WO1993019049A1 - Production de dimeres d'isocyanate au moyen de catalyseurs a liaison polymere - Google Patents

Production de dimeres d'isocyanate au moyen de catalyseurs a liaison polymere

Info

Publication number
WO1993019049A1
WO1993019049A1 PCT/US1993/001795 US9301795W WO9319049A1 WO 1993019049 A1 WO1993019049 A1 WO 1993019049A1 US 9301795 W US9301795 W US 9301795W WO 9319049 A1 WO9319049 A1 WO 9319049A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
catalyst
bound
isocyanate
dimerization catalyst
Prior art date
Application number
PCT/US1993/001795
Other languages
English (en)
Inventor
Stephen L. Goldstein
Theodore C. Kraus
Original Assignee
Olin Corporation
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 Olin Corporation filed Critical Olin Corporation
Priority to EP93907088A priority Critical patent/EP0631574A4/fr
Publication of WO1993019049A1 publication Critical patent/WO1993019049A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms

Definitions

  • This invention relates generally to a process for making uretidione derivatives of isocyanates, and, more specifically, to a process for preparing the isocyanate dimers using a polymer-bound catalyst.
  • Polyuretidione derivatives of polyisocyanates also called isocyanato uretidiones
  • These derivatives provide reduced volatility and an associated reduced toxicity hazard during use, as compared to monomeric polyisocyanates, for example, toluene diisocyanate.
  • isocyanato uretidiones can be used as reactive diluents for other highly viscous or solid isocyanate-group containing coatings components or as a polyisocyanate component in solvent-free and low solvent coatings formulations.
  • the resulting material in the case where the precursor isocyanate is a diisocyanate, is a mixture of oligomers composed of at least 2 (i.e., 2 , 3, 4, and the like) precursor diisocyanate molecules joined by at least one (i.e., 1, 2, 3, and the like) uretidione rings. Usually, this mixture is simply called "dimer”.
  • the reaction is generally stopped well before all the isocyanate groups have been converted to uretidione groups because, otherwise, the resulting product would be an unusable polymer having a very high (theoretically infinite) molecular weight and viscosity.
  • the cost of equipment and energy to remove residual, unreacted precursor isocyanate dictate that the reaction not be stopped too soon.
  • the reaction is run to more than 10% conversion but less than 50% conversion. The preferred range is between 20% and 35%.
  • the reaction is typically stopped using a quenching agent.
  • the reaction between conventional dimerization catalysts and quenching agents typically results in the formation of an insoluble product which is typically removed by filtration using a filter aid.
  • the present invention relates to aprocess for preparing a uretidione-containing cyclodimerized isocyanate by cyclodimerizing an isocyanate in the presence a catalytically effective amount of a polymer-bound dimerization catalyst to form said uretidione-containing cyclodimerized isocyanate.
  • the present invention relates to a process for preparing and isolating a uretidione-containing cyclodimerized isocyanate by the steps of:
  • polyisocyanate are converted to uretidione groups
  • the present invention relates to a process for preparing a uretidione-containing cyclodimerized isocyanate by cyclodimerizing an isocyanate in the presence of a catalytically effective amount of a polymer-bound dimerization catalyst to form an uretidione-containing cyclodimerized isocyanate
  • the polymer-bound dimerization catalyst consists essentially of a polymer having an alkyene group-containing polymer backbone and having dimerization catalyst moieties chemically bound to said polymer, said catalyst moieties being selected from the group consisting of: aromatic tertiary amines, especially 4-dialkylamino pyridines; alkyl- and alkylamino-phosphines and their derivatives; and combinations thereof.
  • polymer-bound dimerization catalysts are suitably prepared which are then employed in a straightforward fashion to provide a facile dimerization reaction.
  • polymer-bound as used herein is intended to designate polymer supported dimerization catalysts which are insoluble in the dimerization reaction medium by virtue of the polymer support, and thus are easily separated from the reaction medium by removal of the polymer-bound catalyst from the reaction medium after the dimerization reaction has proceeded to the desired extent of completion.
  • the catalyst composition useful in the process of the present invention comprises a polymer which is insoluble in the reaction medium and which contains sites that promote the dimerization reaction which are bound to the polymer through ionic or, preferably, covalent bonds.
  • Compounds which promote the reaction converting isocyanate to uretidione are well known in the art. However, heretofore it was not known to the knowledge of the present inventors whether or not these various reaction promoters would still be active dimerization catalysts when bound to a polymer to provide a polymer-bound catalyst.
  • useful moieties thus include polymer bound derivatives of the following: aromatic tertiary amines, especially 4-dialkylamino pyridines; alkyl- and alkylamino-phosphines and their derivatives; and the like.
  • the dialkylamino pyridine containing functional groups are preferred because of their enhanced stability in the reaction medium and their ease of regeneration.
  • the polymer support for the catalyst should be inert in the dimerization medium. Additional factors to be considered in selecting preferred polymer supports are: availability; cost; stability; ease of functionalization; and, ability to be swollen and/or "wet" by the precursor isocyanate. This last characteristic is desired in order to facilitate intimate contact between the precursor isocyanate and the active sites on the polymer and then allow the resulting uretidione to migrate away from the catalytic site, making it available for further reaction.
  • polymer backbones consisting essentially of carbon to carbon bonds, derived from alkenes, are desired, such as: ethylene, propylene, isoprene, styrene, acrylates, methacrylates, and the like.
  • Polystyrenes are most preferred because of their thermal and chemical stability and the ease with which they can be functionalized.
  • the macroscopic form of the polymers that can be employed in the process of this invention can be varied significantly, including solid and/or liquid form.
  • polymers that, by virtue of their low molecular weight, for example, are soluble in the dimerization reaction medium can be precipitated and then filtered from the reaction medium by the addition of an appropriate non-solvent for the polymer when the desired degree of dimer conversion is reached.
  • recovering this non-solvent can entail additional costs.
  • a preferred approach is to use a polymer which is "essentially insoluble" (i.e., not soluble to any substantial degree) in the dimerization reaction medium.
  • the polymer can be utilized in the form of beads or powder or other relatively small particles. However, using the polymer in the form of small beads is generally preferred since this simplifies removal of the polymer bound catalyst through filtration and similar Q such techniques.
  • the solubility of the polymer in the dimerization reaction medium is generally inversely proportional to its crosslink density.
  • the amount of crosslinking is determined by the amount of divinyl benzene co-monomer used in the preparation of the polymer.
  • the crosslink density of the polymer is an important consideration because it positively affects mechanical stability while having a negative impact on the degree of swelling and/or wettability of the polymer. Crosslink densities greater than or equal to 1% and less then 10% are preferred. Those between 1 and 5% are most preferred.
  • the minimum required number of active sites on the catalyst is that amount that provides a "catalytically effective amount", i.e., an amount sufficient to catalyze the dimerization reaction.
  • the upper limit is, in one sense, defined by the composition of the catalyst and the polymer to which it is being bound. This maximum is in practice determined by the amount that provides a catalyst that permits some control over the desired dimerization reaction.
  • the active site content of the polymer-bound catalyst which provides a practically useful catalyst is also a function of the activity of the catalyst that is bound to the polymer.
  • catalytically active sites may be bound to the polymer support using a number of different approaches.
  • a polymerizable- monomer containing the desired functional group for example, N-(2-propenyl)- N-alkyl-4-amino pyridine may be co-polymerized with, for example, styrene.
  • materials such as poly(styrene-co-vinylbenzylchloride) , which are commercially available as so-called Merrifield resins, or the product of the chloromethylation of polystyrene may be condensed with, for example, a 4-alkylamino pyridine. These would yield a polymer bound catalyst containing 4-dialkylamino pyridine groups. Further, for example, aroute involving the bromination of polystyrene, followed by condensation with, for example, (R 2 N)_PC1, where R is lower alkyl, using lithium, will yield a polymer bound catalyst containing phosphine amide groups.
  • the polymer bound catalyst When the polymer bound catalyst is used in the form where it remains as a separate phase, i.e., where it is insoluble in the reaction medium, there are at least two options with respect to the manner in which the precursor isocyanate, optionally in the presence of asolvent, can be contacted with the catalyst, either (a) packed in a cartridge or tube, or (b) dispersed in a stirred reactor. In either case, the system can be operated in batches, e.g., where the system is charged with isocyanate, the reaction is typically run until the desired level of conversion is reached, and then the product is separated from the catalyst by filtration or similar such means.
  • the system can be run as a continuous process wherein isocyanate is continuously added to the system while the product dimer having the desired level of conversion is continuously withdrawn.
  • Potential hardware configurations include: a Continuously Stirred Tank Reactor ("CSTR") with the catalyst dispersed in the isocyanate; a CSTR which serves as a reservoir for the is ⁇ cyanate/dimer mixture that is repetitively passed, in parallel, through a battery of catalyst packed cartridges, wherein relatively low levels of conversion are achieved in each pass; or a catalyst packed tube, wherein the desired level of conversion is reached in a single pass through the tube.
  • CSTR Continuously Stirred Tank Reactor
  • a CSTR which serves as a reservoir for the is ⁇ cyanate/dimer mixture that is repetitively passed, in parallel, through a battery of catalyst packed cartridges, wherein relatively low levels of conversion are achieved in each pass
  • a catalyst packed tube wherein the desired level of conversion is reached in a single pass through the tube.
  • a range of polymer-bound catalyst concentrations
  • the factors to be considered in the selection of preferred catalyst concentrations are: the activity of the catalyst being used; the degree of conversion desired; and, the temperature at which the reaction is conducted. Generally, an amount of between 0.01 and 10 parts of polymer-bound catalyst per 100 parts of precursor isocyanate is preferred. An amount of between 0.05 and 2 parts of polymer-bound catalyst per 100 parts of precursor isocyanate is most preferred.
  • Co-catalysts are optionally and desirably employed in the process of the present invention as a source of active hydrogens for the uretidione formation reactions.
  • the co-catalysts may be any isocyanate reactive hydrogen containing reagents such as amines, alcohols, carbamates, ureas and the like.
  • the preferred co-catalysts are primary and secondary alcohols, such as, for example, methanol, ethanol, 2-propanol, l,3-dihydroxy-2-hexyl propane, triethylene glycol onomethyl ether, and the like.
  • the co-catalyst is employed in an amount of between about 1:1 and about 10:1 molar equivalents based upon the amount of polymer-bound catalyst employed in the process of the present invention.
  • a range of temperatures may be used in the process of this invention. The factors to be considered in the selection of preferred reaction temperatures are the amount and the activity of the catalyst being used and the degree of conversion desired. Generally, somewhat elevated temperatures are preferred because they drive the reaction at a reasonable rate. Temperatures between 20 and 130°C are preferred with temperatures between 20 and 110°C being most preferred.
  • the time required for the process of this invention is dependent on the temperature, the amount and type of catalyst used and the degree of conversion sought. Generally, it is desirable that a combination of temperature, catalyst activity and catalyst concentration be used that achieves the required level of conversion within a period of 0.5 to 8 hours.
  • the cyclodimerization reaction is effectively stopped by removal of the catalyst.
  • the catalyst optionally may be deactivated prior to removal.
  • the catalyst is deactivated by the addition of a suitable blocking agent.
  • Such agents react preferentially with the catalytic sites and block further reaction with isocyanate functional groups.
  • Agents such as hydrogen containing acids or salts of such acids that thermally liberate the acid, alkyl halides and the like, are employed in an amount of between about 1:1 and about 10:1 molar equivalents based upon the amount of polymer-bound catalyst employed in the process of the present invention.
  • WFE wiped film evaporator
  • FFE falling film evaporator
  • TFE thin film evaporator
  • WFE WFE
  • FFE FFE
  • TFE TFE
  • elevated temperatures 60 to 130°C, preferably between 80 and 120°C
  • reduced pressure 0.01 to 5 mm Hg, preferably between 0.1 and 2 mm Hg.
  • the feed rate is dependant on the heated surface area of the apparatus, but should be slow enough to permit the removal of most of the residual diisocyanate monomer but fast enough to assure that the product is not exposed to high temperatures for an unnecessarily long period of time.
  • the residual monomer content should be less than 0.2%, preferably less than 0.1% by weight of the product.
  • the process of the present invention is suitably employed in the production of a wide range of isocyanate dimers, including hexamethylene diisocyanate (“HDI”) dimer, isophorone diisocyanate (“IPDI”) dimer, H.-MDI dimer, toluene diisocyanate (“TDI”) dimer, methlylene diphenylene diisocyanate (“MDI”) dimer, naphthalene diisocyanate (“NDI”) dimer, cyclohexylene diisocyanate (“CHDI”) dimer, 1,4-phenylene diisocyanate (“PPDI”) dimer, bitolyene diisocyanate (“TODI”) dimer, xylyene diisocyanate (“XDI”) dimer, tetramethyl xylyene diisocyanate (“TMXDI”) dimer, l,3-bis(isocyanatomethyl) cyclohexane (“H g MDI”) dim
  • a polymer-bound catalyst namely poly(4-dimethylamino pyridine) , commercially available as POLYDMAP" 1 , a product of Reilly Industries, Inc, was employed in this example. It is supplied as crosslinked gel beads, swollen with toluene (45-47 weight percent) and contains 1.4 meq 4-dimethylamino pyridine per gram of dry resin. It was used as supplied.
  • POLYDMAPTM is a product of Reilly Industries, Inc. It is supplied as crosslinked gel beads, swollen with toluene (45-47 weight percent) and contains 1.4 meq 4-dimethylamino pyridine per gram of dry resin. 200 gms of this material was washed with ethyl acetate and then with toluene, several times and then dried under vacuum, at 60°C, for 16 hours. The resulting amber beads were swollen with an equal weight of dry toluene for at least 2 hours prior to use.
  • HDI dimer as a very pale yellow liquid, containing 0.1% residual HDI, with a viscosity of 33 cps at 25°C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'un dimère qui comprend les étapes suivantes: a) cyclodimérisation d'un polyisocyanate en présence d'un catalyseur de dimérisation à liaison polymère par mise en réaction dudit polyisocyanate avec ledit catalyseur à une température comprise entre environ 20 et 135 °C, en vue de former un isocyanate cyclodimérisé contenant de l'urétidione, dans lequel une partie des fractions d'isocyanate comprenant ledit polyisocyanate sont converties en groupes urétidione; et b) séparation dudit catalyseur dudit isocyanate cyclodimérisé afin d'arrêter ladite réaction après que la quantité désirée de fractions d'isocyanate contenues dans ledit polyisocyanate a été convertie en fractions d'urétidione.
PCT/US1993/001795 1992-03-16 1993-03-01 Production de dimeres d'isocyanate au moyen de catalyseurs a liaison polymere WO1993019049A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP93907088A EP0631574A4 (fr) 1992-03-16 1993-03-01 Production de dimeres d'isocyanate au moyen de catalyseurs a liaison polymere.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US85160492A 1992-03-16 1992-03-16
US851,604 1992-03-16

Publications (1)

Publication Number Publication Date
WO1993019049A1 true WO1993019049A1 (fr) 1993-09-30

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ID=25311187

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Country Status (3)

Country Link
EP (1) EP0631574A4 (fr)
AU (1) AU3781693A (fr)
WO (1) WO1993019049A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0735027A1 (fr) * 1995-03-25 1996-10-02 Hüls Aktiengesellschaft Procédé de préparation d'uretdiones (cyclo)aliphatiques ayant une meilleure qualité de couleur
EP1072622A1 (fr) * 1999-07-30 2001-01-31 Bayer Antwerpen N.V. Catalyse à température critique pour de polyuréthanes réticulables

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2643250A (en) * 1951-11-16 1953-06-23 Du Pont Isocyanate dimers as color forming intermediates
US2683144A (en) * 1951-10-02 1954-07-06 Du Pont Polymerization of isocyanates
US3907780A (en) * 1973-01-15 1975-09-23 Ici Ltd Preparation of carbodiimide-containing isocyanates
US4143063A (en) * 1977-01-31 1979-03-06 The Upjohn Company Preparation of carbodiimide-containing polyisocyanates
US4521338A (en) * 1981-08-12 1985-06-04 Bayer Aktiengesellschaft Process for the preparation of low molecular weight 4,4'-diphenylmethane-uretdione-diisocyanates

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5221743A (en) * 1992-03-02 1993-06-22 Olin Corporation Process for producing isocyanurates by cyclotrimerizing isocyanates using polymer-bound catalysts

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683144A (en) * 1951-10-02 1954-07-06 Du Pont Polymerization of isocyanates
US2643250A (en) * 1951-11-16 1953-06-23 Du Pont Isocyanate dimers as color forming intermediates
US3907780A (en) * 1973-01-15 1975-09-23 Ici Ltd Preparation of carbodiimide-containing isocyanates
US4143063A (en) * 1977-01-31 1979-03-06 The Upjohn Company Preparation of carbodiimide-containing polyisocyanates
US4521338A (en) * 1981-08-12 1985-06-04 Bayer Aktiengesellschaft Process for the preparation of low molecular weight 4,4'-diphenylmethane-uretdione-diisocyanates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0631574A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0735027A1 (fr) * 1995-03-25 1996-10-02 Hüls Aktiengesellschaft Procédé de préparation d'uretdiones (cyclo)aliphatiques ayant une meilleure qualité de couleur
EP1072622A1 (fr) * 1999-07-30 2001-01-31 Bayer Antwerpen N.V. Catalyse à température critique pour de polyuréthanes réticulables

Also Published As

Publication number Publication date
EP0631574A4 (fr) 1996-04-17
EP0631574A1 (fr) 1995-01-04
AU3781693A (en) 1993-10-21

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