Process for the synthesis of polyoxazolidinone compounds

Patent metadata

Field	Value
Publication number	US-11326018-B2
Application number	US-201716325532-A
Country	US
Kind code	B2
Filing date	Aug 16, 2017
Priority date	Aug 19, 2016
Publication date	May 10, 2022
Grant date	May 10, 2022

Abstract

A method for the production of polyoxazolidinone compounds, comprising the step of reacting an isocyanate compound (A) with an epoxide compound (B) in the presence of a catalyst (C), wherein the isocyanate compound (A) comprises a isocyanate compound (A1) wherein the a isocyanate compound (A1) comprising at least two isocyanate groups (I1≥2), preferred two isocyanate groups (I1=2), wherein the epoxide compound (B) comprises a epoxide compound (B1) and an epoxide compound (B2), wherein the epoxide compound (B2) is different from the epoxide compound (B1) wherein the epoxide compound (B1) comprising at least two terminal epoxide groups (F1≥2), preferred two terminal epoxide groups (F1=2), linked together by a linking group (L1) and the epoxide compound (B2) comprising at least two terminal epoxide groups (F2≥2)), preferred two terminal epoxide groups (F2=2), linked together by a linking group (L2), wherein the linking group (L2) comprises acyclic and covalent bonds to each other free of conjugated multiple bonds within the main chain, wherein the epoxide compound (B2) is present in the epoxide compounds B1 and B2, in an amount of ≥0.01 mol-% to <10 mol-%, preferred 1-9 mol-% more preferred 3-8 mol-% based on the molar ratio the terminal epoxide groups in the epoxide compound (B1) and of the sum of the terminal epoxide groups in the epoxide compound (B1) and terminal epoxide groups in the epoxide compound (B2).

First claim

The invention claimed is:

1. A method for the production of a polyoxazolidinone compound, comprising reacting an isocyanate compound (A) with an epoxide compound (B) in the presence of a catalyst (C),
wherein the isocyanate compound (A) comprises a isocyanate compound (A 1 ),
wherein the isocyanate compound (A 1 ) comprising at least two isocyanate groups (I 1 ≥2),
wherein the epoxide compound (B) comprises a epoxide compound (B 1 ) and an epoxide compound (B 2 ),
wherein the epoxide compound (B 2 ) is different from the epoxide compound (B 1 ),
wherein the epoxide compound (B 1 ) comprises at least two terminal epoxide groups (F 1 ≥2) linked together by a linking group (L 1 ) and the epoxide compound (B 2 ) comprises at least two terminal epoxide groups (F 2 ≥2)) linked together by a linking group (L 2 ),
wherein the linking group (L 2 ) comprises acyclic and covalent bonds to each other free of conjugated multiple bonds within the main chain,
wherein the epoxide compound (B 2 ) is present in the epoxide compounds B 1 and B 2 in an amount of ≥0.01 mol-% to <10 mol-% based on the molar ratio the terminal epoxide groups in the epoxide compound (B 1 ) to the sum of the terminal epoxide groups in the epoxide compound (B 1 ) and terminal epoxide groups in the epoxide compound (B 2 ), and
wherein the polyoxazolidinone compound is a thermoplastic polyoxazolidinone, and
wherein the epoxide compound (B 2 ) comprises neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, or a mixture thereof.

2. The method according to claim 1 , which comprises:
adding the isocyanate compound (A 1 ) to the epoxide compound (B 1 ) and the epoxide compound (B 2 ) within the epoxide compound (B) 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 isocyanate compound (A 1 ) added is ≥0.1 weight-% to ≤50 weight-% of the total amount of isocyanate compound (A 1 ) to be added,
or
adding the isocyanate compound (A 1 ) and the epoxide compound (B 1 ) and the epoxide compound (B2) within the epoxide compound (B) at the same time to the reactor optionally comprising the catalyst (C) and/or a solvent in a continuous or step-wise manner with two or more individual addition steps in the step-wise addition.

3. The method according to claim 1 , wherein the epoxide compound (B 1 ) comprises at least one of 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, vinylcyclohexene diepoxide, limonene diepoxide, the diepoxides of double unsaturated fatty acid C1- C18 alkyl esters, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, 4,4′-(3,3,5-trimethylcyclohexyliden)bisphenyl diglycidylether and diglycidyl isophthalate resorcinol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, diglycidyl terephthalate, and diglycidyl o-phthalate.

4. The method according to claim 1 , wherein the polyoxazolidone additionally comprises a monofunctional epoxide compound (B 3 ) with F 3 =1 a monofunctional isocyanate compound (A 2 ) with (I 2 )=1 and/or a monofunctional carbamate compound (A 3 ) with (I 3 )=1.

5. The method according to claim 4 , wherein the monofunctional epoxide compound (B 3 ), the monofunctional isocyanate compound (A 2 ) and/or the monofunctional carbamate compound (A 3 ) comprises at least one of 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, C10 C18 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 C10-C18 alpha-olefines, cyclohexene oxide, vinylcyclohexene monoxide, limonene monoxide, butadiene monoepoxide and/or N-glycidyl phthalimide, n-hexylisocyanate, cyclohexyl isocyanate, co-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 isocyanatate, 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-dodecylphenylisocyanat, 4-cyclohexyl-phenyl isocyanate, 4-pentyl-phenyl isocyanate, 4-t-butyl phenyl isocyanate, 1-naphthyl isocyanate, preferably N-(p-tolyl) carbamate, 4-tert-Butylphenylglycidylether, p-tolyl isocyanate 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 N-octyl carbamate.

6. The method according to claim 1 , wherein the catalyst (C) is represented by formula (II)
[M(R1)(R2)(R3)(R4)] + n Y n−   (II)

wherein
M represents nitrogen, phosphorous or antimony,
(R1), (R2), (R3), (R4) are independently of one another selected from the group comprising linear or branched alkyl groups containing 1 to 22 carbon atoms, optionally substituted with heteroatoms and/or heteroatom containing substituents, cycloaliphatic groups containing 3 to 22 carbon atoms, optionally substituted with heteroatoms and/or heteroatom containing substituents, C1 to C3 alkyl-bridged cycloaliphatic groups containing 3 to 22 carbon atoms, optionally substituted with heteroatoms and/or heteroatom containing substituents and aryl groups containing 6 to 18 carbon atoms, optionally substituted with one or more alkyl groups containing 1 to 10 carbon atoms and/or heteroatom containing substituents and/or heteroatoms,
wherein
(R4) is different from (R1), (R2), and (R3), and
(R4) is selected from the group comprising branched alkyl groups containing 3 to 22 carbon atoms, cycloaliphatic groups containing 3 to 22 carbon atoms, C1 to C3 alkyl-bridged cycloaliphatic groups containing 3 to 22 carbon atoms and aryl groups, containing 6 to 18 carbon atoms, optionally substituted with one or more alkyl groups containing 1 to 10 carbon atoms and/or heteroatom containing substituents and/or heteroatoms,
wherein
(R1), (R2) each r

Assignees

• Covestro Deutschland Ag

Inventors

• Weber Anna
• Rangheard Claudine
• Kessler Michael
• Leitner Walter
• Gürtler Christoph
• Koopmans Carsten
• Müller Thomas Ernst

Classifications

• C08G18/003 Primary

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

• C08G18/7621 Primary

  being toluene diisocyanate including isomer mixtures · CPC title

• D01F6/96

  from other synthetic polymers · CPC title

• C08G18/166

  Catalysts not provided for in the groups C08G18/18 - C08G18/26 · CPC title