EP0000021B1 - Procédé de préparation de mélanges de polyisocyanates portant des groupes acides phosphoniques et des groupes phosphonates - Google Patents

Procédé de préparation de mélanges de polyisocyanates portant des groupes acides phosphoniques et des groupes phosphonates Download PDF

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Publication number
EP0000021B1
EP0000021B1 EP78100033A EP78100033A EP0000021B1 EP 0000021 B1 EP0000021 B1 EP 0000021B1 EP 78100033 A EP78100033 A EP 78100033A EP 78100033 A EP78100033 A EP 78100033A EP 0000021 B1 EP0000021 B1 EP 0000021B1
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EP
European Patent Office
Prior art keywords
weight
phosphite
groups
acid
gew
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
EP78100033A
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German (de)
English (en)
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EP0000021A1 (fr
Inventor
Hans-Joachim Dr. Scholl
Dieter Dr. Dieterich
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.)
Bayer AG
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Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000021A1 publication Critical patent/EP0000021A1/fr
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Classifications

    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
    • C07F9/4065—Esters of acids containing the structure -C(=X)-P(=X)(XR)2, (X = O, S, Se)
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus

Definitions

  • Polyisocyanates with sulfonic acid groups are known (German Offenlegungsschriften 2 227 111, 2 359 614, 2 359 615, 2 524 476, 1 939911). Their manufacture is characterized in that e.g. liquid multicomponent mixtures of aromatic polyisocyanates mixed with heavy field trioxide or an equivalent amount of oleum, sulfuric acid or chlorosulfonic acid and allowed to react.
  • Polyisocyanates containing phosphonate groups are also known (DT-OS 1 127 583).
  • the production of these phosphorus-containing isocyanates takes place e.g. in that polyisocyanates are converted into carbamic acid halides by the action of hydrogen halide and, based on the carbamic acid halide groups, these are reacted with equivalent amounts of trialkyl phosphites in the manner of an Arbusow reaction.
  • Phosgenation products of condensates of aniline and aldehydes or ketones such as e.g. Acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone.
  • reaction products of the above aromatic polyisocyanate mixtures with from 0.2 to 50 ⁇ quivending- 9 6 of polyols are, provided that the viscosity of the reaction products 30000 cP thus obtained at 25 ° C does not exceed the NCO content of the reaction products at least 15 weight % is.
  • Suitable polyols for modifying the starting materials are, in particular, the polyether and / or polyester polyols of the molecular weight range 200 to 6000, preferably 300 to 4000, and low molecular weight polyols of the molecular weight range 62 to 200 known in polyurethane chemistry. Examples of such low molecular weight polyols are ethylene glycol, propylene glycol, glycerin, Trimethylolpropane, 1,4,6-hexanetriol.
  • the aromatic polyisocyanates suitable according to the invention generally have an NCO content of 15-53, preferably 25-48 and particularly preferably 25-35% by weight.
  • Liquid multi-component mixtures of aromatic polyisocyanates with an NCO content of 20 to 48, preferably 25 to 35% by weight and an average NCO functionality of 2.0 are particularly suitable for the process according to the invention.
  • Preferred liquid aromatic polyisocyanate mixtures to be used in the process according to the invention are, in particular, the phosgenation products of aniline / formaldehyde condensates which have a dinuclear diisocyanate content of 20 to 90% by weight, trinuclear triisocyanates of 3 to 40% by weight, tetranuclear tetraisocyanates of 1 to Have 20 wt .-% and higher core polyisocyanates of 1 to 40 wt.
  • Technical tolylene diisocyanate mixtures are also suitable for the process according to the invention.
  • Technical distillation residues such as those obtained in the distillation of technical tolylene diisocyanate mixtures and which have a free tolylene diisocyanate isomer content of less than 70% by weight, are also outstandingly suitable.
  • Such distillation residues can be obtained, for example, by the process of DT-OS 2,035,731 .
  • Also particularly suitable are the distillation residues described in DT-OS 2 123 183, as well as their solutions in phosgenation products of aniline / formaldehyde condensates, which are also described in this last-mentioned German patent application.
  • phosphites of the formula mentioned which have different reset R are of course also suitable for the process according to the invention.
  • suitable phosphites are trimethyl phosphite, triethyl phosphite, tris (2-chloroethyl) phosphite, tributyl phosphite, trioctyl phosphite, tribenzyl phosphite or 0.0'-dimethyl-O "- (2-chloroethyl) phosphite.
  • the trialkyl phosphites mentioned by way of example are preferably used.
  • Tris (halogenoalkyl) phosphites such as, in particular, tris (2-chloroethyl) phosphite are particularly preferred.
  • the reaction partners mentioned by way of example are preferably used in amounts such that 0.01 to 0.5, preferably 0.02 to 0.3 and particularly preferably 0.03 to 0.2 mol are used per mole of aromatically bound isocyanate groups Chlorosulfonic acid and 0.01 to 0.5, preferably 0.02 to 0.3 and in particular 0.03 to 0.2 mol of phosphite Implementation.
  • equimolar amounts of phosphite and chlorosulfonic acid are used, but it is also possible to use chlorosulfonic acid or phosphite in different molar amounts.
  • the process according to the invention is carried out in the temperature range between -10 to + 150 ° C., preferably between 0 and 100 ° C.
  • the reaction according to the invention can be carried out either by directly mixing the three reaction components or in a two-stage process, in which case the polyisocyanate is first reacted with the chlorosulfonic acid and then the reaction with the phosphite is carried out.
  • the process according to the invention can be carried out both in the presence and, in particular, when using low-viscosity starting materials in the absence of solvents which are inert under the reaction conditions to the starting materials and end products of the process according to the invention.
  • Particularly preferred solvents are halogenated hydrocarbons, e.g. Dichloroethane, trichtorethane, fluorotrichloromethane, methylene chloride or chlorobenzene.
  • the solvents preferably have a boiling point between 0 and 140 ° C. If necessary, the invention. Implementation can also be carried out under pressure.
  • the concentration of the reactants in this solvent can vary within wide ranges, in general the solvent is used in such amounts that 20-100% strength by weight solutions of the reactants are present during the reaction according to the invention, the Specify the stated concentration as a percentage of the amount by weight of all reactants based on the weight of the total solution.
  • the polyisocyanate is preferably mixed with the phosphite and any solvent to be used, and the chlorosulfonic acid, which may also be dissolved in an inert solvent, is added to this mixture in a period of a few minutes to several hours with stirring.
  • the chlorosulfonic acid is preferably added at room temperature, after which the reaction mixture is heated to 50-100 ° C. to complete the reaction.
  • the process products according to the invention are liquid even when tolylene diisocyanate and phosgenation products of the aniline-formaldehyde condensation with a high content of 4,4 '- two-core product are used, in particular if not more than 0.2 mol of chlorosulfonic acid per 1 NCO equivalent and not more than 0.2 mol of organic phosphite are used.
  • the isocyanate groups in the process products according to the invention are partly in the form of carbamic acid chloride groups.
  • the numerical values mentioned with regard to the NCO content of the products according to the invention also include such NCO groups which may be in the form of carbamic acid chloride groups, the molecular weight of the NCO group (42) also being used in this case when calculating the NCO contents has been. Since the sulfonic acid groups can be at least partially neutralized or esterified without difficulty after the reaction according to the invention, as explained below, the stated sulfur content relates to the sulfonic acid groups which are optionally at least partially neutralized or esterified.
  • the aromatic polyisocyanates containing sulfonic acid and phosphonate groups according to the invention are valuable starting materials for the production of moldings and compact plastics. They can be processed without difficulty by customary techniques, such as casting processes, and by means of the customary conveying and metering systems.
  • the aromatic phosphonated isocyanatosulfonic acids obtainable by the process according to the invention can, after their preparation, be converted completely or partially into the corresponding isocyanatosulfonates by a neutralization reaction.
  • Suitable neutralizing agents are organic or inorganic bases, such as trimethylamine, triethylamine, tributylamine, dimethylaniline, urotropin, sodium hydrogen carbonate, sodium hydroxide, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, magnesium oxide, zinc oxide, sodium phosphate.
  • Inorganic neutralizing agents which themselves do not react strongly basic, such as calcium carbonate, magnesium carbonate, dolomite, chalk, sodium phosphate, can also be used in a large excess as filler.
  • the hydrophilicity and reactivity of the products according to the invention is increased by converting the sulfonic acid groups into the corresponding sulfonate groups.
  • epoxides include: ethylene oxide, propylene oxide, epichlorohydrin.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (3)

1. Procédé de production de mélanges de polyisocyanates liquides à la température ambiante, qui ont:
(a) une teneur de 10 à 42 % en poids en groupes isocyanate aromatiques liés, existant éventuellement en partie sous forme de chlorure d'acide carbamique,
(b) une teneur de 0,5 à 5 % en poids en soufre présent sous la forme de groupes acide sulfonique en liaison aromatique, éventuellement au moins partiellement neutralisés ou estérifiés,
(c) une teneur de 0,5 à 5 % en poids en phosphore présent sous la forme de groupes ester alkylique ou ester aralkyli- que d'acide phosphonique et
(d) une viscosité de 10 à 50 000 centipoises à 25°C,

caractérisé en ce qu'il consiste à faire réagir des mélanges liquides de plusieurs composants formés de polyisocyanates aromatiques ayant une teneur en NCO- de 20 à 48 % en poids en présence d'un phosphite trialkylique ou tris-(aralkylique)éventuellement substitué par un halogène, avec l'acide chlorosulfonique à une température de -10 à +150°C, en utilisant, par mole de groupes isocyanate en liaison aromatique, 0,01 à 0,5 mole d'acide chlorosulfonique et 0,01 à 0,5 mole de phosphite.
2. Procédé suivant la revendication 1, caractérisé en ce que la réaction est conduite en présence de solvants inertes dans les conditions réactionnelles.
3. Procédé suivant l'une des revendications 1 et 2, caractérisé en ce qu'il consiste à utiliser le phosphite de tris-(2-chloréthyle) comme phosphite trialkylique éventuellement substitué par un halogène.
EP78100033A 1977-06-03 1978-06-01 Procédé de préparation de mélanges de polyisocyanates portant des groupes acides phosphoniques et des groupes phosphonates Expired EP0000021B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772725208 DE2725208A1 (de) 1977-06-03 1977-06-03 Sulfonsaeure- und phosphonatgruppen aufweisende polyisocyanate
DE2725208 1977-06-03

Publications (2)

Publication Number Publication Date
EP0000021A1 EP0000021A1 (fr) 1978-12-20
EP0000021B1 true EP0000021B1 (fr) 1980-07-23

Family

ID=6010691

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100033A Expired EP0000021B1 (fr) 1977-06-03 1978-06-01 Procédé de préparation de mélanges de polyisocyanates portant des groupes acides phosphoniques et des groupes phosphonates

Country Status (4)

Country Link
US (1) US4177206A (fr)
EP (1) EP0000021B1 (fr)
DE (2) DE2725208A1 (fr)
IT (1) IT1104722B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100815411B1 (ko) * 2000-04-06 2008-03-20 코닌클리케 필립스 일렉트로닉스 엔.브이. 객체-조건부 액세스 시스템

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1127583B (de) * 1960-08-25 1962-04-12 Bayer Ag Verfahren zur Herstellung von schwer entflammbaren Kunststoffen, einschliesslich Schaumstoffen
US3959329A (en) * 1973-05-24 1976-05-25 Bayer Aktiengesellschaft Polyisocyanates containing sulphonic acid or sulphonate groups
DE2359614A1 (de) * 1973-11-30 1975-06-05 Bayer Ag Sulfonsaeure- und/oder sulfonatgruppen aufweisende polyisocyanate

Also Published As

Publication number Publication date
EP0000021A1 (fr) 1978-12-20
US4177206A (en) 1979-12-04
DE2725208A1 (de) 1978-12-14
IT1104722B (it) 1985-10-28
IT7849668A0 (it) 1978-06-02
DE2860035D1 (en) 1980-11-13

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