Method for the production of polyoxazolidinone polymer compounds

Patent metadata

Field	Value
Publication number	US-11319398-B2
Application number	US-201816481115-A
Country	US
Kind code	B2
Filing date	Jan 30, 2018
Priority date	Feb 2, 2017
Publication date	May 3, 2022
Grant date	May 3, 2022

Abstract

Method for the production of polyoxazolidinone compounds, comprising the reaction of at least one biscarbamate compound (A) with at least one bisepoxide compound (B) in the presence of at least one base (D), at least one Lewis acid catalyst (E), and optionally at least one compound (C), wherein the compound (C) comprising a mono-carbamate group, a mono-isocyanate group and/or a mono-epoxide group, and wherein the base (D) having a pKb-value of ≤9. The invention is also related to the resulting polyoxazolidinone compounds.

First claim

The invention claimed is:

1. A method for the production of polyoxazolidinone compounds, comprising reacting (A) at least one biscarbamate compound with (B) at least one bisepoxide compound in the presence of (D) at least one base, (E) at least one Lewis acid catalyst, and optionally (C) at least one compound which comprises at least one of a mono-carbamate group, a mono-isocyanate group, and a mono-epoxide group, and (D) the base has a pK b -value of ≤9.

2. The method according to claim 1 , wherein the method comprises:
(α) adding (A) the biscarbamate compound to (B) the bisepoxide compound in a continuous or step-wise manner with two or more individual addition steps in the step-wise addition and in each individual addition step the amount of (A) the biscarbamate compound added is ≥0.1 weight-% to ≤50 weight-% of the total amount of the biscarbamate compound (A) to be added,
or
(β) adding (A) the biscarbamate compound and (B) the bisepoxide compound at the same time to a reactor, optionally, comprising (D) the at least one base and (E) at least one Lewis acid catalyst, and/or a solvent in a continuous or step-wise manner with two or more individual addition steps in the step-wise addition,
or
(γ) charging (A) the biscarbamate compound, (B) the bisepoxide compound, optionally, (C) the compound which comprises at least one of a mono-carbamate group, a mono-isocyanate group, and a mono-epoxide group, (D) the base, and (E) the Lewis acid catalyst and, if applicable, a solvent to a reactor and running the reaction until full conversion is obtained.

3. The method according to claim 1 , wherein (A) the biscarbamate compound comprises at least one of N,N′-tetramethylene biscarbamate, N,N′-hexamethylene biscarbamate, N,N′-(2-methylpentamethylene) biscarbamate, N,N′-2,2,4-trimethyl-hexamethylene biscarbamate, N,N′-dodecanemethylene biscarbamate, N,N′-cyclohexane-1,4-biscarbamate, N,N′-isophorone biscarbamate, N,N′-(4,4′-methylenebis(cyclohexane-4,1-diyl)biscarbamate, N,N′-diphenylmethane biscarbamate, N,N′-(4,4′-methylenebis(2-methylcyclohexane-4,1-diyl))biscarbamate, (−)-N,N′-2,2-dicyclohexylpropane-4,4′-biscarbamate, N,N′-poly(hexamethylene biscarbamate), N,N′-octamethylene biscarbamate, N,N′-tolylene-α,4-biscarbamate, N,N′-poly(propylene glycol) tolylene-2,4-biscarbamate terminated, N,N′-poly(ethylene adipate) tolylene-2,4-biscarbamate terminated, N,N′-2,4,6-trimethyl-1,3-phenylene biscarbamate, N,N′-(4-chloro-6-methyl-1,3-phenylene) biscarbamate, N,N′(poly[1,4-phenylene biscarbamate-co-poly(1,4-butanediol)]) biscarbamate, poly(tetrafluoroethylene oxide-co-difluoromethylene oxide) α,ω-biscarbamate, N,N′-butane-1,4-diylbiscarbamate, N,N′-(1-methylethyl)benzene-1,3-biscarbamate, N,N′-3,3′-dimethyl-4,4′-biphenylene biscarbamate, N,N′-naphthalene-1,5-biscarbamate, N,N′-1,3-phenylene biscarbamate, N,N′-benzene-1,4-biscarbamate, N,N′-2,4- or N,N′-2,5- or N,N′-2,6-biscarbamatotoluene or mixtures of these isomers, N,N′-4,4′-, N,N′-2,4′- or N,N′-2,2′-biscarbamatodiphenylmethane or mixtures of these isomers, N,N′-4,4′-, N,N′-2,4′- or N,N′-2,2′-biscarbamato-2,2-diphenylpropane-p-xylene and α,α,α′,α′-tetramethyl-m- or -p-xylene biscarbamate.

4. The method according to claim 1 , wherein (B) the bisepoxide compound comprises at least one of resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butandiol diglycidyl ether, hydrogenated bisphenol-A diglycidyl ether, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-S digylcidyl ether, 9,9-bis(4-glycidyloxy phenyl)fluorine, tetrabromo bisphenol-A diglycidyl ether, tetrachloro bisphenol-A diglycidyl ether, tetramethyl bisphenol-A diglycidyl ether, tetramethyl bisphenol-F diglycidyl ether, tetramethyl bisphenol-S diglycidyl ether, diglycidyl terephthalate, diglycidyl o-phthalate, 1,4-cyclohexane dicarboxylic acid diglycidyl ester, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutadiene diglycidyl ether, butadiene diepoxide, vinylcyclohexene diepoxide, limonene diepoxide, the diepoxides of double unsaturated fatty acid C 1 -C 18 alkyl esters, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, 4,4′-(3,3,5-trimethylcyclohexyliden)bisphenyl diglycidylether, and diglycidyl isophthalate.

5. The method according to claim 1 , wherein (C) the compound comprises at least one of N-phenyl carbamate, N-(o-tolyl) carbamate, N-(p-tolyl) carbamate, N-(4-chlorophenyl) carbamate, N-(1-naphthyl) carbamate, N-(2-naphthyl) carbamate, N-cyclohexyl carbamate, N-methyl carbamate, N-ethyl carbamate, N-(n-propyl) carbamate, N-isopropyl carbamate, N-butyl carbamate, N-pentyl carbamate N-hexyl carbamate and/or N-octyl carbamate, and/or phenyl glycidyl ether, o-kresyl glycidyl ether, m-kresyl glycidyl ether, p-kresyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, 1-naphthyl glycidyl ether, 2-naphthyl glycidyl ether, 4-chlorophenyl glycidyl ether, 2,4,6-trichlorophenyl glycidyl ether, 2,4,6-tribromophenyl glycidyl ether, pentafluorophenyl glycidyl ether, cyclohexyl glycidyl ether, benzyl glycidyl ether, glycidyl benzoate, glycidyl acetate, glycidyl cyclohexylcarboxylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidylether, C 10 -C 18 alkyl glycidyl ether, allyl glycidyl ether, ethylene oxide, propylene oxide, styrene oxide, 1,2-butene oxide, 2,3-butene oxide, 1,2-hexene oxide, oxides of C 10 -C 18 alpha-olefines, cyclohexene oxide, vinylcyclohexene monoxide, limonene monoxide, butadiene monoepoxide and/or N-glycidyl phthalimide and/or n-hexylisocyanate, 4-tert-butylphenyl glycidyl ether, cyclohexyl isocyanate, ω-chlorohexamethylene isocyanate, 2-ethyl hexyl isocyanate, n-octyl isocyanate, dodecyl isocyanate, stearyl isocyanate, methyl isocyanate, ethyl isocyanate, butyl isocyanate, isopropyl isocyanate, octadecyl isocyanate, 6-chloro-hexyl isocyanate, cyclohexyl isocyanate, 2,3,4-trimethylcyclohexyl isocyanate, 3,3,5-trimethylcyclohexyl isocyanate, 2-norbornyl methyl isocyanate, decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, 3-butoxypropyl isocyanate, 3-(2-ethylhexyloxy)-propyl isocyanate, (trimethylsilyl)isocyanate, phenyl isocyanate, ortho-, meta-, para-tolyl isocyanate, chlorophenyl isocyanate (2,3,4-isomers), dichlorophenyl isocyanate, 4-nitrophenyl isocyanate, 3-trifluoromethylphenyl isocyanate, benzyl isocyanate, dimethylphenylisocyanate (technical mixture and individual isomers), 4-dodecylphenylisocyanate, 4-cyclohexyl-phenyl isocyanate, 4-pentyl-phenyl isocyanate, 4-t-butyl phenyl isocyanate, and 1-naphthyl isocyanate.

6. The method according to claim 1 , wherein the base (D) has a pK b -value of ≤7.

7. The method according to claim 1 , wherein (D) the base comprises at least one of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), triazabicyclodecene (TBD) and hexachlorocyclotriphosphazene, bis(triphenyl-phosphine)iminium chloride, tetramethyl(tris(dimethylamino)-phosphoranylidene)-phosphorictriamid-Et-imin, tert-octylimino-tris(dimethylamino)-phosphorane and tert-Butylimino-tri(pyrrolidino)phosphorane.

8. The method according to claim 1 , wherein (E) the Lewis acid catalyst comprises at least one of
Li(I), Rb(I), Cs(I), Ag(I), Au(I),
Mg(II), Ca(II), Sr(II), Ba(II), Dy(II), Yb(II), Cu(II), Zn(II), V(II), Mo(II), Mn(II), Fe(II),
Co(II)
Ni(II), Pd(II), Pt(II), Ge(II), Sn(II),
Sc(III), Y(III), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III),
Ho(III),
E

Assignees

• Covestro Deutschland Ag

Inventors

• Müller Thomas Ernst
• Gürtler Christoph
• Koopmans Carsten
• Marker Volker
• Rangheard Claudine
• Leitner Walter

Classifications

• C08G18/7671

  containing only one alkylene bisphenyl group · CPC title

• C08G18/282

  Alkanols, cycloalkanols or arylalkanols including terpenealcohols · CPC title

• C08G73/06 Primary

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule · CPC title

• C08G18/161

  containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 · CPC title

• C08G18/003 Primary

  with epoxy compounds having no active hydrogen (with epoxy resins containing active hydrogen C08G18/58) · CPC title