TWI297728B - Polymerizable liquid crystalline dioxetanes, their preparation and use - Google Patents

Description

1297728 k A7 _____ B7 Description of Invention (1) ^ " The present invention generally relates to a new class of liquid crystalline monomers and polymers. More particularly, it is described that polymerizable propylene oxide can be formed into a liquid crystalline polymeric network having better properties, which property makes it particularly useful in optical display elements (LCDs). Due to the anisotropic nature of the directional structure, there is great interest in it. This structure has the highly anisotropic optical, electrical and electrothermal properties desired for a variety of applications. Liquid crystalline (LC) molecules combine with liquid-like properties such as low viscosity and crystalline properties such as anisotropy. The LC phase can be seen between the melting temperature and the anisotropy temperature. There are a variety of LC phases with different permutations, of which the nematic cholesteric phase is of particular interest. In the nematic phase, only the orientation regularity exists, and the molecules tend to align their long axes in a common direction ("director"). In the cholesteric base phase, the molecules are arranged in the nematic layer, and the nematic director is rotated around the helix. This phase can be obtained by including a palm molecule in the nematic system. This phase is characterized by the selective reflection of a circularly polarized band that makes the material appear colored. The nature of this bile base phase can be used in the manufacture of passive optical components. In the LC phase, the molecular systems are arranged in a small area. The orientation of these regions can be obtained in an electric field, a magnetic field, or on a specially treated surface. For example, in a very high electric field (1 volt/micron), molecules with positive dielectric anisotropy can be aligned along the field. The surface of the polymer layer that is subsequently ground is inclined: the LC molecules are facing the rubbing direction. Arrangement. The surface treated by the surfactant tends to align the LC molecules perpendicular to the substrate. These properties allow the lc molecular pole f to be used for any surface geometry to obtain any orientation.

1297728 A7 B7 V. INSTRUCTIONS (2) The properties of the LC system in the LC phase and in the specific phase are highly temperature dependent. Therefore, any attempt to "coagulate" the LC system by polymerization must be carried out isothermally. Changes in temperature may result in aggregation in the wrong phase or in a poorly aligned state. For these reasons, isothermal photopolymerization and e-beam polymerization of LC molecules are preferred methods. For the purpose of photopolymerization, LC molecules having a polymerizable group such as LC propionate, epoxide and vinyl ether and a suitable photoinitiator are usually used together. The use of a monomer having two or more polymerizable groups will result in the formation of a crosslinked network structure having better thermal and chemical stability. The LC system is heated to the desired temperature and after the region disappears (the length of the 谤 guide is aligned), the polymerization is initiated by a UV light source or the like to obtain a three-dimensional network structure in which the orientation of the molecules and the properties of the desired phase are" solidification". For other background information, see, for example, Hikmet R.A.M. et al., Prog. Pol. Sci. 1L: 1165-1209 (1996). Recently, the prior art has mainly disclosed LC mono- and diacrylates for use in photopolymerizable liquid crystals to fabricate optical elements used in liquid crystal displays (LCDs). See, for example, WO 96/24647, WO 97/00600, WO 98/47979. The use of such materials often includes the following disadvantages: (1) the polymerization reaction is inhibited by oxygen, which requires an inert gas during the polymerization procedure; (2) due to the relatively high liquid crystal crystallization temperature, processing must be completed at high temperatures, which causes rotation The coated film is made almost impossible to crystallize first; (3) The polymer network formed from the propionate exhibits stress due to polymerization shrinkage at room temperature, which also causes (4) coating. The optical element having the polymer network structure is deformed. Over the past decade, many authors have revealed liquid crystalline polyoxetanes based on monooxetane monomers, as well as their preparation and properties. See, -6- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1297728 A7 B7 V. Description of invention (3) For example, Kawakami Y et al., Giant Molecule 4531 (1991), Polymer Bulletin 21·· 439 (1991), polym Int•Red: 35 (1993), JP-A-06308462, JP-A-08020641, jp_A-083〇1859; LuY.H. et al., Polymer Bulletin, 11: 551 -5 5 8 (1994), Giant 21: 1673-1680 (1995); Hsu LL· et al., Journal of Polymer Society, 2843·2855 (1997); Ogawa Η· et al., Chemical Association Bulletin, Japan La: 1649-1657 (1997); JP-A-07225370. Ring-opening polymerization of monooxetane initiated by, for example, BF3 etherate complex and resulting in a broad liquid crystalline phase with a flexible polymer backbone and extending from room temperature up to 240 °C The range of liquid crystal polymers in the temperature range can generally be traced as follows:

Ch2-o-x-y-z wherein X generally represents a spacer such as an alkyl group, a divalent group of an ether matrix or a divalent group of a fluorenyl group, γ is a liquid crystal group and Z is a terminal group containing a palm group. However, the liquid crystalline polyoxetane based on a monooxetane monomer exhibits some disadvantages in that the stability of molecular alignment is not too high due to thermal transition or crystallization. Moreover, the relatively high viscosity makes it difficult to obtain a film without a region due to the alignment of the polymer, and the film is unstable to an organic solvent. Therefore, it does not have the above-mentioned shortcomings, but exhibits better properties such as the ability to condense in air. The Chinese National Standard (CNS) A4 specification (210X297 mm) 1297728 A7

There are a need for spin-coating at room temperature, easy alignment, and photopolymerizable liquid crystalline compounds and their polymeric derivatives which exhibit very low polymerization shrinkage, and these properties make them useful in many applications. It has now surprisingly been found that a novel compound, photopolymerizable liquid crystal oxetane and/or polymer products derived therefrom exhibit excellent properties such as liquid crystal mixtures and liquid crystal devices such as liquid crystal displays (LCd). And other applications. Thus, in one feature, the invention provides a compound of formula Z:

Wherein Ri and R2 are independently selected from linear or branched CrCU alkyl and hydrogen; X and X' are independently selected from the group consisting of oxygen, sulfur, single covalent bond, -O-CO-, -C0-0 - and -0-C0-0-; Y and Y' are spacer groups each independently having from 1 to 30 carbon atoms (linear or branched), wherein the carbon chain can be interrupted by oxygen in the ether functional group Or may be blocked by sulfur in the thioether functional group; Z and Z' are independently selected from the group consisting of oxygen, sulfur, single covalent bond, -〇_c〇-, -C0-0-, and -0-C0-0 -; and Μ is any suitable liquid crystal element. In another feature, the present invention provides a liquid crystalline composition comprising one or more compounds of the formula I in combination with one or more liquid crystalline compounds, wherein the liquid -8 - the paper scale is applicable to the Chinese National Standard (CNS) Α 4 specification (210 X 297 mm) 1297728 A7 -- B7 V. INSTRUCTION DESCRIPTION (5) The sinophilic compound is selected from the group consisting of a general non-polymerizable compound and a monooxindole monomer. In a preferred embodiment, the composition comprises one or more palm compounds. In another feature, the present invention provides a process for the preparation of a compound of formula I as defined above and a process for the preparation of the liquid crystal composition, wherein the composition comprises one or more of the formulas and One or more palm compounds are used in the case. In another feature of the invention, one or more compounds of formula I, or compositions comprising one or more compounds of formula I, are provided in the manufacture of, for example, optical display elements, optical precision elements, inductors, cholesteryl liquid crystals. Uses on agents and dyes. These and other features are explained in more detail in the following detailed description and accompanying drawings. Figure 1 shows a typical compound of the invention, 4-[4-(3-methyl-oxetane-3-ylmethoxy)-butoxy]-benzyloxy-2-methylungyl- 4-[4-(3•Methyl-oxetan-3-ylmethoxy)-butoxy]-benzoate, photoactivator Cyracure UVI-6990 and UV light The polymerization conversion C (%) initiated varies with temperature T (° C.). Figure 2 shows the stability of the birefringence Δη as a function of temperature T (°C) after photoinitiated polymerization of the same compound as in Figure 1 at 60 °C. DEFINITIONS As used herein, the term reactive crystalline crystalline compound is equivalent to a reactive rod-like molecule which may be enantiomerically, monomorphic or isotropic, preferably enantiomerically. -9- This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 public ϋ " 1297728 A7 B7 5. Inventive Note (6) As used herein, the term crosslinked liquid crystalline copolymer refers to a kind of orientation. Reticulated Structures Preferred Compounds of Formula I In the compounds of Formula I, suitable 1 and 112 groups include hydrogen, methyl, ethyl, n-propyl and n-butyl, with methyl being particularly preferred. Preferred values for the X' group are oxygen and a direct covalent bond, with oxygen preferably. Preferred spacers Y and Y' primarily comprise up to 30 carbon atoms, preferably from 3 to 12 carbon atoms. An aliphatic alkyl chain which may each have one or more, preferably up to 5 and preferably up to three methyl branches; up to 30 carbon atoms, preferably 3 to 12 carbon atoms Ethylene oxide, which may each comprise one or more branched methyl groups, preferably up to 5, most preferably up to 3 methyl groups. In a particular embodiment of the invention, it is desirable to have branched methyl groups. Because the resulting asymmetric carbon atoms form a biliary (ie, palmitic nematic) phase, which can be used as an interesting optical For example, color separation, generation of polarized light, etc. (see, Hikmet et al., supra). Preferred values for the Z and Z' groups are oxygen and direct covalent bonds, of which oxygen is preferred. It can be used as a liquid crystal moiety. In-depth investigation of suitable liquid crystal elements and their preparation can also be used for the compounds of the formula I according to the invention, see WO 96/24647, WO 97/00600 and WO 98/47979, here The contents are all incorporated by reference. Therefore, suitable liquid crystal elements include Group II: (-Q_x 丨,) PQ, _ (Π) where: -10- This paper scale applies to China National Standard (CNS) A4 Specifications (210X 297 mm) Paper U5

The same or the heterocyclic moiety group I2977^BG12 () 553 material application application Chinese manual replacement page (February 1996) Description of the invention (

Q and Q are independently selected from the group consisting of divalent saturated or unsatisfied, χη is X or X' base ' or .2, one 〇, one-to-one or rt P °. 1, 2 or 3. ^ρ>1 'X" may have the same or different meanings (in the case of P, preferably W2CQ and Q, the ring moiety may also be -, two or three of the same or different fluorine, chlorine, bromine, cyano, hydroxyl, Nitro, methionyl, Cm. alkyl, Cm oxime oxy, Cu oxycarbonyl, % mono-ylamino, alkylcarbonyl, CliG alkylcarbonyloxy, especially when Q and Q5 When it is an aromatic moiety, it is the best benzene derivative. The better Q and Q, the part includes:

And bounds

-11 - 73296-960215.doc This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1297728 A7 B7 V. Description of invention (Preferred liquid crystal elemental basis includes, for example

All of the above preferred liquid crystal group-based aromatic rings may have one or more substituents, wherein the substituents are each independently selected from the group consisting of methyl, fluorine, chlorine, bromine and nitro groups. Tejia is the liquid crystal element of the following chemical formula:

-12- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1297728 A7 B7 V. Inventive Note (9) wherein G and G'' are each independently selected from hydrogen, methyl, and fluorine. a group of chlorine, bromine and nitro groups. Preferably, G is a methyl group and G'' is hydrogen. In a preferred embodiment of the invention, a class of compounds of formula (I) having the formula (Γ) shown below is provided:

〇(CH2)n〇

0(CH2)n〇

Wherein R is preferably a methyl group, and η is preferably 4, 5 or 6. According to another feature of the invention, there is provided a liquid crystal material comprising at least one compound according to formula I. In another feature of the invention, the liquid crystal material comprises one or more asymmetric carbon atoms. Preparation of Compounds of Formula I The literature describes a number of synthetic routes to the preparation of polymerizable liquid crystal compounds. Molecules often increase from "outside" to "inside", but this will of course depend on the nature of the compound being made and the preferences of the manufacturer. In this case, the liquid crystal is based on the first step and is added to the precursor compound which already contains the desired reactive or non-reactive (and possibly palm) groups and spacer units to complete the fabrication. Suitable and preferred starting materials for the preparation of the liquid crystalline oxetane according to the invention include the following commercially available alcohols:

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1297728 A7 B7 V. Description of the invention (1〇 and derivatives of these alcohols such as the following products

The selected oxetane is then attached to a spacer molecule wherein one end of the spacer molecule has a reactive group which can typically be reacted with a suitable oxetane reactive group via addition, condensation or substitution to form a covalent The bond, and the spacer molecule, or the precursor form thereof, has another reactive group at the other end which can form a linkage with a selected liquid crystal based group. Those skilled in the art will be able to select the compound to be joined and the appropriate reaction conditions without difficulty. As a typical example of the preparation of a compound of the formula I according to the invention, the starting material, methyl or 3-ethyl-3-hydroxymethyloxetane, is converted to the corresponding oxetane compound, wherein the hydroxy group is previously The known form is converted to a more reactive group, such as a tosylate group. The terminal reactive group of the side chain of the basic oxetane compound is conveniently reacted with a compound of 4-bromophenoxy-alkyl alcohol to form one of the following compounds of formula III:

Wherein R!, R2, X, X', Y and Y' are as defined above, and q and q each refer to a reactive group (same or different), such as a bromine atom. Then, it is best to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) on the first paper scale. 1297728 A7 B7 V. Invention Description (11) Previously known methods, for example, using a suitable J-compound such as n-butyl The resulting compound of formula III is converted to the corresponding carboxylic acid compound by 4 or via a Grignard compound. In the next step, the resulting diglycidyl derivative having a carboxylic acid group is reacted with a liquid crystal element precursor to form a compound of formula I, or a mixture of such compounds. It is preferable to use a mesogendiol compound (HO-M-OH) or a similar compound having a reactive group as a liquid crystal precursor compound. In a typical alternative preparation of a compound of formula I, the starting material 3-methyl or 3-ethyl-3-hydroxymethyloxetane is converted to the corresponding haloalkyl ether oxetane derivative. (preferably a bromine compound) which is then reacted with a reactive compound such as a hydroxybenzoate or a similar compound to form a compound of formula III, which is then converted to a compound of formula I (or a compound thereof) as indicated above mixture). The type of reaction and alternative routes which are preferred for the preparation of the compounds of formula I are well known to those skilled in the art. The choice of the particular oxetane group and the particular spacer and liquid crystal based group to be used will depend on the choice and preference of the user and/or manufacturer. Moreover, the particular reaction conditions, particularly the reaction temperature, reaction time, reaction pressure, and solvent, will generally depend on the reactants employed and the preferences of the manufacturer. In general, the overall reaction time will vary between minutes and days, and the reaction temperature will generally vary from -80 ° C to the reflux temperature of the reaction mixture. Preferably, all of the reaction is carried out at atmospheric pressure. In general, in contrast to the polymerization of liquid crystalline propionate, it is not necessary to apply a specific inert atmosphere to the polymerization of the compound of formula I. Those skilled in the art can easily adjust the reaction conditions to the optimum state in each of the independent examples, and none of them -15- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1297728 A7 B7 V. Invention Description (12) Proper experimentation and no creative effect. The above reaction schemes illustrate the invention without limitation. Details of the preparation of other compounds of formula I are found in particular in WO 95/22586, WO 95/24454, WO 95/24455, WO 97/00600, and WO 99/43763, the disclosure of which is incorporated herein by reference. It is customary to polymerize a propylene oxide compound of formula I into a liquid crystalline polymer, preferably by techniques well known in the art such as photopolymerization or e-beam polymerization. Thus, in accordance with another feature of the invention, a liquid crystalline material comprising a dipropylene oxide (co)polymer compound substantially derived from one or more propylene oxide monomer compounds of formula I is provided. Since the propylene oxide monomer of the formula I according to the invention will comprise two (or more) polymerizable groups, it is usually also accompanied by crosslinking of the resulting liquid crystalline (co)polymer or liquid crystalline material, thus producing a directional network Structure. In a particular embodiment, the propylene oxide (co)polymer has optically active properties. Preferably, the liquid crystal material comprises a compound of formula I and a polymer compound substantially derived from one or more compounds of formula I. Preferably, the selected compound of formula I is combined with a suitable amount of a photoinitiator in a suitable solvent, such as chlorobenzene, such as commercially available Celebrex (〇γα (: ιικ) υνΐ·6990, and preferably rotated Coating or similar techniques to coat it on a substrate and photopolymerize using a suitable UV source. Alternatively, two or more compositions of the compound of formula I can be mixed with a photoinitiator to form a disulfide oxygen upon irradiation. In a further embodiment of the invention, a composition comprising one or more (usually two or three compounds) of a compound of formula I and a non-reactive liquid crystal or a plurality of first-16-paper scales for use in China National Standard (CNS) Α4 Specifications (210 X 297 mm) 1297728

: a technical precursor or oligomer, such as a liquid crystal, to form a liquid crystalline gel, or a mono- or hetero-butane monomer or an oligomer as disclosed in any of the above references to form another liquid crystalline copolymer, respectively. Or a mixture of polymers. The polymerization temperature and reaction time for preparing various of the above-described propylene oxide polymers are not very critical, and are usually between room temperature and about 85 ° C, usually in the range of minutes to one or two hours. The reaction time within can yield between about 1% and substantially complete conversion. In general, a higher conversion rate can be obtained by adding an annealing step, which is at a higher temperature.

Lw is carried out for about 25 to 1 hour between about 100 and 17 ° C without changing the optical properties. The dipropylene oxide liquid crystalline (co)polymer of the present invention has excellent characteristics, especially when compared with the 5 technology LC polymer. They are preferably used as a film in various application tissues, particularly in optical displays. As stated above, the relatively high crystallization temperature of, for example, liquid crystalline diacrylate, must be carried out at elevated temperatures, making it almost impossible to form a film by spin coating due to poor crystallization. Moreover, the polymer network structure produced at high temperatures tends to exhibit stress at room temperature due to stress and thermal contraction of deformation of the optical element. The present invention can solve these problems by providing these new propylene oxide liquid crystal monomer and (/,) ice 5, liquid crystal mixture and liquid crystal device. The new monooxypropane monomer generally has substantially lower crystallization. The temperature, which is generally as described in the table below in the examples below, thus avoids the problems associated with prior art LC polymers. Moreover, by reforming into a polymerizable acrylate-based fish oxetane, the polymerization reaction is carried out in air rather than in an inert gas because the polymerization is not -17-·

1297728 A7 B7 V. INSTRUCTIONS (14) Limited by oxygen. The propylene oxide compound of formula I or a composition comprising one or more acesulfame compounds of formula I is typically dissolved in a suitable solvent and mixed with a suitable cationic photoinitiator. This solution is then preferably spin coated onto the substrate at room temperature or at a higher temperature and the resulting film is polymerized using a suitable UV source. Alternatively, the polymerization is carried out with e-beam radiation. The polymerization product showed extremely low polymerization shrinkage. The measured polymerization shrinkage volume can be as low as about 2%, i.e., less than half the shrinkage during polymerization of a similar propionate. Thus, liquid crystalline (co)polymers according to the present invention are particularly useful in situations where low polymerization shrinkage is desired, such as in mirrors. Moreover, these polymers have excellent birefringence properties which do not change with temperature over a long temperature range. In another embodiment of the invention, a liquid crystalline composition comprising one or more of the compounds of formula I, i.e., one or more palm compounds, is provided. For the purposes of the present invention, suitable palmitic compounds include, for example, R-811 or S-811, commercially available from Merck under the 2-octanol group, or isosorbide matrices as described in WO-98/00428. Palm-type doping additive. These compositions are suitably used to make polymeric films having a palm crystalline phase for passive optical components (such as cyclopolarizers) or color filters, ie liquid crystalline displays, such as STN, TN, AMD-TN, temperature. Compensatory, guest-host or phase change displays or non-polymer or crystalline polymer stabilized biliary structures (PECT or PSCT) displays. The invention also encompasses polymeric films having a palm liquid crystalline phase which can be obtained in a known manner by (co)polymerizing a liquid crystalline composition as defined above. In another feature of the present invention, there is provided a display trough having two pairs of vertical plates, wherein the plates are permeable to light and have a -18-sheet scale on the side facing each other for the Chinese National Standard (CNS) A4 size (210 X 297 mm) 1297728 V. Description of the invention (Liquid crystal material of the gap of 15, hour: f. Gel form: 2: Net-like knot of liquid 贱7 of f material, for example, reveal And the code of g, binding this into the real c5h"

C=N (8) -〇ξν (b) The paper scale is suitable for x 297 mm)_ 19- 1297728 A7 B7 V. Description of invention (16

Or a mixture thereof. A suitable mixture of the above compounds (a) to (d) is available from BDH under the designation E7 in amounts of 8%, 51°/〇, 25% and 16%, respectively. Alternatively, a liquid crystalline material can be used as the non-polymerizable low molecular weight liquid crystalline material having a polymerizable group, and the polymerizable group does not under the polymerization conditions comprising one or more network structures of the propylene oxide compound according to the present invention. Or almost no aggregation. According to another feature, the present invention provides a method of making an electro-optical device comprising one or more propylene oxide compounds of the formula 1, comprising the steps of: (a) forming a chamber having two separate chamber walls, The inner surface of the wall has an electrode structure formed thereon; (b) providing a mixture comprising a monomer material, wherein the monomer material comprises one or more propylene oxide compounds of the formula 1 and a suitable initiator, preferably photoinitiated (c) introducing the mixture between the walls of the chamber; and (d) polymerizing the mixture as described above. Preferably at least one of the walls is a treated surface to provide liquid crystal alignment. The monomer material can be calibrated in a known manner prior to polymerization and/or the polymer can be calibrated after polymerization. According to another feature, the present invention provides a liquid crystal device comprising two separate chamber walls each having an electrode structure and at least one liquid crystal material layer treated on the surface by the alignment layer and contained between the chamber walls, wherein the liquid crystal The material layer comprises a polymeric material substantially derived from one or more of the propylene oxide compounds of Formula 1 as defined above or a composition comprising one or more of the propylene oxide compounds of Formula 1 as defined above and -20-the paper The scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1297728 A7

5. Description of the invention / or one or more of the propylene oxide compounds of the formula 1. The present invention further provides a scattering type electro-optical system comprising one or more formulas of a dipropylene oxide compound or a formula as defined above, 八#, 々#二,, ^我巴包含一一种一种一种1二A composition of a propylene oxide compound. The invention is additionally useful for having - or a plurality of propylene oxide compounds of formula i or as defined above - or a plurality of such formulas! A coated substrate of a composition of a diepoxypropyl compound. In the following examples, it is proposed that all temperature systems are uncorrected. C is π, and all parts and percentages are based on weight unless otherwise stated. Example 1 Preparation of methyl dioxetane oxypropane gas oxime methyl group _ Li methyl phenyl methyl oxocyclobutane _3 _ 氲 氲 & & 丙 丙 丙 丙 制备 制备 制备The title compound (4) was prepared according to the following reaction scheme:

-21 - ^The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) A7 B7 1297728 V. Description of invention (

〇(CH2)3〇

+ HO

〇(CH2)3〇

Preparation of ruthenium (CH2)30 1.01 3-M-mo-phenoxy)-propan-1-ol (1)

A mixture of 87 g of bromophenol, 27 g of sodium methoxide, 15 g of sodium iodide and 300 ml of methyl ethyl ketone was stirred at room temperature until completely dissolved. 3 -Chloro-1-propanol (42 ml) was added and the solution was heated under reflux for 16 hours. After cooling and drying, the butanone was distilled off. The residue was distributed between 50 ml of diethyl ether and 125 ml of water. After separation, the diethyl ether solution was extracted twice with 125 ml of 10% sodium hydroxide solution and once with 125 ml of brine. After drying over magnesium sulfate, diethyl ether was evaporated. A clear product (90 g, 78%) was obtained. 1·〇2 3-『3_(4-Alanyloxyoxymethylmethyl·3_methyl_negative cone cyclobutane, (2) Preparation 10 g of powdered potassium hydroxide and 30 ml The mixture of dimethyl hydrazine was stirred for 5 minutes. Then, 20 g of 3-(4-bromo-phenoxypropanol (1) was added, followed by the addition of 25 g of 甲-4,3-acid 3-methyl- Oxetane _3_ylmethyl oxime (see: Yong-Hong et al., Jupiter 1995, 28, 1673-80). The mixture is stirred at room temperature for 16 hours and then heated to 5 〇〇c. About 3 hours, add 3 ml of methanol and continue to stir at this temperature for a few hours. After cooling, add 1003⁄4 liters of diethyl ether and extract the mixture twice with 80 liters of water and use the paper size of 4 liters of paper. CNS) M specification (21GX297 public) 1297728 A7 __ B7 V. Invention description (~~)~~~ After brine extraction 6 After distilling off diethyl ether, add 8 ml of dichloromethane. Dry the solution with barium sulfate and After passing through a small vermiculite filler, after evaporation, 21 g of a clear oily product (75%) is obtained. li03 oxetane-3_ a methyl carbonitrile-p-formic acid (3) preparation 3 5 ML 1 Μ n-butyl clock is positive The solution formed by the calcination was added dropwise to 25 g of 3-[3-(4-di-phenoxypropoxymethylmethyl-oxetane (2) dissolved in 1203⁄4 liters and pre-cooled to 7 〇°c dry tetrahydrofuran formed in the solution. After adding, the mixture was dropped at this temperature for one hour, then the solid solid ice was heated until it was completely saturated. Stirring was continued until the solution reached room temperature. Add 12 liters. Diethyl ether and 100 ml of water. After separation, 36 ml of 2.5 mM hydrochloric acid was added dropwise to the uniformly stirred aqueous layer. The precipitate was washed with 15 ml of water and dried in a desiccator to obtain a melting point of l〇2. White powder of 15c (15g, 67%). ^04 Cyclobutane-3-ylmethyl propyl propylene 1-1 methyl methoxy-2-methyl phenyl-4_『3_π_甲- 气 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 4-[3-(3-Methyl-oxetan-3-ylmethoxy)propoxy-benzoic acid (3), 0.6 g of methyl hydroxyphenylhydrazine and (1) ruthenium: ^,: ^'-Dimethylaminopyridine in a solution of 30 ml of dichloromethane. After stirring for 16 hours at room temperature, the mixture was filtered through a small amount of vermiculite and recrystallized from 13 ml of ethanol to obtain a white powder having a melting point (mp) of 10 ° C and a crystal temperature (cp) of 27 ° C ( 2.2 g, 68%) 〇 Example 2 -23- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1297728 A7 B7 20 V. Description of invention (ketomethoxy)·氲1 Preparation of -Phenyl-3-y-methylmethyl)-hexyl ester The title compound (6) was prepared according to the following reaction scheme:

L〇(CH2)6Br + HO

5 °C\:

0(CH2)60

6 2·01 4·『6_··〇Methoxyoxet-3-ylmethyl hydrazine-pu^^^ (5) Preparation 15 g 3-[4-(3-bromo- Propoxy)-butyl]-3-methyl-oxetane (see: Yong-Hong et al., Jupiter 1995, 28, 1673-80), 11 g of ethyl 4-hydroxybenzoate A mixture of 12 g of potassium carbonate and 40 liters of butanone was heated under reflux for 16 hours. After cooling and filtration, the butanone was distilled off and a mixture of 100 ml of diethyl ether and 30 ml of water was added. After separation, the ether layer was extracted twice with 30 ml of a 10% sodium hydroxide solution and extracted once with 30 ml of brine. After distilling off the diethyl ether, 100 ml of a 5% potassium hydroxide solution was added. The mixture was heated under reflux for 8 hours. After cooling, extract the aqueous solution with 50 ml of diethyl ether and stir with vigorously -24 - The paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1297728 * A7 _______Β7 — V. Invention description (21 ) '~— Neutralize by adding 17 ml of 2·5N chloric acid. Wash the sink with 1 ml of water and dry in a desiccator. Obtained 15 g of a white powder product (84%) having a melting point of 62 t. 〇2·02 Cyclobutane-3_ylmethyl hydrazine. 篡V hexane group 1-benzyl yloxy phenyl group 氲齄瑷丁烷_3_A gas-based hexyl benzoate (6) was prepared by stirring 2.1 g of N,N,-dicyclohexylcarbodiimide in an ice bath to add 3.2 g of 4-[ 6-(3-Methyl-oxetane-3-ylmethoxy> hexyloxy]-benzoic acid (5), 0.55 g of hydroquinone and hydrazine·12 g of 4-N,N,-di Methylaminopyridine in a solution of 30 liters of methylene chloride. After stirring at room temperature for 16 hours, the mixture was filtered through a small amount of vermiculite and recrystallized from 25 ml of ethanol. °C and a white powder (66%) having a crystallization temperature of 119 ° C. Examples 3-6 Using the methods described in the above Examples 1 and 2, the following listed melting points and crystallization points were prepared as listed in the following Table 丨Compounds: Table 1

-25- Paper Silver Scale®® Home Standard (CNS) A4 Specification (21GX 297 mm) '"~---^^ 1297728 A7 B7 V. Description of Invention (22 ) 1 ~6 1 1 CH3 1 36 1 73 Example 7 Photopolymerization of bicyclopropane of the present invention and its properties Preparation of a 975 mg of 4-[4-(3-methyl-oxetan-3-ylmethoxy)-butoxy] -benzylideneoxy-2.methylphenyl-4-[4-(3-methyl-oxetan-3-ylmethoxy)-butoxy]-benzoate with 25 A mixture of milligrams of Cyracure UVI-6990. A small amount of this mixture was photopolymerized using a PL 10 watt lamp (7 mW/cm 2 at 365 nm) at various temperatures in an optical DSC apparatus. A good conversion was obtained with an irradiation time of 15 minutes at a temperature higher than 40 °C. Example 8 The stability of the birefringence of a bicyclopropane polymer after photoinitiated polymerization at 60 ° C with a 975 mg of 4-[4-(3•methyl-oxetan-3-ylmethoxy) -butoxy]-benzoic acid oxy-2-mercaptophenyl-4-[4-(3-indolyl-oxa-5-butylene:fe-3_ylmethoxy)-butoxy ]-benzoate (see Example 4) and a mixture of 25 mg of Celebrex (Cyracure® UVUQ^) filled with a 6 micron coated polyimide tank at 80 ° C. 30 minutes at 60 ° C Rapid alignment and photopolymerization. The birefringence of the monomer measured at 60 ° C was 0.09. After polymerization, it increased to 0.11 and became completely unchanged with temperature between 20 and 150 ° C. 2, showing that the polymerization temperature is changed between 40 and 8 (TC, the polymer can obtain a birefringence value between 0.07 and 0.11. Example 9 Rotary coating of the dipropylene oxide composition of the present invention-26- The paper scale applies to the Chinese National Standard (CNS) Α4 specification (210X297 mm).

1297728 A7 B7 V. INSTRUCTIONS (23) Preparation of a 972 mg of 4-[6-(3-methyl-oxetan-3-ylmethoxy)-hexyloxy]-benzoicoxybenzene 4-[6-(3-methyl-oxetanfe-3-ylmethoxyhexyloxy)-benzoate (Example 3) with 28 mg of Cyacure UVI-6990 Mixture. This mixture dissolved in chlorobenzene to make a 25/75 wt/vol solution at 800i: pm was spin coated onto a coated polyimide substrate. The sample was heated at 60 °C. After 15 minutes to obtain a better alignment, it was stored in the room temperature for several days without crystallization. Photopolymerization at 30 ° C gave 50% conversion (DSC) and formed a thin layer with a birefringence of 0.11. A higher polymerization conversion can be obtained at a higher temperature, for example, an annealing step at 150 ° C for 1 hour without changing the optical properties. The present invention is to be considered as illustrative and not limiting of the invention. The scope is indicated by the scope of the attached patent application, and all changes from the same meaning and scope are included. -27- This paper scale applies to the Chinese National Standard (CNS) A4 Specifications (210 X 297 mm)

Claims (1)

Patent application No. 12973⁄4^553 Patent application area replacement (here February '96) patent application area defeat 2. 15 Kind of glacial ice-liquid phenotype dipropylene oxide compound, which has a general formula 1. (I) wherein: Ri and I are independently selected from linear or branched & Ci_C4 alkyl and hydrogen; human X is exclusively selected from the group consisting of oxygen, sulfur, a single covalent bond, and C0_0- and -〇_c〇_〇-; z Z Z series are selected from oxygen, sulfur, a single covalent bond, _ do' and -0-C0-0-; γ and Y' are 3 to 12 a linear aliphatic alkyl chain of a carbon atom, each of which may be branched by one or more methyl groups, or an ethylene oxide (C^H4〇)r^ having 3 to 12 carbon atoms, which may each comprise One or more branched methyl groups; and any suitable liquid crystal elemental group, including the group of formula η··dx, VQ, - (II) wherein: Q and Q'± are selected from the divalent a group consisting of saturated or unsaturated I or a heterocyclic ring, each of which is one, two or three of the same or different fluorine, chlorine, bromine, cyano, S, nitro, τ thiol, Ciig alkyl, c: seven alkoxy, q.1G methoxycarbonyl, Cl_iQ monoalkylaminocarbonyl, ^alkylcarbonyl, Cl_1G alkyloxy substituted, X" is X or X, a group, or -ch2- o-...cuCH2_ -n=n~n==n(〇)·, -ch2s-, _sch2·, -co-o...〇.co· or extended ethyl, and 73296-960215. Doc 1297728 Patent application scope P is 〇, 1, 2 or 3. 2. According to the scope of patent application, the second propylene oxide compound has a general formula Wherein R is methyl and η is 4, 5 or 6. • a composition comprising one or more of the second ring of the scope of claim 2, the propane compound being combined with one or more liquid crystalline compounds, wherein the liquid 4 positive compound is selected from the group consisting of general non-polymerizable compounds and monooxa A group consisting of cyclobutane monomers. According to the composition of claim 3 of the patent application, the composition comprises one or more extractive compounds. • a parent-linked liquid crystalline (co)polymer product substantially in the form of a propylene oxide compound derived from one or more of claims 1 to 2, or derived from a third patent application scope Or a combination of 4 items. 6. Two liquid crystal devices characterized by incorporating a compound of claim 1 or 2 < compound, or a composition of claim 3 or 4, or a product of claim 5 . 7. The liquid crystal device according to the δth item of the patent application, which is a display chamber having two pairs of JL plates, wherein the plates are permeable to light and permeable to light on the side facing each other The electrode of the material, the orientation layer on the electrode, a sealing material interposed between the plates, and a filling material between the plates of 73296-960215.doc 297 mm) 1297728 围范利Special N 6 A BCD into the sealing material "Liquid Crystals of Voids = Contains - Polymerizable Liquid Crystalline Materials, "Graphic Shapes of Crystals = Any of the Applications of the Scope ii to 2 of the Patent Scope", derived from -:, or derived from 1 patent The second range: _• alkylation field, its polymerization formation - a kind of permanently oriented network composition '2 network structure according to a required map;: ^ born from: species 2 to 2;:!:: a bis-glycidyl compound, or a composition as defined in 3 or 4 of the Japanese patent publication: a low polymerization: liquid crystal form (co)polymerization of a liquid crystalline liquid crystal material, wherein a liquid crystal form of a child a (co)polymer product in the non-human low molecular weight liquid crystalline material A permanent mesh orientation: 0 ,,, port 73296-960215.doc configuration of the present paper is suitable China National Standard Scale (CNS) A4 size (210 X 297 mm)