Process for the synthesis of polyoxazolidinone compounds with high stability

Patent metadata

Field	Value
Publication number	US-10385167-B2
Application number	US-201615548817-A
Country	US
Kind code	B2
Filing date	Feb 9, 2016
Priority date	Feb 13, 2015
Publication date	Aug 20, 2019
Grant date	Aug 20, 2019

Abstract

The present invention relates to polyoxazolidinone compounds, a method for the production of polyoxazolidinone compounds, comprising the step of reacting a biscarbamate compound with a bisepoxide compound in the presence of a mono-carbamate, a mono-isocyanate and/or a mono-epoxide compound as chain regulator and a suitable base having a pKb value of ≤9 as catalyst. The invention further relates to the use of polyoxazolidinone compounds with high thermal stability.

First claim

The invention claimed is:

1. A polyoxazolidinone compound corresponding to formula (I) formula (II) and/or formula (III)

wherein
X represents methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene, each of which is unsubstituted or is substituted with one or more heteroatom containing group, cyclohexylene, phenylene, diphenylene or dimethyl phenylene, each of which is unsubstituted or is substituted with one or more heteroatoms, 2-methylpentamethylene, 2,2,4-trimethyl-hexamethylene, dodecanemethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 5-(1-methylene-(1,3,3-trimethylcyclohexane)), all regioisomers of methylene biscyclohexylene, all regioisomers of methylenebisphenylene, methylenebis-(3,3′-dimethylcyclohexane1,4-diyl), propane-2,2-diylbis(cyclohexane-4,1-diyl), propane-2,2-diyl-bis-4,1-phenylene, polyhexamethylene, tolylene, poly(propylene glycol) tolylene, poly(ethylene adipate) tolylene, 2,4,6-trimethyl-1,3-phenylene, 4-chloro-6-methyl-1,3-phenylene, poly [1,4-phenylene], co-poly(1,4-butanediol)], poly(tetrafluoroethylene oxide-co-difluoromethylene oxide), 1,3-bis(1-methylethyl)benzene, 3,3′-dimethyl-4,4′-biphenylene, naphthalene, 1,2-phenylene, 1,3- phenylene, 1,4-phenylene 2,4- or 2,5- or 2,6- tolylene or mixtures of these isomers, methylene 4,4′- or 2,4′- or 2,2′- bisphenylene or mixtures of these isomers, 4,4′-, 2,4′- or 2,2′- 2,2-diphenylpropane-p-xylylene, or α,α,α′,α′-tetramethyl- m- or -p-xylylene;
Y represents methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, polyethylene, polyethyleneglycol, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-tolylene, 1,3-tolylene, 1,4-tolylene, 4,4′-methylenebis(4,1-phenylene), 4,4′-methylenebis(cyclohexane-4,1-diyl), 4,4′-(propane-2,2-diyl)bis(4,1-phenylene), propane-2,2-diyl-bis(cyclohexane-4,1-diyl), or Y can be represented by formula IV

wherein Y′ represents methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, polyethylene, polyethyleneglycol, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-tolylene, 1,3-tolylene, 1,4-tolylene, 4,4′-methylenebis(4,1-phenylene), 4,4′-methylenebis(cyclohexane-4,1-diyl), 4,4′-(propane-2,2-diyl)bis(4,1-phenylene), propane-2,2-diyl-bis(cyclohexane-4,1-diyl) or 4,4′-(3,3,5-trimethylcyclohexyliden)bisphenyl;
each Z independently represents hydrogen, methyl, ethyl, butyl, propyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, C10- C18 alpha-olefins, ethylene, phenyl, unsaturated fatty acid C1 - C18 alkyl esters, methylene methyl ether, methylene ethyl ether, methylene propyl ether, methylene butyl ether, methylene pentyl ether, methylene hexyl ether, methylene cyclohexyl ether, methylene octyl ether, methylene 2-ethylhexyl ether, methylene C10 - C18 alkyl ether, methylene allyl ether, methylene benzyl ether, methylene phenyl ether, methylene 4-tert-butylphenyl ether, methylene 1-naphthyl ether, methylene 2-naphthyl ether, methylene 2-chlorophenyl ether, methylene 4-chlorophenyl ether, methylene 4-bromophenyl ether, methylene 2,4,6-trichlorophenyl ether, methylene 2,4,6-tribromophenyl ether, methylene pentafluorophenyl ether, methylene o-cresyl ether, methylene m-cresyl ether, methylene p-cresyl ether, methylene acetate, methylene cyclohexylcarboxylate, methylene benzoate, or N-methylene phthalimide;
each ZZ independently represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, ω-chlorohexamethylene, n-heptyl, n-octyl, iso-octyl, 2-ethyl hexyl, 2-norbornyl methyl, nonyl, 2,3,4-trimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, stearyl, 3-butoxypropyl, 3-(2-ethylhexyloxy)-propyl, 6-chlorohexyl, benzyl, phenyl, ortho-, meta-, para-tolyl, dimethylphenyl, 4-pentylphenyl isocyanate, 4-cyclohexylphenyl, 4-dodecylphenyl, ortho-, meta-, para-methoxyphenyl, chlorophenyl (2,3,4-isomers), the different dichlorophenyl isomers, 4-nitrophenyl, 3-trifluoromethylphenyl, or 1-naphthyl;
R1, R1′, R2, R2′, R3, R3′, R4, R5, and R6 independent of one another represent hydrogen, chloride, bromide, fluoride, methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, hexyl, methoxy, ethoxy, butoxy, phenyl, methoxyphenyl, chlorophenyl, bromophenyl, nitrophenyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl,
X, Y, Z, ZZ, R1, R1′, R2, R2′, R3, R3′, R4, R5, R6 can be equal or different to each other,
and
n is an integer of ≥1.

2. A compound according to claim 1 , wherein n is an integer of ≥2 and ≤2000.

3. A compound according to claim 1 , wherein
X represents 4,4′-methylenebis(4,1-phenylene) or 2, 4-substituted tolylene;
Y represents 4,4′-(propane-2,2-diyl)bis(4,1-phenylene) or 1,3-phenylene;
Z represents hydrogen, methyl, ethyl, phenyl, methylene butyl ether, methylene benzyl ether, methylene phenyl ether, methylene p-tolyl ether, methylene 4-tert-butylphenyl ether or mixtures thereof;
ZZ represents benzyl, phenyl, ortho-, meta-, para-tolyl, dimethylphenyl, 4-cyclohexylphenyl, ortho-, meta-, para-methoxyphenyl or mixtures thereof;
R1, R1′, R2, R2′, R3, R3′, R4, R5, R6 represent hydrogen.

4. A method for the production of a polyoxazolidinone compound according to claim 1 , comprising reacting at least one biscarbamate with at least one bisepoxide, in the presence of
A) a compound comprising a mono-carbamate group, a mono-isocyanate group and/or a mono-epoxide group
and/or
B) a base having a pK b -value of ≤9.

5. A method for the production of a polyoxazolidinone compound according to claim 1 , comprising reacting at least one diisocyanate compound with at least one bisepoxide compound, in the presence of
A) a compound comprising a mono-carbamate group, a mono-isocyanate group and/or a mono-epoxide group,
and/or
B) a base having a pK b -value of ≤9.

6. A method according to claim 4 , wherein the reaction occurs at a temperature of ≥100° C.

7. A method according to claim 4 , wherein the base B) has a pK b -value of ≤7.

8. A method according to one of claim 4 , wherein A) is a compound comprising a mono-carbamate group and/or a mono-epoxide group.

9. A method according to claim 4 , wherein the biscarbamate is selected from the group consisting 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, N,N′-poly(ethylene adipate) tolylene-2,4-biscarbamate, 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

Assignees

• Covestro Deutschland Ag

Inventors

• Müller Thomas Ernst
• Gürtler Christoph
• Basu Susmit
• Rangheard Claudine
• Rivillo David
• Leitner Walter
• Köhler Burkhard

Classifications

• C08G18/7621

  being toluene diisocyanate including isomer mixtures · CPC title

• C08G18/8064

  with monohydroxy compounds · CPC title

• C08G18/71 Primary

  Monoisocyanates or monoisothiocyanates · CPC title

• C08G18/168

  Organic compounds · CPC title

• C08G18/282

  Alkanols, cycloalkanols or arylalkanols including terpenealcohols · CPC title