CN1178585A - Non-linear optical polycarbonates - Google Patents
Non-linear optical polycarbonates Download PDFInfo
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- CN1178585A CN1178585A CN 96192531 CN96192531A CN1178585A CN 1178585 A CN1178585 A CN 1178585A CN 96192531 CN96192531 CN 96192531 CN 96192531 A CN96192531 A CN 96192531A CN 1178585 A CN1178585 A CN 1178585A
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Abstract
The invention relates to non-linear optically active (NLO) polycarbonates and to NLO active waveguides containing these polycarbonates. Waveguides containing these NLO polycarbonates have a low loss of signal, a high glass transition temperature and good polability and a high stability of the Pockel's coefficient.
Description
The photonic element that the present invention relates to the optically active nonlinear polycarbonate and comprise these polycarbonate.Specifically, the present invention relates to novel non-linear optical polycarbonates, this polymkeric substance shows polarizability (polability) height, the stable height of Pockels effect.
Nonlinear optical material is generally used for the modulation and the laser frequency conversion of optical signalling.This nonlinear optical material generally comprises the optical activity group, and this group comprises the not pi system of localization, and a side of this system links to each other with the group that electronics is provided, and opposite side links to each other with the group of accepting electronics.Term " donor-π-acceptor (D π A) system " often uses in this article.
When under the nonlinear optical material electric field force effect outside when polarized, people observe many nonlinear optical phenomenas, comprise doubling frequency and Pockels effect.Utilize these phenomenons, it is possible using nonlinear optical material in waveguide component (such as optical switch and frequency multiplier).
In general, the nonlinear optical material that has been used for electro-optic device is a mineral crystal, as lithium niobate or potassium dihydrogen phosphate.Recently in development based on the nonlinear optical material of organic molecule, particularly based on the nonlinear optical material of polar organic molecule.Organically the advantage of nonlinear optical material is that their optically active nonlinear degree on the basis of molecule are than higher, their the frequent abilities switched fast and their low-k in electro-optic device, this makes than higher electrooptical modulation frequency and can be achieved under given power consumption, and make integrated equipment easily, particularly when adopting the nonlinear optical material of polymer form, all the more so.
In existing technology, more known non-linear optical polymers.For example, United States Patent (USP) U.S.5,208,299 disclose various non-linear optical polymers (NLO polymkeric substance), and these polymkeric substance originate from dihydroxy aryl hydrazone.This base polymer can be polycarbonate, polyestercarbonate and polyhydroxy ether.Introduced polycarbonate in an embodiment, it is polymerized by dihydroxy phenylhydrazone and bisphenol-A.Although these material lists reveal by the nonlinear optical activity of direction and have than higher glass temperature,, have found that their optical clarity is lower than optimum value.Japanese patent application, No.J-05-142,600 have also disclosed some NLO polymkeric substance, comprise fluorochemical urethane, polyimide, polyester, polyamide, polycarbonate and polyethers.It is said that these materials all show nonlinear optical activity and have the refractive index that is easy to control, and are convenient to be complementary with the quartz type waveguide medium.The european patent application No.571 that has announced, 271 have disclosed second order NLO polymkeric substance and their production method.Polysiloxane, polymethacrylate, polyester, polyurethane, polyamide, polyimide, polyacrylate, polystyrene, polycarbonate, polyethers and their derivant and (or) multipolymer all is included among the described optic polymer.The nonlinear optics composition is connected on the main chain of polymkeric substance by chemical bond-linking.Our common pending trial european patent application No.94202733 has disclosed some non-linear optical polycarbonates, they comprise D π A system, this system comprises a donor that is bonded to aromatic yl group, this aromatic yl group is connected by conjugated bond on the annular group of an aromatic yl group or conjugation, the annular group of this aromatic yl group or conjugation again successively key link on the acceptor.These materials present that the loss of signal is low, polarizability good and glass temperature is high.
The major defect of the polymer waveguides of being made by above-mentioned polymkeric substance is that they do not provide best performance combination.Specifically, this base polymer material should have high glass transition temperature, good polarizability, high stability Pu Keersi coefficient and the minimum loss of signal.Although above-mentioned polymkeric substance shows good performance aspect one or two of these fields,, there is not a kind of material that the best of breed of these performances is provided in these materials.
The invention provides a kind of NLO polycarbonate, this polymkeric substance has low loss, good polarizability, high stability Pu Keersi coefficient and high glass transition temperature.
Feature of the present invention is that the NLO polycarbonate is to be obtained by monomer mixture, and this potpourri comprises:
-satisfy the NLO dibasic alcohol of structural formula (I),
Wherein, D is the electron-donating group of trivalent, it comprises 2 to 30 carbon atoms aliphatic series, alicyclic ring, aromatics or heterocycle and comprises the atom of selecting in the oxygen atom, sulphur atom, selenium atom, nitrogen-atoms from alkoxy at least that this atom connects or is connected by conjugated bond with the direct key of phenyl ring; R selects from the alkyl of hydrogen, (halo) 1 to 6 carbon and cyano group; R1 from halogen ,-R2 ,-OR2 ,-COR
2,-CN and-CF
3Among select; And R
2Among the alkyl of 1 to 6 carbon of the alkyl of hydrogen, halogen, 1 to 6 carbon and halo, select,
-according to the compound of structural formula (II):
Wherein, P representative-Cl, O-R
3, imidazoles,
Q representative-Cl, O-R
3, imidazoles,
R
3Representative has (halo) alkyl, (halo) phenyl of 1 to 6 carbon atom,
A represents following structure:
Wherein, Y representative--SO
2--, have the haloalkyl of 1 to 6 carbon atom, preferably :-CF
2-,-C (CF3)
2,-O-,-naphthenic base of S-, 4 to 12 carbon atoms, two anhydrohexose bases ,-C (C
6H
5)
2-,
X is the haloalkyl of halogen, 1 to 6 carbon,
A is 0 to 4 integer, and the X group is identical or different,
B is 0 to 4 integer, and the X group is identical or different,
C is 0 to 4 integer, and the X group is identical or different,
M is 0 to 5 integer, and the A group is identical or different.
Importantly in order to obtain the low polycarbonate of light loss does not comprise aliphatic series according to the compound of structural formula (II) c h bond.Employing has obtained polycarbonate according to the monomer of structural formula (I), and this polycarbonate provides the waveguide with good polarizability and high stability Pu Keersi coefficient.The stability of Pu Keersi coefficient refer to electric field close after the Pu Keersi coefficient keep intact degree.Further show the glass temperature height according to polycarbonate of the present invention.
Polycarbonate of the present invention is to obtain with the monomer reaction that satisfies structural formula (II) in alkaline solution by the dibasic alcohol that satisfies structural formula (I), and this alkaline solution comprises the pyridine solution that contains tertiary amine or tetrahydrofuran solution etc.If wish to obtain the specific molecule amount, can between polymerization period, use some chain stoppers.Typical chain stopper is a phenol.Further details about the preparation of polycarbonate can be consulted
Comp.Pol.Sci.:The Synthesis, Characterization, Reactions and Applications of Polymer (polymer science collection of thesis: synthetic, the feature, anti-of polymkeric substance Should with use)In the 5th the volume (Pergamon publishing house), the 345th page to 356 pages in the 20th chapter.In addition, at United States Patent (USP) U.S.3,248,414, U.S.3,153,008, U.S.3,215,668, U.S.3,187,065, U.S.3,028,365, U.S.2,999,846, U.S.2,964,974, U.S.2,970,137, U.S.1,991, all stated the preparation method of polycarbonate resin in 273 and U.S.2,999,835.
The term of Shi Yonging " electron-donating group " refers to any substituting group in this article, and it provides electronics to the electronic structure of conjugation, and the resonant structure of polarization is provided whereby.With the Hammett sigma constant ability size that can quantize to power.This known constant all has narration in many documents, for example the Advanced Organic Chemistry of J.March (McGraw-Hill Book Company, NewYork,! 977 Edition) (modern age organic chemistry, McGraw-HIll bibliogony company, New York, version in 1977), the 251st page to 259 pages.For electron-donating group, the σ value is a negative value.
In polycarbonate of the present invention, use (among the structural formula I) preferably electron-donating group D row are as follows:
Wherein, the hydroxyl among the OH representative structure formula I, x, y and z represent 0 to 4 integer, R
4Representative--(halo) alkyl or the phenyl of H, 1 to 6 carbon atom.
In the middle of these electron-donating groups D, particularly preferably be and comprise two electron-donating groups at least by the hydroxyl of aryl replacement.The oh group that is replaced by aryl refers to oh group and directly is attached on the aromatic ring.
Suitable compound according to structural formula II is the bischloroformate of various halos.Bischloroformate can be by the base catalyzed reactions preparation of dibasic alcohol and phosgene.Usually dibasic alcohol is dissolved in the toluene, and under zero degree, adds phosgene lentamente, next add alkali lentamente.The best dibasic alcohol that is used to prepare the structural formula II compound is hexafluoro bisphenol-a and hexafluoro tetrabromobisphenol A, because these two kinds of materials provide the loss of signal low-down polycarbonate usually.If wish to improve refractive index, such as, in monomer mixture, can comprise 4,4-sulphonyl xenol bischloroformate or hexafluoro tetrabromobisphenol A.Therefore, by changing bromo-, the chloro-and 4 in the monomer mixture, the content of 4-sulphonyl xenol group just can accurately be adjusted refractive index.
Group P and Q are so long as good leaving group, and they can be any groups.
Except mentioned component, polycarbonate of the present invention can also comprise additional monomer, and using these monomers is in order to make final polycarbonate become crosslinkable polycarbonate.The example of this class monomer is dibasic alcohol or the bischloroformate that contains crosslinkable groups.This crosslinkable group can be alkenyl (such as allyl, vinyl), epoxy radicals, isocyano, (methyl) propylene acid group or maleimide base group.Polyisocyanates or epoxy polymer can also be added in the monomer mixture in order to obtain crosslinkable polycarbonate.The application that crosslinkable materials is made waveguide to the polycarbonate that adopts spin coating successively is reasonable.So the present invention is also relevant with the crosslinkable polycarbonate that is obtained by above-mentioned monomer mixture and crosslinked two kinds of polycarbonate of polycarbonate, this monomer mixture comprises the monomer that contains crosslinkable groups or additional crosslinking chemical.
Can also comprise antioxidant according to polycarbonate of the present invention.Suitable antioxidant is existing narration on the 7th page of EP-A2-0608 493, incorporates it into the present invention at this.
Can make the optical waveguide elements of layer structure according to polycarbonate of the present invention, the polycarbonate ducting layer is clipped in refractive indices of two layers and is lower than between the material of waveguide polycarbonate refractive index in this layer structure.One of method of definition waveguide channels is to change refractive index selectively by radiation in layer of polycarbonate.This technology is referred to as bleaching usually, and normally reduces the refractive index of makrolon material.Comprise the NLO group according to polycarbonate of the present invention, this group is not only bleached easily but also can be become the optically active nonlinear group by polarization.Waveguide channels can also be determined by other technology, such as rie, molding, laser ablation.Therefore, polycarbonate of the present invention is adapted at using in active waveguide element and two kinds of elements of passive wave guide element, and is adapted at using in heat-optical waveguide components.
Having found that polycarbonate polarized film of the present invention has fabulous thermal stability, mainly is its glass transition temperature height.In addition, with Pu Keersi coefficient (r
33) when tolerance, the non-linear optical property of polycarbonate membrane of the present invention and other NLO polymer phase are than being good.Particularly the stability of Pu Keersi coefficient is good especially.At last, these NLO polycarbonate are in the loss of signal minimum of telecommunication window (approximately being 1300nm to 1370nm and 1500nm to 1600nm).
It is a kind of that polycarbonate is applied to the method that base material gets on is spin-coating method.For can the spin coating polycarbonate, at first polycarbonate to be dissolved in a kind of can wettingly treating in the solvent of spin coating base material.Thus obtained polycarbonate solution also should filter.The solvent that is used for the spin coating polycarbonate comprises tetrahydrofuran, o-xylene, 1,3,5-trimethylbenzene, gamma-butyrolacton, ethylene diacetate, diethylene glycol dimethyl ether, cyclohexyl acetate, tetrachloroethane, cyclopentanone, 2-methyl cyclohexanone, 2-Methoxy acetic acid ethyl ester etc.After being coated in solution on the base material, evaporating solvent stays polycarbonate membrane.Then, can induce the Pockels effect technology to make the polycarbonate membrane polarization by so-called DC-.This technology relates to alternating voltage and DC voltage is added on the sample.DC voltage makes molecular orientation and brings out Pockels effect, and alternating current is had a meeting, an audience, etc. well under one's control and is used to measure the Pu Keersi coefficient.Typical DC voltage field strength is at 10V/ μ m to 30V/ μ m.In order to obtain the enough thick film as optical waveguide, one deck connects the spin coating of one deck ground, and to count the strata carbonic ester may be necessary.And then, should protective mulch on NLO optically-active layer.This protective seam can enoughly be made according to crosslinkable polycarbonate of the present invention, because these crosslinkable materials just no longer can dissolve in solvent after local or all crosslinked at their.The invention still further relates to the NLO waveguide that comprises according to polycarbonate of the present invention, and other the photonic device that comprises polycarbonate of the present invention.Set forth the present invention now with reference to following embodiment.
Embodiment
Embodiment 1: polycarbonate 1 synthetic
Monomer 1: Synthetic 2-4-[two (2-hydroxyethyl) amino] phenyl }-3-cyano group-maleonitrile
Satisfy group D in structural formula 1 and the structure and be in instructions, be listed in DA (x, monomer y=1) prepares with following method:
The N-phenyldiethanol-amine of 4.5g (0.025mol) and 3.4g (0.026mol) TCNE at the N of 25ml, are mixed in the dinethylformamide, and this potpourri stirred 17 hours down at 20 ℃.
After solvent evaporation, utilize the methylene chloride (95%) and the mixed solvent of methyl alcohol (5%) to make eluent and make the post layer with the 200g silica gel chromatographic column and separate, obtain the monomer 1 of 5.8g (82%).Fusing point is 164 ℃ to 167 ℃.
By monomer 1 and 4, bischloroformate polymerization in tetrahydrofuran of 4-(hexafluoro isopropylidene) diphenol prepares polycarbonate.The glass temperature of thus obtained polycarbonate is 130 ℃ to 135 ℃, and weight-average molecular weight is 14,000.
The rete of polycarbonate 1 is spin-coated on the silicon substrate.The film of Xing Chenging is induced the polarization of Pockels effect technology by means of above-mentioned DC like this.This film through the Pu Keersi of overcorrect coefficient (r
33) be 0.51 (under the 841nm wavelength, measuring), the ratio (η of the Pu Keersi coefficient that Pu Keersi coefficient that electric field is closed and electric field are opened
33) measured, this ratio is 0.95.η
33High the stable very good of Pu Keersi coefficient of representing.
Embodiment 2: polycarbonate 2 synthetic
Monomer 2: Synthetic 2-[4-(3,4-dihydroxy pyrrolidine-1-yl) phenyl]-3-cyano group-maleonitrile
Satisfying structural formula DE (y=0) given in structural formula 1 and the operation instructions prepares with following method as the monomer of group D:
With the N-phenyl-3 of 4.5g (0.025mol), 4-dihydroxy pyrrolidine and 3.4g (0.026mol) TCNE mixes in the dinethylformamide at the N of 25ml, and this potpourri stirred 18 hours down at 20 ℃.
After solvent evaporation, product by post layer isolation technics, utilize the mixed solvent of 94% methylene chloride and 6% methyl alcohol to make eluent, on 200g silica gel, make purification process.Productive rate is 5.5g (78%).Fusing point is at 216 to 219 ℃.
Make solvent with tetrahydrofuran, by monomer 2 and 4, the bischloroformate polymerization of 4-(hexafluoro isopropylidene) diphenol prepares polycarbonate.Thus obtained polymer glass temperature is 184 ℃ to 194 ℃, and weight-average molecular weight is 8,100.
Polycarbonate 2 is dissolved in the cyclopentanone, is spun on the silicon substrate then.The rete of polycarbonate 2 on silicon substrate is by means of induce the polarization of Pockels effect technology through the DC that revises.Then, utilizing wavelength is that 841 millimicrons flash ranging must be through the Pu Keersi of overcorrect coefficient (r
33) be 0.25.The η that measures
33Be 0.95.
Embodiment 3: polycarbonate 3 synthetic
Monomer 3: Synthetic 2-4-[N-methyl-two (4-hydroxyphenyl) methyl-methylene diazanyl] phenyl }-3-cyano group-maleonitrile
Satisfy group D in structural formula 1 and the structure and be the group DE (R in the instructions
4=CH
3) monomer prepare with following method:
4,4 dihydroxy-benzophenone of 10.7g (0.050mol), 1-methyl 1-phenyl hydrazine and three concentrated sulphuric acids of 6.1g (0.050mol) are mixed in 50ml ethanol, and this potpourri refluxes and heated 64 hours, and the hot water with 150ml is added in the potpourri of heat then.When being cooled to 20 ℃, crystallization appears.Collect product with suction filtration, obtain the yellow crystals of 11.2g (73%) after drying, its fusing point is 192 ℃ to 192.5 ℃.The TCNE of this hydrazone of 6.4g (0.020mol) and 2.6g (0.020mol) at 25ml N, is mixed in the dinethylformamide, and this potpourri stirred 16 hours down at 20 ℃.After solvent evaporation, product by the silica gel chromatographic column of 200g, utilize the mixed solvent of ethyl acetate (30%) and hexane (70%) to carry out purification process as eluent.Obtain the general green black crystals of 6.1g (73%) like this.
By monomer 3 and 4, bischloroformate polymerization in tetrahydrofuran of 4-(hexafluoro isopropylidene)-two-(2, the 6-dibromophenol) prepares polycarbonate.
The glass temperature of thus obtained carbonate polymer is 198 ℃ to 205 ℃, and weight-average molecular weight is 8,950.
Embodiment 4: polycarbonate synthesis 4
By monomer 3 and 4, bischloroformate polymerization in tetrahydrofuran of 4-(hexafluoro isopropylidene) bis-phenol prepares polycarbonate 4.The glass temperature of thus obtained polymkeric substance is 179 ℃ to 186 ℃, and weight-average molecular weight is 9900.
Polycarbonate 4 is dissolved in the cyclopentanone, and is spun on the silicon substrate.Then, spin-coating film utilizes DC to induce the polarization of Pockels effect technology.Then, utilizing wavelength is that 841 millimicrons flash ranging must be through the Pu Keersi of overcorrect coefficient (r
33) be 0.62.The η that measures
33Be 0.90.By rolling up (1992) at magazine " Optics Letters " 17, the prism of introducing in the 1506-1508 page or leaf is coupled into the commercial measurement optical loss, the result is that optical loss is 0.42dB/cm under 1305 millimicrons of wavelength, and optical loss is 0.63dB/cm under 1565 millimicrons of wavelength.
Comparative examples 5: polycarbonate 5
*
By satisfy structural formula I's and wherein group D be DK (R
4=H) monomer prepares U.S.5 with the bisphenol-A polymerization, 208,299 embodiment 18 described polycarbonate.The glass temperature of thus obtained polymkeric substance is 180/211 ℃, and weight-average molecular weight is 16,500.
With polycarbonate 5
*Be dissolved in the tetrahydrofuran, and it is spun on the silicon substrate.Induce the Pockels effect technology to make polycarbonate 5 by the DC-that revises
*Rete polarization on silicon substrate.Then, utilize wavelength be 841 millimicrons photo measure through the Pu Keersi of overcorrect coefficient, the result is 0.35pm/V.The η that measures
33Be 0.52.By prism be coupled into optical loss that technology measures at 1305nm with according to the optical loss of polycarbonate of the present invention identical (0.4dB/cm) substantially.But the optical loss at 1565nm is compared then much bigger (4dB/cm) with foundation polycarbonate of the present invention.
The above embodiments and only be for illustrative purposes to narration of the present invention should not be interpreted into limitation of the present invention.Scope of the present invention is determined by claims.
Claims (10)
1. an optically active nonlinear polycarbonate is characterized in that polycarbonate is polymerized by monomer mixture, and this monomer mixture comprises:
-satisfy the NLO dibasic alcohol of structural formula (I),
Wherein, D is the electron-donating group of trivalent, comprise 2 to 30 carbon atoms aliphatic series, alicyclic ring, aryl or heterocycle and comprise the atom of selecting in the oxygen atom, sulphur atom, selenium atom, nitrogen-atoms from alkoxy at least, this atom connects or is connected by conjugated bond with the direct key of phenyl ring; R selects from the alkyl of hydrogen, (halo) 1 to 6 carbon and cyano group; R1 from halogen ,-R
2,-OR
2,-COR
2,-CN and-CF3 among select; And R
2Among the alkyl of 1 to 6 carbon of the alkyl of hydrogen, halogen, 1 to 6 carbon and halo, select, and
-according to the compound of structural formula (II):
Wherein, P representative-Cl, O-R
3, imidazoles,
Q representative-Cl, O-R
3, imidazoles,
R
3Representative has (halo) alkyl, (halo) phenyl of 1 to 6 carbon atom,
A represents following structure:
Wherein, Y representative--SO
2--, have the haloalkyl of 1 to 6 carbon atom, preferably:--CF
2--,--C (CF
3)
2,--O--,--naphthenic base of S--, 4 to 12 carbon, two anhydrohexose bases,--C (C
6H
5)
2--,
X is the alkyl of halogen, 1 to 6 carbon,
A is 0 to 4 integer, and the X group is identical or different,
B is 0 to 4 integer, and the X group is identical or different,
C is 0 to 4 integer, and the X group is identical or different,
M is 0 to 5 integer, and the A group is identical or different.
2. according to the non-linear optically rotation polymer of the side chain polycondensation of claim 1, it is characterized in that group D selects from following structure:
Wherein, the hydroxyl among the OH representative structure formula I, x and y represent 0 to 4 integer, R
4Representative--alkyl, phenyl or the CF of H, 1 to 6 carbon atom
3
4. according to any one optically active nonlinear polycarbonate in the claim 1 to 3, the monomer that it is characterized in that satisfying structural formula II comprises the bischloroformate of hexafluoro bisphenol-a.
5. according to any one optically active nonlinear polycarbonate in the claim 1 to 3, the monomer that it is characterized in that satisfying structural formula II comprises the bischloroformate of hexafluoro tetrabromobisphenol A.
6. according to any one optically active nonlinear polycarbonate in the claim 1 to 5, it is characterized in that group D is a group shown in the structural formula DK in the monomer that satisfies structural formula I.
7. according to any one optically active nonlinear polycarbonate in the claim 1 to 6, it is characterized in that polycarbonate is crosslinkable or crosslinked.
8. according to any one optically active nonlinear polycarbonate in the claim 1 to 7, it is characterized in that group D comprises the hydroxyl that at least two aryl replace in the monomer that satisfies structural formula I.
9. optically active nonlinear waveguide component is characterized in that it comprises according to any one optically active nonlinear polycarbonate in the claim 1 to 7.
10. hot optical waveguide components is characterized in that it comprises according to any one optically active nonlinear polycarbonate in the claim 1 to 7.
11. a passive wave guide element is characterized in that it comprises according to any one optically active nonlinear polycarbonate in the claim 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96192531 CN1178585A (en) | 1995-03-13 | 1996-02-28 | Non-linear optical polycarbonates |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95200598.1 | 1995-03-13 | ||
| CN 96192531 CN1178585A (en) | 1995-03-13 | 1996-02-28 | Non-linear optical polycarbonates |
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| Publication Number | Publication Date |
|---|---|
| CN1178585A true CN1178585A (en) | 1998-04-08 |
Family
ID=5128326
Family Applications (1)
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|---|---|---|---|
| CN 96192531 Pending CN1178585A (en) | 1995-03-13 | 1996-02-28 | Non-linear optical polycarbonates |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111868612A (en) * | 2018-03-02 | 2020-10-30 | 帝人株式会社 | Polycarbonate having electro-optical effect, method for producing same, and light control element using same |
| CN114616096A (en) * | 2019-10-29 | 2022-06-10 | 帝人株式会社 | Conductive film for antenna and antenna |
| CN115322356A (en) * | 2022-08-09 | 2022-11-11 | 万华化学集团股份有限公司 | Copolycarbonate with high heat resistance and high chemical stability resistance, and preparation method and application thereof |
-
1996
- 1996-02-28 CN CN 96192531 patent/CN1178585A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111868612A (en) * | 2018-03-02 | 2020-10-30 | 帝人株式会社 | Polycarbonate having electro-optical effect, method for producing same, and light control element using same |
| CN114616096A (en) * | 2019-10-29 | 2022-06-10 | 帝人株式会社 | Conductive film for antenna and antenna |
| CN114616096B (en) * | 2019-10-29 | 2023-11-10 | 帝人株式会社 | Conductive film for antenna and antenna |
| CN115322356A (en) * | 2022-08-09 | 2022-11-11 | 万华化学集团股份有限公司 | Copolycarbonate with high heat resistance and high chemical stability resistance, and preparation method and application thereof |
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