Liquid crystal compounds having a fluoroether terminal portion

• US 5,399,291 A
• Filed: 09/30/1993
• Issued: 03/21/1995
• Est. Priority Date: 09/30/1993
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Company
• Inventors: Snustad, Daniel C., Savu, Patricia M., Spawn, Terence D., Radcliffe, Marc D., Janulis, Eugene P., Johnson, Gilbert C.
• Primary Examiner(s): WU, SHEAN CHIU
• Application Number:
  US08/129,258
• Time in Patent Office: 537 Days
• Field of Search: 252/299.01, 252/299.61, 252/299.62, 252/299.63, 252/299.64, 252/299.65, 252/299.66, 252/299.67, 544/298, 544/335, 546/270, 546/315, 546/322, 546/326, 549/369, 549/374, 549/180, 560/64, 560/65, 568/325, 568/331, 568/332, 568/642, 570/129, 359/104
• US Class Current: 252/299.01
• CPC Class Codes: C07D 213/80 in position 3
• CPC Class Codes: C07D 239/26 with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• CPC Class Codes: C09K 19/04 characterised by the chemical structure of the liquid crystal components , e.g. by a specific unit
• CPC Class Codes: C09K 19/126 Compounds containing at least one asymmetric carbon atom
• CPC Class Codes: C09K 19/2007 the chain containing -COO- or -OCO- groups
• CPC Class Codes: C09K 19/3068 chain containing -COO- or -OCO- groups
• CPC Class Codes: C09K 19/322 Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
• CPC Class Codes: C09K 19/3444 the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine
• CPC Class Codes: C09K 19/3469 Pyrimidine with a specific end-group other than alkyl, alkoxy or -C*-
• CPC Class Codes: C09K 2019/325 containing a tetrahydronaphthalene, e.g. -2,6-diyl (tetralin)

Abstract

Fluorine-containing, chiral and achiral liquid crystal compounds comprise (a) an aliphatic fluorocarbon terminal portion comprising a perfluorinated or partially-fluorinated alkylene group and a terminal hydrocarbon alkyl group, the groups optionally containing at least one catenary ether oxygen atom; (b) an aliphatic hydrocarbon terminal portion; and (c) a central core connecting the terminal portions. The compounds have smectic mesophases or latent smectic mesophases and are useful, for example, in liquid crystal display devices.

Claims

1. Fluorine-containing, chiral and achiral liquid crystal compounds having smectic mesophases or latent smectic mesophases, the compounds comprising (a) an aliphatic fluorocarbon terminal portion comprising a perfluorinated alkylene group and a terminal hydrocarbon alkyl group, said groups optionally containing at least one catenary ether oxygen atom;

(b) an aliphatic hydrocarbon terminal portion; and

(c) a central core connecting said terminal portions.

2. The compounds of claim 1 wherein said aliphatic fluorocarbon terminal portion is represented by the formula --D--R_f --R_h, wherein D is selected from the group consisting of a covalent bond, ##STR52## and combinations thereof, where r and r'"'"' are independently integers of 1 to about 20, s is independently an integer of 1 to about 10 for each (C_s H_2d O), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;

R_f is a linear or branched, perfluorinated alkylene group having from 1 to about 10 carbon atoms and optionally containing one or more catenary ether oxygen atoms; and

R_h is a linear or branched alkyl group having from 1 to about 14 carbon atoms and optionally containing one or more catenary ether oxygen atoms.

3. The compounds of claim 2 wherein said R_f is a linear perfluoroalkylene group having from about 2 to about 6 carbon atoms;

said R_h is a linear alkyl group having from about 3 to about 10 carbon atoms; and

at least one of the groups R_h and R_r contains at least one catenary ether oxygen atom.

4. The fluorine-containing, achiral liquid crystal compounds of claim 1 wherein said compounds are represented by the general formula (I):

##STR53## where M, N, and P are each independently selected from the group consisting of ##STR54## a, b, and c are each independently zero or an integer of from 1 to 3, with the proviso that the sum of a+b+c be at least 1;

each A and B are non-directionally and independently selected from the group consisting of a covalent bond, ##STR55## --(CH₂ CH₂)_k -- where k is 1 to 4, ##STR56## --O--;

each X, Y, and Z are independently selected from the group consisting of --H, --Cl, --F, --Br, --I, --OH, --OCH₃, --CH₃, --CF₃, --OCF₃ --CN, and --NO₂ ;

each 1, m, and n are independently zero or an integer of 1 to 4;

D is selected from the group consisting of a covalent bond, ##STR57## and combinations thereof where r and r'"'"' are independently integers of 1 to about 20, s is independently an integer of 1 to about 10 for each (C_s H_2s O), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;

R is selected from the group consisting of ##STR58## where R'"'"' is selected from the group consisting of --Cl, --F, --CF₃, --NO₂, --CN, --H, ##STR59## where q and q'"'"' are independently integers of 1 to about 20, w is an integer of 1 to about 10, and R can be linear or branched;

R_f is a linear or branched, perfluorinated alkylene group having from 1 to about 10 carbon atoms and optionally containing one or more catenary ether oxygen atoms;

and R_h is a linear or branched alkyl group having from 1 to about 14 carbon atoms and optionally containing one or more catenary ether oxygen atoms.

5. The compounds of claim 4 wherein said R_f is a linear perfluoroalkylene group having from about 2 to about 6 carbon atoms;

said R_h is a linear alkyl group having from about 3 to about 10 carbon atoms; and

at least one of the groups R_h and R_f contains at least one catenary ether oxygen atom.

6. The fluorine-containing, chiral liquid crystal compounds of claim 1 wherein said compounds are represented by the general formula (I):

##STR60## where M, N, and P are each independently selected from the group consisting of ##STR61## a, b, and c are each independently zero or an integer of from 1 to 3, with the proviso that the sum of a+b+c be at least 1;

each A and B are non-directionally and independently selected from the group consisting of a covalent bond, ##STR62## --(CH₂ CH₂)_k -- where k is 1 to 4, --C═

CH--, --C═

C--, --CH═

N--, --CH₂ --O--, ##STR63## and --O--;

each X, Y, and Z are independently selected from the group consisting of --H, --Cl, --F, --Br, --I, --H, OCH₃, --CH₃, --CF₃, --OCF₃ --CN, and --NO₂ ;

each 1, m, and n are independently zero or an integer of 1 to 4;

D is selected from the group consisting of a covalent bond, ##STR64## and combinations thereof, where r and r'"'"' are independently integers of 1 to about 20, s is independently an integer of 1 to about 10 for each (C_s H_2s O), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;

##STR65## where R'"'"' is selected from the group consisting of --Cl, --F, --CF₃, --NO₂, --CN, --H, ##STR66## where q and q'"'"' are independently integers of 1 to about 20, w is an integer of 1 to about 10, and R can be linear or branched, with the proviso that R is chiral;

R_f is a linear or branched, perfluorinated alkylene group having from 1 to about 10 carbon atoms and optionally containing one or more catenary ether oxygen atoms;

and R_h is a linear or branched alkyl group having from 1 to about 14 carbon atoms and optionally containing one or more catenary ether oxygen atoms.

7. The compounds of claim 6 wherein said R_f is a linear perfluoroalkylene group having from about 2 to about 6 carbon atoms;

said R_h is a linear alkyl group having from about 3 to about 10 carbon atoms; and

at least one of the groups R_h and R_f contains at least one catenary ether oxygen atom.

22. A mixture of liquid crystal compounds comprising at least one fluorine-containing liquid crystal compound of claim 1.

23. A liquid crystal display device containing at least one fluorine-containing liquid crystal compound of claim 1.

8. The compounds represented by the formula ##STR67## where d is an integer of about 4 to about 10, x is an integer of 1 to about 10, and y is an integer of 1 to about 12.

9. The compounds represented by the formula ##STR68## where d is an integer of about 4 to about 10, x is an integer of 1 to about 10, and y is an integer of 1 to about 12.

10. The compounds represented by the formula ##STR69## where d is an integer of about 4 to about 10, x is an integer of 1 to about 10, and y is an integer of 1 to about 12.

11. The compounds represented by the formula ##STR70## where d is an integer of about 4 to about 10, x is an integer of 1 to about 10, and y is an integer of 1 to about 12.

12. The compounds represented by the formula ##STR71## where d is an integer of about 4 to about 10, x is an integer of 1 to about 10, and y is an integer of 1 to about 12.

13. The compounds represented by the formula ##STR72## where d is an integer of about 4 to about 10, x is an integer of 1 to about 10, and y is an integer of 1 to about 12.

14. The compounds represented by the formula ##STR73## where d is an integer of about 4 to about 10, x is an integer of 1 to about 10, and y is an integer of 1 to about 12.

15. The compounds represented by the formula ##STR74## where d is an integer of about 4 to about 10, x is an integer of 1 to about 10, and y is an integer of 1 to about 12.

16. The compounds represented by the formula ##STR75## where x is an integer of 1 to about 10;

y is an integer of 1 to about 12;

j is an integer of 0 or 1;

said q is an integer of 2 to about 10;

said R'"'"' is selected from the group consisting of hydrogen, fluorine, chlorine, and perfluoromethyl; and

said C_q H_2q is linear or branched.

17. The compounds represented by the formula ##STR76## where x is an integer of 1 to about 10;

y is an integer of 1 to about 12;

j is an integer of 0 or 1;

said q is an integer of 2 to about 10;

said R'"'"' is selected from the group consisting of hydrogen, fluorine, chlorine, and perfluoromethyl; and

said C_q H_2q is linear or branched.

18. The compounds represented by the formula ##STR77## where x is an integer of 1 to about 10;

y is an integer of 1 to about 12;

j is an integer of 0 or 1;

said q is an integer of 2 to about 10;

said R'"'"' is selected from the group consisting of hydrogen, fluorine, chlorine, and perfluoromethyl; and

said C_q H_2q is linear or branched.

19. The compounds represented by the formula ##STR78## where x is an integer of 1 to about 10;

y is an integer of 1 to about 12;

j is an integer of 0 or 1;

said q is an integer of 2 to about 10;

said R'"'"' is selected from the group consisting of hydrogen, fluorine, chlorine, and perfluoromethyl; and

said C_q H_2q is linear or branched.

20. The compounds represented by the formula ##STR79## where x is an integer of 1 to about 10;

y is an integer of 1 to about 12;

j is an integer of 0 or 1;

said q is an integer of 2 to about 10;

said R'"'"' is selected from the group consisting of hydrogen, fluorine, chlorine, and perfluoromethyl; and

said C_q H_2q is linear or branched.

21. The compounds represented by the formula ##STR80## where x is an integer of 1 to about 10;

y is an integer of 1 to about 12;

j is an integer of 0 or 1;

said q is an integer of 2 to about 10;

said R'"'"' is selected from the group consisting of hydrogen, fluorine, chlorine, and perfluoromethyl; and

said C_q H_2q is linear or branched.

24. Fluorine-containing intermediate compounds represented by the general formula ##STR81## where N and P are each independently selected from the group consisting of ##STR82## b and c are each independently zero or an integer of from 1 to 3;

B is non-directionally selected from the group consisting of a covalent bond, ##STR83## --(CH₂ CH₂)_k '"'"' where k is 1 to 4, --CH═

CH--, --C.tbd.C--, --CH═

N--, --CH₂ --O--, ##STR84## and --O--;

A" is selected from the group consisting of --OH, --COOH, --CH (CH₂ OH)₂, --SH, --SeH, --the, --NH₂, --COCl, --CHO, --OSO₂ R_f '"'"', and --CH₂ COOH, where R_f '"'"' is a perfluoroalkyl group having from 1 to about 10 carbon atoms;

Y and Z are independently selected from the group consisting of --H, --Cl, --F, --Br, --I, --OH, --OCH₃ , --CH₃, --CF₃, --OCF₃, --CN, and --NO₂ ;

m and n are independently zero or an integer of 1 to 4;

D is selected from the group consisting of a covalent bond, ##STR85## and combinations thereof, where r and r'"'"' are independently integers of 1 to about 20, s is independently an integer of 1 to about 10 for each (C_s H_2s O), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;

R_f is a linear or branched, perfluorinated or partially-fluorinated alkylene group having from 1 to about 10 carbon atoms and optionally containing one or more catenary ether oxygen atoms; and

R_h is a linear or branched alkyl group having from 1 to about 14 carbon atoms and optionally containing one or more catenary ether oxygen atoms.