Mixture of polymerizable compound and method of producing the same

Patent metadata

Field	Value
Publication number	US-2018099921-A1
Application number	US-201615560646-A
Country	US
Kind code	A1
Filing date	Mar 30, 2016
Priority date	Mar 31, 2015
Publication date	Apr 12, 2018
Grant date	—

Abstract

Disclosed is a mixture containing compound (I) and polymerizable compound (II) wherein compound (I) accounts for 50 mol % or more of the entire mixture and 1,4-cyclohexanedicarboxylic acid accounts for less than 5 mol % of the entire mixture; a method of producing the mixture which includes reacting in a water-immiscible organic solvent 1,4-cyclohexanedicarboxylic acid dichloride with compound (IV) in the presence of a base, and washing the obtained reaction solution with a weakly acidic buffer solution; etc. The disclosure provides mixtures useful for low-cost production of polymerizable compounds which have low melting points suitable for practical use, show superior solubility to general-purpose solvents, can be produced at low costs, and allow for provision of optical films capable of uniform polarized light conversion over a wide wavelength range, and methods of producing the mixtures.

where A represents hydrogen, methyl group or chlorine, and n represents an integer of 1 to 20.

First claim

1 . A mixture comprising:
compound (I) having the following Formula (I):

where A represents hydrogen, methyl group or chlorine, and n represents an integer of 1 to 20; and
polymerizable compound (II) having the following Formula (II):

where A and n are as defined above
wherein compound (I) accounts for 50 mol % or more of the entire mixture, and 1,4-cyclohexanedicarboxylic acid as an impurity accounts for less than 5 mol % of the entire mixture.

2 . A method of removing 1,4-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid dichloride, comprising:
reacting in an organic solvent a hydroxy compound having the formula Q-OH where Q represents an organic group which may have a substituent with 1,4-cyclohexanedicarboxylic acid dichloride or 1,4-cyclohexanedicarboxylic acid to afford a reaction solution containing a monoester compound having the following Formula (IB):

where Q is as defined above
and 1,4-cyclohexanedicarboxylic acid dichloride or 1,4-cyclohexanedicarboxylic acid; and
washing the reaction solution with a weakly acidic buffer solution to remove 1,4-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid dichloride from the reaction solution.

3 . A method of producing a mixture of claim 1 , comprising:
reacting in a water-immiscible organic solvent 1,4-cyclohexanedicarboxylic acid dichloride with compound (IV) having the following formula (IV):

where A represents hydrogen, methyl group or chlorine, and n represents an integer of 1 to 20
in the presence of a base to afford a reaction solution; and
washing the reaction solution with a weakly acidic buffer solution.

4 . A method of producing a mixture of claim 1 , comprising:
reacting in a water-immiscible organic solvent 1,4-cyclohexanedicarboxylic acid dichloride with compound (IV) having the following formula (IV):

where A represents hydrogen, methyl group or chlorine, and n represents an integer of 1 to 20
in the presence of a base to afford a reaction solution;
washing the reaction solution with water; and
washing the reaction solution after washing with water with a weakly acidic buffer solution.

5 . The method of claim 3 , wherein the buffer solution is a buffer solution having a pH of 5.0 to 6.0.

6 . The method of claim 3 , wherein the buffer solution is a mixed buffer solution of acetic acid and sodium acetate, or a mixed buffer solution of potassium hydrogen phthalate and sodium hydroxide.

7 . The method of claim 3 , wherein the water-immiscible organic solvent is an organic solvent having a Hildebrand solubility parameter of 14.0 to 22.0 (MPa 1/2 ).

8 . The method of claim 3 , further comprising, after washing with the weakly acid buffer solution, cooling an obtained organic layer to 5° C. or lower to precipitate polymerizable compound (II), and removing the precipitate.

9 . A method of producing a compound having the following Formula (2):

where A represents hydrogen, methyl group or chlorine, and n represents an integer of 1 to 20
the method comprising:
reacting in a solvent either 1) compound (I) contained in a mixture of claim 1
or 2) a compound having the following Formula (IA) derived from compound (I) contained in the mixture:

where A and n are as defined above and L′ represents a leaving group other than hydroxyl group
with benzaldehyde compound (1) having the following Formula (1):

at a molar ratio of compound (I) contained in the mixture to benzaldehyde compound (1) of 1:0.3 to 1:0.5.

10 . A method of producing a polymerizable compound having the following Formula (III):

where A represents hydrogen, methyl group or chlorine, R represents hydrogen or C1-C20 organic group, Ax represents aromatic group which may have a substituent, and n represents an integer of 1 to 20
the method comprising:
reacting in a solvent either 1) compound (I) contained in a mixture of claim 1
or 2) a compound having the following Formula (IA) derived from compound (I) contained in the mixture:

where A and n are as defined above and L′ represents a leaving group other than hydroxyl group
with benzaldehyde compound (1) having the following Formula (1):

at a molar ratio of compound (I) contained in the mixture to benzaldehyde compound (1) of 1:0.3 to 1:0.5 to afford a compound having the following Formula (2):

where A and n are as defined above; and
reacting the compound having Formula (2) with a hydrazine compound having the following Formula (3):

where R and Ax are as defined above.

11 . The method of claim 10 , wherein Ax has the following Formula (4):

where Rx each independently represents hydrogen, halogen, C1-C6 alkyl group, cyano group, nitro group, C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, disubstituted amino group, or —C(═O)—O—R 1 where R 1 represents hydrogen or C1-C10 alkyl group which may have a substituent, and where each C—R x constituting the ring may be replaced by nitrogen.

12 . The method of claim 10 , wherein the hydrazine compound has Formula (3) where R is C1-C20 alkyl group which may have a substituent, C2-C20 alkenyl group which may have a substituent, C2-C20 alkynyl group which may have a substituent, C3-C12 cycloalkyl group which may have a substituent, or C1-C20 organic group having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon ring and aromatic heterocyclic ring.

Assignees

• Zeon Corp

Inventors

• Sakamoto Kei
• Okuyama Kumi
• SANUKI Kanako

Classifications

• C07C67/08

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C07C69/017

  Esters of hydroxy compounds having the esterified hydroxy group bound to a carbon atom of a six-membered aromatic ring · CPC title

• G02B5/30

  Polarising elements (light-modulating devices with active elements G02F1/00) · CPC title

• C07C67/52

  by change in the physical state, e.g. crystallisation · CPC title