WO2002102875A2 - Polymere mit cf2o-strukturelementen - Google Patents
Polymere mit cf2o-strukturelementen Download PDFInfo
- Publication number
- WO2002102875A2 WO2002102875A2 PCT/EP2002/006658 EP0206658W WO02102875A2 WO 2002102875 A2 WO2002102875 A2 WO 2002102875A2 EP 0206658 W EP0206658 W EP 0206658W WO 02102875 A2 WO02102875 A2 WO 02102875A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chain
- monomers
- polycycles
- shaped
- terminated
- Prior art date
Links
- 0 CC1(*)C=CC(NNN*N*N(C)NNC2=CC=CC(C)(*)C=C2)=CC=C1 Chemical compound CC1(*)C=CC(NNN*N*N(C)NNC2=CC=CC(C)(*)C=C2)=CC=C1 0.000 description 7
- VGLGZYCOGHDPEV-UHFFFAOYSA-N Nc(cc1)ccc1Nc(cc1)ccc1I Chemical compound Nc(cc1)ccc1Nc(cc1)ccc1I VGLGZYCOGHDPEV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
Definitions
- the invention relates to chain-like polycycles with CF 2 0 structural elements and to polymers obtainable from them.
- LCDs Liquid crystal displays
- Examples are wristwatches, notebook computers, TV sets and display displays in the instrument panel of motor vehicles or in the aircraft cockpit.
- a liquid crystal display consists of a liquid crystalline layer with opposite sides, a set of electrodes on each side of the liquid crystalline layer and a polymeric orientation layer between each set of electrodes and the liquid crystalline layer.
- the liquid-crystalline molecules are oriented at a certain angle, which is referred to as the angle of inclination, with respect to the plane of the inside of the two substrates, for example glass plates, plastic films or quartz plates, which carry the electrodes.
- the inside of the substrates have a coating of sets of transparent electrodes (electrical conductors), usually of indium tin oxide.
- the orientation process is carried out by applying the organic polymer from solution to the two substrates coated with indium tin oxide.
- the substrate surfaces are usually rubbed or polished in a certain direction with fabric.
- the rubbing or polishing is used to produce a uniform optical direction.
- polishing the two substrates they are rotated by 70 to 360 ° to one another, connected to one another with suitable spacers and using organic adhesives, and filled with a wide variety of mixtures of liquid-crystalline materials.
- polarizing films are often applied to the outer substrate surfaces by lamination. Finally, the electrical connections to both substrates are made.
- Polyimide films are the most commonly used orientation films today.
- Polyimide films serve to control the orientation and the angle of inclination of the liquid crystal molecules in liquid crystal displays and are very thin, generally their thickness is between 100 and 2000 A. Orientation in a single direction is induced by polishing with special textile materials. The actual angle of inclination is determined as a function of the order of the polymers on the surface of the resulting surface energy, the type of textile material used to polish the surface, and the size of the work involved in polishing.
- the object of the invention is to provide new polymer materials which are suitable for producing polymeric orientation films in liquid crystal displays.
- chain-shaped polycycles containing 2 to 12 identical or different chain-standing cycles, selected from 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1,4-cyclohexylene, Bicyclopentylene, bicyclooctylene and cubylene, which can be mono- or polysubstituted by halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy, the cycles being bridged by groups selected from a single bond, -CF 2 O-, -OCF 2 -, -O-, -S-, -SO 2 -, -CO-, -NH-, - (CH 2 ) 1-10 -, - (CF 2 ) ⁇ .
- Particularly preferred chain polycylene are those of the general formula (I)
- A, B, C and D may be the same or different and 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 2,7-naphthylene, 1,4-cyclohexylene, bicyclopentylene, bicylooctylene and cubylene, the can be mono- or polysubstituted by halogen, cyano, alkyl, fluoroalkyl, alkoxy and / or fluoroalkoxy,
- X 1 and X 2 are the same or different, are independently bound in the 3- or 4-position and have the meaning of X as defined in claim 2, and
- w, x, y and z are independently 0 or 1.
- A, B are as defined above, z ⁇ z - ⁇ Z 2
- Z "2 , Z 3 have the meaning of Z 1 - Z 5 as defined above with the
- Examples are chain polycylene of the general formulas (Ha) - (Vc)
- the chain-shaped polycyclic bisanhydrides according to the invention are obtained by the methods of preparative organic chemistry known per se, as described in Houben-Weyl, Methods of Organic Chemistry, Stuttgart, DE.
- an aromatic halide is first converted into a Grignard compound or into a lithiated compound and then converted into the dithiocarboxylic acid with carbon disulfide.
- the dithiocarboxylic acid is converted into a thioester with a phenol in the presence of an alkali metal hydride and iodine.
- the desired -O-CF 2 bridge is then formed from the thioester using a fluorinating agent.
- a cyclohexanone is first reacted with hexamethylphosphoric triamide and dibromodifluoromethane, a difluorohexylidene derivative being obtained.
- Bromine is first added to this and then etherified by reaction with a phenolate with simultaneous elimination of hydrogen bromide to form a -CF 2 -O bridge.
- a bis (alkylthio) carbenium salt is first in the presence of a base with at least one
- Hydroxyl group-containing compound reacted and then, preferably in situ, with a fluorinating agent and an oxidizing agent to connect with at least one -CF 2 -O-bridge in the molecule oxidatively fluorinated.
- the bis (alkylthio) carbenium salts can be prepared very easily from the corresponding carboxylic acids or activated carboxylic acid derivatives.
- Suitable carboxylic acid derivatives are, for example, carboxylic acid halides, carboxylic acid pseudohalides, carboxylic acid sulfonylates, which are suitably substituted, for example a trifluoromethanesulfonylate.
- Carboxylic anhydrides and alkyl or phenyl carboxylic acid esters can also be used. The salts precipitate out of the reaction solution in clean form and can be used in the next stage without further purification.
- the bis (alkylthio) carbenium salt is first converted to the dithioorthoester by reaction with the compound containing at least one hydroxyl group.
- This dithioorthoester is generally not isolated, but is immediately implemented further.
- the oxidative fluorination to give a compound containing a -CF 2 -O group takes place under very mild, slightly basic conditions and, in contrast to conventional methods, is therefore compatible with a large number of unprotected functional groups, for example a nitrile group.
- a further advantage is that the stereochemistry of the radicals, for example an ice or trans-cyclohexylene radical, is retained in the reaction.
- the basic steps are summarized in Figure 1 below.
- Fig. 1 Reaction scheme for the production of connections with a CF 2 O bridge.
- the carboxylic acid derivative A in which X represents, for example, -OH, halogen, pseudohalogen, substituted sulfonate, an anhydride, alkoxy or phenoxy, is reacted with an alkylthiol to form the bis (alkylthio) carbenium salt B.
- Dithiols which lead to the formation of a cyclic cation are preferably used.
- Ethanedithiol, propanedithiol or 1,2-benzenedithiol, which lead to the formation of dithianylium or dithiolanylium salts, are therefore particularly suitable.
- This salt B is then reacted with a hydroxy compound R b -OH to give the orthoester C.
- the orthoester C is generally not isolated, but instead is converted directly to the compound D by oxidation.
- the method can be used universally, so that R a and R b are not subject to any restrictions.
- R a and R b can thus be, for example, independently of one another an alkyl, an aryl, a cycloalkyl or an alkenyl radical, where these radicals can in turn be substituted as desired, for example by halogen, pseudohalogen, hydroxyl or carbonyl groups.
- Advantages of the process described last are that it leads to good yields with satisfactory reaction rates. Intermediate and end products are easy to clean.
- the present invention furthermore relates to polymers with -CF 2 O groups, obtainable by polycondensation of one or more different chain-shaped polycycles, as described above, as monomers A and, if appropriate, one or more different further chain-shaped polycycles as monomers B, where the monomers A and, if appropriate, B are terminated by suitable reactive and coreactive groups.
- polyesters obtainable by polycondensation of
- chain-shaped polycycles as defined above, as monomers A2 and optionally further chain-shaped polycycles as monomers B2, the monomers A2 and B2 at both chain ends by -COOH, -COCI, -COF or -COOalkyl or by - Are terminated with chain-shaped polycycles, as defined in one of claims 1-5, as monomers A3 and / or further chain-shaped polycycles as monomers B3, the monomers A3 and B3 at both chain ends by —OH and by —COOH , -COCI, -COF or -COOalkyl are terminated.
- polymers according to the invention are also polyamides obtainable by polycondensation of a) chain-shaped polycycles, as defined above, as monomers A1 and optionally further chain-shaped polycycles as monomers B1, the monomers A1 and optionally B1 at one chain end in each case by -COOH, -COCI, -COF or
- chain-shaped polycycles as defined above, as monomers A2 and optionally further chain-shaped polycycles as monomers B2, the monomers A2 and B2 at both chain ends by -COOH, -COCI, -COF or -COOalkyl or by - NH 2 are terminated, with chain-shaped polycycles as defined above as monomers A3 and / or further chain-shaped polycycles as monomers B3, the monomers A3 and B3 at both chain ends by -NH 2 and by -COOH, - COCI, -COF or -COOalkyl are terminated.
- polymers according to the invention are furthermore polyurethanes, obtainable by polyaddition of
- chain-like polycycles as defined above, as monomers A1 and optionally further chain-like polycycles as monomers B1, the monomers A1 and B1 being terminated at one chain end by -NCO and at the other chain end by -OH, or from
- Chain ends are terminated by -NCO or -OH, with chain-like polycycles as defined above as monomers A3 and / or further chain-like polycycles as monomers B3, the monomers A3 and B3 at both chain ends through - OH or -NCO are scheduled.
- Examples of polymers according to the invention are also polyureas obtainable by polyaddition of
- chain-shaped polycycles as defined above, as monomers A1 and optionally further chain-shaped polycycles as monomers B1, the monomers A1 and B1 being terminated at one chain end by -NCO and at the other chain end by -NH 2 , or from
- chain-shaped polycycles as defined above, as monomers A2 and optionally further chain-shaped polycycles as monomers B2, the monomers A2 and B2 being terminated at both chain ends by -NCO or -NH 2 , with chain-shaped polycycles, as described above are defined as monomers A3 and / or further chain polycyclics as monomers B3, the monomers A3 and B3 being terminated at both chain ends by - NH 2 or -NCO.
- polymers according to the invention are also polycarbonates, obtainable by polycondensation of chain-like polycycles as defined above as monomers A2 and optionally further chain-like polycycles as monomers B2, the monomers A2 and B2 terminating at both chain ends with -OH with COCI 2 .
- the monomers mentioned are notable for very good solubility in the customary organic solvents.
- the relative number of linking positions is reduced by the size of the repetitive units. These linking positions can contribute to the binding of ionic impurities to the polymer and thus impair the usability of the polymer as a component of electronic components, for example by reducing the electrical resistance.
- the reduction in the number of linking positions based on the molecular weight is therefore a decisive advantage.
- Advantages of the polymers according to the invention are furthermore their high thermal, photochemical and chemical stability, their high lipophilicity, their high electrical resistance and their low affinity for ionic impurities. These properties offer particular advantages when the polymers are used in electronic components, for example as orientation material in LCDs or organic light-emitting diodes (OLEDs) or as insulation material for electronic circuits.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
- Polyesters Or Polycarbonates (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020037016558A KR100893654B1 (ko) | 2001-06-19 | 2002-06-17 | Cf2o 구조 성분을 포함하는 중합체 |
JP2003506344A JP2005506399A (ja) | 2001-06-19 | 2002-06-17 | Cf2o構造要素を含むポリマー |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10129276 | 2001-06-19 | ||
DE10129276.7 | 2001-06-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002102875A2 true WO2002102875A2 (de) | 2002-12-27 |
WO2002102875A3 WO2002102875A3 (de) | 2003-03-13 |
Family
ID=7688535
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/006658 WO2002102875A2 (de) | 2001-06-19 | 2002-06-17 | Polymere mit cf2o-strukturelementen |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP2005506399A (de) |
KR (1) | KR100893654B1 (de) |
DE (1) | DE10225426A1 (de) |
WO (1) | WO2002102875A2 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100334493C (zh) * | 2004-05-28 | 2007-08-29 | 友达光电股份有限公司 | 用于聚合物稳定配向过程的单体以及包括该单体生成的聚合物的液晶显示面板 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5536442A (en) * | 1987-09-25 | 1996-07-16 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Fluorinated liquid crystal compounds and liquid crystal medium containing same |
DE10008505A1 (de) * | 1999-03-03 | 2000-10-12 | Merck Patent Gmbh | Schwefeltetrafluorid -Derivate und flüssigkristallines Medium |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW343232B (en) * | 1994-10-13 | 1998-10-21 | Chisso Corp | Difluorooxymethane derivative and liquid crystal composition |
JP3807576B2 (ja) * | 1998-01-28 | 2006-08-09 | シャープ株式会社 | 重合性化合物、重合性樹脂材料組成物、重合硬化物及び液晶表示装置 |
-
2002
- 2002-06-07 DE DE10225426A patent/DE10225426A1/de not_active Withdrawn
- 2002-06-17 KR KR1020037016558A patent/KR100893654B1/ko not_active IP Right Cessation
- 2002-06-17 WO PCT/EP2002/006658 patent/WO2002102875A2/de active Application Filing
- 2002-06-17 JP JP2003506344A patent/JP2005506399A/ja active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5536442A (en) * | 1987-09-25 | 1996-07-16 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Fluorinated liquid crystal compounds and liquid crystal medium containing same |
DE10008505A1 (de) * | 1999-03-03 | 2000-10-12 | Merck Patent Gmbh | Schwefeltetrafluorid -Derivate und flüssigkristallines Medium |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100334493C (zh) * | 2004-05-28 | 2007-08-29 | 友达光电股份有限公司 | 用于聚合物稳定配向过程的单体以及包括该单体生成的聚合物的液晶显示面板 |
Also Published As
Publication number | Publication date |
---|---|
KR100893654B1 (ko) | 2009-04-17 |
DE10225426A1 (de) | 2003-01-02 |
WO2002102875A3 (de) | 2003-03-13 |
KR20040027520A (ko) | 2004-04-01 |
JP2005506399A (ja) | 2005-03-03 |
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