GB2222158A - Glass forming polycyclic compounds - Google Patents
Glass forming polycyclic compounds Download PDFInfo
- Publication number
- GB2222158A GB2222158A GB8917661A GB8917661A GB2222158A GB 2222158 A GB2222158 A GB 2222158A GB 8917661 A GB8917661 A GB 8917661A GB 8917661 A GB8917661 A GB 8917661A GB 2222158 A GB2222158 A GB 2222158A
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- GB
- United Kingdom
- Prior art keywords
- coo
- glass
- smectic
- phase
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/25—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing liquid crystals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C235/58—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C235/60—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
1 2222158 Low molecular weight glass forming compounds and their use The
invention relates to low molecular weight glass forming compounds for mixtures of liquid
crystalline substances which are capable of forming smectic phases and of changing to a glass state when the temperature is lowered. Orientations imprinted on the smectic phase by external influences) e.g. electric or magnetic fields, can be retained upon the transfer to the solid glass state, so providing an opportunity to use these substances for storing date and for producing optical components.
Since glass transitions into low molecular liquid crystalline phases have long since been of purely theoretical interest (N. Greboviez, B. Wunderlich. Mol. Cryst.Liq.Cryst. 76, 287 [1981]), it is only in the last few years that the industrial application of nematic glass forming low molecular substances has for the first time become known. (DD WP 242626t DD WP 247227). The main problem with the industrial use of such phases resides in preventing crystallisation which easily occurs due to the low molecular character of the compounds and of consequently improving the durability of data which has been stored.
Solid anisotropic optical media are required for the production of optical components and for thermoelectrooptical storage displays having a good mechanical stability, low temperature dependency of the optical properties and good stability against crystallisation at room temperature.
The object of the invention is to find substances which, while they themselves solidify nematically to a gldss-like form and which only have smectic phases in exceptional cases, do in mixtures with other liquid crystalline components form p induced smectic phases which are characterised by an extremely high inertia in respect of crystallisation and a good capacity for storing imprinted data.
According to the invention2 low molecular glass forming compounds to the general Formula I are R -G z -Q z -G R# X R' IG z -c z -G R' 11 7 (1) in which Rv Ils R 9 It Ill's (1ddentical or different) lit - py 01, Br, C1,1, - 0ON9 - SON9 NOS, 1,100, (CH 2- WN9 - 0- (011 2-)n ON# N021 0 n 11 2n+11 - Oon"?-n+l' - 0000'n"2n+11 COOC n H 2n+19 - N(C n 11 2n+1)2 Z sinole bond -COO- 1 -000-l -N=N-1 -1q=N-l 0 W -CO-NII-S -N=CII-p -011=N-1 (CH2)n_ v R R? X COO-oll 2)n-000- (CII A700C 1119 Rift coo- (011 2 n (C112 li-00 c W' R"' R 111 R R, coo- (C11 2)n-0-1 -0- (C"2)k7000 R" R119R11 R" R RIR RY Coo- (CII 2)n-e-o-(cli 2)n-OOC r---% 1---.
11 11 R' 0 W, W" 00-NII- (C11 2)n-NII-00 - in which n = 1, 2, 3, - 12 These compounds are suitable for the production of solid optically anisotropic media for optical components or thermoelectro-optical memory displays in mixture with one another, in which case at least one partner must possess a smectic phase, or with other liquid crystalline substances.
Examples of the substances according to the invention are listed in Table 1. The new class of substances is characterised by the quality of forming induced smectic phases together with other liquid crystalline - smectic or non-smectic - mixture partners. The said mixtures can be so orientated by the action of external fields that they can be used as optical compensators and prisms after the addition of dichroitic colouring agents as polarisers. When correiponding cells are used, thermo-electro-optical memory displays can be produced.
The advantage when using the new class of substances as a mixture partner in liquid crystalline mixtures is founded in the extraordinary inertia vis-a-vis crystallisation and in the time-related stability of orientations once these have been imprinted in the glass phase, qualities based on the induced smectic phase. These properties make it possible to apply relatively low cooling rates of between 0.5 and 40 K min-1, in order to convert the liquid crystalline phase to a glass state. The orientations frozen in once the glass state is achieved are retained unchanged for months.
IF All the said substances can be shown chemically in a high degree of purity and are stable in respect of chemical and thermal external influences. Using them in mixtures with suitable parameters will produce nematic or smectic and in certain ranges of concentration reliably smectic media which will set like glass with a high glass transfer and softening interval, a high clarification temperature and a low melting temperature.
Table 1: l, c- -, 1 ev., o f soIc representatives of the riew cl at,.s of low c)lecular glass-f orming substances c 811 17 O-G coo --,Q- OOC-G oc 8 11 z It call 17 0-0-COO- -00c-GOC811 17 A, Ring iwin compounds - No.
A1 z 17 coo- (CII)-000 - 16 2)2-0-G 0- (C112 COO- (CH2)',50-Q-0(Cl'2)2000 - 12 C113 A3 - Coo- (CH2)20-QO- (C112)2 000 10 C2115 A4 - Coo(C"2)20-QO- (G112)2000 12 cl - coo- (C11 2)20-GGO- (all 2)2000 A6 coo-cl] 00c 2 'H 2 CH ' 0 A7 - COO-C112 C112- 00c OCH 3 - -- T A /00 Tp/OC T EI /00 11210177,0 120t814292 1064130p8 125,611796 21 9978179,6 ? 120,o 158,0 17 14016127,4 p A I 1 v] r h iii il_-L).ri d R f-,] twi n com 12ound s Tic. 7, T 9 /OC Tp/C)C T SCN/OC T NI /0c B1 00-""'-(C"2)3 -NII-CO - 41 143,0 (109) (14.1,0) J32 ("o-lqll-(C"2)4- Till-GO - 154,0 (115) 172,5 12190 (80,5) 154,0 B 3 CO-MI-(("112)5_]'111-CO 134 ("0-1.1"-(C"2)6-1411-CO 145,5 - 160,0 - CO-1'111-(0)12)7_ Ull-CO 115,0 - 14495 B6 CO-1fil-(CI12)8-Nll-CO 137,0 - 14210 137 - CO-""'-((".12)9-1ii-co 119,0 132,5 In - C0-jill-(G112)1D Nil-CO 146,0 - (127,0) B9 - 151lO - (123,0) T... bottom limit of glass transition interval TF... melting temperature of the stable crystal phase TScN 0 phase conversion temperature for the transition between smectic phase type C and the nematic phase TNI... clarification temperature of the nematic phase The figures in brackets represent a phase transition which takes place in a range which is sub-cooled in respect of a stable phase.
7 - Examples of embodiment Example of manufacture Synthesis of compound 1 12-bis/2.5 bis IF (4-n-oetyloxy-benzoyloxy)benzamido/dodecarie C8 11 170-GCOO- 00C3-GOC381',17 0=0 1 Nil 1 (Ull) 1 2 12 NII 1 U=U call 17 OOCOO-GOOC-GOCBH 17 0.01 mol 1.12-diamino-dodecanLare dissolved in 30 ml absolute toluene and mixed with 0.03 triethyl amine and 0.005 mol 4dimethyl-amino-pyridine. Accompanied by agitation and with the exclusion of moistureq a solution of 0.022 mol 2,5-bis (4-n-octyloxy benzoyloxy)benzoylehloride in 30 ml absolute toluene is added to this dropwise at 10 to 15%. This is followed by agitation for 8 hours at room temperature and the result is then warmed to 80% over a period of 4 hours. Hydrochloride which is deposited is separated in the heat and the reaction solution is maintained at OOC for 8 hours. Deposited product is extracted with a vacuum, washed with a little cold toluene and recrystallised at least three times from ethanol or a little pentanol-1.
Melting point 149-151C; clarification point 1230CYield: 27% p 8 Examples of application Example 1 Mixtures of various compositions which contain the two components 0 8 11 1 70-G C007.Q 00C3-G 00811 17 COO-(C11 2)2-0 1 (A) COO-(CH2)2-0 call 170-0-Coo-50()0""GOCB"1 7 T1p= 11290 0 0 1 TITI,2 1779 0 00 1 T 9 = 1600 and c 5 ill 100C \ / C=Cll-G-ooc-000-GCII=C C. 5 H11000 /COOC 5 H,, GOOC 5 Ill 1 (B) Tp= 96,4 OC 1 1P NI= 152,400 9 TS c N = 60 0 C 9 T g = -1700 are prepared.
The physico-chemical parameters of the resultant mixtures can be seen in Table 1. Colourless mixtures are created, the smectic phases of which can be orientated in the electrical or magnetic field. In this case, only one partner in the mixture carries a type C smectic phase, but in addition a smectic phase of type A is induced in a certain range of concentrations. This provides the essential conditions whereby orientations brought about by external influences are retained without interference for long periods when the medium is cooled below the glass transition interval. This transition interval can be shifted to higher temperatures by varying the terminal alkyl chRins.
9 - In the Tables, the abbreviations have the following meanings:
K P K,, K2 SA SC N Nre Is XA 0. 0 0 0 0 0..
crystalline solid phase crystal modifications smectic phase type A smectic phase type C nematic phase re-entrant nematic phase isotropic liquid phase glass transition interval of.... UP to.... molar fraction of component A Existing phases are identified by +. Numbers shown between two '+' identify the conversion temperatures between the associated phases in OC.
Symbols in brackets identify phases which occur in the subcooled range.
Non-existing phases are shown by -.
Table 2: Physico-chemical parameters of mixtures of components A and B IF X A K S 0 1.1 re S A 0 0,15 0,25 0,30 0910 OP50 0,6o 0,625 0j75 + 96,4 (+ 60) + 77 + 88,5 + 86 + 95 + 97 (+ 96) + 111 (+ 95) + 117 (+ 139) + 119 (+ 82,5) + 117,5 (+ 8015 + 102 + 112 ------------------------ X A SA + 83) + ------------- 1:8 - - - ---- 6 T 9 0 + 15214 + -17 -8 0v15 + 156 + -12 -4 0,25 + 115/116 + 159 + - 90040 0 0,30 + 128/130 + 16195 + 8,, 2 0,40 + 138 + 165 + -5 5 + 137 + 167 + lee 8 0,60 + 128/130 + 170 + 1. 10 0e625 + 123. + 171 + 2 12 + 17395 +.14 1 - + 177 + 25 -1 R - 1 1 - Example 2
Mixtures of different compositions which contain the two components IF 0 8H 17 -Qo0'3-COCB"17 O-GCe)o C=0 1 liqjl 2)3 8 17 00C '00 H 8 17 0 Ty'. 129905 c 9 TNI= 136j800 9 T S N= 1090 0 Ag- 4 l oc c and 0 5 ill c 5 H 11 00C (C) lOOC \ / 000C 5 1111 / c= CII-G 00 C-O-G COO-C>C1l=c \ CO0C 5 H 11 (D) TF= 96,40C y TNI= 152y4OC TSCN= 60001 l TS = -170C are prepared.
The physico-chemical data of the resultant mixtures are shown in Table 3. Colourless mixtures result which, in certain ranges of concentration, have glass transition intervals whichare above room temperature. A particular feature of the mixture partners resides in the fact that, in the pure state, 1 both are capable of forming smectic phases of type C. Thus, over the transformation range, a smectic phase is always in existence so that a sufficiently high time-related stability of the orientations is guaranteed. In addition, a smectic phase type A occurs in a certain range of concentrations.
The liquid crystalline phases can, in the high temperature range, be satisfactorily orientated with the help of electrical fields. The orientated ranges retain their optical properties after the transition to the glass state.
Table 3 Physico-chemical parameters of components B and C X C K 1 K 2 S C Nre S A mixtures of 0 + 76 + 9694 ( + 60 0,08 + 76 94 ( + 63 + 73/75) 0,10 + 75 + 93 ( + 64 + 68 + 0920 + 74 + 92 ( + 59 + 0,30 + 73 + 90 ( + 52) - + 0940 + 70 + 79 + 58 + o, 6o + 97 + 92 + 09 '15 + 111 + 119 + 0,85 + 127 + 125 + 09875 + 129 - ( + 124) - - 0990 1 + 143 + log 13 - X c S A 1.1 Is zs T 9 i 0 + 152,4 + -18 0 0 0-10 09 on + 94/96 + 150/151 + _pp 0910 + 102/104 + 151 + -12. - 6 0,20 + 134/136 150/152 + + 150/153 154/156 + - 5 6 0v40 + 159/161 + 7 17 o,6o + 158/160 + 10 20 0s75 + 150/154 + + 125/131 + 146/148 + 29 41 0#875 + 147 + 099 28 40 1 (+ 141 + 41 51 1 1 14- Cl aj ni-- 1 - i glass-f ormi rig compound of t:c)t ffitila -CC wherein R, R', R-'. R''' are independently selected from -H, - F. - Cl, - Br. - CN,-WN, SC;N, - NCS, -NCO, - (CH2)n-CN, _CriH2In + 11 0 - (CH2)n-CN, - N02, _Ocri H2ri + 1 - OOCC H -COOCnH2n + 11 - N (CnH2n + 1)2 Z is single bond, C02-c -02 C-, -N = N-, -N = N- -CH = CH- 0 n -"' n + 1.
1 -CONH, -COCH2, -N = CH-, -CH=N-, -(CH2)n- X is -CO 2 (CH A0 R / W _ 0 It tli, R -CO 2 (CH 2)n 0 (CI12)n_02C_ 9, R', it, p -CO 2(CH2)n_0 0 (CH A02C_ lz let I v, 'i R,,,j _W2 (CH2) n -/ \ (CH 2)n02C_ te f 11;1 Tel O(CH 2) n 02 c- -"H (CH 2)JHCC)_ and 15, n is an integer- f rom 1 to 1 compound as claimea in claim 1 wherein n is i 3. A glass- to r.rfii ng compound substantial Pv, as described herein with reference to the examples.
4. A forming mixture with smectic phases suitable for producing optical components and for thermoelectrooptical data storage comprising a mixture of:
i. a compound as claimed in any one of claims 1 to 3. and ii. another. liquid crystalline substance.
5. A mixture as claimed in claim 4 wherein component ii is a compound as claimed in any one of claims 1 to 3 and at least one of i) and ii) possess a smectic phase.
6. A glass forming mixture substantially as described herein with reference to the examples.
7. The use of a compound as claimed in any one of the claims 1 to 3 in an optical component or thermoelectrDoptical storage display.
6. A pr.c)c,.ess for preparing a compound as- claimed in any one of claims 1 to 25 substantially as described herein.
Published 1990&tThe Patent OMee.State House. 8#3.7 t High Ho3burn. London WC1R4TP- PUrthar copies May be obtwndfroMTh6 Pat4z"Mce' Sales Branch, St Mary Cray, Orpington. KartSIL5 3P.D. Printed b-v Multiplex techniques Itd. St Mary Cray, Kent. COM 1/57 04188 branch, St Mary Cray. Orpington. Karit 18.tt5 3p.D. printed bv Multlv,Lx techniclues ltd, St Mary Cray, aenTuo= jaur
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD31857188A DD274441B5 (en) | 1988-08-02 | 1988-08-02 | LOW-MOLECULAR GLASS-FORMING MIXTURES WITH SMEKTICAL PHASES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8917661D0 GB8917661D0 (en) | 1989-09-20 |
| GB2222158A true GB2222158A (en) | 1990-02-28 |
| GB2222158B GB2222158B (en) | 1992-06-03 |
Family
ID=5601455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8917661A Expired - Lifetime GB2222158B (en) | 1988-08-02 | 1989-08-02 | Glass forming polycyclic compounds |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH0288542A (en) |
| CH (1) | CH678189A5 (en) |
| DD (1) | DD274441B5 (en) |
| DE (1) | DE3921809A1 (en) |
| GB (1) | GB2222158B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2188048A (en) * | 1986-03-05 | 1987-09-23 | Werk Fernsehelektronik Veb | Liquid crystalline esters |
-
1988
- 1988-08-02 DD DD31857188A patent/DD274441B5/en not_active IP Right Cessation
-
1989
- 1989-07-03 DE DE19893921809 patent/DE3921809A1/en not_active Withdrawn
- 1989-07-03 CH CH246789A patent/CH678189A5/de not_active IP Right Cessation
- 1989-08-02 GB GB8917661A patent/GB2222158B/en not_active Expired - Lifetime
- 1989-08-02 JP JP1199524A patent/JPH0288542A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2188048A (en) * | 1986-03-05 | 1987-09-23 | Werk Fernsehelektronik Veb | Liquid crystalline esters |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0288542A (en) | 1990-03-28 |
| GB8917661D0 (en) | 1989-09-20 |
| DD274441A1 (en) | 1989-12-20 |
| GB2222158B (en) | 1992-06-03 |
| DD274441B5 (en) | 1993-11-04 |
| CH678189A5 (en) | 1991-08-15 |
| DE3921809A1 (en) | 1990-02-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930802 |