CN100510810C - Optical waveguides and methods thereof - Google Patents

Optical waveguides and methods thereof Download PDF

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CN100510810C
CN100510810C CNB2004800400494A CN200480040049A CN100510810C CN 100510810 C CN100510810 C CN 100510810C CN B2004800400494 A CNB2004800400494 A CN B2004800400494A CN 200480040049 A CN200480040049 A CN 200480040049A CN 100510810 C CN100510810 C CN 100510810C
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norborene
developable
monomer
multipolymer
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CN1902515A (en
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长木浩司
森哲也
R·拉维奇兰
藤原诚
高浜启造
渡边启
野中启孝
大竹有美子
A·拜尔
L·罗德斯
D·阿姆罗梭
松山睦宏
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Sumitomo Bakelite Co Ltd
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Abstract

Embodiments in accordance with the present invention provide waveguide structures and methods of forming such structures where core and laterally adjacent cladding regions are defined. Some embodiments of the present invention provide waveguide structures where core regions are collectively surrounded by laterally adjacent cladding regions and cladding layers and methods of forming such structures.

Description

Optical waveguide and forming method thereof
The cross reference of related application
The application requires the right of priority of U.S. Provisional Application No.60/523978 that submitted on November 21st, 2003 and the No.60/585235 that submitted on July 2nd, 2004.The content of these applications is introduced by reference at this in full.
Technical field
Relate generally to optical waveguide of the present invention and their method of formation.
Background technology
Use becomes important just day by day by the optical frequency carrier data transmission that the radiation source such as laser or light emitting diode generates.Conducting or guiding a kind of mode of this optical frequency carrier wave from any to another point is optical waveguide.Optical waveguide comprises second medium that first medium of the light substantial transparent of optical frequency carrier wave and refractive index is lower than first medium.First medium is surrounded or or seals within it by second medium.The light that is incorporated into first medium, one end with second medium experience total internal reflection at the interface, therefore the spindle guide along first medium draws.The optical transmission medium of normal use is the glass that forms elongated fibers.
Yet although glass optical fiber is easily for long Distance Transmission data, they are not easy to complicated high-density circuit, and this is because the high density of sort circuit makes its use be a problem and costliness.On the other hand, polymeric material has huge prospect in order to make effective, reliable, the passive and active integrated package of cost that can bring into play function that integrated optics requires.
Therefore, sizable effort is directed to and forms Light Coupled Device and nearest optical waveguide, and they can use the photo-hardening technology to be formed by polymeric material.For example, in people's such as Booth U.S. Patent No. 5292620, disclose structure and used the photo-hardening technology to form the method for these structures with prespecified geometric.Structure in the US5292620 patent is included in the channel waveguide of at least a embedding in the lamination matrix, wherein at first forms this waveguide and any syndeton in removably placing the suprabasil photo-hardening film of support.This at first be shaped after, unload photohardenable film from supporting substrate, and between the first and second photohardenable layers lamination.In such a way, the photohardenable layer region adjacent with any syndeton with the class of waveguide channels zone serves as the overlay area in this layer plane, and first and second photohardenable layer serves as the overlayer of this above and below, plane.
On the other hand, Japanese laid-open patent communique Nos.2004-35838H10-48443 and 2001-296438 disclose polymer film have been exposed under the actinic radiation, to change the chemical constitution of polymkeric substance, so that obtain the method for waveguiding structure.
Description of drawings
Below with reference to accompanying drawing embodiment of the present invention are described.
Fig. 1,2 and 3 describes in a simplified manner according to the embodiment that exemplifies of the present invention, but forms the synoptic diagram of the order of waveguide region in the waveguide patterned film;
Fig. 4 is electron probe micro-analysis (EPMA) figure according to the structure of the formation of the order described in Fig. 1,2 and 3;
Fig. 5,6,7,8 and 9 describes in a simplified manner according to of the present invention another and exemplifies embodiment, but forms the synoptic diagram of the order of waveguide region in the waveguide patterned film; With
Figure 10 is described in to select under the wavelength, at RHODORSIL
Figure C200480040049D0006194151QIETU
PHOTOINITIATOR2074 (available from Rhodia USA Inc., Cranbury, in UV spectrum NJ) and the stacked absorption spectrum, the histogram of the energy by the output of typical mercury vapor light.
Embodiment
Embodiment of the present invention are below described.Based on content disclosed by the invention, this various modifications, reorganization or the variation that exemplifies embodiment described herein will be readily apparent to persons skilled in the art.Be appreciated that all this modifications, reorganization or the variation that depend on the present invention's instruction are regarded as in scope of the present invention and spirit, wherein can pass through these modifications, reorganization or variation, these instructions have obtained progress in the art.
For example use term " norborneol vinyl monomer " to be meant to contain monomer material herein, use term " norbornene polymer " to be meant the polymeric material that forms and have at least one repetitive of same basis structure B for example shown below by this monomer herein according at least one norborene part of structure A shown below.
Figure C200480040049D00071
Using term " norborneol vinyl monomer " also to comprise herein can be by the polycyclic olefin of cationic palladium initiating agent polymerization, described cationic palladium initiating agent will cause species to increase, in this species increase, can not exist β-hydride to eliminate or suitable end process, use term " norbornene polymer " further to comprise the polymeric material that forms by this monomer herein.
Use term " crosslinking chemical " and " cross-linking monomer " herein interchangeably, be meant the monomer that contains at least two norborene class parts, for example above monomer with " A " expression, wherein each monomer is polymerisable.This crosslinking chemical comprises fused polycycle system and the polycyclic system that is connected, and below will describe more fully.
Term " class of waveguide channels " or " nuclear core (core) " are meant to have square or square-section section and in some embodiments, the range of size of square or square-section section is about 1 micron-Yue 200 microns, in other embodiments, be about 5 microns-Yue 100 microns, with in other embodiment, be about 10 microns-Yue 60 microns a part of polymer film.This class of waveguide channels or nuclear core zone are further characterized in that refractive index is higher than the refractive index of the side direction neighboring region that is called as the overlay area.Can use the wavelength of wide region, usually, but be not limited to 600nm-1550nm, for example use optical waveguide according to embodiments of the present invention in the data communication.Usually operative wavelength depends on material and optical signature thereof.
At first with reference to figure 1, according to embodiment of the present invention, photoinduced heat-developable material (PITDM) but part of waveguide patterned film 10 be described to be deposited on and support in the substrate 5.Usually, substrate 5 is silicon, silicon dioxide, glass or quartz substrate, or polyethylene terephthalate (PET) film.
PITDM comprises norbornene polymer material matrix 15 and the dispersion material 20 within it that for example has a plurality of norborene class repetitives.Material 20 can comprise for example light trigger material, procatalyst material and norborene class monomer material.Be appreciated that herein term " light trigger material " comprise kation and negative ion light trigger material the two, they also are called as " photo-acid generator " and " photic generated base alkaline agent " respectively.In general, PITDM in the film 10 also comprises one or more antioxidant materials, to prevent that non-required free radical from generating and the autoxidation of norborene class material, but PITDM does not experience under the time period condition of limited of oxidizing condition or wherein this exposure therein, comprises that this antioxidant may choose wantonly.In the material 20 each basically evenly and random distribution in matrix 15.Therefore, when forming film 10, this material 20 basically evenly and random distribution within it.
Use any in several suitable applying methods, apply PITDM to substrate 5, form film or layer 10.This method includes, but not limited to spin coating, spraying, dip-coating and is coated with the scraper shop.In an embodiment that exemplifies of the present invention, the solution of PITDM (being also referred to as " varnish " or " varnish solution " herein) is poured on the substrate of glass and uses the scraper shop to paint homogeneous thickness basically.In some embodiments of the present invention, this layer homogeneous thickness basically is about 5 microns-Yue 200 microns, and in other embodiments, the thickness of layer 10 is about 10 microns-Yue 100 microns, with in other embodiment, the thickness of layer 10 is about 15 microns-Yue 65 microns.After the shop is coated with, the substrate of glass of coating is left standstill, on the levelling plate that ventilates so that levelling comes from the surface imperfection degree that applying method causes, and is convenient to solvent evaporation and forms solid film, for example at the PITDM film 10 described in Fig. 1.Be noted that by the shop solution of varnishing to become homogeneous thickness basically, generate PITDM film 10, and the material 20 that comprises in this varnish solution and matrix 15 evenly and randomly are distributed in the film 10 basically.
Matrix 15 generally includes polymkeric substance, the norbornene polymer (hereinafter, using term " first repetitive " to be meant two kinds of different repetitives herein) that for example has two or more different norborene class repetitives with " second repetitive ".In some embodiments of the present invention, come from the multipolymer that polymkeric substance that the first-class substantially amount hexyl of polymerization norborene (HxNB) and diphenyl methyl norborene methoxy silane (diPhNB) obtain causes can be used for matrix 15.Yet when matrix 15 can comprise two or more different norborene class repetitives, for embodiments more of the present invention, matrix 15 can be suitable norborene class homopolymer.Recognize that described in embodiments of the invention norbornene polymer that exemplifies and monomer can provide the optical waveguide with good heat resistant feature.Further will recognize, thereby the improvement of the norbornene polymer that exemplifies described in embodiment of the present invention hydrophobicity provides the damage to water, for example because of suction being caused as the less sensitive film of change in size.Although embodiment of the present invention have been described the PITDM that comprises norbornene polymer, the invention is not restricted to this polymkeric substance.For example, the polymkeric substance that is used for PITDM comprise concerning the optical waveguide purpose enough transparent or colourless and with the polymkeric substance of mhc monomer.Term " compatible " is meant that monomer is miscible at least and does not have to produce in polymeric matrix to be separated herein.For example, other norbornene polymer is as the various polymerizations by the norborneol vinyl monomer, ring-opening metathesis polymerization (ROMP) for example, ROMP combines with hydrogenation, by free radical or cationic polymerization and those synthetic polymkeric substance, and can use the copolymerization of ethylene-norbornene.In addition, can use other norbornene polymer, for example by using initiating agent or the catalyzer except the cationic palladium initiating agent, for example nickel and other transition metal initiators synthesize those.Polymkeric substance except norbornene polymer comprise concerning the optical waveguide purpose enough transparent or colourless and with the polymkeric substance of mhc monomer, this polymkeric substance can serve as monomer polymerization within it or crosslinked, and/or comprises the matrix of the side group that can dissociate within it.When polymerization single polymerization monomer in matrix, should be transparent as the polymkeric substance of matrix.The polymkeric substance that exemplifies is polyester, polyacrylate, polymethacrylate, epoxide and polystyrene etc.
Matrix 15 also can comprise the repetitive with the side group that can dissociate.Term " side group that can dissociate " is meant that following side group, described side group comprise that in a single day side group wherein or its at least a portion are exposed to the energy from the energy, for example actinic radiation and/or heat energy following time the part or the site of dissociating.Usually proton, negative ion or free radical be with this part or in this site interaction, causes or cause that side group or its at least a portion dissociate from matrix.Therefore, embodiment of the present invention can have " side group that can dissociate ", that is " side group that acid (proton) can be dissociated ", " side group that alkali (negative ion) can dissociate " or " side group that free radical can dissociate ".
After dissociating, the side group that can dissociate can be removed from matrix, so that change refractive index.On the other hand, the side group that can dissociate then can remain in the matrix if it plays the effect that differing refraction indices is provided between exposure and unexposed area.For example, the side group that can dissociate or at least a portion wherein can at least a portion be dissociated and are caused and reset in polymeric matrix or crosslinked, thereby cause refractive index to change.In a single day therefore use term " photobleaching " to be meant when being exposed under actinic radiation and/or the heat energy, the side group that then can dissociate part or substep from polymeric matrix, dissociate and remove, rearrangement or when crosslinked, any variation of refractive index in polymeric matrix descends no matter increase still.Being appreciated that term " actinic radiation " is meant comprises any radiation that can cause the photochemistry type reaction, and further comprises electron beam irradiation, x-ray etc. herein.
In some embodiments of the present invention, matrix 15 have band-O-,-the Si-phenyl or-side group of OSi-part.In other embodiments of the present invention, matrix 15 have band-Si-diphenyl or-side group of OSi-diphenyl part.In other embodiments of the present invention, matrix 15 is homopolymer or multipolymers of diPhNB monomer.
According to embodiments more of the present invention, material 20 comprises the monomer that one or more are different, and wherein at least a such monomer is a cross-linking monomer.Find that the available crosslinking chemical that exemplifies is two (norborene ethoxy) dimethylsilane (SiX).
Promotor (being also referred to as the activator (being also referred to as initiating agent) that makes the procatalyst activation).For example, this activation can comprise the promotor (hereinafter being also referred to as " WCA ") that Weakly coordinating anions is provided, and wherein this WCA substitutes the leaving group on the procatalyst.This WCA that exemplifies is four (pentafluorophenyl group) borate (FABA), SbF 6 -, four (pentafluorophenyl group) gallate, aluminate, stibate, other borate, gallate, carborane and halo carborane.According to embodiments more of the present invention, in a single day promotor is exposed to the next decomposition of actinic radiation of suitable wavelength, in relevant part, forms kation, for example proton and the WCA that is used to activate procatalyst.Providing under the situation of crosslinkable side group, can advantageously select to have this Weakly coordinating anions FABA -Or SbF 6 -Kation or negative ion light trigger.
The material that exemplifies that can be used for embodiment of the present invention is available from Rhodia USA Inc., Cranbury, NJ's
Figure C200480040049D00101
PHOTOINITIATOR 2074, CAS178233-72-2 and available from Toyo Ink Mfg.Co., Ltd., Tokyo, the TAG-372R photo-acid generator of Japan, CAS 193957-54-9.In addition, available from Midori KagakuCo., Ltd., Tokyo, the MPI-103 of Japan, CAS 87709-41-9, available from Toyo Ink Mfg.Co., Ltd., Tokyo, the TAG-371 of Japan, CAS 193957-53-8 and available from Toyo GoseiCo., Ltd., Tokyo, three (4-tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borates (being also referred to as " TTBPS-TPFPB ") of Japan.
Although embodiment of the present invention have been described about being used for the PITDM that contains specific light initiating agent (photo-acid generator) of promotor, the invention is not restricted to this light trigger.As long as change the activation temperature (this is that actinic radiation causes) of (for example raising or reduction) procatalyst (catalyzer), perhaps, then can use any promotor or light trigger as long as the specific part in the side group of matrix dissociates (this is that actinic radiation causes).
When PITDM comprises procatalyst, the part represented of its optional personal following formula I a and Ib usually:
(E (R) 3) 2Pd (Q) 2Ia; With
[(E(R) 3) aPd(Q)(LB) b] p[WCA]r Ib。
In Formula I a and Ib, E (R) 3Represent the sub-part of the neutral power supply of the 15th family, wherein E is the element that is selected from the 15th family in the periodic table of elements, part and Q that on behalf of hydrogen one of (or its isotope) or negative ion, R contain alkyl independently are the anion ligands that is selected from carboxylic acid group, thiocarboxylic acid base and the carbodithioic acid base.In formula Ib, LB is a lewis base, the negative ion of the weak coordination of WCA representative, a represents integer 1,2 or 3, b represents integer 0,1 or 2, wherein the a+b sum is 1,2 or 3, and on behalf of palladium kation and Weakly coordinating anions, p and r work to be equilibrated at the integer of multiple of the numerical value of the structural electric charge of formula Ib.In the embodiment that exemplifies, p and r are independently selected from integer 1 and 2.Such procatalyst that exemplifies is Pd (PCy 3) 2(OAc) 2(hereinafter referred to as " Pd785 "), wherein Cy writes a Chinese character in simplified form, and it represents the cyclohexyl part, and Ac writes a Chinese character in simplified form, and it represents the acetic acid esters part.Recognize, more than and the described in some embodiments of the present invention procatalyst that exemplifies can come polymerization norborneol vinyl monomer by addition polymerization, so produce polymkeric substance or polymeric material with good heat resistant feature.
Although embodiment of the present invention have been described about comprising the PITDM of concrete procatalyst, the invention is not restricted to this procatalyst.As long as change (for example raising or reduction) activation temperature (this is owing to actinic radiation causes), can use any procatalyst.
Under the situation in antioxidant is included in material 20, find available from Ciba SpecialtyChemicals Corporation, Tarrytown, NY's
Figure C200480040049D00111
Figure C200480040049D00112
1076 Hes
Figure C200480040049D00113
Figure C200480040049D00114
The 168th, useful, but also can use other suitable antioxidant.Other antioxidant that exemplifies comprises
Figure C200480040049D00116
129,
Figure C200480040049D00117
1330,
Figure C200480040049D00119
Figure C200480040049D001110
1010,
Figure C200480040049D001111
Figure C200480040049D001112
1790, 3114 Hes
Figure C200480040049D001115
Figure C200480040049D001116
3125.
Now, show the film 10 that a part spreads out referring to Fig. 2.In abundant drying, allegedly after any basically solvent evaporation of using in containing the solution of PITDM, the film 10 that spreads out becomes dry basically solid film.The desciccator diaphragm 10 of PITDM has first refractive index (RI), and wherein a RI is the function that is evenly dispersed in the material 20 in the matrix 15.
As described, by mask element 35, the zone 25 of film 10 is exposed to actinic radiation 30 times, and wherein the source of actinic radiation 30 is selected the susceptibility of this radiation as cation light initiator based on promotor in material 20.Optionally, any suitable sensitizer can be included in the various varnish solution of the present invention.Term " sensitizer " be meant improve light trigger to actinic radiation susceptibility and what and/or the wavelength that changes actinic radiation that reduce its reaction or decompose required time and/or energy to light trigger to the material type under its most responsive wavelength.This suitable sensitizer include, but not limited to anthracene (for example, DBA (9,10-dibutoxy anthracene; CAS76275-14-4), xanthone and anthraquinone).In addition, depend on the absorption peak wavelength, can use other group sensitizer suitably, for example luxuriant and rich with fragrance,
Figure C200480040049D0012194418QIETU
(chrysene), benzopyrene, fluoranthene, rubrene, perylene, indanthrene, thioxanthene-9-one and composition thereof.In the embodiment that some exemplify, suitable sensitizer comprises 2-isopropyl-9H-thioxanthene-9-one, 4-isopropyl-9H-thioxanthene-9-one, 1-chloro-4-propoxyl group thioxanthones, benzothiazine and composition thereof.The typical amount of sensitizer is at least 0.01 weight % of varnish liquid composite, in some cases, at least 0.5 weight % and in other cases, at least 1 weight %.The consumption that is present in the sensitizer in the varnish solution of embodiment of the present invention changes between above any numerical value of enumerating.In film 10, use
Figure C200480040049D00121
Under 2074 the situation, use mercury vapor light,, cause the Rhodorsil decomposition and aforesaid kation and WCA are provided so that the enough energy that is lower than 300 nanometers (nm) to be provided as ultraviolet (UV) radiation source.With exposed areas 25 side direction adjacency be unexposed regional 40, it avoids radiation 30 by the opaque section of described mask element 35.
It is also understood that, mask element 35 is described to only have two openings and passes on the zone 25 that arrives film 10 for radiant rays 30, this description is simplified and mask element 35 can provide and has various more complicated patterns to determine one or more optical waveguide components and/or coupled apparatus.Should be noted that also and can come exposure area 25, in this case, do not need to use any mask element by using laser emission or other accurate beam radiation source.Waveguide can for example be used for data communication applications according to embodiments of the present invention, for example " On board Chip to ChipInterconnects ", " Optical Switches "; Use with various optical backplanes, for example Optical Add Drop Multiplexers (OADM); MultipleXers and Demultiplexers; Arrayed Waveguide Gratings (AWG); Microelectro-mechanical Systems (MEMS) and Microoptoelectro-mechanical Systems (MOEMS).In addition, manufacture method of the present invention can be used for forming diffraction grating, holographic film, lens, microlens array and lens cover structure.Therefore, recognize, can use method manufacturing of the present invention waveguiding structure type mostly just the availability of the photomask by having pattern that this application requires limit.Yet irrelevant with the complicacy of the employed any pattern of definite optical waveguide components, each exposed areas 25 of being determined by this pattern has and one or more unexposed regional 40 of its side direction adjacency.
When being exposed to radiant rays 30 times, the promotor in exposure area 25 is under exposure, and reaction or decompose discharges the negative ion (WCA) of proton or other kation and weak coordination.Proton and WCA play and cause procatalyst on the spot, that is change into activity but be the effect of the active catalyzer of diving in the exposure area 25 of film 10.Be appreciated that, procatalyst or catalyzer being described as " active but for dive active " or " it is active to dive " is meant and does not have any extra variation/reaction, for example under the situation of Sheng Wening, this latent procatalyst or catalyzer at room temperature will can not cause the norborene class monomer polymerization that is enough to form function or using light waveguide in zone 25.Therefore, be required if store, then can not cause norborene class monomer polymerization at for example about-40 ℃ temperature dive procatalyst.
In some embodiments of the present invention, in order to obtain activity but be the purpose of the active catalyst of diving, it is 0.1J/cm that the PITDM film is exposed to exposure energy 2-9J/cm 2Perhaps 0.5J/cm 2-5J/cm 2Actinic radiation under.Typically, the PITDM film is exposed to peak wavelength under this actinic radiation of 200 nanometers-450 nanometer, but can uses other wavelength, other wavelength has funtcional relationship with employed promotor and/or sensitizer.
Active but have the activation temperature that is lower than the procatalyst activation temperature for the active catalyzer of diving.In some embodiments of the present invention, active but have activation temperature for the active catalyzer of diving than low 10 ℃-80 ℃ of the activation temperature of procatalyst.
Referring to Fig. 3, show the structure of Fig. 2 after heat curing.That is to say, to first temperature, be heated under second temperature higher through second period then than first temperature through the structure of first period heating Fig. 2.First temperature is enough to cause activity but is that latent active catalyzer becomes active catalyst and causes norborene class monomer polymerization in zone 25.Second temperature is enough high, so that promotor thermal decomposition or reaction, so in unexposed zone, activate procatalyst.
In some embodiments of the present invention, polymerization single polymerization monomer in matrix forms another polymkeric substance that is different from matrix polymer.In other embodiments of the present invention, monomer (crosslinking chemical) plays the effect of cross-linked polymer matrix.In some of the other embodiments of the present invention, polymerization single polymerization monomer is also hung group by the main chain of matrix polymer or side and is formed branched polymers.
Any be exposed to actinic radiation 30 times before, PITDM film 10 has first refractive index (RI).After this exposure and heating subsequently, the unexposed area 40 that exposed areas 25 has the 2nd RI and side direction adjacency has the 3rd RI, and wherein the 2nd RI and the 3rd RI differ from one another.As mentioned above, can be chosen in the norborneol vinyl monomer that uses in some embodiments of the present invention, they during polymerization, make the RI of this exposure area 25 change to the 2nd RI from a RI in exposure area 25 with box lunch.Therefore use term " selective polymerization " to be meant in selecting the zone, in case this regional exposure under actinic radiation and heat energy, monomer polymerization in polymeric matrix then.Be subjected under the situation of theory not wishing, think that norborneol vinyl monomer from unexposed area 40 is diffused in the exposure area 25 and polymerizations within it and monomer are diffused into exposure area 25 like this from unexposed area 40 and cause changing to the 3rd RI at the RI in zone 40 from a RI.Advantageously, think that also this diffusion process provides the extra monomer in exposure area 25 for polymerization, thereby the RI of auxiliary aforesaid this exposure area changes.
For the poor of the 2nd RI and the 3rd RI is provided, matrix 15 has the refractive index that is different from monomer usually.In some embodiments of the present invention, matrix 15 has the refractive index that is higher than monomer.
Think that the result of diffusion is, exposure area 25 has than the high monomer of unexposed area 40 or the repetitive or the unit concentration of crosslinking chemical.
The 2nd RI of exposure area 25 is lower than under the situation of the 3rd RI of unexposed area 40 therein, and this unexposed area 40 serves as the overlay area that optical waveguide nuclear core or channel and exposure area 25 serve as the side direction adjacency.Perhaps, be higher than at the 2nd RI under the situation of the 3rd RI, the overlay area that optical waveguide nuclear core or channel and unexposed area 40 serve as the side direction adjacency is served as in exposure area 25.
Should be noted that above-described hot step is especially favourable when very first time section is enough to be aggregated in 25 in the zone basically fully.In addition, advantageously, second temperature is high enough to and causes any residual promotor, for example cation light initiator thermal decomposition and formation and the foregoing same species that produces by radiation 30.Be subjected under the situation of invention theory not wishing once more, think that heating not only causes any residual still unpolymerized norborneol vinyl monomer polymerization in exposure area 25 for the second time, and cause any this monomer polymerization that remains in the unexposed area 40.In such a way, be heated to second temperature and play stable effect with optical waveguide channel (or nuclear core) resulting structures of the overlay area of side direction adjacency.Optionally, can adopt extra heating, and in this case, carry out extra heating under the high 20 ℃ temperature than heating for the second time usually for further stable.
Except this circulation of two-stage cure at least, also advantageously, in some embodiments of the present invention, before the heat curing round-robin first step of beginning exposure structure body, wait for about 30 minutes-Yue 60 minutes time period.Although why still uncertain this stand-by period section is favourable, delayed heat curing can make more complete or evenly transform procatalyst and become latent catalyst, thereby polymerization more uniformly is provided in the exposure area.
In some embodiments of the present invention, interacted by part or site in light trigger proton that generates and the side group that can dissociate, at least a portion that this side group takes place the result is dissociated.Be subjected under the situation of theory not wishing, think when some or all of side groups heats in the moment that receives suitable exposure energy and/or under suitable temperature, partially or completely dissociate.
According to the present invention, with reference to some embodiment V21-25 that exemplifies and V51, film 10 can comprise matrix 15, and described matrix 15 comprises diphenyl methyl norborene methoxy silane (diPhNB) and photo-acid generator, for example RHODORSIL
Figure C200480040049D0015194521QIETU
The homopolymer of PHOTOINITIATOR 2074 or multipolymer.When by photomask, this film is exposed to actinic radiation following time, cause variation or reaction in matrix 15 in zone 25.
In the embodiment of the matrix 15 that uses norbornene polymer,, zone 25 is exposed to 1J/cm for the purpose of dissociating and to dissociate side group 2-9J/Gm 2And 3-6J/cm especially 2Exposure energy under.For example, zone 25 can be exposed to peak wavelength under the actinic radiation of 200 nanometer to 450 nanometers.
After exposure, heat this film, refractive index changes in exposure area 25 as a result.Not being bound by under the theoretical situation, think that when heating film the side of dissociating is hung group and removed from matrix.In view of the waveguiding structure that forms the differing refraction indices zone, therefore, in some embodiments, heating film in other embodiments, is heated to more than or equal under 85 ℃ the temperature to more than or equal under 70 ℃ the temperature.The upper limit of temperature is the stable on heating function of film.Under the situation of norbornene polymer, the upper limit is generally about 200 ℃.Therefore, for this film that comprises norbornene polymer, the scope of heating is generally 70 ℃-195 ℃ and typically be 85 ℃-150 ℃.
Therefore, in some embodiments of the present invention, the concentration of unexposed regional 40 side group is higher than exposure area 25.
In embodiments of the invention, can by or the effect of selective polymerization or the effect of photobleaching, perhaps by the combine effect of selective polymerization with photobleaching, thus acquisition different refractive index in exposure area 25 and unexposed area 40.According to embodiments more of the present invention, in order to obtain the effect of selective polymerization, PITDM comprises aforesaid polymeric matrix, monomer, promotor and procatalyst.In order to obtain the effect of photobleaching, PITDM comprises aforesaid polymeric matrix and the light trigger that contains the side group that can dissociate.In order to obtain these effects simultaneously, PITDM comprises aforesaid monomer and procatalyst, contains the polymeric matrix of the side group that can dissociate and suitable light trigger.
In order to obtain the effect of selective polymerization, use heating steps usually, and in order to obtain the effect of photobleaching, only adopting, a step heating steps is enough greater than a step.Should be noted that in addition the heating after, procatalyst, promotor and/or its remnants can be retained in the gained waveguiding structure.By the effect of described selective polymerization in embodiments of the invention, effect or its combination of photobleaching, compare with glass optical waveguide, can and in less time, provide optical waveguide by the processing simplified more.
With reference to figure 4, show according to the present invention the electron probe micro-analysis of the waveguide patterns that in the film that exemplifies, forms (EPMA) figure.For the purpose of the susceptibility that improves EPMA, in the film that exemplifies, use crosslinking chemical monomer SiX, so increase the detection that is used for silicon.On the top of EPMA, described the concentration of silicon and in each vertically extending zone corresponding to unexposed area, with respect to the corresponding neighboring region in exposure area, silicon concentration descends.Possibly and think that this EPMA is that some SiX monomers are diffused into a kind of indication of SiX monomer the exposure area of this polymerization from unexposed area.
In some embodiments of the present invention, after forming optical waveguide, that is form after the overlay area of nuclear core zone and side direction adjacency, can be from substrate 5 except that striping 10, and film 10 can be laminated to or place serve as tectal on one or more layers.Can select or form this overlayer, so that their refractive index (RI) is similar to the RI of overlay area of the side direction adjacency of film 10.
Fig. 5-9 shows according to the order of sequence according to embodiments more of the present invention, forms the method for multilayer lightguide structure.
In Fig. 5, in substrate 100, form the ground floor 110 of the first varnish solution with homogeneous thickness basically.In general, substrate 100 is films of glass, quartz or polyethylene terephthalate (PET).
In some embodiments of the present invention, ground floor 110 has about 5 microns-Yue 200 microns, about 10 microns-Yue 100 microns or about 15 microns-Yue 65 microns homogeneous thickness basically.For the even shakedown solution of varnishing in substrate, can use any suitable coating process, comprising at described in the embodiment of above Fig. 1-3 those.
In Fig. 6, show the second layer 120 of photoinduced heat-developable material (PITDM) to place form on the ground floor 110.Can in addition before dry ground floor 110 basically, by using suitable shop coating method, the shop is coated with the second varnish solution that contains PITDM, forms the second layer 120 on ground floor 110.
Although think that layer 110 and 120 keeps differing from one another basically, in some embodiments of the present invention, in its certain blending of varnish solution of genetic horizon 110 and layer 120 at the interface.Although be not wishing to be bound by theory, think that when finishing the multilayer lightguide structure this blending of two kinds of varnish solution can help improving bonding between layer 110 and the layer 120.Evenly be coated with the shop with required thickness in order to control this blending and to keep the first and second varnish solution, varnish solution can have certain viscosity.For example, in some embodiments of the present invention, the first and second varnish solution can have the viscosity of about 100 centipoises-Yue 10000 centipoises, the viscosity of perhaps about 150 centipoises-Yue 5000 centipoises, the viscosity of perhaps about 200 centipoises-Yue 3500 centipoises.In some embodiments of the present invention, the second varnish solution can have the viscosity that is higher than the first varnish solution.In some embodiments of the present invention, layer 120 has about 5 microns-200 microns, and about 15 microns-125 microns, the thickness that perhaps about 25 microns-Yue 100 microns former states shop is coated with.
Referring to Fig. 7, show the 3rd layer 130 of the 3rd varnish solution to place the form on the second layer 120, thereby form three layers of waveguiding structure 200.Layer 130 is applied on the layer 120 to be similar to the mode of layer 120.
In some embodiments of the present invention, layer 130 has about 5 microns-200 microns, and about 10 microns-100 microns, the thickness that perhaps about 15 microns-65 microns former state shop is coated with.Then,, heat this three-layer structure, allow at least some solvent evaporations in the varnish solution to about 25 ℃-40 ℃ temperature through about 15 minutes-60 minutes.
In the three-layer structure 200 of Fig. 7, to be similar to mode, in layer 120, form waveguide with the zone 40 and the zone 25 on upper strata 10, that is, the overlay area of nuclear core zone and side direction adjacency.Yet, in Fig. 5-9, first with the 3rd layer 110 and 130 different overlay area, overlay area that forms with side direction adjacency in layer 120.Therefore, in the more described embodiments of Fig. 5 of the present invention-9, overlayer is not laminated on nuclear core or the ducting layer.That is to say, although can not have dry situation lower berth coating 110,120 and 130 basically, in some embodiments of the present invention, can be in certain dry lower berth coating 110,120 and 130.
As previously mentioned, but layer is convenient in three layers of waveguiding structure body finishing bonding 110,120 and 130 in its blending at the interface.In some embodiments of the present invention, layer 110 and 130 can use and layer 120 similar varnish solution.Therefore, can be in layer 110 and 130, the polymerization of monomer takes place layer 120 at the interface.
Referring to Fig. 8, to pass through mask element 350, the form that is exposed under the actinic radiation 300 shows three-layer structure 200.Zone 150 is exposed to actinic radiation 300 times by mask element 350; But this exposure is avoided by the opaque section of mask element 350 in zone 140.Based on promotor, for example the susceptibility of cation light initiator is selected actinic radiation sources 300.Therefore, in layer 120, use RHODORSIL
Figure C200480040049D0018194600QIETU
Under 2074 the situation, mercury vapor light, causes the Rhodorsil decomposition and kation and WCA is provided in exposure area 150 so that the enough energy that is lower than 300 nanometers (nm) to be provided as ultraviolet (UV) radiation source.
Pass wherein two openings although mask element 350 shown in Figure 8 has radiant rays 300, mask element 350 can have any pattern to determine one or more optical waveguide components and/or coupled apparatus.
With reference to figure 9, show the structure of Fig. 8 after heat curing.That is to say, at first heat structure shown in Figure 9 to first temperature through first period, the feasible any residual solvent of removing in structure 200, be heated to for the second time under second temperature higher through second period then than first temperature, after the 3rd period be heated to for the third time than under the 3rd high temperature of second temperature.Second temperature is enough to cause activity but is that latent active catalyzer becomes active catalyst and causes the polymerization in exposure area 150 of norborneol vinyl monomer.Under situation about being not wishing to be bound by theory, think in a single day except being exposed to 300 times norborene class monomer polymerizations in zone 150 of actinic radiation, the norborneol vinyl monomer also is diffused in the exposure area 150 and in this polymerization from layer 120 interior unexposed area 140.In structure 200, exposure of each layer and heat curing are similar at described in the embodiment of Fig. 1-3 those.Therefore, after heating for the second time, can expose therein and one of unexposed area 150 and 140 are that nuclear core zone and another are to see waveguide patterns in the structure 200 of overlay area of side direction adjacency.
Although in zone 150, second temperature is for being enough the polymerization fully basically, and the 3rd temperature can be enough high, so that any residual promotor is thermal decomposited and forms and the identical species of species by radiation 300 generations.Under situation about being not wishing to be bound by theory, think that once more heating causes any residual polymerization of unconverted monomer still in exposure area 150 for the third time, and also cause the monomer polymerization that remains in the unexposed area 140.Recognize that the 3rd temperature plays the effect of stablizing gained optical waveguide structure body.
In some embodiments of the present invention, layer 110 and 130 can comprise procatalyst, polymeric matrix, monomer and promotor.Can select layer 110 and 130 to use material based on the effect of selective polymerization and photobleaching.When layer 110 and 130 served as overlayer, the polymeric matrix of layer 110 and 130 can be different from layer 120 employed polymeric matrix.For example, have under the situation of high relatively refractive index (RI) at the polymeric matrix of layer 120, layer 110 can have relative low RI with 130 polymeric matrix.Therefore, layer 110 and 130 does not form different nuclear core and overlay area.In addition, this layer 110 and 130 usefulness monomers can be the monomers identical with layer 120, and scalable is lower than layers 120 at the ratio of layer 110 and 130 inner catalysts and monomer.Just because of this, layer 110 can have and the identical or similar refractive index of the monomer that comprises within it with 130 polymeric matrix, and still avoids different nuclear core and the overlay areas of formation in layer 110 and 130.In addition, in some embodiments of the present invention, layer 110 and 130 comprises that repetitive does not have the polymeric matrix of the side group that can dissociate, and/or does not comprise photo-acid generator, thereby avoids the effect of photobleaching in layer 110 and 130.Under situation about being not wishing to be bound by theory, think that monomer from layer 110 and 130 is diffused in the layer 120 and aggregates into polymer chain in adjoining course.Bonding being improved between these adjoining courses.Can take in and/or estimate other varnish solution that is used for layer 110 and 130.For example, in some embodiments of the present invention, be used for layer 110 and 130 varnish solution and mix wherein that at least one norborene class repetitive comprises the norbornene polymer of the side group with epoxide moiety and produces sour material, thereby the open loop of epoxide moiety is provided.Also bonding between the improving layer 110 and 130 of this varnish solution.
In some embodiments of the present invention, varnish solution can comprise that wherein its at least one repetitive comprises the side group with epoxide moiety or the norbornene polymer of TMSE (trimethoxysilylethylgroup group) part group.The norbornene polymer that exemplifies is the multipolymer of hexyl norborene (HxNB) and norborene methyl glycidyl ether (AGENB), the varnish solution that exemplifies comprises this HxNB/AGENB multipolymer and is suitable for causing the acid agent material of its epoxy moieties open loop.This varnish solution provides the overlay area good cohesive of ducting layer with nuclear core and side direction adjacency.In some embodiments, the acid agent material can be a light trigger, for example RHODORSIL 2074 or TAG-372R, and it is suitable for making the epoxy moieties open loop in the forming process of adjacent ducting layer.In some embodiments of the present invention, can select the acid agent material, so that the open loop of epoxy moieties can be independent of the formation of adjacent wave conducting shell.For example, can select acid agent, so that it does not absorb the actinic radiation that is suitable for the promotor in the ducting layer, perhaps it is by thermal activation, rather than photoactivation.In some embodiments of the present invention, can in varnish solution, use photic generated base alkaline agent of nonabsorbable (PBG) or thermic generated base alkaline agent (TBG).This generated base alkaline agent also can provide the epoxy moieties open loop.
As mentioned above, can use the varnish solution that comprises norborene class repetitive and epoxy moieties in some embodiments of the present invention, form three layers of waveguiding structure body.
Monomer
As mentioned above, monomer can be included in the PITMD.In some embodiments of the present invention, monomer can comprise the norborneol vinyl monomer.For example, norborneol vinyl monomer of the present invention can be represented with following structure C:
Figure C200480040049D00211
Wherein " a " represents singly-bound or two key, R 1-R 4Represent hydrogen, alkyl or sense substituent independently, m is integer 0-5 and when " a " is two key, R 1, R 2One of and R 3, R 4One of do not exist.
When substituting group is alkyl, R 1-R 4Can be halo alkyl or perhalogeno alkyl, perhaps even isocyanides base (perhalocarbyl) (for example, trifluoromethyl).In one embodiment, R 1-R 4Representative is selected from hydrogen, straight or branched C independently 1-C 10Alkyl, straight or branched C 2-C 10Alkenyl, straight or branched C 2-C 10Alkynyl, C 4-C 12Naphthenic base, C 4-C 12Cycloalkenyl group, C 6-C 12Aryl and C 7-C 24Alkyl in the aralkyl, halo alkyl and perhalogeno alkyl, R 1And R 2Or R 3And R 4Can represent C together 1-C 10Alkylidene (alkylidenyl).Representative alkyl includes, but not limited to methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, neopentyl, hexyl, heptyl, octyl group, nonyl and decyl.Representative alkenyl includes, but not limited to vinyl, allyl, butenyl group and cyclohexenyl group.Representative alkynyl includes, but not limited to ethinyl, 1-propinyl, 2-propynyl, 1-butynyl and 2-butynyl.Representative naphthenic base includes, but not limited to cyclopentyl, cyclohexyl and ring octyl group substituting group.Representative aryl includes, but not limited to phenyl, naphthyl and anthryl.Representative aralkyl includes, but not limited to benzyl and phenethyl.Representative alkylidene comprises methene base (methylidenyl) and ethidine (ethylidenyl).
In one embodiment, the perhalogeno alkyl comprises perhalogeno phenyl and alkyl.Available haloalkyl is by halogenation partially or completely and be straight or branched in the embodiment of the present invention, and has chemical formula C zX ｀ ｀ 2z+1, wherein X ｀ ｀ is that halogen or hydrogen and z are selected from integer 1-20 independently.In another embodiment, each X ｀ ｀ is independently selected from hydrogen, chlorine, fluorine and/or bromine.In an embodiment again, each X ｀ ｀ is or hydrogen or fluorine independently.
The perfluorinate substituting group comprises perfluorophenyl, perfluoro-methyl, perfluor ethyl, perfluoro propyl, perfluoro butyl and perfluoro hexyl in another embodiment.Except halogenic substituent, can further use straight or branched C 1-C 5Alkyl and haloalkyl, aryl and naphthenic base are come substituted cycloalkyl, aryl and aralkyl.
When side group is sense substituent, R 1-R 4Representative is selected from (CH independently 2) n-CH (CF 3) 2-O-Si (Me) 3,-(CH 2) n-CH (CF 3) 2-O-CH 2-O-CH 3, (CH 2) n-CH (CF 3) 2-O-C (O)-O-C (CH 3) 3,-(CH 2) n-C (CF 3) 2-OH, (CH 2) nC (O) NH 2, (CH 2) nC (O) Cl, (CH 2) nC (O) OR 5, (CH 2) n-OR 5,-(CH 2) n-OC (O) R 5, (CH 2) nC (O) R 5, (CH 2) n-OC (O) OR 5,-(CH 2) nSi (R 5) 3,-(CH 2) nSi (OR 5) 3, (CH 2) n-O-Si (R 5) 3(CH 2) nC (O) OR 6In group, wherein n represents integer 0-10 independently, and R 5Represent hydrogen, straight or branched C independently 1-C 20Alkyl, straight or branched C 1-C 20Halo or whole haloalkyl, straight or branched C 2-C 10Alkenyl, straight or branched C 2-C 10Alkynyl, C 5-C 12Naphthenic base, C 6-C 14Aryl, C 6-C 14Halo or perhalogeno aryl and C 7-C 24Aralkyl.Following R 5The representative alkyl of listing in the definition and above at R 1-R 4Definition in list those are identical.As above at R 1-R 4Definition in list R 5The alkyl of definition can be by halo and perhalogeno.For example, work as R 5Be C 1-C 20When halo or whole haloalkyl, R 5Available following formula C zX ｀ ｀ 2z+1Be representative, wherein z and X ｀ ｀ as defined above, and at least one the X ｀ ｀ on alkyl must be halogen (for example, Br, Cl or F).Recognize that when alkyl during by perhalogeno, all X ｀ ｀ substituting groups are by halogenation.The example of whole haloalkyl include, but not limited to trifluoromethyl, trichloromethyl ,-C 7F 15With-C 11F 23The example of perhalogeno aryl includes, but not limited to five chlorophenyl and pentafluorophenyl group.R 6The base representative is selected from-C (CH 3) 3,-Si (CH 3) 3, CH (R 7) OCH 2CH 3,-CH (R 7) OC (CH 3) 3Or the sour l fraction in the following cyclic group:
Figure C200480040049D00221
R wherein 7Represent hydrogen or straight or branched (C 1-C 5Alkyl).Alkyl comprises methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, amyl group, tertiary pentyl and neopentyl.In said structure, outstanding singly-bound line is meant the position to the sour substituting group of ring protection group bonding wherein from cyclic group.R 6The example of base comprises 1-methyl isophthalic acid-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuran base, oxinane acyl group, 3-oxygen basic ring caproyl, first Wa Nongji lactone group (mevalonic lactonyl), 1-ethoxyethyl group and 1-tert-butoxy ethyl.
R 6Base also can be represented bicyclic methyl propyl (Dcpm) and the dimethyl cyclopropyl methyl of representing with following structure (Dmcp):
Figure C200480040049D00231
With
Figure C200480040049D00232
In some embodiments of the present invention, above-described monomer polymerizable is also used polymeric matrix as photoinduced heat-developable material (PITDM).In order to obtain to have the polymeric matrix of high relatively RI, can select to have aromatics usually, the monomer and the polymerization of nitrogen, Br or Cl part.On the other hand, in order to obtain to have the polymeric matrix of relatively low RI, can select to have alkyl usually, the monomer and the polymerization of F and/or ether moiety.In addition, in some embodiments of the present invention, in preparation varnish solution, above-described monomer can be used in the norborneol vinyl monomer.
Although embodiment of the present invention have been described about containing the PITDM of norborneol vinyl monomer, the invention is not restricted to this monomer.Therefore, the monomer except the norborneol vinyl monomer is also in scope of the present invention and spirit.This monomer comprises can use the polymerization that exemplifies herein, perhaps by any suitable addition polymerization process and/or ring-opening polymerization method polymerization or crosslinked those.The monomer that exemplifies comprises acrylate, methacrylate, epoxide, styrene etc.
Cross-linking monomer
Except norborneol vinyl monomer with structure " C " expression,, also can use " cross-linking monomer ".In some embodiments, this cross-linking monomer can be the norborneol vinyl monomer.For example, can be by norborneol vinyl monomer and the polyfunctional group norborene class cross-linking monomer of listing with structure C more than the copolymerization, the preparation cross-linked polymer.Polyfunctional group norborene class cross-linking monomer is meant that this cross-linking monomer contains at least two norborene class parts (norborneol alkene double bond), the wherein polymerizables in the presence of catalyst system of the present invention of functionality separately.Crosslinkable monomers comprises polycyclic system that condenses and the polycyclic system that is connected.The example of the crosslinking chemical that condenses has been shown in the following structure.In brief, norbornadiene is comprised as many rings crosslinking chemical of condensing and is regarded as containing two polymerisable norborneol alkene double bonds.Cross-linking monomer provides at least a following advantages: the cross-linking monomer polymerization is very fast, so shorten technology; In the heating steps process, they are less sensitive to evaporating, so suppress vapour pressure; Improve the thermotolerance of optical waveguide with them.
Figure C200480040049D00241
Wherein Y represents methylene (CH 2-), m represents integer 0-5 independently, and when m was 0, Y represented singly-bound.Below listed representative monomers with aforementioned chemical formula:
Figure C200480040049D00242
Many rings crosslinking chemical of connection generally is shown by following structure:
Wherein " a " represents singly-bound or two key independently, and m is integer 0-5 independently, R 9Be the divalent group that is selected from bivalent hydrocanbon radical, divalence ether and the divalence silicyl, n equals 0 or 1.Divalence is meant that the free valence state at each end group place of this group is connected on the norborene class part.In one embodiment, bivalent hydrocanbon radical is alkylidene and divalent aryl.Alkylidene is with following chemical formula-(C dH 2d)-be representative, wherein d represents the carbon number in alkylidene chain, and is integer 1-10.In one embodiment, alkylidene is selected from straight or branched (C 1-C 10) alkylidene, for example methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl and inferior decyl.When considering sub-branched alkyl, be appreciated that hydrogen atom in alkylen backbone is by straight or branched (C 1-C 5) the alkyl replacement.
Divalent aryl is selected from divalence phenyl and divalence naphthyl, divalence ether following radicals is representative:
-R 10-O-R 10-
R wherein 10Independently with R 9Identical.The example of many rings crosslinking chemical of concrete connection is representative with following structure:
Figure C200480040049D00251
In one embodiment, crosslinking chemical is selected from shown below those:
Figure C200480040049D00252
It is two [dicyclo [2.2.1] hept-2-ene"-5-methoxyl] silane of dimethyl (being also referred to as two (norborene methoxyl) silane or the SiX of dimethyl herein),
Wherein n is 0-4,
With,
The norborene based cross-linker of some other types includes, but not limited to those that following formula represents.
Wherein m and n then are integer 1-4 if be present in the following formula independently.
In another embodiment, use fluorine-containing norborene based cross-linker.For example, in one embodiment, can use in the following norborene crosslinking chemical of fluoridizing one or more.
Figure C200480040049D00272
With
Figure C200480040049D00281
Should recognize that the monomer that can be used for embodiment of the present invention is not limited to above-mentioned.In addition, can separately or be used in combination the monomer that exemplifies listed above.
After formation has the polymeric matrix of required RI, prepare the solution of this matrix polymer and other material.As mentioned above, other material includes, but are not limited to, one or more different monomers as mentioned above, procatalyst and promotor, the norborneol vinyl monomer that for example wherein at least a such monomer is crosslinked norborneol vinyl monomer, cation light initiator and antioxidant optionally.The RI of this solution or be higher than or be lower than polymeric matrix.The monomer of selecting for varnish solution is a function for the treatment of the relative RI of exposure area.Therefore, wish that therein the exposure area has in embodiments more of the present invention of high relatively RI, can use polymeric matrix with relatively low RI and the monomer that obtains relative high RI when the polymerization together.Yet, in the overlay area that forms one or more waveguide cores cores and side direction adjacency, can use any other combination of polymeric matrix and at least a monomer, to obtain different refractive index in exposure and unexposed area.
Term " height ", " high relatively ", " low ", " low relatively " are not meant the absolute value of RI.This term only is the indication of each zone, polymkeric substance or material refractive index relative to each other.That is to say, think that this material or polymkeric substance have the RI of " height " or " high relatively " when comparing with another material, polymkeric substance or zone with low RI.
Procatalyst
As mentioned above, embodiments more of the present invention are used the procatalyst part as representative with formula Ia and Ib:
(E (R) 3) 2Pd (Q) 2Ia; With
[(E(R) 3) aPd(Q)(LB) b] p[WCA] r Ib。
In Formula I a and Ib, R, E, Q and LB such as front define.The procatalyst that exemplifies according to formula Ia includes, but not limited to Pd (P-i-Pr 3) 2(OAc) 2, Pd (PCy 3) 2(OAc) 2, Pd (PCy 3) 2(O 2CCMe 3) 2, Pd (PCp 3) 2(OAc) 2, Pd (PCy 3) 2(O 2CCF 3) 2And Pd (PCy 3) 2(O 2CC 6H 5) 3, wherein Cp is that cyclopentyl and Cy are cyclohexyl.
The synthetic Embodiment C 1-C4 of following procatalyst has illustrated some available in embodiments of the invention procatalysts that exemplify of preparation.
Embodiment C 1
Preparation Pd (OAc) 2(P (i-Pr) 3) 2
In being furnished with the flask of filling of tap funnel, dropwise add P (i-Pr) with nitrogen 3(8.51ml, CH 44.6mmol) 2Cl 2Solution (20ml) is to Pd (OAc) 2(5.00g is 22.3mmol) at CH 2Cl 2(30ml) in the bronzing suspending liquid of Nei-78 ℃ of stirrings.Suspending liquid becomes clarification gradually and is yellow-green soln, makes it to be warming to room temperature, stirs 2 hours, and the filtrator that passes through 0.45 micron then filters.Filtrate is concentrated to about 10ml then adds hexane (20ml) and obtains yellow solid, filters this solid in air, with hexane (5 * 5ml) washings, and vacuum drying.Output 10.937g (89%).The NMR data: 1HNMR (δ, CD 2C l 2): 1.37 (dd, 36H, CHCH 3), 1.77 (s, 6H, CCH 3), 2.12 (m, 6H, CH). 31P NMR(δ，CD 2Cl 2)：32.9(s)。
Embodiment C 2
Preparation Pd (OAc) 2(P (Cy) 3) 2
In being furnished with two neck round-bottomed flasks of tap funnel, Pd (OAc) 2(5.00g is 22.3mmol) at CH 2Cl 2(50ml) Nei bronzing suspending liquid is set in-78 ℃ of stirrings down.In tap funnel, introduce P (Cy) 3(13.12g, CH 44.6mmol) 2Cl 2(30ml) solution in 15 minutes time period, is added drop-wise in the suspending liquid of stirring then, thereby causes being gradually varied to yellow from bronzing.After-78 ℃ are stirred 1 hour down, make this suspending liquid be warming to room temperature, stirred extra 2 hours, use hexane (20ml) dilution then.In air, filter this yellow solid then, with pentane (5 * 10ml) washings, and vacuum drying.By ℃ also filtration of cooling filtrate to 0, washing and dry as previously mentioned, thus separate second batch of cutting (crop).Output 15.42g (88%).The NMR data: 1H NMR (δ, CD 2Cl 2): 1.18-1.32 (brm, 18H, Cy), 1.69 (brm, 18H, Cy), 1.80 (brm, 18H, Cy), 1.84 (s, 6H, CH 3), 2.00 (br d, 12H, Cy). 31P NMR(δ，CD 2Cl 2)：21.2(s)。
Embodiment C 3
Prepare trans-Pd (O 2C-t-Bu) 2(P (Cy) 3) 2
In 100ml Schlenk flask, with Pd (O 2C-t-Bu) 2(1.3088g 4.2404mmol) is dispersed in CH 2Cl 2(10ml), the content of cooling flask is to-78 ℃ and stirring.In above-mentioned solution, slowly add P (Cy) by syringe 3(2.6749g, CH 9.5382mmol) 2Cl 2(15ml) solution stirred 1 hour down and at room temperature stirred 2 hours at-78 ℃.Add hexane (20ml) in above-mentioned reaction mixture, obtain title complex compound (1.391g) with the yellow solid form.Filter this solid, with hexane (10ml) washing, and drying under reduced pressure.From filtrate, remove and desolvate, obtain orange solids, then it is dissolved in CHCl 3In/the hexanes mixtures (1/1:v/v), and in fuming cupboard, evaporate gained solution, obtain more title complex compound (648mg).Total production=2.039g (2.345mmol), 55.3%.Computational analysis is C 46H 84O 4P 2Pd:C63.54, H9.74%.
Embodiment C 4
Preparation Pd (OAc) 2(P (Cp) 3) 2
In the flask that nitrogen is filled, Pd (OAc) 2(2.00g is 8.91mmol) at CH 2Cl 2Bronzing suspending liquid in the (～25ml) is set in-78 ℃ and stirs down.In 10 minutes time period, adopt sleeve pipe, will be at CH 2Cl 2P (Cp) in the (～20ml) 3(4.25,17.83mmol) be added drop-wise in the suspending liquid of stirring, thereby cause from the tenne yellow that is gradually varied to.Make this suspending liquid be warming to room temperature, and stirred extra 1 hour.Concentrated solvent (～5ml), then add hexane (～15ml), obtain yellow solid, in air, filter, with hexane (5 * 10ml) washings, and vacuum drying.As listing among the embodiment 3, by ℃ also filtration of cooling filtrate to 0, washing is also dry, thereby separates second batch of cutting.Output 4.88g (85%).The NMR data: 1HNMR (δ, CD 2Cl 2): 1.52-1.56 (brm, 12H, Cp 3), 1.67-1.72 (brm, 12H, Cp 3), 1.74 (s, 6H, CH 3), 1.85-1.89 (brm, 12H, Cp 3), 1.96-1.99 (brd, 6H, Cp 3), 2.03-2.09 (brm, 12H, Cp 3). 31P NMR(δ，CD 2Cl 2)：22.4(s)。
Polymkeric substance
Embodiment P1-P6, P8 and P9
Embodiment P1-P6, P8 and P9 have illustrated according to embodiment of the present invention synthetic as the norbornene polymer of matrix polymer.
Embodiment P1
Hexyl norborene (HxNB)/diphenyl methyl norborene methoxy silane (diPhNB)
Synthesizing of multipolymer (P1)
In the 250ml serum bottle in conjunction with HxNB (8.94g, 0.05mol), diPhNB (16.1g, 0.05mol), (4.2g 0.05mol) and toluene (142.0g), and is heated to 120 ℃ to the 1-hexene in oil bath, form solution.In this solution, add [Pd (the PCy of the dense dichloromethane solution form of respectively doing for oneself 3) 2(O 2CCH 3) (NCCH 3)] four (pentafluorophenyl group) borate (Pd1446) (5.8E-3g, 4.0E-6mol) and N, accelerine four (pentafluorophenyl group) borate (DANFABA) (3.2E-3g, 4.0B-6mol).After adding, the gained potpourri maintain 120 ℃ following 6 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make the multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 80 ℃, dry in the baking oven under vacuum.After drying, obtain 12.0g (48%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=16,196 and Mn=8,448.Measure the 54/46HxNB/diPhNB that consists of of multipolymer by 1H-NMR.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5569 and in the TM pattern, be determined as 1.5555.The multipolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the copolymer solution of 10wt%.
Embodiment P2
Synthesizing of hexyl norborene/phenethyl norbornene copolymer (P2)
In the 250ml serum bottle in conjunction with HxNB (2.78g, 0.0156mol), phenethyl norborene (PENB, CAS 29415-09-6) (7.22g, 0.036mol), (2.18g 0.026mol) and toluene (57.0g), and is heated to 120 ℃ to the 1-hexene in oil bath.In this solution, add methylene chloride strong solution form Pd1446 (3.0E-3g, 2.1E-6mol) and DANFABA (6.7E-3g, 8.4E-6mol).After adding, the gained potpourri maintain 120 ℃ following 1 hour.After cool to room temperature, by dripping methyl alcohol in reaction mixture, thereby make the multipolymer precipitation.By the solid collected by filtration multipolymer, and under 80 ℃, dry in vacuum drying oven.This dissolution of solid polymer an amount of 1,3, in the 5-trimethylbenzene, is obtained the copolymer solution of 10wt% solid.After drying, obtain 8.0g (80%).By the GPC method, the molecular weight (polystyrene standards) of measuring this polymkeric substance in THF is Mw=127332 and Mn=39206.By 1H-NMR measures the HxNB/PENB=22/78 that consists of of this polymkeric substance.By 1H NMR measures the 54/46HxNB/diPhNB that consists of of this multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5601 and in the TM pattern, be determined as 1.5585.The multipolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the copolymer solution of 10wt%.
Embodiment P3
Synthesizing of HxNB/diPhNB multipolymer (P3)
Take by weighing HxNB (8.94g, 0.050mol), diPhNB (16.1g, 0.050mol), (2.95g 0.035mol) and toluene (142g), puts into the 250ml serum bottle, and be heated to 80 ℃ in oil bath the 1-hexene.In this solution, add Pd1446 (5.8E-3g, 4.0E-6mol) and DANFABA (3.2E-3g, 4.0E-6mol).The ratio of norbornene monomer/Pd1446/DANFABA is 25K/1/1.Potpourri maintain 80 ℃ following 7 hours, afterwards by adding 20ml acetonitrile quencher Pd activity of such catalysts.Afterwards, by dripping methyl alcohol in reaction mixture, precipitate this polymkeric substance.By the multipolymer of filtration collecting precipitation, and under 65 ℃, dry in vacuum drying oven.Then this multipolymer is dissolved in 1,3, in the 5-trimethylbenzene, obtains the copolymer solution of 10wt% solid.After drying, obtain 19.8g (79%).By the GPC method, use polystyrene as reference material, in THF, measure the molecular weight Mw=86186 and the Mn=21602 of this polymkeric substance.By 1H-NMR measures that the ratio of HxN2B/diPhNB is in this polymkeric substance: HxNB/diPhNB=46/54.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5569 and in the TM pattern, be determined as 1.5556.The Tg of this polymkeric substance (measuring based on thermo-mechanical analysis (TMA)) is 203 ℃.The multipolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the copolymer solution of 10wt%.
Embodiment P4
Synthesizing of HxNB/diPhNB multipolymer (P4)
Take by weighing HxNB (8.94g, 0.050mol), diPhNB (16.1g, 0.050mol), (20.0g 0.239mol) and toluene (142g), puts into the 250ml serum bottle, and be heated to 80 ℃ in oil bath the 1-hexene, forms solution.In this solution, add Pd1446 (5.80E-3g, 4.0E-6mol) and DANFABA (3.21E-3g, 4.01E-6mol).Potpourri maintain 80 ℃ following 6 hours, afterwards by adding 20ml acetonitrile quencher Pd activity of such catalysts.Afterwards, by dripping methyl alcohol in reaction mixture, precipitate this polymkeric substance.By the multipolymer of filtration collecting precipitation, and under 65 ℃, dry in vacuum drying oven.Then with this polymer dissolution 1,3, in the 5-trimethylbenzene, obtain the copolymer solution of 10wt% solid.By the GPC method, use polystyrene as reference material, in THF, measure the molecular weight Mw=20586 and the Mn=11613 of this polymkeric substance.By 1H-NMR measures that the ratio of HxNB/diPhNB is in this polymkeric substance: HxNB/diPhNB=60/40.By 1H-NMR measures the 54/46HxNB/diPHNB that consists of of this multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5547 and in the TM pattern, be determined as 1.5540.The multipolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the copolymer solution of 10wt%.
Embodiment P5
Synthesizing of hexyl norborene/diphenyl methyl norborene methoxy silane multipolymer (P5)
In the 500ml serum bottle in conjunction with HxNB (8.94g, 0.050mol), diPhNB (16.06g, 0.050mol), (5.0g 0.060mol) and toluene (142g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution, add the methylene chloride strong solution form of respectively doing for oneself Pd1446 (2.90E-3g, 2.00E-6mol) and DANFABA (3.2E-3g, 4.01E-6mol).After adding, the gained potpourri maintain 80 ℃ following 6 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make the multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 19.3g (77%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=58749 and Mn=18177.By 1H-NMR measures the 53/47HxNB/diPhNB that consists of of multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5572 and in the TM pattern, be determined as 1.5558.The multipolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the copolymer solution of 10wt%.
Embodiment P6
Synthesizing of butyl norborene/diphenyl methyl norborene methoxy silane multipolymer (P6)
In the 500ml serum bottle in conjunction with the butyl norborene (BuNB, CAS22094-81-1) (2.62g, 0.038mol), diPhNB (22.38g, 0.057mol), 1-hexene (8.83g, 0.011mol) and toluene (141.4g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (5.05E-3g, 3.49E-6mol) and DANFABA (1.12E-2g, 1.40E-5mol).After adding, the gained potpourri maintain 80 ℃ following 2 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make the multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 7.5g (30%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=32665 and Mn=19705.By 1H-NMR measures the 28/72HxNB/diPhNB that consists of of multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5785 and in the TM pattern, be determined as 1.5771.The multipolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the copolymer solution of 10wt%.
Embodiment P8
Synthesizing of hexyl norborene homopolymer (P8)
In the 250ml serum bottle in conjunction with HxNB (10.0g, 0.056mol), (4.71g 0.056mol) and toluene (56.7g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution, add the methylene chloride strong solution form of respectively doing for oneself Pd1446 (4.10E-4g, 2.80E-7mol) and DANFABA (2.20E-4g, 2.80E-7mol).After adding, the gained potpourri maintain 80 ℃ following 40 minutes.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this homopolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 5.8g (58%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=121541 and Mn=59213.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5146 and in the TM pattern, be determined as 1.5129.The Tg of this polymkeric substance (measuring based on thermo-mechanical analysis (TMA)) is 208 ℃.The homopolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the homopolymer solution of 10wt%.
Embodiment P9
Basic norborene/diphenyl methyl norborene methoxy silane multipolymer (P9) closes
Become
In the 500ml serum bottle in conjunction with HxNB (9.63g, 0.054mol), diPhNB, CAS376634-34-3) (40.37g, 0.126mol), (4.54g 0.054mol) and toluene (333g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution, add the methylene chloride strong solution form of respectively doing for oneself Pd1446 (1.04E-2g, 7.20E-6mol) and N, accelerine four (pentafluorophenyl group) borate (DANFABA) (2.30E-2g, 2.88E-5mol).After adding, the gained potpourri maintain 80 ℃ following 2 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make the multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 19.0g (38%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=118000 and Mn=60000.By 1H-NMR measures the 32/68HxNB/diPhNB that consists of of multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5695 and in the TM pattern, be determined as 1.5681.The multipolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the copolymer solution of 10wt%.
Embodiment P11-P34
Embodiment P11-P34 has illustrated synthesizing as the norbornene polymer of the matrix polymer of embodiment of the present invention material.
Embodiment P11
Synthesizing of diphenyl methyl norborene methoxy silane homopolymer (P11)
In the 250ml serum bottle in conjunction with diPhNB (30g, 0.094mol), (1.57g 0.019mol) and toluene (170.0g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution, add [Pd (the PCy of the methylene chloride strong solution form of respectively doing for oneself 3) 2(O 2CCH 3) (NCCH 3)] four (pentafluorophenyl group) borate (Pd1446) (1.4E-2g, 9.4E-6mol) and N, accelerine four (pentafluorophenyl group) borate (DANFABA) (3.0E-2g, 3.7E-5mol).After adding, the gained potpourri maintain 80 ℃ following 4 hours.By dripping this solution in the methyl alcohol of vigorous stirring, thereby make this homopolymer precipitation.By the homopolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 15.0g (productive rate 50%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=91000 and Mn=44000.
Embodiment P12
Synthesizing of hexyl norborene/diphenyl methyl norborene methoxy silane multipolymer (P12)
In the 250ml serum bottle in conjunction with HxNB (10.72g, 0.06mol), diPhNB (19.28g, 0.06mol), (3.5g 0.04mol) and toluene (170.0g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution, add [Pd (the PCy of the methylene chloride strong solution form of respectively doing for oneself 3) 2(O 2CCH 3) (NCCH 3)] four (pentafluorophenyl group) borate (Pd1446) (7.0E-3g, 4.8E-6mol) and N, accelerine four (pentafluorophenyl group) borate (DANFABA) (3.9E-3g, 4.8E-6mol).After adding, the gained potpourri maintain 80 ℃ following 3.5 hours.By dripping this solution in the methyl alcohol of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 18.6g (productive rate 62%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=102000 and Mn=38000.By 1H-NMR measures the 54/46HxNB/diPhNB that consists of of multipolymer.The multipolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the copolymer solution of 30wt%.
Embodiment P13
Synthesizing of butyl norborene/diphenyl methyl norborene methoxy silane multipolymer (P13)
In the 500ml serum bottle in conjunction with the butyl norborene (BuNB, CAS22094-81-1) (2.62g, 0.038mol), diPhNB (22.38g, 0.057mol), 1-hexene (8.83g, 0.011mol) and toluene (141.4g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (5.05E-3g, 3.49E-6mol) and DANFABA (1.12E-2g, 1.40E-5mol).After adding, the gained potpourri maintain 80 ℃ following 2 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make the multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 7.5g (30%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=32665 and Mn=19705.By 1H-NMR measures the 28/72HxNB/diPhNB that consists of of multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5785 and in the TM pattern, be determined as 1.5771.
Embodiment P14
Synthesizing of hexyl norborene/diphenyl methyl norborene methoxy silane multipolymer (P14)
In the 250ml serum bottle in conjunction with HxNB (9.63g, 0.054mol), diPhNB (1.92g, 0.006mol), (5.04g 0.060mol) and toluene (56.7g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (4.30E-4g, 3.00E-7mol) and DANFABA (2.40E-4g, 3.00E-7mol).After adding, the gained potpourri maintain 80 ℃ following 2 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make the multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 7.7g (67%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=82000 and Mn=40000.By 1H-NMR measures the 89/11HxNB/diPhNB that consists of of multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5238 and in the TM pattern, be determined as 1.5225.The multipolymer of drying is dissolved in 1,3 of capacity, in the 5-trimethylbenzene, causes the copolymer solution of 30wt%.
Embodiment P15
Synthesizing of diphenyl methyl norborene methoxy silane homopolymer (P15)
In the 500ml serum bottle in conjunction with diPhNB (30.00g, 0.094mol), (2.36g 0.028mol) and toluene (170.0g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.0135g, 9.36E-6mol) and DANFABA (0.030g, 3.74E-5mol).After adding, the gained potpourri maintain 80 ℃ following 4 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this homopolymer precipitation.By the homopolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 25.18g (21%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=54000 and Mn=29000.By 1What H-NMR measured multipolymer consists of the diPhNB homopolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5926 and in the TM pattern, be determined as 1.5910.The homopolymer of drying is dissolved in the toluene of capacity, causes the homopolymer solution of 30wt%.
Embodiment P16
Synthesizing of butyl norborene/phenethyl norbornene copolymer (P16)
In the 500ml serum bottle in conjunction with BuNB (4.78g, 0.032mol), PENB (25.22g, 0.127mol), (13.36g 0.16mol) and toluene (170.0g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.0092g, 6.36E-06mol) and DANFABA (0.020g, 2.54E-5mol).After adding, the gained potpourri maintains to be kept under 80 ℃ 50 minutes.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make the multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 23.60g (79%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=73000 and Mn=28000.By 1What H-NMR measured multipolymer consists of (15/85) BuNB/PENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5684 and in the TM pattern, be determined as 1.5657.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P17
Synthesizing of hexyl norborene/phenethyl norbornene copolymer (P17)
In the 500ml serum bottle in conjunction with HxNB (6.00g, 0.034mol), PENB (26.69g, 0.135mol), (11.31g 0.135mol) and toluene (185.35g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.0097g, 6.73E-06mol) and DANFABA (0.022g, 2.69E-5mol).After adding, the gained potpourri maintain 80 ℃ following 50 minutes.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make the multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 22.21g (68%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=95000 and Mn=26000.By 1What H-NMR measured multipolymer consists of (17/83) HxNB/PENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5477 and in the TM pattern, be determined as 1.5454.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P18
Synthesizing of decyl norborene/phenethyl norbornene copolymer (P18)
In the 500ml serum bottle in conjunction with the decyl norborene (DeNB, CAS22094-85-5) (6.84g, 0.029mol), PENB (23.16g, 0.117mol), 1-hexene (12.26g, 0.146mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.0084g, 5.84E-06mol) and DANFABA (0.019g, 2.33E-5mol).After adding, the gained potpourri maintain 80 ℃ following 50 minutes.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make the multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 19.74g (66%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=78000 and Mn=36000.By 1What H-NMR measured multipolymer consists of (19/81) DeNB/PENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5640 and in the TM pattern, be determined as 1.5622.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P19
Synthesizing of benzyl norborene homopolymer (P19)
In the 500ml serum bottle in conjunction with benzyl norborene (BzNB, CAS 265989-73-9) (30.00g, 0.163mol), triethyl silicane (0.227g, 1.95E-03mol), ethanol (0.360g, 7.81E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.0188g, 1.30E-05mol) and DANFABA (0.042g, 5.21E-5mol).After adding, the gained potpourri maintain 80 ℃ following 1.5 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this homopolymer precipitation.By the homopolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 15.07g (50%).By GPC, the molecular weight (polystyrene standards) of measuring this homopolymer in the THF solvent is Mw=46000 and Mn=28000.By 1What H-NMR measured homopolymer consists of the BzNB homopolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5778 and in the TM pattern, be determined as 1.5757.The homopolymer of drying is dissolved in the toluene of capacity, causes the homopolymer solution of 30wt%.
Embodiment P20
Synthesizing of hexyl norborene/benzyl norbornene copolymer (P20)
In the 500ml serum bottle in conjunction with HxNB (8.79g, 0.049mol), BzNB (21.21g, 0.115mol), triethyl silicane (0.23g, 1.97E-03mol), ethanol (0.36g, 7.89E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.019g, 1.32E-05mol) and DANFABA (0.042g, 5.26E-5mol).After adding, the gained potpourri maintain 80 ℃ following 1.5 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 18.59g (62%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=52000 and Mn=30000.By 1What H-NMR measured multipolymer consists of (35/65) HxNB/BzNB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5597 and in the TM pattern, be determined as 1.5579.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P21
Synthesizing of decyl norborene/benzyl norbornene copolymer (P21)
In the 500ml serum bottle in conjunction with DeNB (6.84g, 0.029mol), BzNB (21.56g, 0.117mol), (12.26g 0.146mol) and toluene (170.0g), and is heated to 80 ℃ to the 1-hexene in oil bath, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.0084g, 5.84E-06mol) and DANFABA (0.019g, 2.33E-5mol).After adding, the gained potpourri maintain 80 ℃ following 1.5 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 20.73g (73%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=64000 and Mn=31000.By 1What H-NMR measured multipolymer consists of (27/73) DeNB/BzNB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5680 and in the TM pattern, be determined as 1.5662.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P22
Synthesizing of butyl norborene/methyl glycidyl ether norbornene copolymer (P22)
In glove box, with BuNB (10.52g, 0.07mol), methyl glycidyl ether norborene (AGENB, CAS 3188-75-8) (5.41g, 0.03mol), toluene (58.0g) joins in the serum bottle.In oil bath, stir this solution down at 80 ℃.In this solution, add (η 6-toluene) Ni (C 6F 5) 2(0.69g, toluene solution 0.0014mol) (5g).After adding, kept the gained potpourri at room temperature 4 hours.(87.0g) joins in this reaction solution with toluene solution.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 12.74g (80%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=75000 and Mn=30000.By 1What H-NMR measured multipolymer consists of (78/22) BuNB/AGENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5162 and in the TM pattern, be determined as 1.5157.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P23
Synthesizing of hexyl norborene/methyl glycidyl ether norbornene copolymer (P23)
In glove box, with HxNB (12.48g, 0.07mol), AGENB (5.41g, 0.03mol), toluene (58.0g) joins in the serum bottle.In oil bath, stir this solution down at 80 ℃.In this solution, add (η 6-toluene) Ni (C 6F 5) 2(0.69g, toluene solution 0.0014mol) (5g).After adding, kept the gained potpourri at room temperature 4 hours.(87.0g) joins in this reaction solution with toluene solution.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 13.78g (77%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=78000 and Mn=33000.By 1What H-NMR measured multipolymer consists of (79/21) HxNB/AGENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5159 and in the TM pattern, be determined as 1.5153.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P24
Synthesizing of decyl norborene/methyl glycidyl ether norbornene copolymer (P24)
In glove box, with DeNB (16.4g, 0.07mol), AGENB (5.41g, 0.03mol), toluene (58.0g) joins in the serum bottle.In oil bath, stir this solution down at 80 ℃.In this solution, add (η 6-toluene) Ni (C 6F 5) 2(0.69g, toluene solution 0.0014mol) (5g).After adding, kept the gained potpourri at room temperature 4 hours.(87.0g) joins in this reaction solution with toluene solution.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 17.00g (87%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=75000 and Mn=30000.By 1What H-NMR measured multipolymer consists of (77/23) DeNB/AGENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5153 and in the TM pattern, be determined as 1.5151.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P25
Synthesizing of butyl norborene/norbornenylethyl trimethoxy silane multipolymer (P25)
In the 300ml serum bottle, in conjunction with BuNB (25.44g, 0.169mol), norbornenylethyl trimethoxy silane (TMSENB, CAS 68245-19-2) (4.56g, 0.019mol), triethyl silicane (0.11g, 9.41E-04mol), ethanol (0.10g, 2.26E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.022g, 1.50E-05mol) and DANPABA (0.036g, 4.51E-5mol).After adding, the gained potpourri maintain 80 ℃ following 4 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 22.60g (69%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=20000 and Mn=13000.By 1What H-NMR measured multipolymer consists of (91/9) BuNB/TMSENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5106 and in the TM pattern, be determined as 1.5105.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P26
Synthesizing of hexyl norborene/norbornenylethyl trimethoxy silane multipolymer (P26)
In the 300ml serum bottle, in conjunction with HxNB (13.03g, 0.073mol), TMSENB (1.97g, 0.0081mol), triethyl silicane (0.019g, 1.62E-04mol), ethanol (0.030g, 6.50E-04mol) and toluene (85.0g), and in oil bath, be heated to 80 ℃, form solution.[Pd (the P (iPr) of injection methylene chloride strong solution form in this solution 3) 2(OCOCH 3) (NCCH 3)] four (pentafluorophenyl group) borate (Pd1206) (0.0078g, 6.50E-06mol).After adding, the gained potpourri maintain 80 ℃ following 4 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 3.30g (22%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=53000 and Mn=33000.By 1What H-NMR measured multipolymer consists of (93/7) HxNB/TMSENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5126 and in the TM pattern, be determined as 1.5114.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P27
Synthesizing of decyl norborene/norbornenylethyl trimethoxy silane multipolymer (P27)
In the 500ml serum bottle, in conjunction with DeNB (22.31g, 0.095mol), TMSENB (7.69g, 0.032mol), triethyl silicane (0.44g, 3.81E-04mol), ethanol (0.70g, 1.52E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.015g, 1.02E-05mol) and DANFABA (0.024g, 3.05E-5mol).After adding, the gained potpourri maintain 80 ℃ following 4 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 12.2g (40.7%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=34000 and Mn=24000.By 1What H-NMR measured multipolymer consists of (77/23) DeNB/TMSENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5063 and in the TM pattern, be determined as 1.5062.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P28
Synthesizing of butyl norborene/triethoxysilyl norbornene copolymer (P28)
In the 500ml serum bottle, in conjunction with BuNB (25.22g, 0.168mol), triethoxysilyl norborene (TESNB, CAS 18401-43-9) (4.78g, 0.019mol), triethyl silicane (0.011g, 9.32E-05mol), ethanol (0.10g, 2.24E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.The Pd1206 of injection methylene chloride strong solution form in this solution (0.018g, 1.49E-05mol).After adding, the gained potpourri maintain 80 ℃ following 9 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 20.58g (69%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=238000 and Mn=96000.By 1What H-NMR measured multipolymer consists of (85/15) BuNB/TESNB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5061 and in the TM pattern, be determined as 1.5041.The Tg of this polymkeric substance (measuring based on thermo-mechanical analysis (TMA)) is 276 ℃.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P29
Synthesizing of hexyl norborene/triethoxysilyl norbornene copolymer (P29)
In the 500ml serum bottle, in conjunction with HxNB (20.33g, 0.114mol), TESNB (3.26g, 0.013mol), triethyl silicane (0.030g, 2.54E-03mol), ethanol (0.07g, 1.52E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.The Pd1446 of injection methylene chloride strong solution form in this solution (0.015g, 1.01E-05mol).After adding, the gained potpourri maintain 80 ℃ following 9 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 7.31g (31%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=234000 and Mn=110000.By 1What H-NMR measured multipolymer consists of (83/17) HxNB/TESNB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5053 and in the TM pattern, be determined as 1.5042.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P30
Synthesizing of decyl norborene/triethoxysilyl norbornene copolymer (P30)
In the 500ml serum bottle, in conjunction with DeNB (26.77g, 0.114mol), TESNB (3.26g, 0.013mol), triethyl silicane (0.030g, 2.54E-03mol), ethanol (0.07g, 1.52E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.The Pd1446 of injection methylene chloride strong solution form in this solution (0.015g, 1.01E-05mol).After adding, the gained potpourri maintain 80 ℃ following 9 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 18.01g (60%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=283000 and Mn=118000.By 1What H-NMR measured multipolymer consists of (84/16) DeNB/TESNB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5034 and in the TM pattern, be determined as 1.5018.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P31
Synthesizing of butyl norborene/trimethoxysilylnorbo.nene multipolymer (P31)
In the 500ml serum bottle, in conjunction with BuNB (10.97g, 0.073mol), trimethoxysilylnorbo.nene (TMSNB, CAS 7538-46-7) (12.95g, 0.073mol), triethyl silicane (0.34g, 2.91E-04mol), ethanol (0.80g, 1.75E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.017g, 1.16E-05mol) and DANFABA (0.028g, 3.49E-5mol).After adding, the gained potpourri maintain 80 ℃ following 4 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 15.5g (65%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=48000 and Mn=27000.By 1What H-NMR measured multipolymer consists of (47/53) BuNB/TMSNB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5093 and in the TM pattern, be determined as 1.5089.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P32
Synthesizing of hexyl norborene/trimethoxysilylnorbo.nene multipolymer (P32)
In the 500ml serum bottle, in conjunction with HxNB (13.02g, 0.073mol), TMSNB (12.95g, 0.073mol), triethyl silicane (0.34g, 2.91E-04mol), ethanol (0.80g, 1.75E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.017g, 1.16E-05mol) and DANFABA (0.028g, 3.49E-5mol).After adding, the gained potpourri maintain 80 ℃ following 4 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 17.7g (68%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=55000 and Mn=27000.By 1What H-NMR measured multipolymer consists of (46/54) HxNB/TMSNB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5081 and in the TM pattern, be determined as 1.5078.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P33
Synthesizing of decyl norborene/trimethoxysilylnorbo.nene multipolymer (P33)
In the 500ml serum bottle, in conjunction with DeNB (17.05g, 0.073mol), TMSNB (12.95g, 0.073mol), triethyl silicane (0.34g, 2.91E-04mol), ethanol (0.80g, 1.75E-03mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.017g, 1.16E-05mol) and DANFABA (0.028g, 3.49E-5mol).After adding, the gained potpourri maintain 80 ℃ following 4 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 21.1g (70%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=82000 and Mn=31000.By 1What H-NMR measured multipolymer consists of (46/54) DeNB/TMSNB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5029 and in the TM pattern, be determined as 1.5016.The multipolymer of drying is dissolved in the toluene of capacity, causes the copolymer solution of 30wt%.
Embodiment P34
Synthesizing of hexyl norborene/diphenyl methyl norborene methoxy silane/norbornenylethyl trimethoxy silane terpolymer (P34)
In the 500ml serum bottle, in conjunction with HxNB (5.94g, 0.033mol), diPhNB (21.36g, 0.067mol), TMSENB (2.69g, 0.011mol), the 1-hexene (3.73g, 0.044mol) and toluene (170.0g), and in oil bath, be heated to 80 ℃, form solution.In this solution the injection respectively do for oneself methylene chloride strong solution form Pd1446 (0.0064g, 4.44E-06mol) and DANFABA (0.0036g, 4.44E-6mol).After adding, the gained potpourri maintain 80 ℃ following 3.5 hours.By dripping methyl alcohol in the reaction mixture of vigorous stirring, thereby make this multipolymer precipitation.By the multipolymer of filtration collecting precipitation, and under 60 ℃, vacuum drying in baking oven.After drying, obtain 10.26g (34%).By GPC, the molecular weight (polystyrene standards) of measuring this multipolymer in the THF solvent is Mw=105000 and Mn=54000.By 1What H-NMR measured multipolymer consists of (38/54/8) HxNB/diPhNB/TMSENB multipolymer.Measure the refractive index of this polymkeric substance by the prism-coupled method, and under the wavelength of 633 nanometers, in the TE pattern, be determined as 1.5586 and in the TM pattern, be determined as 1.5572.The terpolymer of drying is dissolved in the toluene of capacity, causes the terpolymer solution of 30wt%.
Table 1 provides the overview of above-described each exemplary polymers.
Table 1
Varnish
EXAMPLE V 1-V13, V38-V48 and V63-V66
EXAMPLE V 1-V13, V38-V48 and V63-V66 have illustrated varnish solution formula according to embodiments of the present invention, and described varnish solution formula comprises matrix polymer, norborneol vinyl monomer, procatalyst, acid agent, optional antioxidant and solvent.Be noted that when below each varnish solution of exemplifying when mixing photochromics, then this solution of preparation under gold-tinted.
EXAMPLE V 1
Take by weighing HxNB (42.03g, 0.24mol) and two-(7.97g 0.026mol) puts into vial to norborene methoxyl dimethylsilane (SiX, CAS 376609-87-9).In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00501
IRGANOX
Figure C200480040049D00502
(0.5g) and
Figure C200480040049D00503
Figure C200480040049D00504
(the two is all available from Ciba SpecialtyChemicals Corporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 3.0g, Pd (PCy in the P1 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (4.94E-4g, 6.29E-7mol is in the 0.1ml methylene chloride),
Figure C200480040049D00505
PHOTOINITIATOR 2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (2.55E-3g, 2.51E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 2
(5g 0.0164mol) puts into vial to take by weighing SiX.In SiX, add Irganox1076 (0.05g) and Irgafos168 (0.013g), form SiX solution.By mixing SiX solution (3g), Pd-785 liquid storage (3.10E-4g, 3.94E-7mol is in the 0.1ml methylene chloride), Rhodorsil 2074 liquid storage (1.60E-3g, 1.58E-6mol, in the 0.1ml methylene chloride) and P2 copolymer solution (30g, solid 3g), preparation varnish solution V2.The ratio of multipolymer/monomer is 1/1 weight, and the ratio of monomer/Pd catalyzer/photo-acid generator (PAG) is the 25K/1/4 mole.Varnish solution filters by the filtrator of 0.2 micron hole.
EXAMPLE V 3
Take by weighing HxNB (42.03g, 0.24mol) and SiX (7.97g 0.026mol) puts into vial.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00506
IRGANOX
Figure C200480040049D00507
(0.5g) and
Figure C200480040049D00508
168 (0.125g) form monomer-antioxidant solution.In 30.0g copolymer solution (10g P3+20g P4), add this monomer-antioxidant solution of 3.0g, Pd785 (4.93E-4g, 6.28E-7mol is in the 0.1ml methylene chloride),
Figure C200480040049D005010
PHOTOINITIATOR 2074 (2.55E-3g, 2.51E-6mol is in the 0.1ml methylene chloride) forms varnish solution V3.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 4
The same varnish solution V4 for preparing with above V3, different is that the 30.0g copolymer solution is 15g P3 and 15g P4, forms varnish solution V4.This solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 5
The same varnish solution V5 for preparing with above V3, different is that the 30.0g copolymer solution is 20g P3 and 10g P4, forms varnish solution V5.This solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 6
The same varnish solution V6 for preparing with above V3, different is that the 30.0g copolymer solution is 30g P3, forms varnish solution V6.This solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 7
(40.33g, 0.23mol) (9.67g 0.039mol) puts into vial with norbornenylethyl trimethoxy silane (TMSENB, CAS 68245-19-2) to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants, IRGANOX (0.5g) and
Figure C200480040049D00513
Figure C200480040049D00514
168 (0.125g) form monomer-antioxidant solution.In the described above-mentioned copolymer solution of 30.0g table 1 (15g P3+15g P4), add this monomer-antioxidant solution of 3.0g, Pd785 (5.02E-4g, 6.39E-7mol is in the 0.1ml methylene chloride),
Figure C200480040049D00515
PHOTOINITIATOR 2074 (2.59E-3g, 2.55E-6mol is in the 0.1ml methylene chloride) forms varnish solution V7.This solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 8
Take by weighing HxNB (42.03g, 0.24mol) and SiX (7.97g 0.026mol) puts into vial.In this monomer solution, add two kinds of antioxidants, IRGANOX1076 (0.5g) and
Figure C200480040049D00517
IRGAFOS168 (0.125g) forms monomer-antioxidant solution.Add in copolymer p 5 solution that more than 18.3g, prepare this monomer-antioxidant solution of 3.06g, Pd785 (3.85E-4g, 4.91E-7mol is in the 0.1ml methylene chloride),
Figure C200480040049D00518
PHOTOINITIATOR 2074 (1.99E-3g, 1.96E-6mol is in the 0.1ml methylene chloride) and 1.30g1,3, the 5-trimethylbenzene forms varnish solution.
EXAMPLE V 9
Take by weighing HxNB (42.03g, 0.24mol) and SiX (7.97g 0.026mol) puts into vial.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00521
IRGANOX1076 (0.5g) and IRGAFOS168 (0.125g) forms monomer-antioxidant solution.Add in copolymer p 6 solution that more than 9.15g, prepare this monomer-antioxidant solution of 1.53g, Pd785 (2.52E-4g, 3.21E-7mol is in the 0.1ml methylene chloride), PHOTOINITIATOR 2074 (1.30E-3g, 1.28E-6mol is in the 0.1ml methylene chloride) and 0.645g1,3, the 5-trimethylbenzene forms varnish solution.
EXAMPLE V 10
Take by weighing HxNB (42.03g, 0.24mol) and SiX (7.97g 0.026mol) puts into vial.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00524
IRGANOX1076 (0.5g) and
Figure C200480040049D00525
IRGAFOS168 (0.125g) forms monomer-antioxidant solution.Add in copolymer p 3 solution that more than 20g, prepare this monomer-antioxidant solution of 2.4g, Pd785 (3.95E-4g, 5.03E-7mol is in the 0.1ml methylene chloride), PHOTOINITIATOR 2074 (2.55E-3g, 2.51E-6mol is in the 0.1ml methylene chloride) and 2.5g toluene form varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 11
Take by weighing HxNB (42.03g, 0.24mol) and SiX (7.97g 0.026mol) puts into vial.In this monomer solution, add two kinds of antioxidants, IRGANOX1076 (0.5g) and
Figure C200480040049D00528
IRGAFOS168 (0.125g) forms monomer-antioxidant solution.Add in the homopolymer P8 solution that more than 20g, prepares this monomer-antioxidant solution of 2.4g, Pd785 (3.95E-4g, 5.03E-7mol is in the 0.1ml methylene chloride),
Figure C200480040049D00529
PHOTOINITIATOR 2074 (2.55E-3g, 2.51E-6mol is in the 0.1ml methylene chloride) and 6.12g toluene form varnish solution.This varnish solution filtrator by 5 microns holes before using filters.
EXAMPLE V 12
(42.03g, 0.24mol) He (SiX) (7.97g 0.026mol) puts into vial to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D005210
IRGANOX (0.5g) and
Figure C200480040049D005212
168 (0.125g) form monomer-antioxidant solution.Add this monomer-antioxidant solution of 1.0g, Pd (PCy in copolymer p 9 solution that more than 30g, prepare 3) 2(OAc) 2(Pd785) (1.65E-4g, 2.10E-7mol is in the 0.1ml methylene chloride),
Figure C200480040049D00531
PHOTOINITIATOR 2074 (8.51E-4g, 8.38E-7mol is in the 0.1ml methylene chloride) and 5.0g toluene form varnish solution.
EXAMPLE V 13
(42.03g, 0.24mol) He (SiX) (7.97g 0.026mol) puts into vial to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00532
IRGANOX
Figure C200480040049D00533
(0.5g) and
Figure C200480040049D00535
168 (0.125g) form monomer-antioxidant solution.Add this monomer-antioxidant solution of 2.0g, Pd (PCy in copolymer p 14 solution that more than 30g, prepare 3) 2(OAc) 2(Pd785) (3.29E-4g, 4.19E-7mol, in the 0.1ml methylene chloride), TAG-372R photo-acid generator (CAS193957-54-9, available from Toyo InkMfg.Co., Ltd., Tokyo, Japan) (7.63E-4g, 8.38E-6mol, in the 0.1ml methylene chloride) and 10.0g toluene, varnish solution formed.Varnish solution V13 is poured over the SiO of 4 ｀ ｀ 2Also solidify on the wafer of coating, form desciccator diaphragm.The Tg of this polymkeric substance (measuring based on thermo-mechanical analysis (TMA)) is 251 ℃.
EXAMPLE V 38
(16.64g, 0.093mol) (33.36g 0.110mol) puts into vial with two norborene methoxyl dimethylsilane (SiX, CAS 376609-87-9) to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants, IRGANOX
Figure C200480040049D00537
(0.5g) and
Figure C200480040049D00538
Figure C200480040049D00539
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 2.16g, Pd (PCy in the P3 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and
Figure C200480040049D005310
PHOTOINITIATOR 2074 (CAS178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 39
(16.64g, 0.093mol) (33.36g 0.110mol) puts into vial with two norborene methoxyl dimethylsilane (SiX, CAS 376609-87-9) to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00541
IRGANOX (0.5g) and
Figure C200480040049D00543
Figure C200480040049D00544
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 2.16g, Pd (PCy in the P34 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and
Figure C200480040049D00545
PHOTOINITIATOR 2074 (CAS178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 40
(16.64g, 0.093mol) (33.36g 0.110mol) puts into vial with two norborene methoxyl dimethylsilane (SiX, CAS 376609-87-9) to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00546
IRGANOX
Figure C200480040049D00547
(0.5g) and
Figure C200480040049D00548
Figure C200480040049D00549
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 2.16g, Pd (PCy in the P12 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride), DBA (CAS76275-14-4, available from Kawasaki-kaseiCo., Ltd., Kanagawa, Japan) (4.86E-2g, 1.51E-4mol is in the 0.1ml methylene chloride) and
Figure C200480040049D005410
PHOTOINITIATOR 2074 (CAS178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 41
(16.64g, 0.093mol) (SiX, CAS376609-87-9) (33.36g 0.110mol) puts into vial with two norborene methoxyl dimethylsilane to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D005411
IRGANOX
Figure C200480040049D005412
(0.5g) and
Figure C200480040049D005413
Figure C200480040049D0054200434QIETU
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 2.16g, Pd (PCy in the P16 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and
Figure C200480040049D00551
PHOTOINITIATOR 2074 (CAS178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 42
(16.64g, 0.093mol) (33.36g 0.110mol) puts into vial with two norborene methoxyl dimethylsilane (SiX, CAS 376609-87-9) to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00552
IRGANOX
Figure C200480040049D00553
(0.5g) and (the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 2.16g, Pd (PCy in the P17 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and PHOTOINITIATOR 2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 43
(16.64g, 0.093mol) (33.36g 0.110mol) puts into vial with two norborene methoxyl dimethylsilane (SiX, CAS 376609-87-9) to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00557
IRGANOX (0.5g) and
Figure C200480040049D00559
Figure C200480040049D005510
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 2.16g, Pd (PCy in the P18 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and
Figure C200480040049D005511
PHOTOINITIATOR 2074 (CAS178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 44
(SiX, CAS376609-87-9) (50.0g 0.164mol) puts into vial to take by weighing two norborene methoxyl dimethylsilane.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00561
IRGANOX (0.5g) and
Figure C200480040049D00563
Figure C200480040049D00564
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 1.44g, Pd (P (i-Pr) in the P19 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd545) (1.02E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and
Figure C200480040049D00565
PHOTOINITIATOR 2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 45
(SiX, CAS376609-87-9) (50.0g 0.164mol) puts into vial to take by weighing two norborene methoxyl dimethylsilane.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00566
IRGANOX (0.5g) and
Figure C200480040049D00568
Figure C200480040049D00569
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 1.44g, Pd (P (i-Pr) in the P20 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd545) (1.02E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and
Figure C200480040049D005610
PHOTOINITIATOR 2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 46
(SiX, CAS376609-87-9) (50.0g 0.164mol) puts into vial to take by weighing two norborene methoxyl dimethylsilane.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D005611
IRGANOX
Figure C200480040049D005612
(0.5g) and
Figure C200480040049D005613
Figure C200480040049D00571
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 1.44g, Pd (P (i-Pr) in the P21 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd545) (1.02E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and PHOTOINITIATOR 2074 (CAS 178233-72-2, available from RhodiaInc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 47
(16.64g, 0.093mol) (33.36g 0.110mol) puts into vial with two norborene methoxyl dimethylsilane (SiX, CAS 376609-87-9) to take by weighing HxNB.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00573
IRGANOX
Figure C200480040049D00574
(0.5g) and
Figure C200480040049D00575
Figure C200480040049D00576
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 2.16g, Pd (PCy in the P17 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (CAS 193957-54-9 is available from Toyo InkMfg.Co. for (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and TAG-372R photo-acid generator, Ltd., Tokyo, Japan) (6.86E-3g, 7.54E-6mol, in the 0.1ml methylene chloride), form varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 48
(SiX, CAS376609-87-9) (50.0g 0.164mol) puts into vial to take by weighing two norborene methoxyl dimethylsilane.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00577
IRGANOX
Figure C200480040049D00578
(0.5g) and (the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 1.44g, Pd (P (i-Pr) in the P20 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd545) (CAS 193957-54-9 is available from ToyoInkMfg.Co. for (1.02E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and TAG-372R photo-acid generator, Ltd., Tokyo, Japan) (6.86E-3g, 7.54E-6mol, in the 0.1ml methylene chloride), form varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 63
(SiX, CAS376609-87-9) (50.0g 0.164mol) puts into vial to take by weighing two norborene methoxyl dimethylsilane.In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00581
IRGANOX
Figure C200480040049D00582
(0.5g) and
Figure C200480040049D00583
Figure C200480040049D00584
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 1.44g, Pd (PCy in the P24 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and PHOTOINITIATOR 2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 64
(20.2g, 0.0834mol) (SiX, CAS376609-87-9) (29.80g 0.0979mol) puts into vial with two norborene methoxyl dimethylsilane to take by weighing trimethoxysilylethylgroup group norborene (TMSENB, CAS 68245-19-2).In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00586
IRGANOX
Figure C200480040049D00587
(0.5g) and
Figure C200480040049D00588
Figure C200480040049D00589
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 2.16g, Pd (PCy in the P26 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and
Figure C200480040049D005810
PHOTOINITIATOR 2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 65
(20.2g, 0.0834mol) (SiX, CAS376609-87-9) (29.80g 0.0979mol) puts into vial with two norborene methoxyl dimethylsilane to take by weighing trimethoxysilylethylgroup group norborene (TMSENB, CAS 68245-19-2).In this monomer solution, add two kinds of antioxidants,
Figure C200480040049D00591
IRGANOX
Figure C200480040049D00592
(0.5g) and
Figure C200480040049D00593
Figure C200480040049D00594
(the two is all available from Ciba Specialty ChemicalsCorporation, and Tarrytown NY), forms monomer-antioxidant solution for 168 (0.125g).Add this monomer-antioxidant solution of 2.16g, Pd (PCy in the P14 copolymer solution that more than 30.0g, prepares 3) 2(OAc) 2(Pd785) (1.47E-3g, 1.88E-6mol is in the 0.1ml methylene chloride) and
Figure C200480040049D00595
PHOTOINITIATOR 2074 (CAS178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.67E-3g, 7.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 66
In 5g P14 multipolymer, add 20g1,3,5-trimethylbenzene, IRGANOX
Figure C200480040049D00596
(0.05g),
Figure C200480040049D00597
Figure C200480040049D00598
168 (1.25E-2g) (the two is all available from CibaSpecialty Chemicals Corporation, Tarrytown, NY) and
Figure C200480040049D00599
PHOTOINITIATOR 2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (4.0E-3g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
Table 2,3 and 4 provides the general introduction of above-described each varnish solution composition.
Table 2
Table 3
Figure C200480040049D00611
Table 4
Figure C200480040049D00621
Figure C200480040049D00622
Be meant and use Rhodorsil 2074 and T to be meant TAG-372R.
EXAMPLE V 21-V31, V51-V55, V61 and V62
EXAMPLE V 21-V31, V51-V55, V61 and V62 have illustrated the prescription of varnish solution according to embodiments of the present invention, described prescription comprises matrix polymer, acid agent, optional antioxidant and solvent.Note when below each varnish solution of enumerating when mixing photochromics, then this solution of preparation under gold-tinted.
EXAMPLE V 21
In the 5gP12 multipolymer, add 20g1,3,5-trimethylbenzene, 0.05g Irganox1076,0.0125g Irgafos 168 and PHOTOINITIATOR2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (4.0E-3g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 22
In 5g P13 multipolymer, add 20g1,3,5-trimethylbenzene, 0.05g Irganox1076,0.0125g Irgafos 168 and
Figure C200480040049D00624
PHOTOINITIATOR2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (4.0E-3g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 23
In 5g P14 multipolymer, add 20g1,3,5-trimethylbenzene, 0.05g Irganox1076,0.0125g Irgafos 168 form varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 24
In 0.9g P11 homopolymer, add 3.6g1,3,5-trimethylbenzene, 9.0E-3g Irganox1076,2.3E-3g Irgafos 168 and
Figure C200480040049D00631
PHOTOINITIATOR2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (1.1E-3g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 25
In 0.9g P11 homopolymer, add 3.6g1,3,5-trimethylbenzene, 9.0E-3g Irganox1076,2.3E-3g Irgafos 168 and
Figure C200480040049D00632
PHOTOINITIATOR2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.5E-4g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 26
In 0.9g P11 homopolymer, add 3.6g1,3,5-trimethylbenzene, 9.0E-3g Irganox1076,2.3E-3g Irgafos 168 and TAG-372R photo-acid generator (dimethyl (2-(2-naphthyl)-2-oxygen base ethyl) sulfonium four (pentafluorophenyl group) borate, CAS 193957-54-9) available from Toyo Ink Mfg.Co., Ltd.Tokyo, Japan) (7.5E-4g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 27
In 0.9g P11 homopolymer, add 3.6g1,3,5-trimethylbenzene, 9.0E-3g Irganox1076,2.3E-3g Irgafos 168 and
Figure C200480040049D00633
PHOTOINITIATOR2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (1.1E-3g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 28
In 0.9g P11 homopolymer, add 3.6g1,3,5-trimethylbenzene, 9.0E-3g Irganox1076,2.3E-3g Irgafos 168 and TAG-372R photo-acid generator (dimethyl (2-(2-naphthyl)-2-oxygen base ethyl) sulfonium four (pentafluorophenyl group) borate, CAS 193957-54-9) available from Toyo Ink Mfg.Co., Ltd.Tokyo, Japan) (7.5E-4g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 29
In 0.9g P11 homopolymer, add 3.6g1,3,5-trimethylbenzene, 9.0E-3g Irganox1076,2.3E-3g Irgafos 168 and TAG-372R photo-acid generator (dimethyl (2-(2-naphthyl)-2-oxygen base ethyl) sulfonium four (pentafluorophenyl group) borate, CAS 193957-54-9) available from Toyo Ink Mfg.Co., Ltd.Tokyo, Japan) (1.1E-3g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 30
In 0.9g P11 homopolymer, add 3.6g1,3,5-trimethylbenzene, 9.0E-3g Irganox1076,2.3E-3g Irgafos 168 and
Figure C200480040049D00641
PHOTOINITIATOR2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (7.5E-4g is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 31
In 0.9g P11 homopolymer, add 3.6g1,3,5-trimethylbenzene, 9.0E-3g Irganox1076,2.3E-3g Irgafos 168 and TAG-372R photo-acid generator (dimethyl (2-(2-naphthyl)-2-oxygen base ethyl) sulfonium four (pentafluorophenyl group) borate, CAS 193957-54-9), available from Toyo Ink Mfg.Co., Ltd.Tokyo, Japan) (1.1E-3g, in the 0.1ml methylene chloride), form varnish solution.This varnish solution filters by the filtrator of 0.2 micron hole.
EXAMPLE V 51
Add RHODORSIL in the P15 homopolymer solution that more than 4.0g, prepares PHOTOINITIATOR 2074 (CAS 178233-72-2, available from Rhodia Inc., Cranbury, N.J.) (1.56E-3g, 1.54E-6mol is in the 0.1ml methylene chloride) forms varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 52
(CAS 193957-54-9 is available from Toyo Ink Mfg.Co., Ltd.Tokyo to add the TAG-372R photo-acid generator in the P15 homopolymer solution for preparing more than 4.0g, Japan) (1.56E-3g, 1.54E-6mol, in the 0.1ml methylene chloride), form varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 53
(CAS 193957-53-8 is available from Toyo Ink Mfg.Co., Ltd.Tokyo to add the TAG-371 photo-acid generator in the P15 homopolymer solution for preparing more than 4.0g, Japan) (1.56E-3g, 1.54E-6mol, in the 0.1ml methylene chloride), form varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 54
Add three (4-tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate photo-acid generators in the P15 homopolymer solution that more than 4.0g, prepares and (be also referred to as " TTBPS-TPFPB ", available from ToyoGosei Co., Ltd., Tokyo, Japan) (1.56E-3g, 1.54E-6mol, in the 0.1ml methylene chloride), form varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 55
(CAS 85342-62-7 is available from Midor ikagaku.Co., Ltd. to add the NAI-105 photo-acid generator in the P15 homopolymer solution for preparing more than 4.0g, Tokyo, Japan) (1.56E-3g, 1.54E-6mol, in the 0.1ml methylene chloride), form varnish solution.This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 61
Add two kinds of antioxidants in the P24 copolymer solution that more than 16.7g, prepares: IRGANOX 1076 (0.05g),
Figure C200480040049D00653
Figure C200480040049D00654
168 (1.25E-2g) (the two is all available from Ciba Specialty Chemicals Corporation, Tarrytown, NY) and
Figure C200480040049D00655
PHOTOINITIATOR 2074 (CAS 178233-72-2, available from RhodiaInc., Cranbury, N.J.) (0.1g is in the 0.5ml methylene chloride).This varnish solution filtrator by 0.2 micron hole before using filters.
EXAMPLE V 62
Add two kinds of antioxidants in the P24 copolymer solution that more than 16.7g, prepares:
Figure C200480040049D00661
IRGANOX
Figure C200480040049D00662
1076 (0.05g),
Figure C200480040049D00664
(the two is all available from Ciba Specialty Chemicals Corporation for 168 (1.25E-2g), Tarrytown, NY) and TAG-372R photo-acid generator (dimethyl (2-(2-naphthyl)-2-oxygen base ethyl) sulfonium four (pentafluorophenyl group) borate, CAS193957-54-9) available from Toyo Ink Mfg.Co., Ltd.Tokyo, Japan) (0.1g is in the 0.5ml methylene chloride).This varnish solution filtrator by 0.2 micron hole before using filters.
Table 5 provides the composition general introduction of above-described each varnish solution.
Table 5
Figure C200480040049D00665
Waveguide
Embodiment WG1-WG5
Embodiment WG1-WG5 has illustrated the manufacturing according to the individual layer of embodiment of the present invention and three layers of waveguiding structure.Be noted that when employed each varnish solution mixes photochromics in the simplified method of following formation waveguiding structure, then under gold-tinted, form this structure.
Embodiment WG1
The formation of individual layer waveguiding structure
The suitable varnish of filtration solution is poured on the 4 ｀ ｀ glass sheet, and uses scraper to spread out homogeneous thickness basically.The glass sheet of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.(dosage=3000mJ) be exposed to (365nm) under the UV light in baking oven, heated 30 minutes down at 85 ℃ then, then heated extra 60 minutes down at 150 ℃ by photomask with this film.After hot step for the first time, as seen waveguide patterns becomes.
Embodiment WG2
The formation of three layers of waveguiding structure
Varnish solution V8 is poured on the PET film of 250 micron thickness, and uses scraper to spread out basically homogeneous thickness (wet thick=70 microns).On ground floor, topple over varnish solution V9 then, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).At last, on the second layer, topple over varnish solution V8, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).PET film with coating places on the hot plate then, and heats 30 minutes down at 50 ℃, makes toluene evaporates, and forms the solid built up film.And by positive toner photomask, with this film (exposure dose=3000mJ/cm 2) be exposed to (365nm) under the UV light, on hot plate, placed 30 minutes down then at 45 ℃, then solidified 30 minutes down and solidified 60 minutes down at 85 ℃ respectively at 150 ℃.Film is placing 45 ℃ hot plate after last 10 minute, and as seen waveguide patterns becomes.Use " cut and subtract (cut back) method ", measure the transmission loss of this waveguide, and be determined as 6.0dB/cm.
Embodiment WG3
The formation of three layers of waveguiding structure
The varnish solution V11 that has filtered is poured on the PET film of 250 micron thickness, and uses scraper to spread out basically homogeneous thickness (wet thick=70 microns).On ground floor, topple over the varnish solution V10 that has filtered then, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).At last, on the second layer, topple over the varnish solution V11 that has filtered, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).PET film with coating places on the hot plate then, and heats 45 minutes down at 50 ℃, makes toluene evaporates, and forms the solid built up film.And by positive toner photomask, with this film (exposure dose=3000mJ/cm 2) be exposed to (365nm) under the UV light, then, place 50 ℃ baking oven 30 minutes, then solidified 30 minutes down and solidified 60 minutes down at 85 ℃ respectively at 150 ℃.After placing 50 ℃ baking oven 10 minutes, as seen waveguide patterns becomes.Use " cut and subtract method ", measure the transmission loss of this waveguide, and be determined as 3.0dB/cm.
Embodiment WG4
The formation of three layers of waveguiding structure
Varnish solution V13 is poured on the PET film of 250 micron thickness, and uses scraper to spread out basically homogeneous thickness (wet thick=70 microns).On ground floor, topple over the varnish solution V12 that has filtered then, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).At last, on the second layer, topple over varnish solution V13, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).PET film with coating places on the hot plate then, and heats 45 minutes down at 50 ℃, makes toluene evaporates, and forms the solid built up film.And by positive toner photomask, with this film (exposure dose=3000mJ/cm 2) be exposed to (365nm) under the UV light, then, place 50 ℃ baking oven 30 minutes, then solidified 30 minutes down and solidified 60 minutes down at 85 ℃ respectively at 150 ℃.This film is after placing 50 ℃ baking oven 10 minutes, and as seen waveguide patterns becomes.
Embodiment WG5
The formation of three layers of waveguiding structure
With Avatrel
Figure C200480040049D0068083439QIETU
(available from Promerus LLC, Brecksville OH) is poured on the 4 ｀ ｀ glass sheet 2000P solution, and uses scraper to spread out basically homogeneous thickness (wet thick=1 micron).Then, be placed on the hot plate, and heated 10 minutes down, and do not having to be exposed to (exposure dose=400mJ/cm under the UV light under the situation of photomask at 100 ℃ 2), then solidified 15 minutes down and solidified 1 hour down at 110 ℃ respectively at 160 ℃.
On the surface of the Avatrel2000P layer that solidifies, topple over varnish solution V12 then, and use scraper to spread out basically homogeneous thickness (wet thick=70 microns).The glass sheet of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.Second day, will pass through photomask (exposure dose=3000mJ/cm by the solid film that solution V12 forms 2) be exposed to (365nm) under the UV light, then ageing at room temperature is 30 minutes, at first solidifies 30 minutes down at 85 ℃, solidifies 60 minutes down at 150 ℃ then.After 85 ℃ of following these films of curing 30 minutes, as seen waveguide patterns becomes.
On the surface of the cured layer of varnish solution V12, topple over the Avatrel2000P solution of second portion then, and use spinner to spread out basically homogeneous thickness (wet thick=1 micron).The glass sheet of coating is placed on the hot plate, and heated 10 minutes down, and do not having under the situation of photomask, be exposed to (exposure dose=400mJ/cm under the UV light at 100 ℃ 2), then solidified 15 minutes down at 110 ℃ respectively, and solidified 1 hour down at 160 ℃.Still as seen waveguide patterns but sees through top cover layer, and this film appears as brown.
The measurement of transmission loss
Use " cut and subtract method ", measure the transmission loss of each waveguide that forms by 5 kinds of varnish solution V3-V7.The individual layer waveguide that each waveguide is made for the method for using embodiment WG1.The light (830nm) that is produced by the LASER diode is input to by optical fiber in first end of the waveguide cores core that is formed by each varnish solution, and wherein waveguide has first length.Measure the other end, the output intensity at the second end place." cut and subtract " waveguide and become the length of short at least twice, and measure, in the light output of second output for each length.
Total light loss is for measuring each time:
Total light loss (dB)=-101og (P n/ P 0)
P wherein nBe for each length P 1, P 2... P n, the output valve that the second end place of waveguide is measured, and P 0It is the measured output valve of optical fiber connector place light source before this fiber is coupled to first end of waveguide cores core.Then, exemplify, curve is made in total light loss as following graticule 1.Represent the straight line that this data gained is best with following formula:
y＝mx+b
Wherein m is that transmission loss and b are coupling losses.
Graticule 1
Listed for each varnish solution V3-V7 the result of transmission loss when using " cut and subtract " method in the following table 6.
Table 6
Varnish solution # V3 V4 V5 V6 V7
Transmission loss [dB/cm] 0.183 0.157 0.112 0.087 0.474
Embodiment WG11-WG20
Embodiment WG11-WG20 has illustrated the manufacturing of individual layer and three layers of waveguiding structure according to embodiments of the present invention.Employed each varnish solution mixes photochromics in the simplified method of the following waveguiding structure of formation.Under gold-tinted, form this structure.
Embodiment WG11
The formation of individual layer waveguiding structure
The varnish solution V24 that has filtered is poured on the substrate of glass, and uses scraper to spread out homogeneous thickness basically.The substrate of glass of placing coating on the levelling plate that ventilates is spent the night then, makes solvent evaporation and forms dry basically solid film.This film is passed through photomask (UV dosage 6J/cm 2) be exposed to (365nm) under the UV light, in baking oven, heated 30 minutes down then at 85 ℃, then heated extra 60 minutes down at 150 ℃.After hot step for the first time, waveguide patterns is visible.
Embodiment WG12
The formation of individual layer waveguiding structure
The varnish solution V25 that has filtered is poured over 4 ｀ ｀ SiO 2On the wafer of coating, and use scraper to spread out homogeneous thickness basically.The wafer of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.This film is passed through photomask (UV dosage 3J/cm 2) be exposed to (365nm) under the UV light, in baking oven, heated 30 minutes down then at 85 ℃, then heated extra 60 minutes down at 150 ℃.After hot step for the first time, waveguide patterns is visible.
Embodiment WG13
The formation of individual layer waveguiding structure
The varnish solution V26 that has filtered is poured over 4 ｀ ｀ SiO 2On the wafer of coating, and use scraper to spread out homogeneous thickness basically.The wafer of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.This film is passed through photomask (UV dosage 6J/cm 2) be exposed to (365nm) under the UV light, in baking oven, heated 30 minutes down then at 85 ℃, then heated extra 60 minutes down at 150 ℃.After hot step for the first time, waveguide patterns is visible.
Embodiment WG14
The formation of individual layer waveguiding structure
The varnish solution V27 that has filtered is poured over 4 ｀ ｀ SiO 2On the wafer of coating, and use scraper to spread out homogeneous thickness basically.The wafer of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.This film is passed through photomask (UV dosage 3J/cm 2) be exposed to (365nm) under the UV light, in baking oven, heated 30 minutes down then at 85 ℃, then heated extra 60 minutes down at 150 ℃.After hot step for the first time, waveguide patterns is visible.
Embodiment WG15
The formation of individual layer waveguiding structure
The varnish solution V28 that has filtered is poured over 4 ｀ ｀ SiO 2On the wafer of coating, and use scraper to spread out homogeneous thickness basically.The wafer of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.This film is passed through photomask (UV dosage 3J/cm 2) be exposed to (365nm) under the UV light, in baking oven, heated 30 minutes down then at 85 ℃, then heated extra 60 minutes down at 150 ℃.After hot step for the first time, waveguide patterns is visible.
Embodiment WG16
The formation of individual layer waveguiding structure
The varnish solution V29 that has filtered is poured over 4 ｀ ｀ SiO 2On the wafer of coating, and use scraper to spread out homogeneous thickness basically.The wafer of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.This film is passed through photomask (UV dosage 3J/cm 2) be exposed to (365nm) under the UV light, in baking oven, heated 30 minutes down then at 85 ℃, then heated extra 60 minutes down at 150 ℃.After hot step for the first time, waveguide patterns is visible.
Embodiment WG17
The formation of individual layer waveguiding structure
The varnish solution V30 that has filtered is poured over 4 ｀ ｀ SiO 2On the wafer of coating, and use scraper to spread out homogeneous thickness basically.The wafer of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.This film is passed through photomask (UV dosage 6J/cm 2) be exposed to (365nm) under the UV light, in baking oven, heated 30 minutes down then at 85 ℃, then heated extra 60 minutes down at 150 ℃.After hot step for the first time, waveguide patterns is visible.
Embodiment WG18
The formation of individual layer waveguiding structure
The varnish solution V31 that has filtered is poured over 4 ｀ ｀ SiO 2On the wafer of coating, and use scraper to spread out homogeneous thickness basically.The wafer of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.This film is passed through photomask (UV dosage 6J/cm 2) be exposed to (365nm) under the UV light, in baking oven, heated 30 minutes down then at 85 ℃, then heated extra 60 minutes down at 150 ℃.After hot step for the first time, waveguide patterns is visible.
Embodiment WG19
The formation of three layers of waveguide
Varnish solution V23 is poured on the thick glass plate of 1mm, and uses scraper to spread out basically homogeneous thickness (wet thick=70 microns).On ground floor, topple over varnish solution V21 then, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).At last, on the second layer, topple over varnish solution V23, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).Glass plate with coating places on the hot plate then, and heats 30 minutes down at 50 ℃, makes 1,3, the evaporation of 5-trimethylbenzene, and form the solid built up film.And by positive toner photomask, with this film (exposure dose=3000mJ/cm 2) be exposed to (365nm) under the UV light, and heated 30 minutes down and heated 60 minutes down at 150 ℃ at 85 ℃ respectively.After 85 ℃ were heated 30 minutes down, as seen waveguide patterns became at glass plate.Use " cut and subtract method ", measure the transmission loss of this waveguide, and be determined as 3.0dB/cm.
Embodiment WG20
The formation of three layers of waveguide
Varnish solution V23 is poured on the thick glass plate of 1mm, and uses scraper to spread out basically homogeneous thickness (wet thick=70 microns).On ground floor, topple over varnish solution V22 then, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).At last, on the second layer, topple over varnish solution V23, and use scraper to spread out basically homogeneous thickness (wet thick=80 microns).Glass plate with coating places on the hot plate then, and heats 30 minutes down at 50 ℃, makes 1,3, the evaporation of 5-trimethylbenzene, and form the solid built up film.And by positive toner photomask, with this film (exposure dose=3000mJ/cm 2) be exposed to (365nm) under the UV light, and heated 30 minutes down and heated 60 minutes down at 150 ℃ at 85 ℃ respectively.After 85 ℃ were heated 30 minutes down, as seen waveguide patterns became at glass plate.Use " cut and subtract method ", measure the transmission loss of this waveguide, and be determined as 2.0dB/cm.
The measurement of transmission loss
Measure by each individual layer waveguide of 8 kinds of varnish solution V24-V31 formation with by two kinds of varnish solution V21-V22 that are used for core layer and the transmission loss that is used for three layers of waveguide of tectal a kind of varnish solution V23 formation in the mode identical with the above.
The transmission loss result of individual layer waveguide has been shown in the table 7, and the transmission loss result of three layers of waveguide has been shown in following table 8.
Table 7
Varnish solution V24 V25 V26 V27 V28 V29 V30 V31
The UV exposure can (J/cm 2) 6 3 6 3 3 3 6 6
Waveguide WG11 WG12 WG13 WG14 WG15 WG16 WG17 WG18
Transmission loss [dB/cm] 0.6 0.3 0.4 0.4 0.4 0.2 0.5 0.2
Table 8
Be used for tectal varnish solution V23 V23
The varnish solution that is used for core layer V21 V22
The UV exposure can (J/cm 2) 3 3
Waveguide WG19 WG20
Transmission loss [dB/cm] 3.0 2.0
Embodiment WG21
The formation of individual layer waveguiding structure
The varnish solution V38 that has filtered is poured on the quartz glass wafer, and uses scraper to spread out homogeneous thickness basically.On the levelling plate that ventilates, place this quartz glass wafer then and spend the night, make solvent evaporation and form dry basically solid film.This film is exposed to (365nm) under the UV light by photomask (UV dosage 3000mJ), then in baking oven, 45 ℃ of heating 30 minutes down, 85 ℃ of heating 30 minutes down, then 150 ℃ of extra 60 minutes of heating down.After hot step for the first time, as seen waveguide patterns becomes.
Embodiment WG22-WG36
Embodiment WG22-WG36 has illustrated the manufacturing of individual layer waveguiding structure according to embodiments of the present invention.With the above the same embodiment WG22-WG36 for preparing of WG21, different is to change varnish solution and radiant quantity.
Table 9 provides the transmission loss general introduction of individual layer waveguide WG21-WG36.
Table 9
Varnish solution V38 V39 V40 V41 V42 V43 V44 V45
The UV exposure can (J/cm 2) 3 3 1.5 3 3 3 3 3
Waveguide WG21 WG22 WG23 WG24 WG25 WG26 WG27 WG28
Transmission loss [dB/cm] 0.10 0.12 0.08 0.32 0.13 0.26 0.62 0.40
Varnish solution V46 V47 V48 V51 V52 V53 V54 V55
The UV exposure can (J/cm 2) 3 6 6 3 3 3 6 6
Waveguide WG29 WG30 WG31 WG32 WG33 WG34 WG35 WG36
Transmission loss [dB/cm] 0.28 0.18 0.53 0.11 0.15 0.19 0.26 0.48
Embodiment WG51
The formation of three layers of waveguiding structure
V61 is poured on the glass sheet of 4 ｀ ｀, and uses spin coater to spread out basically homogeneous thickness (wet thick=1 micron).Then, place it on the hot plate, and heated 10 minutes down, and do not having under the situation of photomask, be exposed to (exposure dose 400mJ/cm under the UV light at 100 ℃ 2), then solidified 15 minutes down and solidified 1 hour down at 110 ℃ respectively at 160 ℃.
Then, varnish solution V38 is poured on the surface of V1 layer of curing, and uses scraper to spread out basically homogeneous thickness (wet thick=70 microns).The glass sheet of placing coating on the levelling plate that ventilates spends the night then, makes solvent evaporation and forms dry basically solid film.Second day, will pass through photomask (exposure dose=3000mJ/cm by the solid film that solution V38 forms 2) be exposed to (365nm) under the UV light, then 45 ℃ of following ageings 30 minutes, at first solidified 30 minutes down at 85 ℃, solidified 60 minutes down at 150 ℃ then.After 85 ℃ of following these films of curing 30 minutes, as seen waveguide patterns becomes.
On the surface of the cured layer of varnish solution V38, topple over the V61 of second portion then, and use spin coater to spread out basically homogeneous thickness (wet thick=1 micron).The glass sheet of coating is placed on the hot plate, and heated 10 minutes down, and do not having under the situation of photomask, be exposed to (exposure dose=400mJ/cm under the UV light at 100 ℃ 2), then solidified 15 minutes down at 110 ℃ respectively, and solidified 1 hour down at 160 ℃.Still as seen waveguide patterns but sees through top cover layer, and this film appears as brown.
Embodiment WG52
Peel off individual layer guide membrane (WG21) from substrate of glass, use many water rinses, in baking oven, drying is 1 hour under 45 ℃ then.
V61 is poured on the PET film with varnish solution, and uses scraper to spread out basically homogeneous thickness (wet thick=50 microns).Be placed on the hot plate then, and heated 10 minutes down, and do not having under the situation of mask, be exposed to (exposure dose=3000mJ/cm under the UV light at 45 ℃ 2).At last, use pocket knife, this coverlay is divided into two, and peels off them from the PET film.
Between above-mentioned two-layer coverlay, insert the WG21 film, and in baking oven, under 150 ℃, under the pressure of 10MPa, heated 1 hour.Use " cut and subtract method " to measure the transmission loss of these three layers of waveguides, and be determined as 0.08dB/cm.By 90 degree disbonded tests, the bond strength that is determined between nuclear core and the overlayer is 50gf/cm.
Embodiment WG53
Peel off individual layer guide membrane (WG21) from substrate of glass, use many water rinses, in baking oven, drying is 1 hour under 45 ℃ then.
V63 is poured on the PET film with varnish solution, and uses scraper to spread out basically homogeneous thickness (wet thick=50 microns).Be placed on the hot plate then, and heated 10 minutes down, and do not having under the situation of mask, be exposed to (exposure dose=3000mJ/cm under the UV light at 45 ℃ 2).At last, use pocket knife, this coverlay is divided into two, and peels off them from the PET film.
Between above-mentioned two-layer coverlay, insert the WG21 film, and in baking oven, under 150 ℃, under the pressure of 10MPa, heated 1 hour.Use " cut and subtract method " to measure the transmission loss of these three layers of waveguides, and be determined as 0.08dB/cm.By 90 degree disbonded tests, the bond strength that is determined between nuclear core and the overlayer is 60gf/cm.
Embodiment WG54
Peel off individual layer guide membrane (WG21) from substrate of glass, use many water rinses, in baking oven, drying is 1 hour under 45 ℃ then.
V64 is poured on the PET film with varnish solution, and uses scraper to spread out basically homogeneous thickness (wet thick=50 microns).Be placed on the hot plate then, and heated 10 minutes down, and do not having under the situation of mask, be exposed to (exposure dose-3000mJ/cm under the UV light at 45 ℃ 2).At last, use pocket knife, this coverlay is divided into two, and peels off them from the PET film.
Between above-mentioned two-layer coverlay, insert the WG21 film, and in baking oven, under 150 ℃, under the pressure of 10MPa, heated 1 hour.Use " cut and subtract method " to measure the transmission loss of these three layers of waveguides, and be determined as 0.08dB/cm.By 90 degree disbonded tests, the bond strength that is determined between nuclear core and the overlayer is 300gf/cm.
Embodiment WG55
Peel off individual layer guide membrane (WG21) from substrate of glass, use many water rinses, in baking oven, drying is 1 hour under 45 ℃ then.
V65 is poured on the PET film with varnish solution, and uses scraper to spread out basically homogeneous thickness (wet thick=50 microns).Be placed on the hot plate then, and heated 10 minutes down, and do not having under the situation of mask, be exposed to (exposure dose=3000mJ/cm under the UV light at 45 ℃ 2).At last, use pocket knife, this coverlay is divided into two, and peels off them from the PET film.
Between above-mentioned two-layer coverlay, insert the WG21 film, and in baking oven, under 150 ℃, under the pressure of 10MPa, heated 1 hour.Use " cut and subtract method " to measure the transmission loss of these three layers of waveguides, and be determined as 0.08dB/cm.By 90 degree disbonded tests, the bond strength that is determined between nuclear core and the overlayer is 200gf/cm.
Embodiment WG56
Peel off individual layer guide membrane (WG32) from substrate of glass, use many water rinses, in baking oven, drying is 1 hour under 45 ℃ then.
V66 is poured on the PET film with varnish solution, and uses scraper to spread out basically homogeneous thickness (wet thick=50 microns).Be placed on the hot plate then, and heated 10 minutes down, and do not having under the situation of mask, be exposed to (exposure dose=3000mJ/cm under the UV light at 45 ℃ 2).At last, use pocket knife, this coverlay is divided into two, and peels off them from the PET film.
Between above-mentioned two-layer coverlay, insert the WG32 film, and in baking oven, under 150 ℃, under the pressure of 10MPa, heated 1 hour.Use " cut and subtract method " to measure the transmission loss of these three layers of waveguides, and be determined as 0.12dB/cm.By 90 degree disbonded tests, the bond strength that is determined between nuclear core and the overlayer is 50gf/cm.
Recognize that norbornene polymer described in the embodiment of the present invention and/or norborneol vinyl monomer provide the optical waveguide with excellent transparency and transmission loss.
Table 10 and 11 provides the general introduction of WG2-WG5, WG19-20 and employed polymkeric substance of WG51-56 and material.
Table 10
Figure C200480040049D00781
Figure C200480040049D0078083621QIETU
R is meant and uses Rhodorsil 2074 and T to be meant TAG-372R
Table 11
Figure C200480040049D00791
Figure C200480040049D0079083628QIETU
R is meant and uses Rhodorsil 2074 and T to be meant TAG-372R

Claims (23)

1. the solid film of a photoinduced heat-developable, it comprises:
Polymeric matrix with first refractive index, this polymeric matrix comprise first repetitive and second repetitive;
Compatible with this polymeric matrix and have second refractive index that is different from first refractive index at least a monomer;
Procatalyst; With
Promotor, wherein promotor is used for procatalyst being changed into latent activity form being exposed to actinic radiation following time, and latent activity form then can change into activity form by being heated to first temperature.
2. the solid film of the photoinduced heat-developable of claim 1, wherein under the situation that is not exposed to actinic radiation, by being heated to than under the second high temperature of first temperature, then procatalyst can change into activity form.
3. the solid film of the photoinduced heat-developable of claim 1 further comprises at least a antioxidant.
4. the solid film of the photoinduced heat-developable of claim 1, wherein polymeric matrix comprises one of homopolymer and multipolymer.
5. the solid film of the photoinduced heat-developable of claim 4, wherein the multipolymer in the polymeric matrix is a terpolymer.
6. the solid film of the photoinduced heat-developable of claim 1, wherein first repetitive comprises that the alkyl norborene repetitive and second repetitive comprise norborene class repetitive.
7. the solid film of the photoinduced heat-developable of claim 6, wherein alkyl norborene repetitive comprises that hexyl norborene repetitive and norborene class repetitive comprise diphenyl methyl norborene methoxy silane repetitive.
8. the solid film of the photoinduced heat-developable of claim 6, wherein alkyl norborene repetitive comprises that hexyl norborene repetitive and norborene class repetitive comprise benzyl norborene repetitive.
9. the solid film of the photoinduced heat-developable of claim 6, wherein alkyl norborene repetitive comprises that hexyl norborene repetitive and norborene class repetitive comprise phenethyl norborene repetitive.
10. the solid film of the photoinduced heat-developable of claim 1, wherein said at least a monomer comprises at least a norborneol vinyl monomer.
11. the solid film of the photoinduced heat-developable of claim 10, wherein said at least a norborneol vinyl monomer comprises the norborneol vinyl monomer with pendent alkyl groups.
12. the solid film of the photoinduced heat-developable of claim 10, wherein said at least a norborneol vinyl monomer comprise hexyl norborene and two norborene methoxyl dimethylsilane.
13. the solid film of the photoinduced heat-developable of claim 11, wherein polymeric matrix comprises hexyl norborene repetitive and diphenyl methyl norborene methoxy silane repetitive.
14. the solid film of the photoinduced heat-developable of claim 1, wherein said at least a monomer comprises the crosslinking chemical monomer.
15. the solid film of the photoinduced heat-developable of claim 14, wherein the crosslinking chemical monomer comprises norborene class crosslinking chemical monomer.
16. the solid film of the photoinduced heat-developable of claim 1, wherein promotor comprises light trigger.
17. the solid film of the photoinduced heat-developable of claim 16, wherein light trigger comprises cation light initiator, described cation light initiator is by being exposed under the actinic radiation, then produce the negative ion of kation and weak coordination, and procatalyst changes into the latent activity form that associates with Weakly coordinating anions.
18. the solid film of the photoinduced heat-developable of claim 2, wherein procatalyst following formula (E (R) 3) 2Pd (Q) 2Expression, wherein E (R) 3Represent the sub-part of the neutral power supply of the 15th family, E is the element that is selected from the 15th family's element in the periodic table of elements, at E (R) 3In R be that one of hydrogen, its isotope and the part that contains alkyl and Q are the anion ligands that is selected from carboxylic acid group, thiocarboxylic acid base and the carbodithioic acid base.
19. the solid film of the photoinduced heat-developable of claim 2, wherein procatalyst following formula [(E (R) 3) aPd (Q) (LB) b] p[WCA] rExpression, wherein E (R) 3Represent the sub-part of the neutral power supply of the 15th family, E is the element of the 15th family, and R is hydrogen, its isotope independently and contains one of part of anionic hydrocarbyl, Q is the anion ligand that is selected from carboxylic acid group, thiocarboxylic acid base and the carbodithioic acid base, and LB is a lewis base, and WCA represents Weakly coordinating anions, a is an integer 1,2 or 3, b is an integer 0,1 or 2, and wherein a+b is 1,2 or 3, and on behalf of palladium kation and Weakly coordinating anions, p and r get to make at [(E (R) 3) aPd (Q) (LB) b] p[WCA] rThe integer of the multiple of the numerical value of structural charge balance.
20. the solid film of the photoinduced heat-developable of claim 19, wherein p and r are independently selected from integer 1 and 2.
21. the solid film of the photoinduced heat-developable of claim 1, wherein polymeric matrix comprises repetitive, at least some repetitives comprise the side group that can dissociate separately, they are exposed to the result who continues to be heated to second temperature higher than first temperature under the actinic radiation then and dissociate to small part from this polymeric matrix and remove from the film of photoinduced heat-developable, thereby change first refractive index.
22. the solid film of the photoinduced heat-developable of claim 21, wherein the side group that can dissociate comprise be selected from-O-,-the Si-phenyl and-at least a component among the OSi-.
23. the solid film of the photoinduced heat-developable of claim 1 further comprises sensitizer.
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