Method for producing trans-bis(aminomethyl)cyclohexane, method for producing bis(isocyanatomethyl)cyclohexane, bis(isocyanatomethyl)cyclohexane, polyisocyanate composition, and polyurethane resin

Patent metadata

Field	Value
Publication number	US-9969675-B2
Application number	US-201414908875-A
Country	US
Kind code	B2
Filing date	Jul 25, 2014
Priority date	Aug 1, 2013
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

A method for producing trans-bis(aminomethyl)cyclohexane includes a trans-isomerization step in which cis-dicyanocyclohexane is isomerized into trans-dicyanocyclohexane by heating dicyanocyclohexane containing cis-dicyanocyclohexane in the presence of a tar component produced by distillation of dicyanocyclohexane; and an aminomethylation step in which trans-dicyanocyclohexane produced by the trans-isomerization step is allowed to contact with hydrogen to produce trans-bis(aminomethyl)cyclohexane.

First claim

The invention claimed is:

1. A method for producing trans-bis(aminomethyl)cyclohexane, the method including the steps of:
a high boiling point component separation step in which a high boiling point component is separated by distillation from a mixture containing dicyanocyclohexane and the high boiling point component, wherein the dicyanocyclohexane comprises a mixture of trans-dicyanocyclohexane and cis-dicyanocyclohexane, and wherein the high boiling point component is taken out as a tar component from a column bottom of a distillation column,
a trans isomer separation step in which trans-dicyanocyclohexane is separated from the mixture,
a trans-isomerization step in which the tar component is supplied to remaining cis-dicyanocyclohexane in the mixture, and the remaining cis-dicyanocyclohexane is isomerized into trans-dicyanocyclohexane by heating the remaining cis-dicyanocyclohexane in the presence of the tar component, and
an aminomethylation step in which trans-dicyanocyclohexane produced by the trans isomer separation step and the trans-isomerization step is allowed to contact with hydrogen to produce trans-bis(aminomethyl)cyclohexane.

2. The method for producing trans-bis(aminomethyl)cyclohexane according to claim 1 , wherein in the trans-isomerization step, 2 to 30 parts by mass of the tar component is present relative to 100 parts by mass of the dicyanocyclohexane.

3. The method for producing trans-bis(aminomethyl)cyclohexane according to claim 1 , wherein:
the high boiling point component separation step, the trans isomer separation step, and the trans-isomerization step are performed using a single distillation column,
trans-dicyanocyclohexane is taken out from a column top of the distillation column, and the tar component is taken out from a column bottom of the distillation column, and
the tar component that is taken out is added back into the distillation column.

4. The method for producing trans-bis(aminomethyl)cyclohexane according to claim 3 , wherein the distillation column has
a column top temperature of 140° C. or more and 220° C. or less,
a column bottom temperature of 200° C. or more and 320° C. or less, and
the residence time at the column bottom is 1 hour or more and 50 hours or less.

5. A method for producing bis(isocyanatomethyl)cyclohexane, comprising:
a step of producing trans-bis(aminomethyl)cyclohexane by a process including:
a high boiling point component separation step in which a high boiling point component is separated by distillation from a mixture containing dicyanocyclohexane and the high boiling point component, wherein the dicyanocyclohexane comprises a mixture of trans-dicyanocyclohexane and cis-dicyanocyclohexane, and wherein the high boiling point component is taken out as a tar component from a column bottom of a distillation column,
a trans isomer separation step in which trans-dicyanocyclohexane is separated from the mixture,
a trans-isomerization step in which the tar component is supplied to remaining cis-dicyanocyclohexane from the mixture, and the remaining cis-dicyanocyclohexane is isomerized into trans-dicyanocyclohexane by heating the remaining cis-dicyanocyclohexane in the presence of the tar component, and
an aminomethylation step in which trans-dicyanocyclohexane produced by the trans isomer separation step and the trans-isomerization step is allowed to contact with hydrogen to produce trans-bis(aminomethyl)cyclohexane, and

a step of producing bis(isocyanatomethyl)cyclohexane by isocyanizing the obtained trans-bis(aminomethyl)cyclohexane.

6. A method for producing a polyisocyanate composition comprising:
a step of producing trans-bis(aminomethyl)cyclohexane by a process including:
a high boiling point component separation step in which a high boiling point component is separated by distillation from a mixture containing dicyanocyclohexane and the high boiling point component, wherein the dicyanocyclohexane comprises a mixture of trans-dicyanocyclohexane and cis-dicyanocyclohexane, and wherein the high boiling point component is taken out as a tar component from a column bottom of a distillation column,
a trans isomer separation step in which trans-dicyanocyclohexane is separated from the mixture,
a trans-isomerization step in which the tar component is supplied to remaining cis-dicyanocyclohexane in the mixture, and the remaining cis-dicyanocyclohexane is isomerized into trans-dicyanocyclohexane by heating the dicyanocyclohexane the remaining cis-dicyanocyclohexane in the presence of the tar component, and
an aminomethylation step in which trans-dicyanocyclohexane produced by the trans isomer separation step and the trans-isomerization step is allowed to contact with hydrogen to produce trans-bis(aminomethyl)cyclohexane,

a step of producing bis(isocyanatomethyl)cyclohexane by isocyanizing the obtained trans-bis(aminomethyl)cyclohexane, and
a step of modifying the obtained bis(isocyanatomethyl)cyclohexane to produce a polyisocyanate composition containing at least one functional group of (a) to (e) below:
(a) an isocyanurate group,
(b) an allophanate group,
(c) a biuret group,
(d) a urethane group, and
(e) a urea group.

7. A method for producing a polyurethane resin comprising:
a step of producing trans-bis(aminomethyl)cyclohexane by a process including:
a high boiling point component separation step in which a high boiling point component is separated by distillation from a mixture containing dicyanocyclohexane and the high boiling point component, wherein the dicyanocyclohexane comprises a mixture of trans-dicyanocyclohexane and cis-dicyanocyclohexane, and wherein the high boiling point component is taken out as a tar component from a column bottom of a distillation column,
a trans isomer separation step in which trans-dicyanocyclohexane is separated from the mixture,
a trans-isomerization step in which the tar component is supplied to the remaining cis-dicyanocyclohexane in the mixture, and the remaining cis-dicyanocyclohexane is isomerized into trans-dicyanocyclohexane by heating the remaining cis-dicyanocyclohexane in the presence of the tar component, and
aminomethylation step in which trans-dicyanocyclohexane produced by the trans isomer separation step and the trans-isomerization step is allowed to contact with hydrogen to produce trans-bis(aminomethyl)cyclohexane,

a step of producing bis(isocyanatomethyl)cyclohexane by isocyanizing the obtained trans-bis(aminomethyl)cyclohexane, and
a step of producing a polyurethane resin by allowing the obtained bis(isocyanatomethyl)cyclohexane to react with an active hydrogen compound.

8. A method for producing a polyurethane resin, comprising:
a step of producing trans-bis(aminomethyl)cyclohexane by a process including:
a high boiling point component separation step in which a high boiling point component is separated by distillation from a mixture containing dicyanocyclohexane and the high boiling point component, wherein the dicyanocyclohexane comprises a mixture of trans-dicyanocyclohexane and cis-dicyanocyclohexane, and wherein the high boiling point component is taken out as a tar component from a column bottom of a distillation column,
a trans isomer separation step in which trans-dicyanocyclohexane is separated from the mixture,
a trans-isomerization step in which the tar component is supplied to remaining cis-dicyanocyclohexane in the mixture, and the remaining cis-dicyanocyclohexane is isomerized into trans-dicyanocyclohexane by heating the remaining cis-dicyanocyclohexane in the presence of the tar component, and
an aminomethylation step in which trans-dicyanocyclohexane produced by the trans isomer separation step and the trans-isomerization step is allowed to contact with hydrogen to produce trans

Assignees

• Mitsui Chemicals Inc

Inventors

• Fukuda Takeshi
• Kosumi Kazuhiro
• Takahashi Jun
• Takuno Keita
• Shinagawa Ryo
• Shimamoto Masashi
• Alejandro Gran Martinez
• Yamasaki Satoshi
• Kuwamura Goro

Classifications

• C07C209/48 Primary

  by reduction of nitriles · CPC title

• C07C253/30

  by reactions not involving the formation of cyano groups · CPC title

• C07C263/10

  by reaction of amines with carbonyl halides, e.g. with phosgene · CPC title

• C08G18/7837

  containing allophanate groups · CPC title

• C07C265/14

  containing at least two isocyanate groups bound to the same carbon skeleton · CPC title