Isocyanurate preparation by catalytic, aminosilyl initiated cyclotrimerization of isocyanates

• US 4,412,073 A
• Filed: 02/01/1982
• Issued: 10/25/1983
• Est. Priority Date: 02/03/1981
• Status: Expired due to Term

• Current Assignee: Rhone-Poulenc Specialites Chimiques (Sanofi )
• Original Assignee: Rhone-Poulenc Specialites Chimiques (Sanofi )
• Inventors: Robin, Jean
• Primary Examiner(s): Ford, John M.
• Application Number:
  US06/344,797
• Time in Patent Office: 631 Days
• Field of Search: 544/193, 544/222, 521/128, 521/902, 528/52, 526/194
• US Class Current: 544/193
• CPC Class Codes: C07D 251/34 Cyanuric or isocyanuric esters
• CPC Class Codes: C08G 18/022 the polymeric products containing isocyanurate groups
• CPC Class Codes: Y10S 521/902 Cellular polymer containing an isocyanurate structure

Abstract

Monomeric or polymeric isocyanurates, e.g., polyisocyanate/polyisocyanurates, are prepared by catalytically cyclotrimerizing an isocyanate, e.g., an aliphatic or cycloaliphatic isocyanate, in the presence of an aminosilyl catalysis initiator, e.g., a mono- or diaminosilane, a silylurea or a silazane, having the structural formula:

R.sub.(4-n) Si--NR'"'"'R"].sub.n                               (I)

wherein R is a saturated or unsaturated, aliphatic, cycloaliphatic, aryl, aralkyl or alkylaryl monovalent hydrocarbon radical, or halo or cyano substituted such radical, and further wherein any two radicals R may together form a single divalent such hydrocarbon radical; R'"'"' is R, SiR₃ or an amido radical having the structural formula: ##STR1## wherein R'"'"'" is R or SiR₃, with R being as above defined, and further wherein R'"'"', when R'"'"' is neither the amido radical nor SiR₃, may, together with the radical R", form a single divalent such radical; R" is R, or a hydrogen atom when R'"'"' is not the amido radical; and n is either 1 or 2, but when n is 2, R'"'"' is R.

Claims

1. A process for the preparation of a monomeric or polymeric isocyanurate compound, comprising catalytically cyclotrimerizing an isocyanate in which the isocyanate moiety is not directly bonded to an aromatic carbon atom, in the presence of an effective amount of an aminosilyl catalysis initiator having the structural formula:

space="preserve" listing-type="equation">R.sub.(4-n) Si--NR'"'"'R"].sub.n (I)

wherein R is a saturated or unsaturated, aliphatic, cycloaliphatic, aryl, aralkyl or alkylaryl monovalent hydrocarbon radical, or halo or cyano substituted such radical, and further wherein any two radicals R may together form a single divalent such hydrocarbon radical;

R'"'"' is R, SiR₃ or an amido radical having the structural formula;

##STR4## wherein R'"'"'" is R or SiR₃, with R being as above defined, and further wherein R'"'"', when R'"'"' is neither the amido radical nor SiR₃, may, together with the radical R", form a single divalent such radical;

R" is R, or a hydrogen atom when R'"'"' is not the amido radical; and

n is either 1 or 2, but when n is 2, R'"'"' is R.

2. The process as defined by claim 1, said aminosilyl catalysis initiator being a monoaminosilane.

3. The process as defined by claim 1, said aminosilyl catalysis initiator being a diaminosilane.

4. The process as defined by claim 1, said aminosilyl catalysis initiator being a silylurea.

5. The process as defined by claim 1, said aminosilyl catalysis initiator being a silazane.

6. The process as defined by claim 1, said isocyanate starting material being an aliphatic isocyanate.

7. The process as defined by claim 1, said isocyanate starting material being a cycloaliphatic isocyanate.

8. The process as defined by claim 1, wherein the aminosilyl catalysis initiator having the structural formula (I), R is an alkyl, alkenyl, halogenoalkyl or halogenoalkenyl radical having from 1 to 5 carbon atoms and containing from 1 to 6 chlorine and/or fluorine atoms, a cycloalkyl, cycloalkenyl, halogenocycloalkyl or halogenocycloalkenyl radical having from 3 to 8 carbon atoms and containing from 1 to 4 chlorine and/or fluorine atoms, an aryl, alkylaryl or halogenoaryl radical having from 6 to 8 carbon atoms and containing from 1 to 4 chlorine and/or fluorine atoms, or a cyanoalkyl radical having from 3 to 4 carbon atoms, and further wherein any two substituents R borne by one and the same silicon atom may together from a single divalent hydrocarbon radical having 1 to 4 carbon atoms;

R'"'"' is R, SiR₃ or CO(NR)--R'"'"'", wherein R'"'"'" is R or SiR₃, with R being as above defined, and further wherein R'"'"' may, together with R, form a single alkylene radical having from 4 to 6 carbon atoms; and

R" is an alkyl or alkenyl radical having from 1 to 4 carbon atoms, a cycloalkyl or cycloalkenyl radical having from 4 to 6 nuclear carbon atoms, a phenyl, tolyl or xylyl radical, or a hydrogen atom if R'"'"' is not an amido radical.

9. The process as defined by claim 1, wherein the aminosilyl catalysis initiator having the structural formula (I), R is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, α

-pentyl, t-butyl, chloromethyl, dichloromethyl, α

-chloroethyl, α

,β

-dichloroethyl, fluoromethyl, difluoromethyl, α

,β

-difluoroethyl, 3,3,3-trifluoropropyl, trifluorocyclopropyl, 4,4,4-trifluorobutyl, 3,3,3,4,4,5,5-heptafluoropentyl, β

-cyanoethyl, γ

-cyanopropyl, phenyl, p-chlorophenyl, m-chlorophenyl, 3,5-dichlorophenyl, trichlorophenyl, tetrachlorophenyl, o-, p- or m-tolyl, α

,α

,α

-trifluorotolyl, 2,3-dimethylphenyl or 3,4-dimethylphenyl, and further wherein any two radicals R may together form a methylene, ethylene or propylene radical;

R'"'"' is R, SiR₃ or --CO--(NR)--R'"'"'", with R being as above defined, and wherein R'"'"'" is R or SiR₃, with R also being as above defined, and further wherein R'"'"' may, together with R", form a butylene, pentylene or hexylene radical; and

R" is hydrogen, methyl, butyl, cyclohexyl, phenyl or tolyl.

10. The process as defined by claim 1, wherein the aminosilyl catalysis initiator having the structural formula (I), R is methyl, ethyl, propyl, vinyl or phenyl, or chlorinated and/or fluorinated such radicals;

R'"'"' is methyl, ethyl, propyl, butyl, SiR₃, --CO--NR--R or --CO--NR--SiR₃, with R being as above defined; and

R" is methyl, ethyl, propyl, butyl or hydrogen, and further wherein R'"'"' may, together with R", form a butylene or pentylene radical.

11. The process as defined by any of claims 1, 8, 9 or 10, said aminosilyl catalysis initiator having the structural formula:

space="preserve" listing-type="equation">R.sub.3 SiNR'"'"'R".

12. The process as defined by any of claims 1, 8, 9 or 10, said aminosilyl catalysis initiator having the structural formula:

space="preserve" listing-type="equation">R.sub.2 Si(NR'"'"'R").sub.2.

13. The process as defined by any of claims 1, 8, 9 or 10, said aminosilyl catalysis initiator having the structural formula:

##STR5##

14. The process as defined by any of claims 1, 8, 9 or 10, said aminosilyl catalysis initiator having the structural formula:

##STR6##

15. The process as defined by claim 1, for the preparation of a polyisocyanate/polyisocyanurate by catalytically cyclotrimerizing an aliphtic or cycloaliphatic polyisocyanate, or polyisocyanate adduct or prepolymer thereof, and comprising destruction of the catalysis initiator when the degree of isocyanurate formation has attained the desired level.

16. The process as defined by claim 15, said catalysis initiator destruction being effected by addition of an acid compound to the reaction medium.

17. The process as defined by claims 15 or 16, further comprising removal of residual polyisocyanate upon completion of the reaction.

18. The process as defined by claim 1, said isocyanate catalytically cyclotrimerized being hexamethylene diisocyanate.

19. The process as defined by claim 1, said aminosilyl catalysis initiator being methylamino-trimethylsilane, dimethylamino-trimethylsilane, diethylamino-trimethylsilane, dibutylamino-trimethylsilane, diethylamino-dimethyl-vinylsilane, diethylamino-dimethyl-phenylsilane, bis-dimethylamino-dimethylsilane, bis-diethylamino-dimethylsilane, bis-dibutylamino-dimethylsilane, bis-dimethylamino-methyl-phenylsilane, N-methyl-N-trimethylsilyl-N'"'"'-methyl-N'"'"'-butylurea, N-trimethylsilyl-N-methyl-N'"'"',N'"'"'-dimethylurea, N-trimethylsilyl-N-ethyl-N'"'"',N'"'"'-dimethylurea, N-trimethylsilyl-N-butyl-N'"'"'-butyl-N'"'"'-trimethylsilylurea, hexamethyldisilazane, heptamethyldisilazane, 1,3-diethyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3,-tetramethyldisilazane, hexaethyldisilazane or 1,3-diphenyl-1,1,3,3-tetramethyldisilazane.

20. The process as defined by claim 1, said isocyanate catalytically cyclotrimerized being methyl isocyanate, butyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 1,2-bis-(isocyanatomethyl)-cyclobutane, bis-(4-isocyantocyclohexyl)-methane or 3,3,5-trimethyl-5-isocyanatomethyl-1-isocyantocyclohexane.