CN102372808B - Photoreactive polymer and preparation method thereof - Google Patents

Photoreactive polymer and preparation method thereof Download PDF

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CN102372808B
CN102372808B CN201110197337.2A CN201110197337A CN102372808B CN 102372808 B CN102372808 B CN 102372808B CN 201110197337 A CN201110197337 A CN 201110197337A CN 102372808 B CN102372808 B CN 102372808B
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halogen
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CN102372808A (en
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崔大胜
全成浩
元永喆
柳东雨
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LG Corp
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LG Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Abstract

This disclosure relates to photoreactive polymer exhibiting more rapid photoreaction speed and excellent alignment, a preparation method thereof, and an alignment layer comprising the same. The photoreactive polymer comprises a specific repeat unit including an azo type functional group in the content of 50 mole % or more of the total polymer.

Description

Photoreactive polymer and preparation method thereof
Technical field
The present invention relates to a kind of oriented layer showing photoreactive polymer of photoresponse speed faster and excellent orientation and preparation method thereof and comprise this photoreactive polymer.
Background technology
In recent years, because liquid-crystal display has lightweight, that energy consumption is low advantage, the indicating meter of the most competitive power that can replace Braun tube is regarded as.Especially, the Thin Film Transistor-LCD (TFT-LCD) driven by thin film transistor, due to each pixel of independent drive, therefore liquid crystal response speed is quickly, can realize the dynamic image of high definition, its range of application expands to notebook computer, wall-mounted TV etc.
In order to be used as photoswitch by liquid crystal in these TFT-LCD, initial orientation in certain direction on the layer needing to make liquid crystal to be formed at display unit (cell) innermost thin film transistor, adopts liquid crystal aligning layer for this reason.
In order to obtain this liquid crystal aligning, once adopted friction process (rubbing process).That is, transparent glass is coated with the thermotolerance polymers such as polyimide, with stratification (stratification) macromolecular orientation layer, and high speed rotating is wound with the rotating roller of the friction cloth such as nylon, regenerated fiber, makes its orientation with wiping oriented layer.
But, when friction process rubs, mechanical mark can be produced on the surface at liquid crystal aligning agent, or cause strong electrostatic, therefore may destroy thin film transistor.In addition, due to the micro fiber etc. that friction cloth produces, there are substandard products, obstacle is defined to the raising of casting yield.。
In order to overcome Problems existing in above-mentioned friction process, and the liquid crystal aligning mode brought innovation to production efficiency aspect and propose is the liquid crystal aligning (hereinafter referred to as " light orientation ") adopting the light such as ultraviolet (UV).
Light orientation refers to the photosensitivity functional group be combined on the photoreactivity polymer of regulation, photoresponse is caused under the effect of the UV of linear polarization, high molecular main chain arranges in certain direction in the process, and result forms the mechanism making the photo-polymerization type liquid crystal aligning layer of liquid crystal aligning.
The representative instance of this smooth orientation is the people (Jpn.J.Appl.Phys. such as M.Schadt, Vol 31,1992,2155), people's (United States Patent (USP) the 5th such as Dae S.Kang, 464, No. 669), Yuriy Reznikov (Jpn.J.Appl.Phys.Vol.34,1995, L1000) deliver based on photopolymerisable smooth orientation.The light orientated polymer mainly poly-laurate base polymer such as PVCN (poly (vinylcinnamate)) or PVMC (poly (vinylmethoxycinnamate)) used in these patents and paper.When making its light orientation, pass through irradiated ultraviolet (UV), the double bond of laurate can produce [2+2] cycloaddition ([2+2] cycloaddition) reaction, and generate tetramethylene (cyclobutane), and form anisotropy thus, liquid crystal molecule is arranged to a direction, to cause liquid crystal aligning.
But, because the thermostability of its high polymer main chain is low, there is the orientation stability or thermostability that reduce oriented layer in above-mentioned smooth orientated polymer in the past, or liquid crystal aligning shortcoming not fully.Such as, there is following shortcoming in the polymkeric substance with acrylic backbone, namely greatly reduces oriented layer stability because thermostability is low, and when photosensitivity functional group is fettered by main chain, the polarized light irradiated in oriented layer can not be reacted rapidly, thus reduce liquid crystal aligning or speed of orientation.As mentioned above, when liquid crystal aligning or speed of orientation decline, process efficiency decline or the liquid crystal aligning of liquid crystal display device abundant not, cause dichroic ratio to diminish contrast gradient deterioration.
On the other hand, Bull.Korean Chem.Soc.2002, Vol.23, in 957, propose the photoreactive polymer that the part comprised as repeating unit is combined with the repeating unit of azo-group.But it is abundant not still to there is orientation in this photoreactive polymer, and due to photoresponse speed slow and reduce process efficiency, or the problem such as the contrast gradient deterioration of liquid crystal display device.
Summary of the invention
The object of the present invention is to provide and a kind ofly show photoreactive polymer of photoresponse speed faster and excellent orientation and preparation method thereof.
Another object of the present invention is to provide a kind of oriented layer, and it comprises described photoreactive polymer, can be used for liquid crystal display device etc.
The invention provides a kind of photoreactive polymer, it comprises content is more than the 50mol% of total polymer, the repeating unit represented by following chemical formula 3 or 4.
[chemical formula 3] [chemical formula 4]
In described chemical formula 3 and 4, n to be 50 ~ 5000, p be 0 ~ 4 integer, R 1, R 2, R 3and R 4in at least one is selected from the group in the group that is made up of following chemical formula 1a, 1b and 1c, remaining is separately selected from by hydrogen; Halogen; Substituted or unsubstituted C1 ~ C20 alkyl; Substituted or unsubstituted C2 ~ C20 thiazolinyl; Substituted or unsubstituted C2 ~ C20 alkynyl; Substituted or unsubstituted C3 ~ C12 cyclic hydrocarbon radical; Substituted or unsubstituted C6 ~ C40 aryl; And comprise and be selected from group that in oxygen, nitrogen phosphate and sulfur, silicon and boron, the polar functional group of at least one forms, as described R 1~ R 4when not being hydrogen, halogen or polar functional group, R 1and R 2, or R 3and R 4be interconnected and form the alkylidene (alkylidene group) of C1 ~ C10, or R 1or R 2with R 3and R 4in one connect and form the aromatic ring of the saturated of C4 ~ C12 or undersaturated ring or C6 ~ C24,
[chemical formula 1a]
[chemical formula 1b]
[chemical formula 1c]
In described chemical formula 1a, 1b and 1c, n1, p1, r1 and m1 are the integer of 0 ~ 4, n2, p2, r2 and m2 are the integer of 0 ~ 5, A is substituted or unsubstituted C1 ~ C20 alkylidene group, carbonyl ,-COO-, substituted or unsubstituted C6 ~ C40 arylidene or singly-bound, B is oxygen, sulphur ,-NH-or singly-bound, R 9for singly-bound, substituted or unsubstituted C1 ~ C20 alkylidene group, substituted or unsubstituted C2 ~ C20 alkenylene, substituted or unsubstituted C2 ~ C20 alkynylene, the sub-aralkyl of substituted or unsubstituted C3 ~ C12 sub-cyclic hydrocarbon radical, substituted or unsubstituted C6 ~ C40 arylidene or substituted or unsubstituted C7 ~ C15, R 10and R 11for hydrogen, halogen, substituted or unsubstituted C1 ~ C20 alkyl, substituted or unsubstituted C1 ~ C20 alkoxyl group, substituted or unsubstituted C6 ~ C30 aryloxy or substituted or unsubstituted C6 ~ C40 aryl.
In addition, the present invention also provides a kind of preparation method of described photoreactive polymer, it comprises: comprising under the existence with the pre-catalyst of the 10th race's transition metal and the catalyst composition of promotor, the monomer that addition polymerization is represented by chemical formula 1 and form the step of the repeating unit represented by chemical formula 3.
[chemical formula 1]
In described chemical formula 1, p, R 1, R 2, R 3and R 4as described in chemical formula 3 define.
The present invention also provides a kind of preparation method of described photoreactive polymer, it comprises: comprising under the existence with the 4th race, the 6th race or the pre-catalyst of the 8th race's transition metal and the catalyst composition of promotor, the monomer that addition polymerization is represented by chemical formula 1 and form the step of the repeating unit represented by chemical formula 4.
In addition, the invention provides a kind of oriented layer comprising described photoreactive polymer.
The present invention also provides a kind of liquid crystal retardation film of the liquid crystal layer comprised in described oriented layer and this oriented layer.
The present invention also provides a kind of display device comprising described oriented layer.
By comprising the norbornylene repeating unit with high-vitrification invert point as predominant repeat unit, excellent thermostability can be demonstrated according to photoreactive polymer of the present invention.Further, by comprising the norbornylene repeating unit containing specific azo-type photoreactive group of high relative contents, described photoreactive polymer can demonstrate orientation and the light utilization efficiency of photoresponse speed and the excellence be greatly improved.
Therefore, the oriented layer, liquid crystal retardation film etc. that use described photoreactive polymer to provide there is excellent properties, and greatly can improve production efficiency.
Accompanying drawing explanation
Fig. 1 represents the 1H NMR data of polymkeric substance obtained in embodiment 1.
Fig. 2 represents the 1H NMR data of polymkeric substance obtained in comparative example 1.
Fig. 3 is the figure representing anisotropy and ultraviolet (UV) the photoreactivity detected result measured in test example 3.
Embodiment
Below, describe photoreactive polymer of the embodiment of the present invention and preparation method thereof in detail, and comprise the oriented layer of this photoreactive polymer.
There is provided a kind of photoreactive polymer according to embodiments of the invention, it comprises content is more than the 50mol% of total polymer, the repeating unit represented by following chemical formula 3 or 4.
[chemical formula 3] [chemical formula 4]
In described chemical formula 3 and 4, n to be 50 ~ 5000, p be 0 ~ 4 integer, R 1, R 2, R 3and R 4in at least one for being selected from the group in the group that is made up of following chemical formula 1a, 1b and 1c, remaining is separately selected from hydrogen, halogen, substituted or unsubstituted C1 ~ C20 alkyl, substituted or unsubstituted C2 ~ C20 thiazolinyl, substituted or unsubstituted C2 ~ C20 alkynyl, substituted or unsubstituted C3 ~ C12 cyclic hydrocarbon radical, substituted or unsubstituted C6 ~ C40 aryl, and comprise and be selected from group that in oxygen, nitrogen phosphate and sulfur, silicon and boron, the polar functional group of at least one forms, when described R1 ~ R4 is not all hydrogen, halogen or polar functional group, R 1and R 2, or R 3and R 4be interconnected and form C1 ~ C10 alkylidene group, or one of R1 or R2 and R3 and R4 connect and form the aromatic ring of the saturated of C4 ~ C12 or undersaturated ring or C6 ~ C24,
[chemical formula 1a]
[chemical formula 1b]
[chemical formula 1c]
In described chemical formula 1a, 1b and 1c, n1, p1, r1 and m1 are the integer of 0 ~ 4, n2, p2, r2 and m2 are the integer of 0 ~ 5, A is substituted or unsubstituted C1 ~ C20 alkylidene group, carbonyl ,-COO-, substituted or unsubstituted C6 ~ C40 arylidene or singly-bound, B is oxygen, sulphur ,-NH-or singly-bound, R 9for singly-bound, substituted or unsubstituted C1 ~ C20 alkylidene group, substituted or unsubstituted C2 ~ C20 alkenylene, substituted or unsubstituted C2 ~ C20 alkynylene, substituted or unsubstituted C3 ~ C12 sub-cyclic hydrocarbon radical, substituted or unsubstituted C6 ~ C40 arylidene, or the sub-aralkyl of substituted or unsubstituted C7 ~ C15, R 10and R 11be hydrogen, halogen, substituted or unsubstituted C1 ~ C20 alkyl, substituted or unsubstituted C1 ~ C20 alkoxyl group, substituted or unsubstituted C6 ~ C30 aryloxy independently, or substituted or unsubstituted C6 ~ C40 aryl.
This photoreactive polymer comprises the norbornylene class repeating unit represented by chemical formula 3 or 4 of the specific azo photoreactivity functional group being combined with chemical formula 1a ~ 1c as predominant repeat unit.This norbornylene class repeat unit structure is firm, its second-order transition temperature of photoreactive polymer (Tg) comprising this repeating unit is higher, be about more than 300 DEG C, preferably about 300 ~ 350 DEG C, therefore, compared with photoreactive polymer in the past, excellent thermostability can be shown.And, due to described photoreactive polymer in the structural performance of described norbornylene class repeating unit in conjunction with photoreactivity functional group, photoreactivity functional group relatively freely can move in high polymer main chain, therefore can show excellent orientation.
And as the further confirmation obtained by test example described later etc., the experimental result of the present inventor shows, described photoreactive polymer, owing to combining specific azo photoreactivity functional group, shows photoresponse speed faster and speed of orientation than ever.Described azo photoreactivity functional group, its azo-group (-N=N-) absorbing polarization light and carry out cis-trans isomerization reaction (trans-cisisomerization) to a direction, plays the effect causing liquid crystal aligning thus.This photoresponse and epitaxy mechanism, estimate to be exactly the factor that can realize photoresponse speed faster and speed of orientation relative to other photoreactivity functional groups.
Particularly, according to the photoreactive polymer of a described embodiment, about more than the 50mol% of high-content can be comprised, concrete about 50 ~ 100mol%, the more specifically repeating unit represented by chemical formula 3 or 4 being combined with described azo photoreactivity functional group of about 60 ~ 100mol% or 70 ~ 100mol%.Thus, the photoresponse speed of the azo-based class photoreactivity functional group be greatly improved can be characterized.In contrast to this, as the further confirmation obtained by aftermentioned comparative example, comprise about below 50mol%, about below the 40mol% of low levels, the polymkeric substance being combined with the repeating unit of described azo photoreactivity functional group of such as about 20mol%, in fact cannot realize the fast photoresponse speed based on described azo photoreactivity functional group.This may be because content is low, although occur that the photoresponse mechanism of part described azo photoreactivity functional group is as cis-trans isomerization reaction (trans-cisisomerization), but owing to being included in the low levels of the azo photoreactivity functional group in oriented layer, normally can not characterize liquid crystal aligning, or be subject to the impact of other repeating units that random (randomly) disperses, the orientation of pre-determined direction can not be realized.
In contrast, the photoreactive polymer of one embodiment, show photoresponse speed quickly and speed of orientation, show excellent orientation and thermostability simultaneously, therefore the oriented layer etc. of liquid crystal display device is applicable to, and by photoresponse speed fast, significantly process efficiency can be improved.
Below, described photoreactive polymer is further described.
Described photoreactive polymer can be the polymkeric substance being selected from the repeating unit in the repeating unit represented by described chemical formula 3 and 4 only comprising 100mol%, but not affecting in the scope based on the photoreactive polymer effect of the repeating unit represented by described chemical formula 3 and 4, other repeating units can also be comprised.Such as, described photoreactive polymer can be the multipolymer comprising the repeating unit represented by following chemical formula 2a or 2b further, owing to comprising the repeating unit represented by described chemical formula 2a or 2b belonging to norbornylene class further, excellent thermostability can be shown.
[chemical formula 2a] [chemical formula 2b]
In described chemical formula 2a and 2b, m to be 50 ~ 5000, q' be 0 ~ 4 integer, R', R 2', R 3' and R 4' be separately selected from the group represented by chemical formula 2c; Hydrogen; Halogen; Substituted or unsubstituted C1 ~ C20 alkyl; Substituted or unsubstituted C2 ~ C20 thiazolinyl; Substituted or unsubstituted C2 ~ C20 alkynyl; Substituted or unsubstituted C3 ~ C12 cyclic hydrocarbon radical; Substituted or unsubstituted C6 ~ C40 aryl; And comprise and be selected from group that in oxygen, nitrogen phosphate and sulfur, silicon and boron, the polar functional group of at least one forms, described R1' ~ R 4' when not being all hydrogen, halogen or polar functional group, R 1' and R 2', or R 3' and R 4' be interconnected and form C1 ~ C10 alkylidene group, or R 1' or R 2' and R 3' and R 4' one of connect and form the saturated of C4 ~ C12 or undersaturated ring, or C6 ~ C24 aromatic ring,
[chemical formula 2c]
In described chemical formula 2c, l is 0 or 1, D and D' is separately selected from the group that singly-bound, nitrogen, oxygen, sulphur, the straight or branched type alkylidene group of substituted or unsubstituted C1 ~ C20, the sub-cyclic hydrocarbon radical of substituted or unsubstituted C3 ~ C12 and sub-cyclic hydrocarbon radical oxygen base (cycloalkylene oxide) of substituted or unsubstituted C3 ~ C12 form, in the group that the straight or branched type alkyl that X and Y is separately selected from hydrogen, halogen, cyanogen and substituted or unsubstituted C1 ~ C20 forms, R 10' ~ R 14' be separately selected from hydrogen; Halogen; Cyanogen; Substituted or unsubstituted C1 ~ C20 alkyl; Substituted or unsubstituted C1 ~ C20 alkoxyl group; Substituted or unsubstituted C6 ~ C30 aryloxy; Substituted or unsubstituted C6 ~ C40 aryl; Comprise the 14th race, the heteroatomic C6 ~ C40 heteroaryl of the 15th race or the 16th race; And in the group that forms of substituted or unsubstituted C6 ~ C40 alkoxy aryl.
This repeating unit represented by chemical formula 2a or 2b, can be conventional norbornylene class repeating unit, also can be the photoreactivity repeating unit being combined with the cinnamate derivative photoreactivity functional group represented by described chemical formula 2c.Preferably, described R 1', R 2', R 3' and R 4' at least one is the group represented by chemical formula 2c, the repeating unit represented by described chemical formula 2a or 2b is photoreactivity repeating unit.
Described photoreactive polymer comprises this cinnamate derivative photoreactivity repeating unit further, can show more excellent photoreactivity and orientation thus.Particularly, azo photoreactivity functional group is to comparatively showing photoreactivity close to the light of the long wavelength range of visible ray, and cinnamate derivative photoreactivity functional group relatively shows excellent photoreactivity to the light in short wavelength ultraviolet (UV) region.Therefore, while described photoreactive polymer comprises the repeating unit of chemical formula 3 or 4 expression, when comprising the cinnamate derivative repeating unit that chemical formula 2a or 2b represent further, use during conventional lighting sources and can improve light utilization efficiency further, and show more excellent photoreactivity and orientation.
Described photoreactive polymer is except the repeating unit content represented by described chemical formula 3 or 4, such as, can comprise and be greater than 0mol% and below 50mol%, be greater than 0mol% particularly and below 40mol%, or be greater than 0mol% and the repeating unit represented by described chemical formula 2a or 2b of below 20mol%.In addition, comprising at least partially in the repeating unit represented by described chemical formula 2a or 2b is when representing photoreactivity functional group by chemical formula 2c, its content is 10 ~ 50mol%, more specifically 20 ~ 50mol%, to embody the photoreactivity based on this repeating unit.
On the other hand, what form described photoreactive polymer represents repeating unit by chemical formula 3 or 4, and in the repeating unit represented by chemical formula 2a or 2b, the group of the optional free following functional group's composition of described polar functional group.In addition, also can be comprise the various polar functional groups of at least one be selected from oxygen, nitrogen phosphate and sulfur, silicon or boron:
-R 5OR 6、-OR 6、-OC(O)OR 6、-R 5OC(O)OR 6、-C(O)OR 6、-R 5C(O)OR 6、-C(O)R 6、-R 5C(O)R 6、-OC(O)R 6、-R 5OC(O)R 6、-(R 5O) r-OR 6、-(OR 5) r-OR 6、-C(O)-O-C(O)R 6、-R 5C(O)-O-C(O)R 6、-SR 6、-R 5SR 6、-SSR 6、-R 5SSR 6、-S(＝O)R 6、-R 5S(＝O)R 6、-R 5C(＝S)R 6-、-R 5C(＝S)SR 6、-R 5SO 3R 6、-SO 3R 6、-R 5N＝C＝S、-N＝C＝S、-NCO、-R 5-NCO、-CN、-R 5CN、-NNC(＝S)R 6、-R 5NNC(＝S)R 6、-NO 2、-R 5NO 2；
In above-mentioned each functional group, r is the integer of 1 ~ 10, R 5for substituted or unsubstituted C1 ~ C20 alkylidene group, substituted or unsubstituted C2 ~ C20 alkenylene, substituted or unsubstituted C2 ~ C20 alkynylene, the sub-cyclic hydrocarbon radical of substituted or unsubstituted C3 ~ C12, substituted or unsubstituted C6 ~ C40 arylidene, substituted or unsubstituted C1 ~ C20 sub-carbonyl oxygen base, or substituted or unsubstituted C1 ~ C20 alkylene oxide group
R 6, R 7and R 8be selected from the group be made up of hydrogen, halogen, substituted or unsubstituted C1 ~ C20 alkyl, substituted or unsubstituted C2 ~ C20 thiazolinyl, substituted or unsubstituted C2 ~ C20 alkynyl, substituted or unsubstituted C3 ~ C12 cyclic hydrocarbon radical, substituted or unsubstituted C6 ~ C40 aryl, substituted or unsubstituted C1 ~ C20 alkoxyl group and substituted or unsubstituted C1 ~ C20 carbonyl oxygen base.
Form the repeating unit represented by chemical formula 3 or 4 of described photoreactive polymer, and represent repeating unit by chemical formula 2a or 2b, its polymerization degree is 50 ~ 5000, is preferably 100 ~ 4000, is more preferably 1000 ~ 3000.Because these repeating units have the polymerization degree in above-mentioned scope, the alignment agent composition that what described photoreactive polymer can be suitable comprise for the formation of oriented layer, so can show excellent coating.
Below, each substituent definition in described photoreactive polymer structure is described in detail.
First, " alkyl " represents that carbonatoms is 1 ~ 20, preferably 1 ~ 10, the more preferably straight or branched type saturated monovalence hydrocarbon position of 1 ~ 6.Described alkyl not only represents unsubstituted group, can also represent the group replaced by specified substituent as described below.Alkyl can exemplified by methyl, ethyl, propyl group, 2-propyl group, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, dodecyl, methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, iodomethyl, brooethyl etc.
" thiazolinyl " expression has one or more carbon-to-carbon double bond and carbonatoms is 2 ~ 20, is preferably 2 ~ 10, is more preferably the straight or branched type monovalence hydrocarbon position of 2 ~ 6.Thiazolinyl is combined by the carbon atom or saturated carbon atom with carbon-to-carbon double bond.Thiazolinyl not only represents unsubstituted group, also represents the group replaced by specified substituent as described below.Thiazolinyl can exemplified by vinyl, 1-propenyl, 2-propenyl, crotyl, 3-butenyl, pentenyl, 5-hexenyl, laurylene base etc.
" cyclic hydrocarbon radical " represents to have the saturated of 3 ~ 12 ring carbon atoms or undersaturated non-aromatic monovalent monocyclic, two rings or tricyclic hydrocarbon position, also represents the group replaced by specified substituent as described below.Cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, suberyl, ring octyl group, decahydro naphthyl, adamantyl, norbornene (that is, dicyclo [2,2,1]-5-thiazolinyl in heptan) etc. can be exemplified.
" aryl " represents to have 6 ~ 40, preferably has the monovalent monocyclic of 6 ~ 12 annular atomses, two rings or thrcylic aromatic hydrocarbon position, also represents the group replaced by specified substituent as described below.Aryl can exemplified by phenyl, naphthyl and fluorenyl etc.
" alkoxy aryl " represents the base that in described aryl, one or more hydrogen atom alkoxy replaces.Alkoxy aryl can exemplify p-methoxy-phenyl, ethoxyl phenenyl, propoxyphenyl, butoxy phenyl, pentyloxy phenyl, Hexyloxy-phenyl, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, methoxyl group phenylbenzene, methoxyl group naphthyl, methoxyl group fluorenyl or methoxyl group anthryl (anthracenyl) etc.
The base that in the alkyl be defined described in " aralkyl " expression, one or more hydrogen atom is replaced by aryl, can also represent the group replaced by specified substituent as described below.Can exemplified by benzyl, diphenyl-methyl and trityl etc.
" alkynyl " expression has one or more carbon-to-carbon triple bond and carbonatoms is 2 ~ 20, is preferably 2 ~ 10, is more preferably the straight or branched type monovalence hydrocarbon position of 2 ~ 6.Described alkynyl is combined by the carbon atom or saturated carbon atom with carbon-to-carbon triple bond.Alkynyl can also represent the group replaced by specified substituent as described below.Ethynyl and proyl etc. can be exemplified.
" alkylidene group " represents that carbonatoms is 1 ~ 20, is preferably 1 ~ 10, is more preferably the straight or branched type saturated divalent hydrocarbon position of 1 ~ 6.Described alkylidene group can also represent the group replaced by certain substituting group described later.Alkylidene group can exemplify methylene radical, ethylidene, propylidene, butylidene, hexylidene etc.
" alkenylene " expression has one or more carbon-to-carbon double bond and carbonatoms is 2 ~ 20, is preferably 2 ~ 10, is more preferably the straight or branched type divalent hydrocarbon position of 2 ~ 6.Described alkenylene by there is carbon-to-carbon double bond carbon atom and/or saturated carbon atom combined.Alkenylene can also represent the group replaced by specified substituent as described below.
" sub-cyclic hydrocarbon radical " representative ring carbon atom is the saturated or monocyclic, bicyclic or tricyclic hydrocarbon position of unsaturated non-aromatic divalent of 3 ~ 12, can also represent the group replaced by specified substituent as described below.Cyclopropylene, cyclobutene etc. can be exemplified.
" arylidene " represents to have 6 ~ 20, preferably has the monocyclic, bicyclic or tricyclic aromatic hydrocarbon position of divalent of 6 ~ 12 annular atomses, can also represent the group replaced by specified substituent as described below.Aromatic fractions only comprises carbon atom.Arylidene can exemplify phenylene etc.
" sub-aralkyl " represents the divalent position that in described alkyl, one or more hydrogen atom is replaced by aryl, can also represent the group replaced by specified substituent as described below.Benzylidene etc. can be exemplified.
" alkynylene " expression has one or more carbon-to-carbon triple bond and carbonatoms is 2 ~ 20, is preferably 2 ~ 10, is more preferably the straight or branched type divalent hydrocarbon position of 2 ~ 6.Described alkynylene is combined by the carbon atom or saturated carbon atom with carbon-to-carbon triple bond.Alkynylene can also represent the group replaced by specified substituent as described below.Ethynylene or propine support (propynylene) etc. can be exemplified.
In above-mentioned explanation, substituting group ＂ replaces or does not replace ＂ and not only refer to each substituting group itself, also refers to further by the group of certain substituting group replacement.In this specification sheets, the substituting group that can be substituted further such as has halogen, alkyl, thiazolinyl, alkynyl, alkylhalide group, haloalkenyl, alkynyl halide, aryl, halogen aryl, aralkyl, halogen aralkyl, alkoxyl group, halogen alkoxyl group, carbonyl oxygen base, halogen carbonyl oxygen base, aryloxy, halogen aryloxy, silylation or siloxy etc.
Described photoreactive polymer, under the polarisation with about 150 ~ 450nm wavelength exposes, can show its photoreactivity.Such as, can about 200 ~ 400nm wavelength be had, under more specifically the polarisation of about 250 ~ 370nm wavelength exposes, show its photoreactivity.From general only under the intact of short wavelength range ultraviolet (UV) the photoreactivity functional group of display light other kinds reactive different, the photoreactivity functional group comprised in the repeating unit represented by described chemical formula 3 or 4, namely the azo functional group represented by chemical formula 1a ~ 1c, to belonging to visible-range or also showing excellent photoreactivity and photoresponse speed fast close to long wavelength's polarisation of its scope.Accordingly, use conventional i-line light source, described photoreactive polymer and the oriented layer comprising this polymkeric substance also can show excellent light utilization efficiency.This is because conventional lighting sources such as described i-line, although belong to visible ray also can send the light close to visible wavelength accounting for considerable part.That is, when using described photoreactive polymer, the visible ray that sent by this light source can be utilized and carry out photoresponse and orientation close to the light of visible wavelength, therefore can further improve light utilization efficiency.And then, when described photoreactive polymer comprises the repeating unit represented by chemical formula 2a or 2b with cinnamate derivative photoreactivity functional group further, the light of the broader area sent by light source can be utilized to carry out photoresponse and orientation, thus further can improve light utilization efficiency.
In sum, described photoreactive polymer under polarisation in the wavelength region of about 150 ~ 450nm exposes, can show excellent photoreactivity and photoresponse speed fast.More specifically, the light in use about 150 ~ 450nm wavelength region is with 50 ~ 900mJ/cm 2energy, preferably with 50 ~ 500mJ/cm 2energy exposure described in photoreactive polymer time, the stretch mode intensity of the C=C key comprised in described chemical formula 1a ~ 1c reaches the time (t till initial value half 1/2) be about less than 1.5 minutes, be more specifically 1 ~ 1.5 minute, show fast photoresponse speed.
On the other hand, a kind of preparation method of described photoreactive polymer is provided according to another embodiment of the present invention.One embodiment of described preparation method comprises, under the catalyst composition comprising pre-catalyst and the promotor with the 10th race's transition metal exists, and the monomer that addition polymerization is represented by chemical formula 1 and form the step of the repeating unit represented by chemical formula 3.
[chemical formula 1]
In described chemical formula 1, p, R 1, R 2, R 3and R 4as chemical formula 3 define.
Now, described polyreaction can be carried out at 10 DEG C ~ 200 DEG C temperature.If described temperature of reaction is lower than 10 DEG C, can polymerization activity be reduced, if higher than 200 DEG C, then can make catalyst decomposes, therefore inadvisable.
And, described promotor can comprise be selected from by for provide can with the first promotor of the weak complex bound Lewis base of the metal of described pre-catalyst; And for provide the second promotor of the compound containing the 15th race's electron donor ligand to form group at least one.Preferably, described promotor can use the first promotor comprising and provide described Lewis base, and provides the catalyst mixture of the second promotor of the compound selectively containing neutral 15th race's electron donor ligand.
Now, described catalyst mixture, relative to the described pre-catalyst of 1mol, can comprise described first promotor of 1 ~ 1000mol, and described second promotor of 1 ~ 1000mol.If the content of the first promotor or the second promotor is too low, likely normally cannot play catalyst activity, if content is excessive, the activity decrease of catalyzer can be made on the contrary.
In addition, the described pre-catalyst comprising the 10th transition metal can use to have and be easy to participate in Lewis acid-alkali reaction, thus the compound with Lewis base functional group departed from by central metal, thus make this pre-catalyst by providing that the first promotor of Lewis base is easily separated and the center transition metal of making is converted into catalyst activity kind.Such as have [(Allyl) Pd (Cl)] 2(Allyl palladium chloride dimer), (CH 3cO 2) 2pd [Palladium (II) acetate], [CH 3cOCH=C (O-) CH 3] 2pd [Palladium (II) acetylacetonate], NiBr (NP (CH 3) 3) 4, [PdCl (NB) O (CH 3)] 2deng.
In addition, there is provided first promotor that can carry out weak complex bound Lewis base with the metal of described pre-catalyst can use the room being easy to react with Lewis base to form transition metal, and in order to the stable transition metal so formed, and excessive metallic compound carries out weak complex bound compound or provides the compound of this transition metal.Such as there is B (C 6f 5) 3deng boric acid ester, methylaluminoxane (MAO) or Al (C such as borine, xylidine four (pentafluorophenyl group) boric acid esters (dimethylanilinium tetrakis (pentafluorophenyl) borate) 2h 5) 3deng aluminum alkyls, or AgSbF 6etc. transition metal halogenide etc.
In addition, described second promotor of the compound containing neutral 15th race's electron donor ligand is provided can to use alkylphosphines, cyclic hydrocarbon radical phosphorus or phosphniline etc.
In addition, can be used alone described first promotor and the second promotor, after also two kinds of promotors can being made a kind of salt, uses as the compound for deactivated catalyst.Such as, ionic bond alkylphosphines and borine or boric acid ester compound is used and the compound that generates.
The photoreactive polymer of the repeating unit represented by chemical formula 3 and the embodiment comprising this repeating unit can be prepared by aforesaid method.And, also can be prepared the repeating unit represented by chemical formula 2a by this preparation method, also can form the photoreactive polymer of the multipolymer form comprising the repeating unit represented by chemical formula 3 and/or 2a thus.
On the other hand, photoreactive polymer comprises the repeating unit represented by chemical formula 4, or when comprising the repeating unit represented by chemical formula 2b selectively, can according to described preparation method's preparation of another embodiment.The preparation method of another embodiment this comprises: have under the 4th race, the pre-catalyst of the 6th race or the 8th race's transition metal and the catalyst composition of promotor exist comprising, the monomer that ring-opening polymerization is represented by described chemical formula 1 and form the step of the repeating unit represented by chemical formula 4.
In described ring-opening polymerization step, hydrogenation in the double bond in the norbornylene basic ring that the monomer represented by described chemical formula 1 comprises and carry out open loop and polymerization, prepares the repeating unit represented by described chemical formula 4 and the photoreactive polymer comprising this repeating unit.In addition, this preparation method is also applicable to the preparation of the repeating unit represented by chemical formula 2b and the photoreactive polymer comprising this repeating unit.
Described ring-opening polymerization, can at the pre-catalyst containing the 4th race (such as Ti, Zr, Hf), the 6th race (such as Mo, W) or the 8th race (such as Ru, Os) transition metal; There is provided and can carry out the promotor of weak complex bound Lewis base with the metal of described pre-catalyst; And the catalyst mixture of the composition such as the activator (activator) containing neutral 15th race and the 16th race's element that can strengthen described procatalyst metal active selectively exist under carry out.And, under described catalyst mixture exists, the normal olefine (linearalkene) such as 1-alkene, 2-alkene of the adjustable molecular size range of 1 ~ 100mol% is added based on monomer content, be polymerized in 10 DEG C ~ 200 DEG C temperature ranges, and add the catalyzer containing the 4th race (such as Ti, Zr) or the 8th race ~ the 10th race (such as Ru, Ni, Pd) transition metal of 1 ~ 30 % by weight based on monomer content, in 10 DEG C ~ 250 DEG C temperature ranges, carry out the hydrogenation reaction in the double bond in norbornylene basic ring.
If described temperature of reaction is too low, can polymerization activity be reduced, if too high, can catalyst decomposes be made, therefore inadvisable.And, if described hydrogenation reaction temperature is too low, the activity of hydrogenation reaction can be reduced, if too high, can catalyst decomposes be made, therefore inadvisable.
Described catalyst mixture is relative to the pre-catalyst containing the 4th race (such as Ti, Zr, Hf), the 6th race (such as Mo, W) or the 8th race (such as Ru, Os) transition metal of 1mol, thering is provided of 1 ~ 100,000mol is provided and can carries out the promotor of weak complex bound Lewis base with the metal of described pre-catalyst; And the activator (activator) containing neutral 15th race and the 16th race's element that can strengthen pre-catalyst metal active selectively of 1 ~ 100mol.
When the content of described promotor is lower than 1mol, catalyzer loses activity, and when content is more than 100,000mol, can reduce the activity of catalyzer, therefore inadvisable.According to the kind of pre-catalyst, or without the need to using described activator.When the content of activator is lower than 1mol, catalyzer loses activity, and during more than 100mol, can reduce molecular weight, therefore inadvisable.
What hydrogenation reaction used contains the 4th race (such as, Ti, Zr) or the 8th race ~ the 10th race is (such as, Ru, Ni, Pd) transition metal catalyzer content relative in monomer content lower than 1 % by weight time, hydrogenation reaction is insufficient, polymer discoloration when its content is more than 30 % by weight, therefore inadvisable.
Containing described 4th race (such as, Ti, Zr, Hf), the 6th race (such as, Mo, W) or the 8th race is (such as, Ru, Os) pre-catalyst of transition metal, can use have be easy to participate in Lewis acid-alkali reaction and the functional group that departs from central metal as TiCl 4, WCl 6, MoCl 5or the excessive metallic compound such as RuCl3 and ZrCl4, make by providing lewis acidic promotor easily to depart from, thus the center transition metal of making is converted into catalyst activity kind.
In addition, provide and can carry out the promotor of weak complex bound Lewis base with the metal of described pre-catalyst, can use as B (C 6f 5) 3deng borine or boric acid ester, methylaluminoxane (MAO) or Al (C 2h 5) 3or Al (CH 3) Cl 2in aluminum alkyls, halogenated aluminum, haloalkyl aluminium.Or replace aluminium can use the replacement such as lithium (lithium), magnesium (magnesium), germanium (germanium), lead, zinc, tin, silicon.This promotor can comprise, and is easy to react with Lewis base and form the room of transition metal, and in order to the stable transition metal that generates thus with the weak complex bound compound of excessive metallic compound or the compound that this transition metal is provided.
Can activator be added in polymerization, but according to the kind of procatalyst or without the need to using activator.The activator (activator) containing neutral 15th race and the 16th race's element that can strengthen described procatalyst metal active has, water, methyl alcohol, ethanol, Virahol, phenylcarbinol, phenol, sulfur alcohol (ethylmercaptan), ethylene chlorhydrin, Trimethylamine 99, triethylamine, pyridine (pyridine), oxyethane (ethyleneoxide), benzoyl peroxide (benzoylperoxide), tert-butyl peroxide (t-butylperoxide) etc.
What use in hydrogenation reaction contains the 4th race (such as, Ti, Zr) or the 8th race ~ the 10th race is (such as, Ru, Ni, Pd) catalyzer of transition metal is homogeneous (homogeneous) shape that at once can be dissolved in solvent, or described metal catalyst coordination compound is carried on the catalyzer on particle carrier.Described particle carrier, preferred silicon-dioxide, titanium dioxide, silicon-dioxide/chromic oxide, silicon-dioxide/chromic oxide/titanium dioxide, silica/alumina, phosphaljel, silylanizing silica, silica-alumina hydrogel, illiteracy take off clay or zeolite.
The photoreactive polymer of the repeating unit represented by chemical formula 4 and another embodiment comprising this repeating unit can be prepared by aforesaid method.And, the repeating unit represented by chemical formula 2b can be prepared by this preparation method, also can form the photoreactive polymer of the polymer form comprising the repeating unit represented by chemical formula 4 and/or 2b thus.
On the other hand, a kind of oriented layer comprising described photoreactive polymer is provided according to still another embodiment of the invention.Described oriented layer, except comprising form of film, also can comprise the oriented layer of film forms.A kind of liquid crystal retardation film of the liquid crystal layer comprised in described oriented layer and oriented layer is provided according to still another embodiment of the invention.
Except comprising the photoreactive polymer as light orientated polymer, material as known in the art and preparation method can be used to prepare described oriented layer and liquid crystal retardation film.
Such as, mix described photoreactive polymer, adhesive resin and light trigger, and dissolve in organic solvent, after obtaining coating composition, its coating composition is coated on substrate, solidify to form described oriented layer through UV.
Now, described adhesive resin can use acrylate resinoid, can use pentaerythritol triacrylate, double pentaerythritol methacrylate, Viscoat 295, triol (2-acrylyl oxy-ethyl) chlorinated isocyanurates etc. particularly.Described light trigger can use the known Conventional photoinitiators that can be used in oriented layer and be not particularly limited.Such as, known commodity can be used to be called Irgacure907, the light trigger of 819.
In addition, described organic solvent can use toluene, methyl-phenoxide, chlorobenzene, ethylene dichloride, hexanaphthene, pentamethylene, 1-Methoxy-2-propyl acetate etc.Because described photoreactivity norbornylene analog copolymer shows excellent solubleness to most of organic solvent, so be not particularly limited this, various organic solvent can be used.
In described coating composition, the concentration comprising the solid powder of described photoreactive polymer, adhesive resin and light trigger is 1 ~ 15 % by weight, and in order to described oriented layer of casting with film forms, is preferably 10 ~ 15 % by weight, and in order to be formed in the form of a film, be preferably 1 ~ 5 % by weight.
The oriented layer of formation like this can be formed on substrate, and is formed in below liquid crystal to play the effect of orientation.Now, described substrate can use comprise cyclic polymer substrate, comprise the substrate of acrylate copolymer or comprise the substrate etc. of cellulose polymer compound, and use the methods such as scraper coating, rotary coating, scraper plate coating, after being coated with described coating composition over the substrate, be solidified to form oriented layer through UV.
In described UV solidification process, light orientation may occur, can illumination wavelength scope be that the polarization UV of about 150 ~ 450nm is to carry out orientation process in this step.Now, exposure energy is about 50mJ/cm 2~ 10J/cm 2, preferably about 500mJ/cm 2~ 5J/cm 2.
Described UV is applicable be selected from by make UV through or reflect in 1. utilizing silica glass, soda-lime glass, being coated with the polarising means of the substrate of dielectric anisotropy material without transparency carriers such as soda-lime glasss on the surface; 2. the polarization plates of precision deposition aluminium or metal wire; Or the polarization UV 3. carried out based on the method for Brewster (Brewster) polarising means etc. of silica glass reflection in the UV of polarization manipulation.
Substrate temperature when irradiating described UV is preferably normal temperature.But if desired, can base plate heating be irradiated UV under the state in less than 100 DEG C temperature ranges.The thickness of the coating formed by described a series of process is preferably 30 ~ 1000nm.
Form oriented layer by aforesaid method, form liquid crystal layer in the above, thus prepare liquid crystal retardation film in conventional manner.
Above-mentioned oriented layer or liquid crystal retardation film are also applicable to the optical film or optical filter that represent stereopsis.
A kind of display device comprising described oriented layer is provided according to still another embodiment of the invention.This display device can be applicable to, and comprises the liquid-crystal display of described oriented layer in order to liquid crystal aligning, or for comprising the dimensional image display etc. of described oriented layer in the optical film that represents stereopsis or wave filter.The structure of these display devices is except comprising described photoreactive polymer and oriented layer this point, and its structure is as the criterion with the structure of conventional device, and therefore description is omitted.
In order to help to understand the present invention, preferred embodiment is proposed below.But following examples are only used to schematically represent the present invention, only the present invention can not be limited with it.
In the examples below, relate to and all use standard Shu Lunke technology (standard Schlenk technique) or dry box method (dry box method) to implement to all operations of the compound of air or water sensitive.Nucleus magnetic resonance (NMR) spectrum obtains by using Brooker 300 spectrometer (Bruker 300spectrometer), now 1h NMR under 300MHz, and 13c NMR detects respectively under 75MHz.The molecular weight and molecualr weight distribution of open loop hydrogenated polymers detects, now using polystyrene (poly styrene) sample as standard by using GPC (gel permeationchromato graphy).Toluene is by potassium/benzophenone (potassium/benzo phenone) distillatory refining, and methylene dichloride is by CaH 2distillatory refining.
< embodiment 1>: polymerization
In 250mL Shu Lunke (Schlenk) flask, add the 1.26g (3mmol) as monomer with the 3mL toluene by solvent refined.Then, in this flask, the 6.73 ㎎ Pd (OAc) being dissolved in 1mL methylene dichloride are added as catalyzer 2with 7.76mg tricyclohexyl phosphine, 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (dimethylanilinium tetrakiss (pentafluorophenyl) borate) is added, stirring reaction 18 hours at 90 DEG C of temperature as promotor.
React after 18 hours, described reactant is put into excessive ethanol and obtains whit e polymer precipitate thing.Use glass funnel to filter this throw out, with collected polymer, the polymkeric substance collected is obtained 1.19g polymkeric substance (Mw=31,000 in dry 24 hours in 60 DEG C of vacuum drying ovens; PDI=1.7; Productive rate=94%).By the 1HNMR data representation of polymkeric substance obtained in embodiment 1 in FIG.
< embodiment 2>: polymerization
In 250mL schlenk flask, add the 3.0g (6.69mmol) as monomer with the 4mL toluene by solvent refined.Then in this flask, 0.75 ㎎ Pd (OAc) 2 and the 0.86mg tricyclohexyl phosphine being dissolved in 1mL methylene dichloride is added as catalyzer, 0.72mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate is added, stirring reaction 18 hours at 90 DEG C of temperature as promotor.
React after 18 hours, described reactant is put into excessive ethanol and obtains whit e polymer precipitate thing.Use glass funnel to filter this throw out, with collected polymer, and this polymkeric substance collected is obtained 2.55g polymkeric substance (Mw=56,000 in dry 24 hours in 60 DEG C of vacuum drying ovens; PDI=1.9; Productive rate=85%).
< embodiment 3>: with copolymerization
In 250mL schlenk flask, add the 0.628g (1.5mmol) as monomer , 0.249g (1.5mmol) with the 3mL toluene by solvent refined.Then in this flask, 6.73 ㎎ Pd (OAc) 2 and the 7.76mg tricyclohexyl phosphines being dissolved in 1mL methylene dichloride are added as catalyzer, 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate is added, stirring reaction 18 hours at 90 DEG C of temperature as promotor.
React after 18 hours, described reactant is put into excessive ethanol and obtains whit e polymer precipitate thing.Use glass funnel to filter this throw out, with collected polymer, and within 24 hours, obtain 0.75g multipolymer (Mw=29,000 by dry in 60 DEG C of vacuum drying ovens for the polymkeric substance collected; PDI=2.1; Productive rate=86%).
< embodiment 4>: polymerization
In 250mL schlenk flask, add the 1.46g (3mmol) as monomer with the 3mL toluene by solvent refined.Then in this flask, 6.73 ㎎ Pd (OAc) 2 and the 7.76mg tricyclohexyl phosphines being dissolved in 1mL methylene dichloride are added as catalyzer, 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate is added, stirring reaction 18 hours at 90 DEG C of temperature as promotor.
React after 18 hours, described reactant is put into excessive ethanol and obtains yellow polymer throw out.Use glass funnel to filter this throw out, with collected polymer, and within 24 hours, obtain 0.88g multipolymer (Mw=61,000 by dry in 60 DEG C of vacuum drying ovens for the polymkeric substance collected; PDI=2.6; Productive rate=64%).
< embodiment 5>: polymerization
In 250mL Schlenk flask, add the 1.2g (3mmol) as monomer with the 3mL toluene by solvent refined.Then in this flask, 6.73 ㎎ Pd (OAc) 2 and the 7.76mg tricyclohexyl phosphines being dissolved in 1mL methylene dichloride are added as catalyzer, 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate is added, stirring reaction 18 hours at 90 DEG C of temperature as promotor.
React after 18 hours, described reactant is put into excessive ethanol and obtains yellow polymer throw out.Use glass funnel to filter this throw out, with collected polymer, and within 24 hours, obtain 1.06g multipolymer (Mw=47,000 by dry in 60 DEG C of vacuum drying ovens for the polymkeric substance collected; PDI=3.5; Productive rate=51%).
The ring-opening polymerization (ring opening methathesispolymerization) of < embodiment 6>:5-norbornylene-2-methyl alcohol and hydrogenation reaction (hydrogenation)
Under Ar atmosphere, in 250ml Schlenk flask, after adding 6.20g (50mmol) 5-norbornylene-2-methyl alcohol, then add the 34g toluene by solvent refined.Under the state this flask being remained on polymerization temperature 80 DEG C, first add 11.4mg (1.0mmol) triethyl aluminum (triethylaluminum) as promotor.Then 0.01M (mol/L) the toluene solution 1ml (0.01mmol WCl8,0.03mmol ethanol) being mixed with tungsten hexachloride (WCl8) and ethanol with the ratio of 1:3 is added.After finally adding 0.84g (7.5mmol) the 1-octene as molecular weight adjusting agent, stirring reaction 18 hours at 80 DEG C of temperature.After reaction terminates, in polymer fluid, instill a small amount of polymerization terminator ethyl vinyl ether (ethyl vinyl ether) and stir 5 minutes.
Described polymer fluid is transferred in 300mL high-pressure reactor, adds 0.06mL triethyl aluminum (TEA).Then, after adding 0.50g Grace Raney's nickel (grace raney Nickel) (the slurry phase in water), hydrogen pressure is remained on 80atm, and at 150 DEG C of temperature stirring reaction 2 hours.After reaction terminates, polymer fluid is instilled in acetone and carry out precipitating rear filtration, and in 70 DEG C of vacuum drying ovens dry 15 hours.Open loop hydrogenated polymers (ring-opened hydrogenated polymer) (productive rate=90.6% of obtained 5.62g 5-norbornylene-2-methyl alcohol; Mw=69,900; PDI=4.92).
< embodiment 7>: the synthesis of open loop hydrogenated polymers
In 250mL2-wide neck flask (neck flask), add the hydrogenated polymers (15g of 5-norbornylene-2-methyl alcohol obtained in embodiment 6,0.121mol), triethylamine (Aldrich, 61.2g, 0.605mol), after 50mlTHF, the ice-stirred in water bath of 0 DEG C.Make (32.5g, 0.133mol) 60ml be dissolved in after in THF, slowly put into another flask.18 hours are stirred again after temperature of charge being brought up to normal temperature after 10 minutes.Use diluted ethyl acetate solution, use separating funnel shift and use water and NaHCO 3reaction solution for several times, then instills in acetone and precipitate and filter by cleaning, and in 70 DEG C of vacuum drying ovens drying 15 hours (productive rates: 93%).
< embodiment 8>: with copolymerization
In 250mL Schlenk flask, add the 0.674g (1.5mmol) as monomer with 0.43g (1.5mmol) and with the 3mL toluene of solvent refined.Then, in this flask, add as catalyzer and be dissolved in 1mL methylene dichloride 26.73 ㎎ Pd (OAc) and 7.76mg tricyclohexyl phosphines, add 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate as promotor, stirring reaction 18 hours at 90 DEG C of temperature.
React after 18 hours, described reactant is put into excessive ethanol and obtains yellow polymer throw out.Use glass funnel to filter this throw out, with collected polymer, and within 24 hours, obtain 0.91g multipolymer (Mw=92,000 by dry in 60 DEG C of vacuum drying ovens for the polymkeric substance collected; PDI=2.96; Productive rate=82%).
< comparative example 1>: with copolymerization
In 250mL Schlenk flask, add the 0.251g (0.6mmol) as monomer with 0.398g (2.4mmol) and with the 3mL toluene of solvent refined.Then, in this flask, the 6.73 ㎎ Pd (OAc) being dissolved in 1mL methylene dichloride are added as catalyzer 2with 7.76mg tricyclohexyl phosphine, add 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate as promotor, stirring reaction 18 hours at 90 DEG C of temperature.
React after 18 hours, described reactant is put in excessive ethanol and obtains whit e polymer precipitate thing.Use glass funnel to filter this throw out, with collected polymer, and within 24 hours, obtain 0.53g multipolymer (Mw=26,000 by dry in 60 DEG C of vacuum drying ovens for the polymkeric substance collected; PDI=1.88; Productive rate=82%).By the 1HNMR data representation of the polymkeric substance of comparative example 1 in fig. 2.
< preparation example 1>: use the polymkeric substance of embodiment 1 to prepare oriented layer
By what synthesize in the described embodiment 1 of use the photoreactive polymer of monomer, concentration with 2 % by weight is dissolved in c-pentanone (c-pentanone) solvent, polyethyleneterephthalate (the trade(brand)name: SH71 that thickness is 80 microns is coated on rolling method, SKC company of Korea S produces) on substrate, dried thickness reaches then, heat 3 minutes in 80 DEG C of baking ovens, to remove coated film internal solvent, thus form coated film.
Exposure light source adopts intensity to be 200mW/cm 2high voltage mercury lamp, and wiregrating (Wire-grid) polarizer using Moxtek company to manufacture, obtains the UV with film orientation vertical polarization, obtains liquid crystal arrangement second, to form oriented layer by this light source irradiation coated film 5.
Then, by using 95.0 % by weight UV polymerizability cyanobiphenyl base acrylate and be mixed with the solid powder of 5.0 % by weight gorgeous good solid 907 (productions of Ciba-Geigy company of Switzerland) as light trigger, be dissolved in toluene solvant, to make to reach 25 weight parts relative to the liquid crystal content of the liquid crystal solution of 100 weight, thus obtained polymerisable reactive liquid crystalline solution.
Be coated in described established light redirecting layer by obtained liquid crystal solution with roller coating method, until dried thickness reaches 1 μm, at 80 DEG C of temperature, drying makes liquid crystal molecule be able to orientation in 2 minutes afterwards.Be 200mW/cm by intensity 2high voltage mercury lamp as the unpolarized UV of light source, irradiate the liquid crystal film arranged, with fixing liquid crystal state of orientation, thus obtained phase shift films.
For the orientation of above-mentioned obtained phase shift films, measure light leak between polarization plates with printing opacity instrument (transmittance) and compare, and use Axoscan (manufacture of Axomatrix company) to have detected quantitative phase difference.
< compares preparation example 1>
Except replacing use in embodiment 1 pure 100% the photoreactive polymer of monomer-polymer, uses monomer ratio with outside the multipolymer of=2:8 (adding the mol ratio of monomer), prepare oriented layer with preparation example 1 same procedure.
< test example 1>
Photoreactivity evaluates-FT-IR spectrum
For the photoreactive evaluation of oriented layer, observe the FT-IR spectrum of preparation example 1 ~ compare liquid crystal aligning layer obtained in preparation example 1, so that (use has 20mW/cm in exposure 2the mercury lamp of intensity) under described chemical formula 1a ~ 1c polymkeric substance in the intensity of C=C key stretch mode reach time (t till initial value half 1/2) and Energy Conversion value (E 1/2=20mW/cm 2× t 1/2) evaluate as benchmark.Its result represents in table 1 below.
Relatively t 1/2known, with the t comparing preparation example 1 1/2compare, the t of preparation example 1 1/2shorten about more than 1/2, can confirm the polymkeric substance using embodiment thus, the speed of orientation of liquid crystal aligning layer is faster.
[table 1]
< test example 2>
Orientation evaluates (light leak degree evaluation)
For the evaluation of oriented layer orientation, use polarizing microscope between arranged perpendicular two polarizers, observe preparation example 1 and compare liquid crystal retardation film obtained in preparation example 1.Namely, with the polyethyleneterephthalate (trade(brand)name: SH71 of thickness 80 microns, SKC company of Korea S produces) as benchmark, between the polarizer of arranged perpendicular, after putting into preparation example 1 and comparing the obtained liquid crystal retardation film of preparation example 1, observe the degree of irradiating light transmission polarization plates and phase shift films with polarizing microscope, measure light leak degree with this.Its liquid crystal aligning of the phase shift films of preparation example 1 is not by the impact of lambda1-wavelength, and differently-oriented directivity is even, and when the oriented layer of preparation example 1 is compared in use, alignment capability declines, and causes liquid crystal aligning direction uneven.
< test example 3>
The photoreactive polymer of synthesis in embodiment 1 is used to test anisotropy and UV reactivity.By dissolving the 2wt% pentamethylene solution of described polymkeric substance, be spin-coated on after on silicon chip with 1000rpm speed, drying 1 minute in the baking oven of 80 degree.Working strength is the UV by UV lamp (level 82%) polarization of 15mW/cm2, irradiates about 60 seconds (with 365nm standard, 0.9J/cm2 energy exposure), observes its change.Its result represents in figure 3.With reference to Fig. 3, after confirming polarized UV radiation, form anisotropy.When the placement direction of sample is vertical with polarized UV radiation direction, large light absorption ratio (absorbance) value is more beaten in display compared with time parallel, it can thus be appreciated that form anisotropy along the vertical direction of polarization UV.In addition, known by these tests, the photoreactive polymer of embodiment, not easily shows the polarized light of its photoreactive 365nm long wavelength to photoreactive polymer in the past, also shows excellent photoreactivity.
Photoreactive polymer according to the present invention comprises the high norbornylene class repeating unit of second-order transition temperature as predominant repeat unit, therefore can show excellent thermostability.And described photoreactive polymer comprises the relatively many norbornylene class repeating units containing specific azo photoreactivity functional group of content, therefore not only significantly improves photoresponse speed, and shows excellent orientation and light utilization efficiency.
Therefore, use described photoreactive polymer, the oriented layer and liquid crystal retardation film etc. with excellent specific property can be provided, significantly can also improve process efficiency.

Claims (7)

1. a photoreactive polymer, is characterized in that, comprises more than 50mol% that content is total polymer and is less than the repeating unit represented by following chemical formula 3 or 4 of 100mol%: with
Content be total polymer be greater than 0mol% and the repeating unit represented by following chemical formula 2a or 2b of below 50mol%:
In chemical formula 3 or 4, n to be 50 ~ 5000, p be 0 ~ 4 integer,
R 1, R 2, R 3and R 4in at least one be selected from the group in the group that is made up of following chemical formula 1a, 1b and 1c,
Remaining R 1, R 2, R 3and R 4separately be selected from by hydrogen; Halogen; Substituted or unsubstituted C1 ~ C20 alkyl; Substituted or unsubstituted C2 ~ 20 thiazolinyl; Substituted or unsubstituted C2 ~ 20 alkynyl, substituted or unsubstituted C3 ~ 12 cyclic hydrocarbon radical; The aryl of substituted or unsubstituted C6 ~ 40; And in the group that forms of the polar functional group comprising at least one be selected from oxygen, nitrogen phosphate and sulfur, silicon and boron,
Wherein, as described R 1~ R 4when not being all hydrogen, halogen or polar functional group, R 1and R 2or R 3and R 4be interconnected and form the alkylidene of C1 ~ C10, or R 1or R 2with R 3and R 4in one connect and form the saturated of C4 ~ C12 or undersaturated ring or form the aromatic ring of C6 ~ C24,
In described chemical formula 1a, 1b or 1c, n1, p1, r1 and m1 are the integer of 0 ~ 4, and n2, p2, r2 and m2 are the integer of 0 ~ 5,
A is substituted or unsubstituted C1 ~ C20 alkylidene group, carbonyl ,-COO-, substituted or unsubstituted C6 ~ C40 arylidene or singly-bound,
B is oxygen, sulphur ,-NH-or singly-bound,
R 9for the sub-aralkyl of the sub-cyclic hydrocarbon radical of the alkynylene of the alkenylene of the alkylidene group of singly-bound, substituted or unsubstituted C1 ~ C20, substituted or unsubstituted C2 ~ C20, substituted or unsubstituted C2 ~ C20, substituted or unsubstituted C3 ~ C12, the arylidene of substituted or unsubstituted C6 ~ C40 or substituted or unsubstituted C7 ~ C15
R 10and R 11be hydrogen, halogen, substituted or unsubstituted C1 ~ C20 alkyl, substituted or unsubstituted C1 ~ C20 alkoxyl group, the aryloxy of substituted or unsubstituted C6 ~ C30 or substituted or unsubstituted C6 ~ C40 aryl independently;
In described chemical formula 2a or 2b, m to be 50 ~ 5000, q' be 0 ~ 4 integer,
R 1', R 2', R 3' and R 4' be separately selected from the group represented by chemical formula 2c; Hydrogen; Halogen; Substituted or unsubstituted C1 ~ C20 alkyl; Substituted or unsubstituted C2 ~ C20 thiazolinyl; Substituted or unsubstituted C2 ~ C20 alkynyl; Substituted or unsubstituted C3 ~ C12 cyclic hydrocarbon radical; Substituted or unsubstituted C6 ~ C40 aryl; And in the group that forms of the polar functional group comprising at least one be selected from oxygen, nitrogen phosphate and sulfur, silicon and boron,
Wherein, as described R 1' ~ R 4' when not being all hydrogen, halogen or polar functional group, R 1' and R 2' or R 3' and R 4' be interconnected and form the alkylidene of C1 ~ C10, or R 1' or R 2' and R 3' and R 4' in one connect and form the saturated of C4 ~ C12 or unsaturated ring or form the aromatic ring of C6 ~ C24,
In described chemical formula 2c, L is 0 or 1,
D and D' is separately selected from the group be made up of the straight chain of singly-bound, nitrogen, oxygen, sulphur, substituted or unsubstituted C1 ~ C20 or branched chain type alkylidene group, the sub-cyclic hydrocarbon radical of substituted or unsubstituted C3 ~ C12 and substituted or unsubstituted C3 ~ C12 sub-cyclic hydrocarbon radical oxygen base
X and Y is separately selected from the group be made up of the straight chain of hydrogen, halogen, cyanogen and substituted or unsubstituted C1 ~ C20 or branch chain type alkyl,
R 10' ~ R 14' be separately selected from by hydrogen; Halogen; Cyanogen; Substituted or unsubstituted C1 ~ C20 alkyl; Substituted or unsubstituted C1 ~ C20 alkoxyl group; Substituted or unsubstituted C6 ~ C30 aryloxy; Substituted or unsubstituted C6 ~ C40 aryl; Comprise the heteroaryl of the 14th race, the 15th race, the 16th heteroatomic C6 ~ C40 of race; And in the group that forms of the alkoxy aryl of substituted or unsubstituted C6 ~ C40.
2. photoreactive polymer according to claim 1, is characterized in that:
R 1', R 2', R 3' and R 4' at least one be the group represented by chemical formula 2c.
3. photoreactive polymer according to claim 1, is characterized in that, described polar functional group is selected from the group be made up of following functional group:
-R 5OR 6、-OR 6、-OC(O)OR 6、-R 5OC(O)OR 6、-C(O)OR 6、-R 5C(O)OR 6、-C(O)R 6、-R 5C(O)R 6、-OC(O)R 6、-R 5OC(O)R 6、-(R 5O) r-OR 6、-(OR 5) r-OR 6、-C(O)-O-C(O)R 6、-R 5C(O)-O-C(O)R 6、-SR 6、-R 5SR 6、-SSR 6、-R 5SSR 6、-S(＝O)R 6、-R 5S(＝O)R 6、-R 5C(＝S)R 6-、-R 5C(＝S)SR 6、-R5SO 3R 6、-SO 3R 6、-R 5N＝C＝S、-N＝C＝S、-NCO、-R 5-NCO、-CN、-R 5CN、-NNC(＝S)R 6、-R 5NNC(＝S)R 6、-NO 2、-R 5NO 2；
In above-mentioned each functional group, r is the integer of 1 ~ 10, R 5for substituted or unsubstituted C1 ~ C20 alkylidene group, substituted or unsubstituted C2 ~ C20 alkenylene, substituted or unsubstituted C2 ~ C20 alkynylene, the sub-cyclic hydrocarbon radical of substituted or unsubstituted C3 ~ C12, substituted or unsubstituted C6 ~ 40 arylidene, the sub-carbonyl oxygen base of substituted or unsubstituted C1 ~ C20 or substituted or unsubstituted C1 ~ C20 alkylene oxide group
R 6, R 7and R 8be selected from by hydrogen; In the group that the carbonyl oxygen base of halogen, substituted or unsubstituted C1 ~ C20 alkyl, substituted or unsubstituted C2 ~ C20 thiazolinyl, substituted or unsubstituted C2 ~ C20 alkynyl, substituted or unsubstituted C3 ~ C12 cyclic hydrocarbon radical, substituted or unsubstituted C6 ~ C40 aryl, substituted or unsubstituted C1 ~ C20 alkoxyl group and substituted or unsubstituted C1 ~ C20 forms.
4. photoreactive polymer according to claim 1, is characterized in that:
Under the polarizing light irradiation with 150 ~ 450nm wavelength, show photoreactivity.
5. an oriented layer, is characterized in that, comprises the photoreactive polymer according to any one of Claims 1 to 4.
6. a liquid crystal retardation film, is characterized in that, comprises the liquid crystal layer in oriented layer according to claim 5 and oriented layer.
7. a display device, is characterized in that, comprises oriented layer according to claim 5.
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