säuregruppen resultiert. In der Praxis wird man freilich einen deutlichen Überschuß wählen, insbesondere um die Hydrophilie und - ins¬ besondere bei Einsatz von langkettigen Alkoholen - das phy¬ sikalische Erscheinungsbild der Produkte vorteilhaft zu be¬ einflussen. Die Menge des Alkylenoxids kann vorteilhafterwei¬ se auch über die Abnahme der Säurezahl kontrolliert werden. Üblicherweise werden die Estergemische und die Alkylenoxide im molaren Verhältnis von 1 : 1 bis 1 : 20 und insbesondere 1 : 2 bis 1 : 10 - bezogen auf den Phosphorgehalt - eingesetztThe alkoxylation of the mono- / diester mixtures obtained in the first process step is possible without the addition of catalysts, since the mixtures have a sufficiently high acid number. The amount of alkylene oxide is to be selected so that, at least in mathematical terms, all acid groups still free are saturated. In practice, of course, a clear excess will be chosen, in particular in order to advantageously influence the hydrophilicity and - in particular when long-chain alcohols are used - the physical appearance of the products. The amount of the alkylene oxide can advantageously also be controlled via the decrease in the acid number. The ester mixtures and the alkylene oxides are usually used in a molar ratio of 1: 1 to 1:20 and in particular 1: 2 to 1:10, based on the phosphorus content
Die Alkoxylierung, bei der es sich vorzugsweise um die Anla¬ gerung von Ethylenoxid an die sauren Hydroxylgruppen handelt, kann bei vergleichsweise niedrigen Temperaturen von 90 bis 150°C durchgeführt werden. Aus kinetischen Gründen erfolgt überwiegend eine Veresterung der Säuregruppen; die Insertion in Esterbindungen ist demgegenüber benachteiligt und findet allenfalls untergeordnet statt. Es gilt, daß die Selektivität um so höger ist, je milder die Reaktionsbedingungen sind. Die Zugabe des Alkylenoxid erfolgt in der Regel portionsweise, so daß ein autogener Druck von wenigen bar nicht überstiegen wird. Gewerbliche AnwendbarkeitThe alkoxylation, which is preferably the addition of ethylene oxide to the acidic hydroxyl groups, can be carried out at comparatively low temperatures of 90 to 150 ° C. For kinetic reasons, esterification of the acid groups predominates; the insertion in ester bonds, however, is disadvantaged and at most takes place subordinate. It is true that the milder the reaction conditions, the higher the selectivity. The alkylene oxide is generally added in portions so that an autogenous pressure of a few bar is not exceeded. Industrial applicability
Die erfindungsgemäßen Phosphorsäuretriester sind hellfarbig, flüssig und besitzen eine hohe Hydrophilie. Sie eignen sich daher zur Herstellung von Textil- und Faserhilfsmitteln, wie beispielsweise Spinnfaserpräparationen, Netzmitteln für die textile Vorbehandlung, Entschäumer oder Antistatika, in denen sie in Mengen von 0,5 bis 30, vorzugsweise 1 bis 15 Gew.-% - bezogen auf die Mittel - enthalten sein können.The phosphoric acid triesters according to the invention are light colored, liquid and have a high hydrophilicity. They are therefore suitable for the production of textile and fiber auxiliaries, such as, for example, spin fiber preparations, wetting agents for textile pretreatment, defoamers or antistatic agents, in which they are present in amounts of 0.5 to 30, preferably 1 to 15% by weight, based on the Means - may be included.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it.
BeispieleExamples
I. HerstellbeispieleI. Manufacturing examples
Beispiel Hl:Example Hl:
In einem mit Rührer und Thermometer versehenen 1-1-Dreihals- kolben wurden 594 g (4,5 mol) n-Octanol vorgelegt und er¬ wärmt. Bei einer Temperatur von 50 bis 60°C wurden mit Hilfe eines gegen Luftfeuchtigkeit verschlossenen Pulverdosierge¬ rätes gleichmäßig innerhalb von 2 h 213 g (1,5 mol) Phosphor¬ pentoxid zugesetzt. Anschließend ließ man 4 h bei 90°C nach¬ reagieren. Es wurden 807 g eines technischen Phosphorsäure- mono-/di-n-octylesters in Form eines farblosen Öls gewonnen, das folgende Kennzahlen besaß:594 g (4.5 mol) of n-octanol were placed in a 1 liter three-necked flask equipped with a stirrer and thermometer and heated. At a temperature of 50 to 60 ° C with the aid of a powder dosing device sealed against atmospheric humidity, 213 g (1.5 mol) of phosphorus pentoxide were added uniformly within 2 h. The mixture was then left to react at 90 ° C. for 4 h. 807 g of a technical phosphoric acid mono- / di-n-octyl ester were obtained in the form of a colorless oil, which had the following key figures:
Veresterungsgrad : 1,5 Gehalt an freiem Alkohol : 7,8 Gew.-%Degree of esterification: 1.5 Free alcohol content: 7.8% by weight
Das saure Mono-/diester-Gemisch wurde in einen 1-1-Stahlauto- klaven überführt, der danach dreimal mit Stickstoff gespült und evakuiert wurde. Anschließend wurde der Reaktor ver¬ schlossen, auf 110°C erhitzt und portionsweise 356 g (8,1 mol) Ethylenoxid mit einer solchen Geschwindigkeit aufgege¬ ben, daß der autogene Druck 3 bar nicht überstieg. Nach dem Ende der Ethylenoxidzugabe wurde die Reaktionsmischung noch 1 h bei 125°C und etwa 3 bar gehalten, anschließend wurde der Autoklav abgekühlt und entspannt. Es wurden 950 g Phosphor¬ säuretriester in Form eines farblosen Öls (SZ < 5) erhalten. Beispiel H2 :The acidic mono / diester mixture was transferred to a 1-1 steel autoclave, which was then flushed three times with nitrogen and evacuated. The reactor was then closed, heated to 110 ° C. and 356 g (8.1 mol) of ethylene oxide were added in portions at a rate such that the autogenous pressure did not exceed 3 bar. After the end of the ethylene oxide addition, the reaction mixture was kept at 125 ° C. and about 3 bar for a further hour, then the autoclave was cooled and let down. 950 g of phosphoric acid triesters were obtained in the form of a colorless oil (SZ <5). Example H2:
Analog Beispiel Hl wurden 231 g (1,75 mol) n-Octanol und 71 g (0,5 mol) Phosphorpentoxid zur Reaktion gebracht. Die Reak¬ tionstemperatur während der 2-stündigen Dosierung betrug 80 bis 90°C. Es wurden ca. 300 g eines gelblich gefärbten Öls erhalten, das einen Veresterungsgrad von 1,48 und einen Rest¬ gehalt an n-Octanol von 14,8 Gew.-% aufwies. Das Mono-/di- ester-Gemisch wurde mit 290 g (5 mol) Propylenoxid - ent¬ sprechend einem molaren Verhältnis von 1 : 5 - umgesetzt. Es wurden etwa 590 g Phosphorsäuretriester in Form eines farb¬ losen Öls (SZ < 5) erhalten.Analogously to Example HI, 231 g (1.75 mol) of n-octanol and 71 g (0.5 mol) of phosphorus pentoxide were reacted. The reaction temperature during the 2-hour dosing was 80 to 90 ° C. About 300 g of a yellowish oil were obtained which had a degree of esterification of 1.48 and a residual n-octanol content of 14.8% by weight. The mono / diester mixture was reacted with 290 g (5 mol) of propylene oxide, corresponding to a molar ratio of 1: 5. About 590 g of phosphoric acid triesters were obtained in the form of a colorless oil (SZ <5).
Beispiel H3:Example H3
Analog Beispiel Hl wurden 393 g (1,5 mol) Ci6/18~Tal9fettal~ kohol mit 71 g (0,5 mol) Phosphorpentoxid umgesetzt. Die Re¬ aktionstemperatur während der 3-stündigen Dosierung betrug 90°C. Es wurden etwa 460 g einer gelblich gefärbten Flüssig¬ keit erhalten, die einen Veresterungsgrad von 1,5 aufwies. Das Mono-/diester-Gemisch wurde mit 172 g (3,9 mol) Ethylen¬ oxid umgesetzt. Es wurden etwa 630 g Phosphorsäuretriester (SZ < 1) in Form eines weißen Feststoffes erhalten. Analogously to Example HI, 393 g (1.5 mol) of Ci6 / 18 ~ Tal 9 fatty alcohol were reacted with 71 g (0.5 mol) of phosphorus pentoxide. The reaction temperature during the 3-hour metering was 90 ° C. About 460 g of a yellowish colored liquid were obtained which had a degree of esterification of 1.5. The mono / diester mixture was reacted with 172 g (3.9 mol) of ethylene oxide. About 630 g of phosphoric acid triesters (SZ <1) were obtained in the form of a white solid.
Beispiel H4:Example H4
Analog Beispiel Hl wurden 212 g (2 mol) Diethylenglycol por¬ tionsweise mit 220 g (1,31 mol) Polyphosphorsäure umgesetzt. Anschließend wurde die Mischung 2 h auf 80°C erhitzt. Es wurden etwa 400 g einer gelblich gefärbten Flüssigkeit er¬ halten, die einen Veresterungsgrad von 1,05 aufwies. Das Mono-/diester-Gemisch wurde mit 804 g (9,2 mol) Ethylenoxid - entsprechend einem molaren Verhältnis Phosphor : EO = 1 : 7 - umgesetzt. Es wurden etwa 1200 g Phosphorsäuretriester (SZ < 3) in Form einer farblosen Flüssigkeit erhalten. Analogously to Example HI, 212 g (2 mol) of diethylene glycol were reacted in portions with 220 g (1.31 mol) of polyphosphoric acid. The mixture was then heated to 80 ° C. for 2 hours. About 400 g of a yellowish colored liquid were obtained which had a degree of esterification of 1.05. The mono / diester mixture was reacted with 804 g (9.2 mol) of ethylene oxide - corresponding to a molar ratio of phosphorus: EO = 1: 7. About 1200 g of phosphoric acid triesters (SZ <3) were obtained in the form of a colorless liquid.
II. Aπwendungstechι i«ehe UntersuchungenII. Application technology before examinations
Die entschäumende Wirkung der alkoxylierten Phosphorsäure¬ ester wurde im technischen Maßstab bei der Herstellung von Cellulose getestet. Die Messungen wurden bei 70°C durchge¬ führt, die Entschäumerkonzentration betrug 4 Gew.-% bezogen auf die Cellulose. Die Ergebnisse sind in Tabelle 1 zusam¬ mengefaßt.The defoaming effect of the alkoxylated phosphoric acid ester was tested on an industrial scale in the production of cellulose. The measurements were carried out at 70 ° C., the defoamer concentration was 4% by weight, based on the cellulose. The results are summarized in Table 1.
Tabelle 1 Entschäumerwirkung bei der CelluloseherstellungTable 1 Defoamer effect in cellulose production
Bsp. Entschäumer Schaumhδ e in ml nachFor example, defoamer foam height in ml
15" 30" 1' 2' 3' 4'15 "30" 1 '2' 3 '4'
1 A 100 140 160 230 250 250 2 B 100 100 100 100 120 1501 A 100 140 160 230 250 250 2 B 100 100 100 100 120 150
VI C 300 300 270 280 300 300VI C 300 300 270 280 300 300
Legende: A = Phosphorsäuretriester, Basis n-Butanol, umgesetzt mit 5 Mol PropylenoxidLegend: A = phosphoric acid triester, base n-butanol, reacted with 5 moles of propylene oxide
B = Phosphorsäuretriester, Basis 2-Ethylhexanol umgesetzt mit 5 Mol PropylenoxidB = phosphoric acid triester, base 2-ethylhexanol reacted with 5 moles of propylene oxide
C = Entschäumer Bublex(R) 123 der Hispano Quimica C = Bublex ( R ) 123 defoamer from Hispano Quimica

Claims

Pa -pnl-anaprÜChe Pa-pnl-anaprücke
1. Phosphorsäuretriester, dadurch erhältlich, daß man zu¬ nächst primäre Alkohole bzw. deren Alkoxylate der Formel (I)1. phosphoric acid triesters, obtainable by first primary alcohols or their alkoxylates of the formula (I)
R2R2
I R10(CH2CH0)nH (I)IR 1 0 (CH2CH0) n H (I)
in der Rl für einen linearen und/oder verzweigten Alkyl- und/oder Alkenylrest mit 1 bis 22 Kohlenstoffatomen oder einen HOCH2CH2-Rest, R2 für Wasserstoff oder einen Me¬ thylrest und n für 0 oder Zahlen von 1 bis 20 steht, mit Phosphorpentoxid oder Polyphosphorsäure zu einem Phos- phorsäuremono-/diester-Gemisch umsetzt und anschließend noch im Molekül vorhandene freie Säuregruppen mit Alky¬ lenoxiden verestert.in which Rl is a linear and / or branched alkyl and / or alkenyl radical having 1 to 22 carbon atoms or a HOCH2CH2 radical, R 2 is hydrogen or a methyl radical and n is 0 or numbers from 1 to 20, with phosphorus pentoxide or converting polyphosphoric acid to a phosphoric mono / diester mixture and then esterifying free acid groups still present in the molecule with alkylene oxides.
2. Verfahren zur Herstellung von Phosphorsäuretriestern, dadurch gekennzeichnet, daß man zunächst primäre Alko¬ hole bzw. deren Alkoxylate der Formel (I)2. Process for the preparation of phosphoric acid triesters, characterized in that first primary alcohols or their alkoxylates of the formula (I)
R2R2
II.
R10(CH2CHO)nH (I)R 1 0 (CH 2 CHO) n H (I)
in der R1 für einen linearen und/oder verzweigten Alkyl- und/oder Alkenylrest mit 1 bis 22 Kohlenstoffatomen oder einen HOCH2CH2~Rest, R2 für Wasserstoff oder einen Me¬ thylrest und n für 0 oder Zahlen von 1 bis 20 steht, mit Phosphorpentoxid oder Polyphosphorsäure zu einem Phos- phorsäuremono-/diester-Gemisch umsetzt und anschließend noch im Molekül vorhandene freie Säuregruppen mit Alky¬ lenoxiden verestert.in which R 1 is a linear and / or branched alkyl and / or alkenyl radical having 1 to 22 carbon atoms or a HOCH2CH 2 radical, R 2 is hydrogen or a methyl radical and n is 0 or numbers from 1 to 20, with Reacting phosphorus pentoxide or polyphosphoric acid to form a phosphoric acid mono / diester mixture and then esterifying free acid groups still present in the molecule with alkylene oxides.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man als primäre Alkohole Fettalkohole mit 6 bis 22 Koh¬ lenstoffatomen einsetzt.3. The method according to claim 2, characterized in that fatty alcohols having 6 to 22 carbon atoms are used as primary alcohols.
4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß man als primäre Alkohole Ethylenglycol bzw. Polyethylen- glycole mit einem durchschnittlichen Molekulargewicht von 50 bis 2000 einsetzt.4. The method according to claim 2, characterized in that the primary alcohols are ethylene glycol or polyethylene glycols with an average molecular weight of 50 to 2000.
5. Verfahren nach den Ansprüchen 2 bis 4, dadurch gekenn¬ zeichnet, daß man die Alkohole und das Phosphorpentoxid bzw. die Polyphosphorsäure im molaren Verhältnis von 1 : 1 bis 4 : 1 einsetzt.5. Process according to claims 2 to 4, characterized gekenn¬ characterized in that the alcohols and the phosphorus pentoxide or the polyphosphoric acid are used in a molar ratio of 1: 1 to 4: 1.
6. Verfahren nach den Ansprüchen 2 bis 5, dadurch gekenn¬ zeichnet, daß man die Mono-/diester-Gemische und die Alkylenoxide im molaren Verhältnis von 1 : 1 bis 1 : 20 - bezogen auf den Phosphorgehalt - einsetzt.6. Process according to claims 2 to 5, characterized gekenn¬ characterized in that one uses the mono- / diester mixtures and the alkylene oxides in a molar ratio of 1: 1 to 1:20 - based on the phosphorus content.
7. Verfahren nach den Ansprüchen 2 bis 6, dadurch gekenn¬ zeichnet, daß man die Alkoxylierung ohne Zugabe eines Katalysators bei Temperaturen von 90 bis 150°C durch¬ führt. 7. The method according to claims 2 to 6, characterized gekenn¬ characterized in that one carries out the alkoxylation without adding a catalyst at temperatures of 90 to 150 ° C.
8. Verwendung von Phosphorsäuretriestern nach Anspruch 1 zur Herstellung von Textil- und Faserhilfsmitteln, Ent¬ schäumern und Antistatika. 8. Use of phosphoric acid triesters according to claim 1 for the production of textile and fiber auxiliaries, defoamers and antistatic agents.
PCT/EP1995/004558 1994-11-29 1995-11-20 Phosphoric acid triesters WO1996016969A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004042738A1 (en) * 2004-09-03 2006-03-23 Cht R. Beitlich Gmbh Essential neutral textile additives, useful during textile improvement treatment and coloring e.g. cotton, comprises reactive products of phosphorus pentoxide or polyphosphoric acid with alcohols and carbonic acid and/or its derivative

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19848894A1 (en) * 1998-10-23 2000-04-27 Bayer Ag Phosphoric acid esters, useful as leveling agents for the dyeing of nitrogen containing fibers, preferably wool, are prepared by reaction of phosphoroxy chloride with a mixture of alcohols.

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB812390A (en) * 1955-06-06 1959-04-22 Union Carbide Corp Polymeric phosphate esters and their production
US2979523A (en) * 1956-03-06 1961-04-11 Gulf Oil Corp Addition products of dialkyl acid orthophosphate and olefin oxides
US2990421A (en) * 1958-04-01 1961-06-27 Virginia Carolina Chem Corp Neutral esters of phosphoric acid
GB943122A (en) * 1960-09-29 1963-11-27 Exxon Research Engineering Co Improvements in liquid hydrocarbon fuels
US3626035A (en) * 1968-11-05 1971-12-07 Textilana Corp Surface active nonionic 2-hydroxyalkyl 3-alkoxy-2-hydroxyalkyl phosphate esters
DE2134854A1 (en) * 1971-07-13 1973-01-25 Bayer Ag Phosphoric acid esters - as anti-statics and anti-oxidants for synthetic fibrous material
DE2610763A1 (en) * 1975-03-25 1976-10-07 Ciba Geigy Ag Antistatic agents for polymers - pref polyamide PVC or polyester comprising ethoxylated or propoxylated phosphonic or phosphoric acid esters
US4697030A (en) * 1985-05-23 1987-09-29 Stauffer Chemical Company Phosphate-containing and phosphonate-containing phosphate esters

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB812390A (en) * 1955-06-06 1959-04-22 Union Carbide Corp Polymeric phosphate esters and their production
US2979523A (en) * 1956-03-06 1961-04-11 Gulf Oil Corp Addition products of dialkyl acid orthophosphate and olefin oxides
US2990421A (en) * 1958-04-01 1961-06-27 Virginia Carolina Chem Corp Neutral esters of phosphoric acid
GB943122A (en) * 1960-09-29 1963-11-27 Exxon Research Engineering Co Improvements in liquid hydrocarbon fuels
US3626035A (en) * 1968-11-05 1971-12-07 Textilana Corp Surface active nonionic 2-hydroxyalkyl 3-alkoxy-2-hydroxyalkyl phosphate esters
DE2134854A1 (en) * 1971-07-13 1973-01-25 Bayer Ag Phosphoric acid esters - as anti-statics and anti-oxidants for synthetic fibrous material
DE2610763A1 (en) * 1975-03-25 1976-10-07 Ciba Geigy Ag Antistatic agents for polymers - pref polyamide PVC or polyester comprising ethoxylated or propoxylated phosphonic or phosphoric acid esters
US4697030A (en) * 1985-05-23 1987-09-29 Stauffer Chemical Company Phosphate-containing and phosphonate-containing phosphate esters

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004042738A1 (en) * 2004-09-03 2006-03-23 Cht R. Beitlich Gmbh Essential neutral textile additives, useful during textile improvement treatment and coloring e.g. cotton, comprises reactive products of phosphorus pentoxide or polyphosphoric acid with alcohols and carbonic acid and/or its derivative

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