Method for the production of thermoplastic polyoxazolidinone polymers

Patent metadata

Field	Value
Publication number	US-11427671-B2
Application number	US-201917281403-A
Country	US
Kind code	B2
Filing date	Oct 25, 2019
Priority date	Oct 30, 2018
Publication date	Aug 30, 2022
Grant date	Aug 30, 2022

Abstract

A process for producing thermoplastic polyoxazolidinone, comprising the following steps: (i) Reaction of a diisocyanate compound (A) with a bisepoxide compound (B) in the presence of a catalyst (C) and a compound (D) in a solvent (E) forming an intermediate compound (F) and (ii) Reaction of a compound (G) with the intermediate (F) formed in step (i), wherein the bisepoxide compound (B) comprises isosorbide diglycidylether, wherein compound (D) is one or more compounds selected from the group consisting of monofunctional isocyanate and monofunctional epoxide, and wherein compound (G) is an alkylene oxide. The invention is also related to the resulting thermoplastic polyoxazolidinone.

First claim

The invention claimed is:

1. A process for producing a thermoplastic polyoxazolidinone, comprising:
(i) reacting a diisocyanate compound with a bisepoxide compound in the presence of a catalyst and a chain regulator in a solvent to form an intermediate compound, and
(ii) reacting an alkylene oxide with the intermediate compound,

wherein the bisepoxide compound comprises isosorbide diglycidylether, and
wherein the chain regulator comprises monofunctional isocyanate, a monofunctional epoxide, or a mixture thereof.

2. The process according to claim 1 , wherein step (i) comprises:
(i-1) placing the solvent and the catalyst in a reactor to provide a mixture,
(i-2) placing the diisocyanate compound, the bisepoxide compound and the chain regulator in a vessel to provide a mixture and
(i-3) adding the mixture resulting from step (i-2) to the mixture resulting from step (i-1).

3. The process according to claim 2 , wherein the mixture resulting from step (i-2) is added in a continuous manner or step-wise manner with two or more individual addition steps to the mixture of step (i-1).

4. The process according to claim 2 , wherein the alkylene oxide is added in a step-wise manner with two or more individual addition steps or in continuous manner in step (ii) to the intermediate compound.

5. The process according to claim 1 , wherein the catalyst comprises:
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), Er(III), Tm(III), Yb(III), Lu(III), Hf(III), Nb(III), Ta(III), Cr(III), Ru(III), Os(III), Rh(III), Ir(III), Al(III), Ga(III), In(III), Tl(III), Ge(III), Ce(IV), Ti(IV), Zr(IV), Hf(IV), Nb(IV), Mo(IV), W(IV), Ir(IV), Pt(IV), Sn(IV), Pb(IV), Nb(V), Ta(V), Bi(V), Mo(VI), W(VI), a compound represented by the formula (I)
[M(R1)(R2)(R3)(R4)]+ n Yn-   (I)

wherein M is nitrogen, phosphorous or antimony,
wherein (R1), (R2), (R3), and (R4) independently of one another comprise a 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 Y is a halide, carbonate, nitrate, sulfate or phosphate anion, and
wherein n is an integer of 1, 2 or 3,

or a mixture of any two or more of the foregoing catalysts.

6. The process according to claim 1 , wherein the catalyst comprises LiCl, LiBr, LiI, MgCl2, MgBr2, MgI2, SmI3, Ph4SbBr, Ph4SbCl, Ph4PBr, Ph4PCl, Ph3(C6H4-OCH3)PBr, Ph3(C6H4-OCH3)PCl, Ph3(C6H4F)PCl, Ph3(C6H4F)PBr, or a mixture of any two or more thereof.

7. The process according to claim 1 , wherein the chain regulator comprises 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 glycidyl ether, a 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, an oxide of a C10-C18 alpha-olefin, cyclohexene oxide, vinylcyclohexene monoxide, limonene monoxide, butadiene monoepoxide, N-glycidyl phthalimide, 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, 4-dodecylphenylisocyanate, 4-cyclohexyl-phenyl isocyanate, 4-pentyl-phenyl isocyanate, 4-t-butyl phenyl isocyanate, 1-naphthyl isocyanate, or a mixture of any two or more thereof.

8. The process according to claim 1 , wherein the calculated mass ratio of the sum of diisocyanate compound, the bisepoxide compound, and the chain regulator to the sum of diisocyanate compound, the bisepoxide compound, the chain regulator and the solvent in step (i) is from 5 wt-% to 30 wt-%.

9. The process according to claim 2 , wherein the solvent in step (i-1) comprises sulfolane, gamma-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, or a mixture thereof.

10. The process according to claim 1 , wherein the alkylene oxide comprises a monofunctional alkylene oxide.

11. The process according to claim 10 , wherein the monofunctional alkylene oxide comprises 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 glycidyl ether, a 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, an oxide of a C10-C18 alpha-olefin, cyclohexene oxide, vinylcyclohexene monoxide, limonene monoxide, butadiene monoepoxide, N-glycidyl phthalimide, or a mixture of any two or more thereof.

12. The process according to claim 1 , wherein step i) is performed at a reaction time of 1 h to 20 h.

13. The process according to claim 1 , wherein step ii) is performed at a reaction time of 1 h to 20 h.

14. A thermoplastic polyoxazolidinone obtained by the process according to claim 1 , wherein the thermoplastic polyoxazolidinone has a number average molecular weight of 500 to 500,000 g/mol.

Assignees

• Covestro Intellectual Property Gmbh & Co Kg

Inventors

• Koopmans Carsten
• Laemmerhold Kai
• Guertler Christoph
• Frick-Delaittre Elena
• Wolf Aurel
• Simon Joachim
• Wang Min
• Thiel Daniel
• Leitner Walter

Classifications

• C08G18/71

  Monoisocyanates or monoisothiocyanates · CPC title

• C08G18/225

  of alkali or alkaline earth metals · CPC title

• C08G18/7621

  being toluene diisocyanate including isomer mixtures · CPC title

• C08G18/003 Primary

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

• C08G2150/90

  Compositions for anticorrosive coatings · CPC title