CN103270135A - Stabilized electro-optic materials and electro-optic devices made therefrom - Google Patents

Stabilized electro-optic materials and electro-optic devices made therefrom Download PDF

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CN103270135A
CN103270135A CN2011800550542A CN201180055054A CN103270135A CN 103270135 A CN103270135 A CN 103270135A CN 2011800550542 A CN2011800550542 A CN 2011800550542A CN 201180055054 A CN201180055054 A CN 201180055054A CN 103270135 A CN103270135 A CN 103270135A
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electro
group
chromophore
optic polymer
aromatic
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陈宝铨
金丹良
余国民
陈晖�
黄迪允
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Brazil photoelectric products Co., Ltd.
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GigOptix Inc
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Priority claimed from US12/959,898 external-priority patent/US8618241B2/en
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    • 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
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3558—Poled materials, e.g. with periodic poling; Fabrication of domain inverted structures, e.g. for quasi-phase-matching [QPM]

Abstract

According to an embodiment, an electro-optic polymer comprises a host polymer and a guest nonlinear optical chromophore having the structure D-p-A, wherein: D is a donor, p is a p-bridge, and A is an acceptor; a bulky substituent group is covalently attached to at least one of D, p, or A; and the bulky substituent group has at least one non-covalent interaction with part of the host polymer that impedes chromophore depoling.

Description

The electrooptical material of stabilization and from the electro-optical assembly of its manufacturing
The cross reference of related application
The application requires to be called in the co-pending name that on December 3rd, 2010 submitted to the right of priority of No. the 12/959th, 898, the U.S. Patent application of STABILIZED ELECTRO-OPTIC MATERIALS AND ELECTRO-OPTIC DEVICES MADE THEREFROM.The application also requires to be called in the name that on September 15th, 2010 submitted to the benefit of priority of No. the 61/383rd, 282, the U.S. Provisional Patent Application of ELECTRO OPTIC CHROMOPHORE AND HOST POLYMER SYSTEM FOR INTEGRATED CIRCUIT COMMUNICATION.Two priority applications are incorporated into by reference with its integral body, to not with the inconsistent degree of the disclosure of this paper.
About the research of federal funding or the statement of exploitation
Invention disclosed herein is made under United States Government supports for W31P4Q-08-C-0198 number according to NRO contract NRO000-07-C-0123 number and DARPA contract.Accordingly, government can have some right of invention disclosed herein.
Background
Non-linear optical chromophore provides electric light (EO) activity in polarization (poled) the electro-optic polymer device.Electro-optic polymer a lot of years as the inorganic materials in the electro-optical assembly for example the surrogate of Lithium niobium trioxide be studied.Electro-optical assembly can comprise external modulator, RF optical electronic device and optical interconnection line of for example being used for long range communication etc.The stability of high electro-optical activity and electro-optical activity (being also referred to as " time stability ") is important for the device of viable commercial.Electro-optical activity can strengthen in electro-optic polymer by the concentration of increase non-linear optical chromophore and by the electrooptical property that increases chromophore.Yet some technology for increasing chromophore's concentration may reduce time stability.
General introduction
An embodiment is the electro-optic polymer that comprises main polymer and have the object non-linear optical chromophore of structure D-π-A, and wherein: D is donor, and π is π-bridge, and A is acceptor; Large volume substituting group group is covalently attached at least one among D, π or the A; And described large volume substituting group group has noncovalent interaction at least a and a part that hinders the unpolarized described main polymer of chromophore.
An embodiment is to comprise the non-linear optical chromophore of polarization and the electro-optic polymer of main polymer, and wherein said non-linear optical chromophore is replaced by two or more bulky group and described main polymer is configured to cooperate to hinder chromophore's depolarize with described bulky group.
An embodiment is the non-linear optical chromophore with structure D-π-A, wherein D is donor, π is π-bridge, and A is acceptor, and wherein at least one among D, π or the A covalently attached to the substituting group group that comprises the substituting group center that directly is bonded at least three aromatic yl groups.
Another embodiment is the electro-optic polymer that comprises the non-linear optical chromophore with structure D-π-A, wherein D is donor, π is π-bridge, A is acceptor, and at least one among D, π or the A covalently attached to the substituting group group that comprises the substituting group center that directly is bonded to aromatic yl group, and wherein said electro-optic polymer has than time stability big when alkyl group replaces described aromatic yl group.According to embodiment, a plurality of aromatic yl groups can directly be bonded to the substituting group center.
Another embodiment is method, comprise the polymkeric substance that comprises the non-linear optical chromophore with structure D-π-A a) is provided, wherein D is donor, π is π-bridge, A is acceptor, and among D, π or the A at least one covalently attached to the substituting group group that comprises the substituting group center that directly is bonded at least one aromatic yl group; And b) the described polymkeric substance of polarization is to form electro-optic polymer, and wherein said electro-optic polymer has than time stability big when alkyl group replaces described aromatic yl group.
Other embodiment comprises the electro-optical assembly that comprises non-linear optical chromophore and electro-optic polymer.
The accompanying drawing summary
Fig. 1 sets forth the non-linear optical chromophore according to embodiment.
Fig. 2 sets forth synthesizing according to the chromophore of embodiment.
Fig. 3 sets forth synthesizing according to the chromophore of embodiment.
Fig. 4 sets forth synthesizing according to the chromophore of embodiment.
Fig. 5 sets forth donor and is used for having synthetic schemes according to the chromophore of the donor of embodiment.
Fig. 6 sets forth the polymkeric substance according to some embodiments.
The Jonscher that Fig. 7 sets forth according to the time stability of some embodiments analyzes.
Fig. 8 sets forth the tanh model analysis according to the time stability of some embodiments.
The Jonscher that Fig. 9 sets forth according to the time stability of some embodiments analyzes.
Figure 10 sets forth the manufacturing step that is used for polymer modulator.
Figure 11 sets forth Mach refractometer and the electrode according to some embodiments.
Figure 12 sets forth the cross section that polymer modulator is piled up.
Figure 13 sets forth the long-time stability of polymer modulator.
The pi-that Figure 14 sets forth according to some embodiments interacts.
The pi-that Figure 15 sets forth according to some embodiments interacts.
Describe in detail
In the following detailed description, with reference to the accompanying drawing that forms a part that describes in detail.In the drawings, the assembly that the similar sign ordinary representation is similar is unless context illustrates in addition.Describe in detail and accompanying drawing described in illustrative embodiment be not be intended to restrictive.Under the situation of the spirit or scope that do not break away from the theme that this paper presents, other embodiment can be utilized, and other change can be made.
According to embodiment, organic chromophore comprises aryl substituent.Aryl substituent can provide the chromophore of additional space volume (steric bulk) and permission higher concentration for chromophore.Aryl substituent can also provide heat, time and/or other stability to strengthen.
An embodiment is the secondary non-linear optical chromophore with structure D-π-A, wherein D is donor, π is π-bridge, and A is acceptor, and wherein at least one among D, π or the A is covalently bound to the substituting group that comprises the substituting group center, the substituting group center is bonded directly at least two aryl, preferably on three aryl.The meaning such as the term of donor, π-bridge and acceptor; And the general synthetic method that is used to form D-π-A chromophore is known in the art, referring to for example by with reference to the United States Patent (USP) 6,716,995 of incorporating this paper into.
Donor (passes through " D " or " D in chemical structure n" expression, wherein n is integer) comprise atom or atomic group with suboxide electromotive force, wherein said atom or atomic group can provide electronics to acceptor " A " by π-bridge.Donor (D) has than the low electron affinity of acceptor (A), makes that at least when lacking external electrical field, chromophore normally polarizes, and (D) has low relatively electron density at donor.Usually, donor groups comprise have can with at least one heteroatoms of the lone-pair electron of the p-track conjugation that is directly connected to the atom on the heteroatoms, make and to obtain resonance structure, this resonance structure is shifted to lone-pair electron to have the key of the p-track of the atom that is directly connected on the heteroatoms, with formal increase heteroatoms and the multiplicity (multiplicity) that is directly connected to the key between the atom on the heteroatoms (namely, singly-bound is converted to two keys in form, or two keys are converted to triple bond in form), make heteroatoms obtain pro forma positive charge.The p-track that is directly connected to the atom on the heteroatoms can be empty or for about not being the part of the multiple bond of heteroatomic other atom.Heteroatoms can be the substituting group of atom with π key or can be in heterocycle.Exemplary donor groups includes but not limited to R 2N-_ and R nX 1-, wherein R is alkyl, aryl or heteroaryl, X 1Be O, S, P, Se or Te, and n is 1 or 2.Heteroatoms in the donor groups and the sum of carbon can be about 30, and donor groups can also be replaced by alkyl, aryl or heteroaryl.Term " donor " and " acceptor " are known in the art.Referring to, for example United States Patent (USP) the 5th, 670, and No. 091, the 5th, 679, No. 763 and the 6th, 090, No. 332.
Acceptor (passes through " A " or " A in chemical structure n" expression, wherein n is integer) comprise atom or atomic group with low reduction potential, wherein said atom or atomic group can be subjected to electronics from donor by π-bridge joint.Acceptor (A) has than the high electron affinity of donor (D), makes that at least when lacking external electrical field, chromophore normally polarizes, and (D) has high relatively electron density at acceptor.Usually, acceptor groups is included as at least one electronegative heteroatoms of the part of π key (two keys or triple bond), make and to obtain resonance structure, this resonance structure make the electron pair of π key shift to heteroatoms and the multiplicity that reduces the π key concomitantly (namely, two keys are converted to singly-bound or triple bond in form and are converted to two keys in form), make heteroatoms obtain pro forma negative charge.Heteroatoms can be the part of heterocycle.Exemplary acceptor groups includes but not limited to-NO 2,-CN ,-CHO, COR, CO 2R ,-PO (OR) 3,-SOR ,-SO 2R and-SO 3R, wherein R is alkyl, aryl or heteroaryl.Heteroatoms in the acceptor groups and the sum of carbon can be about 30, and acceptor groups can also be replaced by alkyl, aryl or heteroaryl.Term " donor " and " acceptor " are known in the art.Referring to, for example United States Patent (USP) the 5th, 670, and No. 091, the 5th, 679, No. 763 and the 6th, 090, No. 332.
" π-bridge " or " electron conjugated bridge " (passes through " π " or " π in chemical structure n" expression, wherein n is integer) comprise atom or atomic group, by described atom or atomic group, the track of electronics by the atom in the bridge from electron donor (as hereinbefore defined) delocalization to electron acceptor(EA) (as hereinbefore defined).Such group is known in the art.Usually, track will be two key (sp of bonding carbon atom 2) or triple bond (sp) on the p-track, such as being present in thiazolinyl, alkynyl, neutrality or charged aromatic ring and neutral or charged hetero-aromatic ring system.In addition, track can be for such as the p-track on the atom of boron or nitrogen.In addition, track can be the organo-metallic track of p, d or f organo-metallic track or hydridization.In this article, comprise the atom of electronics by the bridge of the track of its delocalization and be called as " crucial atom (critical atoms) ".The number of the crucial atom in the bridge can from 1 to about 30 number.Crucial atom can be replaced by the group of organic or inorganic.Can with the solubleness of improving the chromophore in the polymeric matrix, strengthen chromophore stability purpose or be used for other purpose and select substituting group.
By comprising the multiple connection of singly-bound, single atom, heteroatoms, atoms metal (for example organometallic compound), aliphatic chain, aromatic ring, functional group or its combination, substituting group (or in a plurality of substituting group arbitrarily) can be covalently bound on one or more in D, π or A.The substituting group center (for example can have a plurality of atoms, aryl or aliphatic series ring), can for single atom (for example, carbon, silicon or atoms metal), maybe can (for example make up for it, loop systems, one of them aryl are bonded on the atom of loop systems and other two aryl are bonded on another atom in the loop systems).
For example, in some embodiments, the substituting group center comprises carbon atom, heteroatoms or atoms metal.In other embodiments, the substituting group center can be carbon atom, Siliciumatom, tin atom, sulphur atom, nitrogen-atoms or phosphorus atom.In embodiments, the substituting group center can be for 3-, 4-, 5-or 6-unit ring, as phenyl ring, thiphene ring, furan nucleus, pyridine ring, imidazole ring, pyrrole ring, thiazole ring, oxazole ring, pyrazoles ring, isothiazole ring, isoxazole ring or triazole ring.
The aryl that is bonded to the substituting group center can also be replaced by alkyl, heteroatoms, aryl or its combination.For example, in some embodiments, aryl can comprise benzyl ring, naphthyl ring, xenyl, pyridyl ring, bipyridyl, thienyl group, furan group, imidazole group, pyrrole group, thiazolyl group, oxazole group, pyrazole group, isothiazole group, isoxazole group, triazole group or anthryl (anthracenyl) group independently in each position.
In embodiments, substituting group comprises following structure:
Wherein: X is the substituting group center; Ar 1, Ar 2And Ar 3It is aryl; And L is the covalently bound group (linker) that is connected to D, π or A.According to multiple embodiments, X can be C, Si, N, B, Sn, S, S (O), SO 2, P (O) (phosphine oxide), P (phosphine) or any type aromatic ring.In some embodiments, Ar 1, Ar 2And Ar 3Each comprises benzyl ring replacement or unsubstituted independently, that replace or unsubstituted benzyl rings, that replace or unsubstituted naphthyl ring, that replace or unsubstituted biphenyl group, that replace or unsubstituted pyridine basic ring, that replace or unsubstituted bipyridyl, that replace or unsubstituted thiphene ring, that replace or unsubstituted thionaphthene ring, that replace or unsubstituted imidazole ring, that replace or unsubstituted thiazole ring, that replace or unsubstituted thienothiophene (thienothiophene) group, that replace or unsubstituted replacement or unsubstituted quinolines group or replacement or unsubstituted anthracyl radical.In some embodiments, L comprises following structure:
Figure BDA00003195971500062
Wherein: R 1When occurring each time, be H, alkyl or halogen independently; Y 1For-C (R 1) 2-, O, S ,-N (R 1)-,-N (R 1) C (O)-,-C (O) 2-,-C 6H 6-or-OC 6H 6-, thiophenyl; N is 0-6; And m is 1-3.
The electro-optic polymer that comprises these non-linear optical chromophores can demonstrate high electro-optic coefficient.With comprise wherein alkyl substituting aromatic base, wherein aryl has π (pi)-π (pi) and interacts (in this article between the aryl bulky group in the chromophore and the aryl on the polymkeric substance, being also referred to as pi interacts) the electro-optic polymer of chromophore compare, time stability significantly increases.In the case, symbol " π " can be used in reference to the system of one or more multiple bonds usually, and linear or ring-type, described system is known in this area, rather than the situation of the conjugated pi bridge of expression chromophore.Spatially, aryl can be bigger than alkyl.(for example strengthen in the interact geometrical configuration of complementation that can be by strengthening the interactional aryl of pi of the aryl bulky group in the chromophore and the pi between the aryl on the polymkeric substance, be centered around the aryl pi-interaction (for example, piling up) more effectively that the aryl arranged on the tetrahedron ground, substituting group center in chromophore's bulky group can be advantageously arranged with the carbon tetrahedron ground in polymer backbone).
Donor, acceptor and π-bridge portion can comprise the functional group that can be covalently bound to the L group.
According to embodiment, D comprises a kind of in following:
Figure BDA00003195971500071
π comprises a kind of in following:
Figure BDA00003195971500081
And A comprises a kind of in following:
Wherein: R 1When occurring each time, be H independently; Aliphatic group is such as alkyl or alkoxyl group; Or aryl.R 2When occurring each time, be alkyl, haloalkyl, halogenated aryl or have or do not have substituent aryl independently; Z be singly-bound ,-CH=CH-,-C ≡ C-,-N=N-or-N=CH-; Y 2When occurring each time, be CH independently 2, O, S, N (R 1), Si (R 1), S (O), SO 2,-CH (R 1)-or-C (R 1) 2-; R 3When occurring each time, be cyano group, nitro, ester group or halogen independently; And at least one R 1, R 2Or R 3Comprise substituting group.M is that 1-6 and n are 1-4.
In other embodiments, D has in the following structure:
Wherein, X is the substituting group center; Ar 1, Ar 2, Ar 3, Ar 4, Ar 5And Ar 6Be aryl; Ar 7Be the conjugation aromatic group; The R of D 1When occurring each time, be H, alkyl, haloalkyl, aryl or halogenated aryl independently; P is 2-6; L is 0-2; M is 1-3; And n is 1-3; π has in the following structure a kind of:
Figure BDA00003195971500092
And
The R among the π wherein 1Comprise independently
Figure BDA00003195971500101
Or be H, alkyl, assorted alkyl, aryl or heteroaryl; L is covalently bound group; Z is vinylene, 1, the inferior thiophenyl of 4-phenylene or 2,5-, Y 2Be S, O or SiR 2 2, R wherein 2Be aliphatic group, and m is 1-3.In some embodiments, X is C or Si.
In another embodiment, π comprises:
Figure BDA00003195971500102
And A is:
Wherein: R 1When occurring each time, be H, alkyl or halogen independently; Z be singly-bound or-CH=CH-; Y 2For O, S ,-C (R 1) 2-; R 2When occurring each time, be alkyl or aryl independently; And m=1-3.In embodiments, non-linear optical chromophore comprises a kind of in as shown in Figure 1 the structure, wherein X, R 1And R 2Can be as indicated above.
In another embodiment, A has structure:
Figure BDA00003195971500104
Wherein: R 2When occurring each time, be H independently; Aliphatic group is such as alkyl side chain or unbranched or alkoxyl group; Or that replace or unsubstituted aryl.R 3When occurring each time, be cyano group, CF independently 3, nitro, ester group, halogen or replacement or unsubstituted aryl; Y 2Be CH 2, O, S, N (R 2), Si (R 2) 2Or-C (R 2) 2-.In other embodiments, at least one R of π 1Comprise
Figure BDA00003195971500105
According to embodiment, non-linear optical chromophore has structure D-π-A, and wherein D is donor, and π is π-bridge, and A is acceptor, and wherein at least one among D, π or the A is covalently bound to comprising on following at least one the substituting group:
Figure BDA00003195971500111
And wherein: X is C or Si; Y 1For-C (R 1) 2-, O, S ,-N (R 1)-,-N (R 1) C (O)-,-C (O) 2-; Y 3Be N or P; And Ar 1, Ar 2And Ar 3It is aryl.Aryl, D, π and A can for example be as described above.
Other embodiments comprise one or more electro-optical composite material and the polymkeric substance that comprises in the above-mentioned non-linear optical chromophore.Usually, polymkeric substance with electric field polarization to induce electro-optical activity.Can also use other technologies for example self-organization or photoinduced polarization.Non-linear optical chromophore can covalently be connected in polymeric matrix (for example, as in side chain polymer or cross-linked polymer) or the object that can be used as in the polymeric matrix main body (for example, matrix material) exists.Non-linear chromophore can also as the object in the polymeric matrix exist and then before the polarization, polarizing during or after polarization bonding or be cross-linked to matrix covalently.Can comprise as the polymkeric substance of matrix, for example polycarbonate, poly-(arylene ether), polysulfones, polyimide, polyester, polyacrylic ester and its multipolymer.
In some embodiments, the bulky group in the chromophore is used for changing Tg and the light loss that reduces electric light (EO) polymkeric substance by the physics interaction that changes between polymer body and the chromophore's object.We find, interact and can increase by the particular chemical of selecting isolation (for example, the large volume) group in the chromophore at the physics between main polymer and the guest molecule.Physics interacts and can comprise, for example pi-pi interacts; Size interacts (size interaction), and it hinders chromophore significantly and moves to and be lower than Tg and (for example, do not have enough free volumes to be used for bulky group in polymer composites under Tg Translation(translation), and therefore do not have enough free volumes to be used for the translation of chromophore, the translation of chromophore normally chromophore lax (relaxation) is needed); With pre-organized binding interactions (preorganized binding interaction), wherein bulky group preferentially is engaged in the space of defining on the conformation in the polymkeric substance; Or its any combination.In some embodiments, in the bulky group on polymer chain and the part of aryl, physics interacts by Van der Waals force (for example, keesom force, induction force or London force) control or replenishes.Such noncovalent interaction can increase the time stability when being lower than Tg and reduce light loss, improves chromophore's loading density simultaneously and avoids the harmful effect of the crosslinked degree of registration that polarization is induced.
Pi-pi interacts to be known in the art and in pi-system and another pi-system (for example for example can to comprise, aromatics, heteroaromatic, alkene, alkynes or carbonyl official can), the charged atom of part or atomic group (for example, in the polar link-H ,-F) or complete charged atom or atomic group (for example ,-NR (H) 3 +,-BR (H) 3 -) between interaction.Pi-interacts can be increased chromophore's object to the avidity of polymer body and to increase the energy barrier of chromophore's motion, and the chromophore that moves normally of chromophore is lax and depolarize (depoling) is needed.In some embodiments, pi-interacts can be for the Tg that improves polymkeric substance (for example, by being increased in the interaction between the polymer chain) or the Tg (for example, by being increased in the interaction between polymer body and the chromophore's object) of polymer composites.In some embodiments, when replacing than the interactional part of pi-a little less than the interaction of the pi-on bulky group part is not had the pi-interaction or has, the pi-interaction of bulky group increases the Tg of polymer composites.In some embodiments, the pi-interaction group in the chromophore be selected as preferentially with polymer chain on pi-interaction group interact.Preferential interaction like this can comprise, for example, the face-to-face and/or opposite, limit in the pi-interaction acceptor/donor of the complementation of the pi-interaction donor/acceptor on the bulky group and polymer chain or the space between the pi-interaction group on chromophore and the polymer chain interacts or its any combination.In some embodiments, the multiplephase mutual effect between the one or more parts on chromophore's bulky group and a plurality of parts on the polymer chain or part for example can increase interaction strength and time stability face-to-face and in the face of the limit.(for example strengthen in the interact geometrical configuration of complementation that can be by strengthening the interactional aryl of pi of the aryl bulky group in the chromophore and the pi-between the aryl on the polymkeric substance, the pi-interaction is (for example more effectively to be centered around aryl that the aryl arranged on the tetrahedron ground, substituting group center in chromophore's bulky group can be advantageously arranges with the carbon tetrahedron ground in polymer backbone, pile up), as top view (Figure 14 A) with around the side-view of x axle half-twist (Figure 14 B illustrates part pi-and interacts)).In other embodiments, can because of chain take to be conducive to chromophore on pi-interaction group face-to-face (Figure 15 A) or in the face of some conformation of the interactional pi-interaction group in limit (Figure 15 B) and spatial distribution (for example, pre-organized) and selective polymer.Some embodiments can have between the pi-interaction group in polymkeric substance and the chromophore multiple face-to-face interaction (for example, Figure 15 C) or face-to-face with in the face of the interactional combination of limit pi-(for example, Figure 15 D).In other embodiments, pi-interaction donor has electron rich p-system or track usually, and pi-interaction acceptor has electron-deficient p-system or track usually.In some embodiments, the bulky group in the chromophore have with polymer chain on pi-interaction acceptor or pi-interaction donor or the pi-interaction acceptor of pi-interaction donor complementation.In some embodiments, such pi-interaction acceptor can comprise, for example for example pyridine, pyrazine, oxadiazole etc. of heterocycle, and pi-interaction donor can comprise, for example for example thiophene, furans, carbazole etc. of heterocycle.Pi-interaction donor/acceptor can also comprise coming the aryl of the electron rich/electron-deficient of self-powered/electron-withdrawing substituent.In some embodiments, bulky group comprise with polymer chain at least a pi-interaction acceptor of pi-interaction donor complementation.In some embodiments, bulky group comprise with polymer chain at least a pi-interaction donor of pi-interaction acceptor complementation.
In some embodiments, the size of bulky group (for example, 20 ℃) when being lower than the Tg of matrix material prevents chromophore's translation/depolarize in the polymkeric substance free volume significantly.In some embodiments, bulky group is (large volume that for example, bulky group has around substituting group central atom tetrahedron ground or trigonal bipyramid ground is arranged forms part rather than has around the large volume of substituting group central atom and forms layout plane basically partly or linearity) of 3 dimensions basically.Than the plane or linear bulky group, 3 such dimensions can reduce bulky group and therefore chromophore form the possibility of translation by free volume.Large volume forms group and can comprise independently, for example and have an organic moiety of 5 or more carbon atoms.In some embodiments, large volume forms group can be included in structure fixing on the conformation independently, for example ring.Ring can be aliphatic, aromatics or its any combination.In some embodiments, large volume formation group can comprise aryl (aromatic substance of aromatic substance, polynuclear aromatic compound, replacement, heteroaromatics, the heteroaromatics that encircles heteroaromatics more and replace independently.
In other embodiments, the bulky group zone (for example, bag) that preferentially fits on the conformation of polymkeric substance/define on the space.Such zone can be called as pre-organized for interacting with bulky group.Like this pre-organized can be produced or be produced by the group (for example, side-chain radical) of the polymkeric substance of the conformation of taking to be scheduled to by the polymer backbone of the conformation of taking to be scheduled to.In some embodiments, the pre-organized zone of polymkeric substance can have be arranged on the space preferentially with bulky group on the interactional pi-interaction of complementary portion group, pi-interaction atom, shape-interaction group, H-binding groups etc.The interaction in the pre-organized zone on polymkeric substance and the bulky group can comprise above-mentioned any interaction or its any multiple combination.In some embodiments, interact than only independent stabilization, pre-organizedly provide other stability.For example, the part of pre-organized bag can with bulky group on the pi-part that interacts carry out pi-and interact, and another part of pre-organized bag can interact with Van der Waals force with the identical or distinct portions of bulky group.
In other embodiments, chromophore can comprise more than a bulky group.In some embodiments, chromophore has at least one bulky group on the donor and at least one bulky group on p-bridge or acceptor.Can increase with the interaction of polymer backbone and make translation and depolarize more difficult more than a bulky group on the different piece of chromophore.
An embodiment comprises non-linear optical chromophore and the main polymer of polarization, and wherein non-linear optical chromophore is replaced by two or more bulky group, and main polymer is configured to cooperate with bulky group and hinders chromophore's depolarize.In some embodiments, non-linear optical chromophore has structure D-π-A; D is replaced by bulky group; And π is replaced by bulky group.In another embodiment, bulky group and polymkeric substance interact via pi-and cooperate.In another embodiment, bulky group comprises aryl.In some embodiments, aryl is aryl hydrocarbon, aryl polynuclear hydrocarbon, heteroaryl or polyheteroaromatic independently.In some embodiments, main polymer can be polycarbonate, poly-(arylene ether), polysulfones, polyimide, polyester, polyacrylic ester or its any multipolymer.In some embodiments, main polymer has greater than 150 ℃ Tg and can be polysulfones; Polyester; Polycarbonate; Polyimide; Polyester-imides; Polyarylether; Poly-(methacrylic ester); Poly-(ether ketone); Polybenzothiozole; Polybenzoxazole; Polyphenyl and dithiazole; Ju Ben Bing Er oxazole; Poly-(aryl oxide); Polyetherimide; Poly-fluorenes; Polyarylene vinylene; Poly quinoline; Polyvinyl carbazole; Or its any multipolymer.
Another embodiment is any the electro-optical assembly that comprises in the polymkeric substance described herein, the wherein V of this device πAfter 2000 hours, be exercisable under 85 ℃.In some embodiments, electro-optical assembly has at the V that can not increase after 2000 hours under 85 ℃ above 5% πIn some embodiments, electro-optical assembly has at the V that can not increase after 2000 hours under 85 ℃ above 10% πIn some embodiments, electro-optical assembly has at the V that can not increase after 2000 hours under 85 ℃ above 15% πIn some embodiments, electro-optical assembly has at the V that can not increase after 2000 hours under 85 ℃ above 20% π
In some embodiments, electro-optic polymer comprises non-linear optical chromophore and main polymer, wherein: described non-linear optical chromophore has the large volume substituting group that comprises at least one aryl, and described main polymer has and is selected as and the interactional aryl of substituent aryl.In some embodiments, wherein substituting group comprises 2 or 3 aryl.In some embodiments, chromophore has structure D-π-A, and triaryl has following structure:
Figure BDA00003195971500151
Wherein: D is donor; π is π-bridge; A is acceptor; X is the substituting group center; Ar 1, Ar 2And Ar 3It is aryl; And L is the covalently bound group that is connected in D, π or A.
In another embodiment, electro-optic polymer comprises the non-linear optical chromophore with structure D-π-A, wherein D is donor, π is π-bridge, A is acceptor, and at least one among D, π or the A covalently is connected in the bulky group that comprises at least one aryl, and wherein electro-optic polymer has bigger time stability than when alkyl substituting aromatic base.In some embodiments, bulky group comprises at least two aryl, and electro-optic polymer has bigger time stability than when alkyl substituting aromatic base.In another embodiment, bulky group comprises at least three aryl, and electro-optic polymer has bigger time stability than when alkyl substituting aromatic base.
In another embodiment, electro-optic polymer comprises non-linear optical chromophore and main polymer, wherein said non-linear optical chromophore has the substituting group that comprises at least two aryl, described main polymer comprises the subelement (subunit) that comprises at least two aryl, and the aryl of described non-linear optical chromophore is preferentially aimed at (for example, the aligning shown in Figure 14) with the aryl of described subelement.In some embodiments, main polymer is polysulfones; Polyester; Polycarbonate; Polyimide; Polyester-imides; Polyarylether; Poly-(methacrylic ester); Poly-(ether ketone); Polybenzothiozole; Polybenzoxazole; Polyphenyl and dithiazole; Ju Ben Bing Er oxazole; Poly-(aryl oxide); Polyetherimide; Poly-fluorenes; Polyarylene vinylene; Poly quinoline; Polyvinyl carbazole; Or its any multipolymer.
Study the matrix material that comprises the chromophore with bulky group and consistency and the stability of various main polymers, comprised EO character.Owing to good consistency realizes low light loss, good consistency also changes to prove by clean, single Tg.Characterize the EO coefficient with various main polymers, and under different temperature their time stability of monitoring.Simultaneously, modulator is made by those EO matrix materials, and their stability is further confirmed.
Some embodiments have the chromophore's structure that comprises bulky group.Such chromophore illustrates good with consistency main polymer and cause high second-order transition temperature.The example of two kinds of chromophores shown in Fig. 1-4.Use these chromophores to come object of research-system of subject with the various main polymers with different second-order transition temperatures.Main polymer among Fig. 6 for example 28,29 and 30 belongs to and has low polycarbonate family to high Tg.In some embodiments, the high Tg of main polymer will cause having the higher Tg of the EO matrix material of identical chromophore.
According to embodiment, the EO matrix material with high Tg (＞120 ℃) can have greater than the main polymer of 120 ℃ second-order transition temperature by use to be made.In other embodiments, the EO matrix material with high Tg (＞120 ℃) can have greater than the main polymer of 120 ℃ second-order transition temperature and have by use＞120 ℃ fusing point or the chromophore of Tg make.For example, comprise that in 28 (Tg=286 ℃) the EO matrix material of the 23b of chromophore (Fig. 4) has 167 ℃ matrix material Tg.Similarly, the result is presented at and comprises in the main polymer 29 (Tg=165 ℃) that the EO matrix material of 23b chromophore has 193 ℃ matrix material Tg.Two systems show for the improved stability of prolonged application with maximum operating temperature of 85 ℃.The 23a of chromophore has similar improved stability (following table 1 and table 2).In another embodiment, electro-optical composite material comprises that by weight greater than the chromophore in main polymer of 35% loading capacity, wherein the Tg of matrix material is higher than fusing point or the Tg of chromophore itself.In some embodiments, chromophore's loading capacity by weight is at least 45%, and the Tg of matrix material is greater than 150 ℃.In another embodiment, main polymer can be the semi-crystalline polymer with low Tg, and it forms the amorphous matrix material with high Tg when mixing with chromophore.In some embodiments, the noncovalent interaction between the part of the bulky group in the chromophore and hypocrystalline main polymer increases the Tg of amorphous matrix material.
According to embodiment, other have the Tg that is higher than 150 ℃ main polymer can with the chromophore with bulky group be used in combination to be created in short-term and/or long-term on have high Tg and the therefore compound EO material of high-temperature stability.Illustrative high Tg main polymer can being combined to form by following polymer system and/or they: polysulfones; Polyester; Polycarbonate-based; Polyimide; The polyester-imides class; The polyarylether class; Poly-(methacrylic ester) class; Poly-(ether ketone) class; The polybenzothiozole class; The polybenzoxazole class; Polyphenyl and dithiazole class; Ju Ben Bing Er oxazole class; Poly-(aryl oxide) class; Polyetherimides; Poly-fluorenes class; The polyarylene vinylene class; The poly quinoline class; Polyvinyl carbazole; With their multipolymer.
According to an embodiment, electro-optic polymer comprises the non-linear optical chromophore with structure D-π-A, wherein D is donor, π is π-bridge, A is acceptor, and at least one among D, π or the A covalently is connected in the substituting group that comprises the substituting group center X that directly is bonded to aryl, and wherein electro-optic polymer has bigger time stability than when alkyl substituting aromatic base.Electro-optic polymer can be band material side chain, crosslinked, dendritic or compound.According to an embodiment, substituting group center X is bonded at least three aryl, and electro-optic polymer is than having bigger time stability independently during substituted aryl when alkyl.According to an embodiment, electro-optical composite material is in the time stability that had after 100 hours under 85 ℃ greater than 80%.
Other embodiments comprise the whole bag of tricks for the preparation of electro-optical composite material, and device thus, and wherein electro-optical composite material comprises aforesaid chromophore.According to an embodiment, described method comprises: the polymkeric substance that comprises the non-linear optical chromophore with structure D-π-A a) is provided, wherein D is donor, π is π-bridge, A is acceptor, and among D, π or the A at least one is covalently attached to and comprises that Direct Bonding is to the substituting group at the substituting group center of aryl; And b) polar polymer is in order to form electro-optic polymer, and wherein electro-optic polymer has bigger time stability than when alkyl substituting aromatic base.
Usually, aryl is spatially big than alkyl.Usually, can polymkeric substance be provided as film by the deposition that for example spins, dip-coating or silk screen printing.Can also film be changed over apparatus structure by for example dry-etching, laser ablation and photochemical bleaching.Selectively, can provide polymkeric substance by for example molded or hot padding polymer melt.Polarization can comprise for example contact or corona polarizing.In another method embodiment, the substituting group center key is bonded at least three aryl or is replaced by at least three aryl, and electro-optic polymer has bigger time stability during substituted aryl independently than alkyl.
In some embodiments, polymkeric substance is matrix material.In the certain methods embodiment, aryl is spatially big than alkyl.In another method embodiment, polymkeric substance has T gThan when the alkyl substituting aromatic base, the T of polymkeric substance gBe in about 5 ℃, and than when the alkyl substituting aromatic base, the time stability of polymkeric substance is bigger.
Another embodiment be comprise comprise donor (24, the electro-optic polymer of non-linear optical chromophore Fig. 5):
Figure BDA00003195971500181
R wherein 1Comprise alkyl, assorted alkyl, aryl or heteroaryl independently; R 2When occurring each time, comprise H, alkyl, assorted alkyl, aryl or heteroaryl independently; R 3When occurring each time, comprise halogen, alkyl and assorted alkyl, aryl or heteroaryl independently; And n is 0-3.For example according to the general scheme 25 to 27 shown in Fig. 5, can prepare the chromophore according to this embodiment.According to the chromophore of this embodiment since strong electron-donating group have good non-linear, and can be at-R 1Derive with a plurality of functional groups in the position.In one embodiment ,-R 1Comprise and the interactional bulky group of polymer body, and the π bridge comprises and the interactional bulky group of polymer body.
Other embodiments are the electro-optical assemblys that comprise aforesaid non-linear optical chromophore, electro-optical composite material and electro-optic polymer.This device can comprise slab guide, self-support film, monomode optical waveguide and multimode lightguide and passive (passive) other polymkeric substance (for example, covering polymkeric substance for example acrylate).This device can also have have any in the above-mentioned chromophore and/or with the combination of polymers of other non-linear optical chromophores.In addition, specific device can have two or more different comprise any matrix material in the above chromophore and/or polymkeric substance (for example, the electro-optical transducer core polymkeric substance with high relatively chromophore of specific refractory power with have different chromophores or with the identical chromophore of low concentration so that the lower covering polymkeric substance of the specific refractory power of covering).In some embodiments, this electro-optical assembly comprises mach-zehnder (Mach-Zehnder) interferometer, Michelson (Michelson) interferometer, micro-ring resonator or directional coupler.
Embodiment
Following synthetic embodiment is with reference to figure 2.
Compound 2: the compound 1 in the ice bath in the De diox (50ml) (10.00 gram) add t-BuOK (1M, 55ml) and Methyl Thioglycolate (5.279 restrain).Reactant is heated to 80 ℃ kept 2 hours, and then be heated to 120 ℃ of maintenances 30 minutes.Then, distill out most of diox.Add 1-n-butyl bromide (20ml) and DMSO (80ml).Reaction is heated to 150 ℃ to keep 2 hours.After reaction is cooled to room temperature, come acidification reaction with the acetic acid in the frozen water.Use the dichloromethane extraction product.Isolate dichloromethane layer, pass through MgSO 4Drying, filtration and evaporation by silica gel column chromatography purifying crude product, have obtained the product liquids 2 of 10.7 grams to obtain crude product.
Compound 3: under nitrogen, compound 2 (7.72 gram) is dissolved in the dry ether (dry ether).In the ice-acetone cooling bath of drying, cool off flask.Add LiAlH 4(1.08 gram).Removal cooling bath makes temperature of reaction get back to room temperature, will react at room temperature to keep 6 hours.In ice bath, cool off flask.Dropwise adding methyl alcohol reacts with quencher.Add salt solution.Isolate organic layer.Use the extracted with diethyl ether water layer.Pass through MgSO 4The dry organic layer that merges is by being filled in the filtered through silica gel in the funnel.After the evaporation, obtain the compound 3 of 4.65 grams.
Compound 4: compound 3 (4.65 gram) is dissolved in the chloroform (100ml).In ice bath, cool off flask, add the triphenylphosphine hydrobromate simultaneously.0 ℃ of stirring reaction 30 minutes, at room temperature stirred then 14 hours, then refluxed 3 hours.Reaction mixture precipitates in ether 2 times, has obtained the product 4 of 8.93g.
Compound 6: under nitrogen, be blended in compound 4 (6.71 gram) and compound 5 (5.22 gram) among the dried THF (100ml) and in ice bath, cool off.By pin drip in the mixture t-BuOK (1M in THF, 15ml).At room temperature stirring reaction spends the night and the water quencher.Use the acetic acid neutralise mixt.With the dichloromethane extraction product and use hexane-dichloromethane mixture by flashing tower (flash column) purified product, the compounds 6 of 3.10 grams have been obtained.
Compound 7: under nitrogen, compound 6 (1.68 gram) is dissolved in and does among the THF (35ml).Under-78 ℃ by pin drip n-BuLi (2.5M, 1.15ml).Reaction is remained on-30 ℃ following 70 minutes.Then, under-78 ℃, add DMF (0.30ml) by pin.After 45 minutes, use the frozen water termination reaction.Use the dichloromethane extraction product, pass through MgSO 4Drying, evaporation and by the flashing tower purifying has obtained compound 7 (1.32 gram).
Compound 9: under nitrogen, compound 7 (1.264 gram) and 8 (0.767 gram) (referring to United States Patent (USP) the 7th, 078, No. 542 and citing document are for the preparation of the acceptor compound of this type) is blended among 10ml ethanol and the dried THF of 5ml.With mixture heating up to 45 ℃.By the TLC monitoring reaction.When compound 7 disappears from reaction mixture, evaporating solvent on rotatory evaporator.Precipitate the purifying resistates by the dichloromethane solution in flashing tower and the methyl alcohol, obtained the compound 9 of 1.03 gram black powder shapes.United States Patent (USP) the 7th, 078 is incorporated into by reference at this for No. 542.
Compound 10: under nitrogen, with 9 being dissolved among the THF (100ml) of 5.69 grams altogether.Add the 2N HCl of 5ml.At room temperature stirring reaction is also by the TLC monitoring reaction.When compound 9 disappears, add methylene dichloride (200ml) and salt solution (100ml) from reaction mixture.Use the saturated sodium bicarbonate solution neutralise mixt.Carry out successively organic layer is separated, pass through MgSO 4Drying, evaporation and by the flashing tower purifying obtains the compound 10 of 5.69g.
Compound 11: compound 10 (5.68 gram) is mixed with methylene dichloride (50ml).In ice bath, cool off flask.Add tri-phenyl chloride (6.10 gram) and imidazoles (1.40 gram) successively.Stirring reaction also passes through the TLC monitoring reaction.After about 30 minutes, compound 10 disappears from reaction mixture.Leach salt.Precipitate purified product by the dichloromethane solution in flashing tower and the methyl alcohol, obtained the compound 11 of 4.10 grams.
Adopt similarly reaction and other parent materials to prepare other chromophores.For example, when X=C, can in the reaction that is similar to compound 11, use trityl chloride (Ph 3C-Cl).
The compound 11 of 30wt% has shown r among the APC (-4,4 '-(3,3,5-front three basic ring-hexylidene) the diphenol carbonic ether of APC=[phenylbenzene A carbonic ether-altogether] (28), referring to United States Patent (USP) the 6th, 750, No. 603) 33The time stability of active and extraordinary 85 ℃ 92% reservations after following 20 hours of the extraordinary EO of=81pm/V.The time stability test that the mach-zehnder modulator is carried out has shown and has been better than 85 ℃ of V after following 100 hours π95% keep.
Following synthetic embodiment is with reference to figure 3.
Compound 13: compound 12 is dissolved among the THF of 70mL, adds 1N HCl solution (20mL) simultaneously.At room temperature stirred 2 hours.Use CH 2Cl 2The extraction mixture is used NaHCO 3Solution and water washing and pass through MgSO 4Dry.After solvent evaporated under reduced pressure, use CH 2Cl 2/ MeOH (5/0.5) passes through the column chromatography purified mixture as eluting solvent.Yield with 67% has obtained the compound 13 of 1.65g altogether.
Compound 14: with compound 13 (0.8g, 1.07mmol) and tri-phenyl chloride (0.945g 3.2mmol) is dissolved in the CH of 20mL 2Cl 2In.(0.22g 3.2mmol) afterwards, at room temperature stirred the mixture 1.5 hours adding imidazoles.Then solvent is removed in filtering mixt and decompression.By the column chromatography purified mixture, obtain the compound 14 of solid.
The compound 14 of 50% in unbodied polycarbonate (APC) matrix material has the r of 90pm/V 33, the light loss of 0.881dB/cm, 140 ℃ Tg, 1.6711 specific refractory power and the time stability in the mach-zehnder modulator that is similar to the compound 11 of 30% among the above-described APC 1.55 microns the time.24% compound 12 in the APC matrix material, wherein aryl is replaced (substituting) by alkyl, has the r of 50pm/V 33, the light loss of 1.44dB/cm, 140 ℃ Tg, 1.55: 1.6038 specific refractory power and much lower time stability.
Compound 16: in the 3-L three-necked flask with stirring rod, install 125 gram trimethylammonium-tetrahydroquinolines (15) and 102 gram Anhydrous potassium carbonate (K additional 2CO 3).Make flask be provided with condenser and the feed hopper that contains the right-bromobenzyl bromination things of 173.3 grams in the dried DMF of 500ml.With the air in the nitrogen wash flask.In flask, add the dried DMF of 700ml.In ice-water bath, cool off flask.To flask, drip right-bromobenzyl bromination thing from the feed hopper that attaches to flask, continue simultaneously to stir.After interpolation is finished, at room temperature keep reaction 3 hours.Continue 14 hours (spending the night) 55-60 ℃ of following reacting by heating.Make inclusion be cooled to room temperature, in flask, add 1 liter of hexane.Stir after 10 minutes, filter solid.On rotatory evaporator, solution evaporation is extremely done.Dissolving mixt in ethyl acetate (1L) with salt water washing 2 times, passes through MgSO 4Drying is filtered, then evaporation.By on the silica gel in being filled in chromatographic column and hexane/DCM come purified product as the chromatography of moving phase.
The flask that is equipped with feed hopper and stirring rod of compound 17:2-1 is filled with the compound 16 from previous steps of 66.66 grams.Make the flask degassing and be filled with dried nitrogen.In flask, add anhydrous THF (800ml).In bathing, dry ice-propanone cools off flask.Add n-BuLi (83ml) lentamente from feed hopper.Keep being reflected at-60 ℃ and continue 2.5 hours down.Prepare another and contain 3 liters the 3 neck flasks of 55.7 gram tri-phenyl chlorides and the anhydrous THF of 200ml and cooling in dry ice-propanone is bathed.Under agitation, in 1 hour, add the lithiumation solution from first flask while stirring in second flask.To react to stir and spend the night and with acetic acid aqueous solution (acetic acid of the 0.19mol in 300ml water) and some salt brine solution quenchers.Isolate organic layer and use the salt water washing once, pass through MgSO 4Dry, filtration is evaporated to dried then.By silicagel column, use hexane/DCM to come purified product as moving phase.
Compound 18: under nitrogen, in the 3-L flask, digest compound 17 with 147 and be dissolved among the dried DMF of 1000ml.NBS (51.23 gram) is installed in the feed hopper together with the DMF of 500ml.In ice bath the cooling flask and with aluminium foil parcel so that the reaction lucifuge.In LM-667, drip NBS solution.At room temperature stirring reaction spends the night.Evaporation DMF.In hexane/ethyl acetate (3: 1), stir the mixture.Leach precipitation.Evaporating solns.In methyl alcohol, stir residual mixture. Collect by filtering SolidRepeat methanol wash again.By silica gel column chromatography (hexane/DCM=2: 1) come purifying solid and vacuum-drying.The yield of compound 18 is 95%.
Compound 19: in the 3 neck flasks with stirring rod and feed hopper of 3-l, add 150 compounds 18 that restrain.With nitrogen wash flask 4 times.Add the anhydrous THF of 1200ml via sleeve pipe (cannulation).In bathing, dry ice-propanone cools off flask.Drip the t-BuLi (1.7M) of 286ml from feed hopper.After finishing dropping, with 25ml THF washing funnel.Then, from funnel drip DMF among THF (200ml) (anhydrous, 35.81g).Remove cooling bath so that temperature of reaction reaches 0 ℃ in ice bath-water-bath.With acetic acid aqueous solution (5: 1) quencher reaction, be about 7 until pH value.In mixture, topple over some salt solution and 500ml hexane.Isolate organic layer, pass through MgSO 4Drying is filtered dry then.Use hexane/DCM (3: 1 to 1: 1) and methanol wash to come purified product by silica gel column chromatography.The yield of corresponding aldehyde is 85%.In 1 liter of flask with stirring rod, add this aldehyde (27.8 gram).Add and do THF (500ml).By some heat agitated mixtures to form homogeneous solution.In ice bath, cool off flask.Add the sodium borohydride (NaBH of 1.86 grams 4).Use the nitrogen wash flask.During 2 hours, the 25ml ethanol from feed hopper interpolation 50ml THF.At room temperature keep reaction 18 hours.When solution approached clarification, reaction realized transforming fully.When reaction is finished, add salt solution (50ml) and kept high-speed stirring 45 minutes to reaction.Separate organic layer, pass through MgSO 4Drying, evaporation.Use hexane/ethyl acetate to come purified product by the flash distillation column chromatography.The yield of compound 19 is 95%, and it is directly used in next step and need not other sign.
Compound 20: in the 1-L flask, with altogether 25 the gram compounds 19 be dissolved in the chloroform (200ml).In ice bath, cool off flask.During about 1 hour, in LM-671, drip the Ph that is dissolved in the chloroform (200ml) 3PHBr (15.2g).After at room temperature stirring 3 hours, think highly of new configuration reaction with Dean-Rodney Stark reflux water-dividing, divided dried up in 6 hours to remove chloroform-water distillment by azeotropic.The cooling reaction is evaporated to about 100ml solution.In dry diethyl ether, precipitate strong solution, continue simultaneously to stir.To be dissolved among the DCM by the product that filters collection and also in dry ether, precipitate again.The product of vacuum-drying green 1 day.The yield of compound 20 is 85%.Collect proton N MR with the characterizing compounds structure.
Compound 21: the compound 22 of the 0.1mol altogether in the 200ml dry dichloromethane in frozen water in the cooling flask.Add imidazoles (0.15mol).Use the nitrogen wash flask.Use syringe to drip TERT-BUTYL DIMETHYL CHLORO SILANE.Stirring reaction 1 hour.Leach precipitation.Use the salt solution washing soln, by dried over mgso and evaporation.By flash chromatography on silica gel method (flash chromatography) purified product 10.The yield of corresponding TBDMS ether is 85%.(8.37g) is installed in the flask with stirring rod with TBDMS ether.Make the flask degassing and refill with nitrogen.From the n-Buli of pin dropping hexane.Between-10 ℃ and-20 ℃, keep reaction 2 hours.Then add DMF down at-78 ℃.Reacted by the acetic acid quencher in water.Isolate organic layer, use the salt water washing, evaporate then by dried over mgso.Product mixtures by two kinds of regional isomers of chromatographic column purifying (regioisomer).The yield of compound 21 is 60%.
Compound 23: in flask, install compound 20 (27.01g) and the degassing additional.In flask, add dried THF.At-20 ℃ of n-BuLi that drip down in the hexane.Reaction stirred is 1 hour in ice bath.In second flask, compound 21 (9.511g) is dissolved in does among the THF.Under cooling and stirring, the mixture in first flask is added in second flask.Stirred the mixture under the room temperature 16 hours.By adding water and some salt solution termination reactions.Isolate organic layer, by dried over mgso, filtration is evaporated to dried then.By the purified by flash chromatography mixture, the yield with 66% obtains corresponding Wittig coupled product.In having the flask of stirring rod, coupled product is dissolved among the dried THF.Use the n-BuLi in the syringe interpolation hexane.Keep reaction 2 hours down at-20 ℃.Be added on the DMF among the THF.By salt solution and acetic acid quencher reaction.Isolate organic layer, wash with water, by dried over mgso, use B to filter.Use methylene dichloride-hexanes mixtures to come purified mixture as moving phase by the silica gel chromatographic column method, obtain corresponding aldehyde.Under nitrogen, in flask, this aldehyde is dissolved in the acetone.Add the 3N HCl aqueous solution.The stirring at room mixture is also monitored by TLC.When reaction is reached home, use the saturated sodium bicarbonate neutralise mixt.Evaporation acetone.Use THF-DCM to be further purified product as moving phase with the THF extraction product and by flash column chromatography, obtain the alcohol of corresponding deprotection.(23a): the alcohol with deprotection in flask is dissolved in the dry dichloromethane.Add trityl chloride, diisopropylethylamine, 4-dimethylaminopyridine.Stirring reaction 16 hours.Filtering-depositing.Wash solution with water, use dried over mgso, filter evaporation then.Use the purified by flash chromatography product, obtain corresponding trityl ether.In flask, with this trityl ether and 2-dicyano methylene radical-3-cyano group-4-methyl-5-trifluoromethyl-5-(4 '-phenyl) phenyl-2, the 5-dihydrofuran (8, Fig. 2) be blended in the ethanol.Reaction is heated to 60 ℃ to keep 6 hours.Inclusion is cooled to room temperature.Filtering mixt.Come purifying filtrate by column chromatography in conjunction with methyl alcohol or washing with alcohol, obtained chromophore compound 23a; (23b) in nitrogen, under 60 ℃, in flask with pure and mild 2-dicyano methylene radical-3-cyano group-4-methyl-5-trifluoromethyl-5-(4 '-phenyl) phenyl-2 of deprotection, the 5-dihydrofuran (8, Fig. 2) in ethanol, stir.By the TLC monitoring reaction.After 6 hours, inclusion is cooled to room temperature.Collect dark solid by filtering at B.Be further purified material by silica gel column chromatography and recrystallization, the chromophore-alcohol and the yield that obtain black powder are 60%.In having the flask of stirring rod, chromophore-alcohol is dissolved in the dry dichloromethane.Add imidazoles and tri-phenyl chloride.By the tlc monitoring reaction.After 30 minutes, leach precipitation.Use the salt solution washing soln, by dried over mgso, filter evaporation then.Be further purified compound by flash column chromatography, crystallization with hexane wash.The yield of compound 23b is 70%.
Object-main body EO polymkeric substance is by the 23a of chromophore and 23b and main polymer 28-30 (Fig. 6) preparation.The characteristic that has shown the EO polymkeric substance in table 1 and the table 2.Numeral in the bracket of material reference number back is by weight the loading capacity of chromophore.The main polymer of high Tg causes the EO matrix material with identical chromophore of higher Tg.In table 1 and table 2, has the Tg that 29 matrix material demonstrates 28 matrix materials that are higher than identical loading capacity.Matrix material has similar light loss and EO coefficient.
Table 1: the main EO characteristic of the 23a of chromophore
Figure BDA00003195971500241
Table 2: the main EO characteristic of the 23b of chromophore
Figure BDA00003195971500242
In order to study the permanent stability of EO polymkeric substance, carried out the accelerated deterioration test.In these tests, use indium tin oxide (ITO) as base material polarization EO polymeric film.Then in vacuum environment the sample of sealing polarization to avoid the relevant degraded of possible oxidation and to place in the stove that arranges with different high temperature.Along with the variation that reaches 2000 hours time, the decay r of monitoring EO coefficient 33Study EO polymer composites 28-23a (50%) (Tg175) (Fig. 7 A) down at 85 ℃, 100 ℃ and 110 ℃.Under 85 ℃, r after testing 2000 hours 33Keep initial r 3394%.28-23b (55%) under we have also studied 85 ℃, 100 ℃ and 110 ℃ and 29-23b (55%) (being respectively Fig. 7 B, 7C, 7D).28 and 29 Tg is respectively 167 ℃ and 193 ℃.Fig. 7 B-D has shown the r of the standardized test when reaching 1800 hours digestion time under each temperature 33Value.In Fig. 7 B, 29 matrix materials have shown that stability is better than 28 matrix materials slightly.The difference of stability is relatively little, reason be they separately Tg and 85 ℃ of test conditions between the big temperature difference.Under 100 ℃ (Fig. 7 C), 29 systems have the stability than 28 systems 2.5%.Under 110 ℃ (Fig. 7 D), 29 systems demonstrate the stability than 28 systems 9%.Discovery is under each temperature, and 29 systems have the time stability higher than 28 systems, and the difference of stability is more remarkable under higher application of temperature.The effect of higher main polymer Tg is the Tg that significantly improves matrix material, and therefore strengthens the stability of measured EO coefficient.
In the literature in the different models of Ti Chuing, we find people such as Lindsay, Polymer48 (2007), the disclosed a kind of models show of 6605-6616 (it is incorporated into by reference at this) goes out consistence good between testing data and the model prediction and the most relevant with our work.We use isothermal Ageing Model Jonscher equation
V π(t)/V π(0)＝1+(t/T) /
And the tanh method of Lindsay:
In(T/T p)＝E R(1+tanh[(T c-T)/D])/2RT+E P/RT
Come lax temperature dependency modeling and draw the activation energy of the EO polymeric system of our polarization.In this model, E RAnd E pBe respectively the activation energy of nonbreakable glass attitude and submissive attitude.Tc and D are the width of core temperature and zone of transition.
Fig. 7 E has shown under 85 ℃, 100 ℃ and 110 ℃ of three kinds of differing tempss, the curve-fitting results of the testing data of 28-23a (50%) and use Jonscher equation.As can be seen, there is good consistence between our testing data and the modeling result.Based on the Jonscher equation model, we have obtained fitting parameter T (time constant) and the j (index) of all 5 probe temperatures.We use further the extrapolate r of our EO material 25 years time of these T and j subsequently 33Decay (or V πIncrease).Fig. 7 B has shown under 85 ℃, 100 ℃ and 110 ℃, the standardized V of 28-23a (50%) in 25 years πThe extrapotation that increases.Under 85 ℃ of operations, model prediction goes out only 1.14 times V πIncrease.The permanent stability (80 ℃, Fig. 7 B) that have remarkable enhancing than other existing EO polymeric systems such as CLD-PI (reporting among the Lindsay).
We have also shown the curve-fitting results (Fig. 8) that adopts EO polymkeric substance 28-14 (50%), 28-23a (50%), 28-23b (55%) and the 29-23b (55%) of the tanh model that proposes in Lindsay:
In(T/T P)＝E R(1+tanh[(T c-T)/D])/2RT+E P/RT
Purpose based on the comparison, we have also repainted the curve of CLD-PI (CLD-APEC).28-14 (50%) (1.09eV) and the activation energy of 28-23b (1.14eV) system in similar scope.In addition, be transformed into 28-23a (Tg=175 ℃, Fig. 8 A) or 28-23b (Tg=167 ℃, Fig. 8 B) from 28-14 (50%) (Tg=140 ℃), the zone of transition that stability of material is obviously degenerated is significantly pushed to higher temperature range (high about 20 ℃ in this case).29-23b (Tg=193 ℃, Fig. 8 A and 8B) has been seen similar behavior.
28-23b (55%) under the Jonscher equation also is used for comparing 85 ℃ and 110 ℃ and 29-23b (55%) are (Fig. 9).Under 85 ℃, there is not obvious difference in permanent stability.Under 110 ℃, 29-23b (55%) shows has increased by 33%, and 28-23b (55%) demonstrates and increased by 81%.This shows that higher Tg polymeric system (as 29) demonstrates the advantage aspect the long-term behaviour under higher service temperature.
The mach-zehnder EO polymer modulator with 23a and 23b for preparing to fall ridge waveguide (inverted-rib waveguide) at 3 cun wafers.Figure 10 has explained apparatus and process stream.Bottom electrode is by sputter and be patterned, and handles wafer with the short stick of band mercaptan and polar group then, then rotation and cured base wrap (LP202C (heat-setting, crosslinked sol-gel material), or UV15LV).The ridge waveguide that then will fall prepares at the bottom covering.Behind plasma surface treatment bottom covering and ridge waveguide, the sandwich layer of the matrix material that deposition and thermofixation are made of main polymer and the 23a of chromophore or 23b.After the surface treatment sandwich layer, rotation and thermofixation top covering LP33ND (heat-setting, crosslinked sol-gel material).After the whole optical material that makes up equipment piled up, polarizing electrode was deposited and patterning, then under 164 ℃ to 220 ℃ temperature and 750V in the bias voltage scope of 950V, carry out polarization process with aligning chromophore.Core material is depended in the selection of polarization temperature and voltage.Effect and useful length that polarizing electrode also is designed to play working electrode are 2.1cm.Equipment is cut into single for use in test.Figure 11 has shown that electrode configuration and Figure 12 have shown wherein a kind of cross-sectional view of polymer modulator.
Optical insertion loss (optical insertion loss), half-wave voltage (V have been measured π) and optical extinction coefficient.Summarized equipment V in the table 3 πWith the insertion loss.28 as not having significant difference between the 23a of main polymer and the 23b.It also is similar inserting loss.When using 29 during as the 23b of main polymer, V πHigher.
The V of table 3:EO polymer modulator πWith the insertion loss
The EO polymkeric substance Sheet ID V π(V) Insert loss (dB/cm)
28-23a(50％) V25-25-A 1.28 9.1
28-23a(50％) V25-8-C 1.09 10.8
28-23b(55％) V25-43-C 1.16 9.8
29-23b(55％) V26-14-B 1.42 8.3
The mach-zehnder equipment (Figure 13 A) that reaches 1300-3000 hour use 28-23b (55%) under having studied 85 ℃.Find the standardized V of 28-23b (55%) πIncrease to benchmark (initially) V πAbout 1.02-1.04 doubly, this is equivalent to r 33Reduce 2-4%, this meets film r very much 33Test.Use the Jonscher model to estimate the performance (Figure 13 B) in 25 years, the equipment that expection is made by 28-23b (55%) material will show 11% V in 25 years πIncrease.
Studied the equipment V of the core 29-23b (55%) of higher Tg πStability.Behind following 265 hours of 100 ℃ and 110 ℃, find V respectively πThan initial V πIncrease by 1.04 and 1.07.It is better that we observe the stability of equipment of core of the higher Tg that uses the main polymer 29 comprise higher Tg.We have also tested 29-23b (55%) and have continued 30 minutes up to 150 ℃ with under 170 ℃, and find V πThan initial V πIncrease by 1.12 and 1.49 times respectively.This shows that the short period of time is exposed to high temperature and do not damage equipment performance, thereby makes the equipment of material manufacturing thus and pyroprocessing is more compatible and/or more be not vulnerable to surpass because of short-term the influence of temperature condition initiating failure.
Though this paper discloses many aspects and embodiment, other aspects and embodiment have been imagined.Many aspects disclosed herein and embodiment are based on the explaination purpose, and to be not intended to be restrictive, and actual range and spirit are represented by following claim.

Claims (36)

1. an electro-optic polymer comprises the main polymer that comprises at least one aromatic yl group and the object non-linear optical chromophore with structure D-π-A, and wherein: D is donor; π is π-bridge; A is acceptor; At least one aromatic yl group is covalently attached at least one among D, π or the A; And described at least one aromatic yl group has noncovalent interaction at least a and a part that hinders the unpolarized described main polymer of chromophore.
2. electro-optic polymer according to claim 1, wherein said noncovalent interaction are that pi-interacts, size interacts or pre-organized binding interactions.
3. electro-optic polymer according to claim 2, wherein said pi-interact and comprise that at least one is in the π system on the described bulky group and at least one π system on described main polymer.
4. electro-optic polymer according to claim 3, wherein the described π system on described bulky group comprises aryl, polyaromatic, heterocyclic aryl, many heterocyclic aryls group.
5. electro-optic polymer according to claim 4, wherein the described π system on described main polymer comprises aryl, polyaromatic, heterocyclic aryl, many heterocyclic aryls group.
6. electro-optic polymer according to claim 5 wherein in the described π system on the described bulky group is and the interactional donor of pi-of described π system on described main polymer or the interactional donor of pi-or the pi-interaction receptor of pi-interaction receptor complementation.
7. electro-optic polymer according to claim 1, wherein said electro-optic polymer has second-order transition temperature, and described large volume substituting group hinders chromophore's depolarize being lower than described second-order transition temperature.
8. electro-optic polymer according to claim 1, wherein said chromophore comprises at least two bulky group.
9. electro-optic polymer according to claim 8, one of them bulky group is attached to D and a bulky group is attached to π or A.
10. electro-optic polymer according to claim 1, wherein: described chromophore has the fusing point greater than 120 ℃; Described polymkeric substance has and is higher than 120 ℃ second-order transition temperature; And described electro-optical composite material has and is higher than 120 ℃ second-order transition temperature.
11. electro-optic polymer according to claim 10, the loading density of wherein said chromophore are greater than by weight 20%.
12. electro-optic polymer according to claim 10, the loading density of wherein said chromophore are greater than by weight about 35%.
13. electro-optic polymer according to claim 1, wherein D comprises
Figure FDA00003195971400021
R wherein 1Comprise alkyl, assorted alkyl, aryl or heteroaryl groups independently; R 2When occurring, comprise H, alkyl group, assorted alkyl group, aromatic yl group or heteroaryl groups independently at every turn; R 3When occurring, comprise halogen, alkyl group, assorted alkyl group, aromatic yl group or heteroaryl groups independently at every turn; N is 0-3, and the R bag Draw togetherDescribed bulky group.
14. electro-optic polymer according to claim 13, wherein said electrooptical chromophore also comprises the bulky group that is attached to π or A.
15. an electro-optical composite material comprises the described non-linear optical chromophore of claim 1, wherein said matrix material have under 85 ℃ after 100 hours greater than 80% time stability.
16. an electro-optical assembly comprises the described electro-optic polymer of claim 1.
17. electro-optical assembly according to claim 16, wherein said electro-optical assembly comprises Mach refractometer, Michelson interferometer, micro-ring resonator or directional coupler.
18. electro-optic polymer, the non-linear optical chromophore and the main polymer that comprise polarization, wherein said non-linear optical chromophore are replaced by two or more bulky group and described main polymer is configured to cooperate to hinder chromophore's depolarize with described bulky group.
19. electro-optic polymer according to claim 18, wherein said non-linear optical chromophore have structure D-π-A, and wherein: D is donor; π is π-bridge; A is acceptor; D is replaced by bulky group; And π is replaced by bulky group.
20. interacting by pi-, electro-optic polymer according to claim 19, wherein said bulky group and described polymkeric substance cooperate.
21. electro-optic polymer according to claim 20, wherein said bulky group comprises aromatic yl group.
22. electro-optic polymer according to claim 21, wherein said aromatic yl group are aryl hydrocarbon, aryl polynuclear hydrocarbon, heteroaryl or polyheteroaromatic independently.
23. electro-optic polymer according to claim 21, wherein said main polymer are polycarbonate, poly-(arylene ether), polysulfones, polyimide, polyester, polyacrylic ester or its any multipolymer.
24. electro-optic polymer according to claim 21, wherein said main polymer have greater than 150 ℃ Tg and are polysulfones; Polyester; Polycarbonate; Polyimide; Polyester-imides; Polyarylether; Poly-(methacrylic ester); Poly-(ether ketone); Polybenzothiozole; Polybenzoxazole; Polyphenyl and dithiazole; Ju Ben Bing Er oxazole; Poly-(aryl oxide); Polyetherimide; Poly-fluorenes; Polyarylene vinylene; Poly quinoline, polyvinyl carbazole; Or its any multipolymer.
25. an electro-optical assembly comprises electro-optic polymer according to claim 18, wherein said electro-optical assembly has at the V that did not increase to after 2000 hours under 85 ℃ greater than 5% π
26. an electro-optical assembly comprises electro-optic polymer according to claim 18, wherein said electro-optical assembly has at the V that did not increase to after 2000 hours under 85 ℃ greater than 10% π
27. an electro-optical assembly comprises electro-optic polymer according to claim 18, wherein said electro-optical assembly has at the V that did not increase to after 2000 hours under 85 ℃ greater than 15% π
28. an electro-optical assembly comprises electro-optic polymer according to claim 18, wherein said electro-optical assembly has at the V that did not increase to after 2000 hours under 85 ℃ greater than 20% π
29. electro-optic polymer, comprise non-linear optical chromophore and main polymer, wherein: described non-linear optical chromophore have the large volume substituting group that comprises at least one aromatic yl group and described main polymer have be selected with the interactional aromatic yl group of described substituent described aromatic yl group.
30. electro-optic polymer according to claim 29, wherein said substituting group comprise 2 or 3 aromatic yl groups.
31. electro-optic polymer according to claim 30, wherein said chromophore has structure D-π-A and described triaryl group has structure
Figure FDA00003195971400041
Wherein: D is donor; π is π-bridge; A is acceptor; X is the substituting group center; Ar 1, Ar 2And Ar 3It is described aromatic yl group; And L is the covalently bound group that is attached to D, π or A.
32. electro-optic polymer, comprise the non-linear optical chromophore with structure D-π-A, wherein D is donor, π is π-bridge, A is acceptor, and at least one among D, π or the A covalently attached to the bulky group that comprises at least one aromatic yl group, and wherein said electro-optic polymer has than time stability big when alkyl group replaces described aromatic yl group.
33. electro-optic polymer according to claim 32, wherein said bulky group comprises at least two aromatic yl groups, and wherein said electro-optic polymer has than time stability big when alkyl group replaces described aromatic yl group.
34. electro-optic polymer according to claim 33, wherein said bulky group comprises at least three aromatic yl groups, and wherein said electro-optic polymer has than time stability big when alkyl group replaces described aromatic yl group.
35. an electro-optic polymer comprises non-linear optical chromophore and main polymer, wherein: described non-linear optical chromophore has the substituting group group that comprises at least two aromatic yl groups; Described main polymer comprises the subelement that comprises at least two aromatic yl groups; And the described aromatic yl group of described non-linear optical chromophore is preferentially aimed at the described aromatic yl group of described subelement.
36. electro-optic polymer according to claim 35, wherein said main polymer is polysulfones; Polyester; Polycarbonate; Polyimide; Polyester-imides; Polyarylether; Poly-(methacrylic ester); Poly-(ether ketone); Polybenzothiozole; Polybenzoxazole; Polyphenyl and dithiazole; Ju Ben Bing Er oxazole; Poly-(aryl oxide); Polyetherimide; Poly-fluorenes; Polyarylene vinylene; Poly quinoline, polyvinyl carbazole; Or its any multipolymer.
CN2011800550542A 2010-12-03 2011-09-15 Stabilized electro-optic materials and electro-optic devices made therefrom Pending CN103270135A (en)

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