CN101246222A - Fluorine-contained polyimide optical waveguide material and method for producing the same - Google Patents
Fluorine-contained polyimide optical waveguide material and method for producing the same Download PDFInfo
- Publication number
- CN101246222A CN101246222A CNA2007101910714A CN200710191071A CN101246222A CN 101246222 A CN101246222 A CN 101246222A CN A2007101910714 A CNA2007101910714 A CN A2007101910714A CN 200710191071 A CN200710191071 A CN 200710191071A CN 101246222 A CN101246222 A CN 101246222A
- Authority
- CN
- China
- Prior art keywords
- monomer
- fluorinated polyimide
- solution
- dianhydride
- optical waveguide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Optical Integrated Circuits (AREA)
Abstract
The invention provides a fluorine-containing polyimide optical waveguide material and the preparing method thereof relating to the integrating polymer material preparing method in optical device, which can be applied in waveguide optics device, the material is obtained from condensation and copolymerization of three monomers, that is the fluorine-containing polyimide is condensed and copolymerized from two diamine monomers and one dianlydride monomer or from two diamine monomers and one dianlydride monomer, after purification, the fluorine-containing polyimide n-methyl-2-pyrrolidone solution is obtained, and is then dropped on center of clean substrate for spin coating to form film, and desiccation and curing. The glass transition temperature of the material is above 200 DEG C, in the field of optical communication on 1550nm the optical loss is less than 0.6dB/cm, the refractive index on 1550nm is 1.5-1.6.
Description
Technical field
The present invention relates to a kind of fluorinated polyimide optical waveguide material and preparation method thereof, belong to the preparation category of polymeric material in the integrated optical device, can be applicable to the waveguide optical device.
Background technology
In the optical communication field, polymeric optical material obtains extensive studies with its good performance, at present, the optical waveguide material of using mainly concentrates on the inorganic material, but the birefringence effect of inorganic material is big, and it is relatively more difficult to generate high-quality thick film waveguide at the inorganic material substrate, the equipment complexity that needs.And polymeric material have wide in variety, Adjustable structure is arranged, the preparation method is various, preferably thermal stability, in characteristics such as two near infrared transmission windows (wavelength 1.33 μ m and 1.55 μ m) optical loss are little, adopt polymeric material to prepare optical communication and can make work simplification, for integrated optics provides quick response, advantage cheaply with waveguide device.At present, the polymeric material that is used for optical waveguide mainly contains polymethylmethacrylate, epoxy resin, polyimide, polycarbonate etc., and is wherein maximum with the fluoro derivatives research of resistant to elevated temperatures polyimide.Reason be traditional organic polymer optical waveguide material since in the molecular structure absorption of vibrations of C-H or O-H key caused it bigger propagation absorption loss to be arranged at near-infrared band, and this material of fluorinated polyimide has partly replaced hydrogen atom with fluorine atom, thereby the loss of its near infrared region (communication section wavelength) obviously reduces, thermal stability improves, and can satisfy the requirement of application with this fiber waveguide device for preparing.Polyimide behind the fluoro, then can improve the solubility property of polyimide greatly, when keeping the polyimide high thermal stability, strengthened its dissolving power in usual vehicle (as tetrahydrofuran, acetone) again, drawing abillity is also strengthened greatly, and can avoid polyimide in hot acid imide process, the hole that stays in superpolymer owing to dehydration causes light scattering.Particularly on side chain, introduce a large amount of CF at polyimide
3Behind the group, the coplanarity and the charge transfer structure of polymer molecule are destroyed, and the color of whole fluorinated polyimide material will shoal, and the transparency strengthens.Because it has good thermotolerance, can satisfy the requirement of photoelectricity integrated technique simultaneously.In addition, its refractive index can accurately be regulated with the proportioning of material, and the geometric parameter of making device is easy to control, helps the design and the making of various waveguide devices.CN1978488 discloses fluorinated polyimide and preparation method and its usage, mainly obtains containing the fluorinated polyimide electrooptical material of azobenzene side chain type, and it has good thermally-stabilised, workability energy.CN1569995 disclose a kind of production have outstanding thermotolerance, chemical proofing, water proofing property, insulativity, electrical property and optical property the fluorinated polyimide film method and be applicable to the rotary coating machine of this method.CN101012333 discloses fluorinated polyimide/SiO
2Hybrid inorganic-organic materials and preparation method and application, this hybrid material have higher thermal stability under the prerequisite that does not reduce electro-optical properties.The preparation of the fluorinated polyimide material that these patents relate to is based on two monomer-polymers, seldom relate to the preparation of three monomeric fluoro polyimide, more be not used in the low-loss optical waveguide material of preparation, and almost do not relate to optical loss, refractive index, film forming and Study on mechanical properties.Three monomer polymerizations are the molecular weight and the molecular weight distribution of telomerized polymer effectively, performances such as the filming performance of further effective modulation fluorinated polyimide material, heat resistance, refractive index, especially can improve the mechanical property and the processing characteristics of material, and then make the excellent more optical waveguide fluorinated polyimide material of combination property.
Summary of the invention
Technical matters: the purpose of this invention is to provide a kind of fluorinated polyimide optical waveguide material and preparation method thereof, good, the easy processing of this material solubility, mechanical property and filming performance are good, has higher heat-resistant stability, low optical losses, refractive index is 1.5～1.6 adjustable, and material carries out can be made into polymer waveguide after photoetching, the etching.
Technical scheme: the fluorinated polyimide optical waveguide material is obtained by three monomer condenses copolymerization, promptly form by two diamine monomers and dianhydride monomer condensation copolymerization or by two dianhydride monomers and a diamine monomer condensation copolymerization, the mol ratio of the total amount of the dianhydride monomer that adds when wherein reacting and the total amount of diamine monomer is 1: 1.For molecular weight, film forming, processing characteristics and the mechanical property that improves polymkeric substance, the 3rd monomer is bisphenol-A diamines or bisphenol-A dianhydride or fluoro bisphenol-A diamines or fluoro bisphenol-A dianhydride; In order further to reduce polymkeric substance in the absorption loss of optical communication wave band and the thermal stability of raising material, can select high fluorinated diamine of fluoro degree and fluorine-containing dianhydride monomer for use, can effectively regulate the fluorinated polyimide polymer properties by the addition of regulating three kinds of different monomers, obtain the different fluorinated polyimide optical waveguide material of a series of fluorinated volumes.
The general structure of fluorinated polyimide optical waveguide material is:
Perhaps
Wherein, diamine monomer is:
In one or both potpourri, both mol ratios are 1: 1～1: 10 during mixing;
Wherein, dianhydride monomer is:
In one or both potpourri, both ratios are 1: 1～1: 10 during mixing.
Wherein, m, n are the degree of polymerization, and m is 1～1000, and n is 1～1000, and F is a fluorine atom.
Resulting fluorinated polyimide is dissolved in N-Methyl pyrrolidone, and with this drips of solution on the substrate of cleaning, spin-coating film, and dry, solidify.The spin coating one deck photoresist again that contains on the Kapton after the curing after the oven dry, adds mask plate and carries out mask, and photoetching is developed, and passes through the reactive ion etching process etching again, removes the residue photoresist, forms the polymer plane waveguide at last.
The preparation method of fluorinated polyimide optical waveguide material is:
1.) respectively diamine monomer and dianhydride monomer are dissolved in N, making concentration in the dinethylformamide is diamine monomer solution and the dianhydride monomer solution of 5wt%～50wt%, then under blanket of nitrogen, by the total amine of moles such as adding and total acid anhydride, two diamine monomer solution are mixed with a dianhydride monomer solution or two dianhydride monomer solution are mixed with a diamine monomer solution, behind room temperature reaction 12～72h, by the diamine monomer and the dianhydride monomer general assembly (TW) that add, every gram monomer adds 5～10mL dimethylbenzene, be warming up to 140～200 ℃, continue reaction 3～10h, water generation reaction and dimethylbenzene azeotropic steam;
2.) be cooled to room temperature after, reacted solution is dropped in the mixed solution of methanol and 2N HCl, the amount of required mixed solution is by the diamine monomer and the dianhydride monomer general assembly (TW) that add, required 200～500mL the mixed solution of every gram monomer, separate out precipitation, filter, obtain the fluorinated polyimide crude product;
3.) by the diamine monomer and the dianhydride monomer general assembly (TW) that add, every gram fluorinated polyimide crude product is dissolved in 5～10mL tetrahydrofuran, again this tetrahydrofuran solution is added drop-wise in the mixed solution of methanol and 2N HCl, the amount of required mixed solution is by the diamine monomer and the dianhydride monomer general assembly (TW) that add, required 200～500mL the mixed solution of every gram monomer, separate out precipitation, after the filtration, in cable type extractor according with the methanol eddy sediment of purifying, the extract rotary evaporation is to doing, 30～100 ℃ of following vacuum drying 12～36h get fluorinated polyimide after the cooling;
4. (NMP uses CaH before using) fluorinated polyimide to be dissolved in N-Methyl pyrrolidone (NMP)
2Stir after 12 hours, carry out decompression distillation) in, making concentration is the fluorinated polyimide nmp solution of 5wt%～30wt%, and filter through the polytetrafluoroethylene filter of 0.2～0.6 μ m, the refractive index that adopts twin polishing is that 1.449 piezoid (2*2cm) is as base substrate (piezoid cleans 2～5 times with deionized water, ethanol, acetone respectively before using repeatedly, dries).The piezoid of cleaning is adsorbed on the even glue sucker central authorities of sol evenning machine, then this fluorinated polyimide nmp solution is added drop-wise to substrate center, and covers most surfaces, spin-coating film then.After the film forming, the substrate room temperature that will have thin polymer film is placed 0.5～1h, move to the drying glue platform then and toast 1～5h down at 60～100 ℃, 50～100 ℃ of vacuum drying chamber 4～10h then, move to the drying glue platform at last and solidify the fluorinated polyimide membraneous material after obtaining solidifying at 80～150 ℃ of baking 1～5h.
5.) spin coating one deck photoresist again on the fluorinated polyimide membraneous material after the curing after the oven dry, adds mask plate and carries out mask, and photoetching is developed, and passes through the reactive ion etching process etching again, removes to remain photoresist, forms the polymer plane waveguide at last.
Step 2. among the preparation method of above-mentioned fluorinated polyimide optical waveguide material) and step 3.) in the methanol that relates to and the mixed solution of 2N HCl, the volume ratio of its methanol is 1: 1～1: 3, the volume of 2NHCl accounts for 1% of mixed solution cumulative volume.
Beneficial effect: the invention provides a kind of fluorinated polyimide optical waveguide material and preparation method thereof, good, the easy processing of this material solubility, mechanical property and filming performance are good, have higher heat-resistant stability, low optical losses, refractive index is 1.5～1.6 adjustable, and material carries out can be made into the polymer plane waveguide after mask, photoetching, development, the etching.
Characteristics of the present invention are:
(1) adopt fluorine atom instead of hydrogen atom, greatly reduce material the absorption loss of optical communication wave band (＜0.6dB/cm), the fluorinated polyimide dissolubility of preparation is good, processing characteristics and mechanical property obviously improve.
Preferred bisphenol-A diamines of (2) the 3rd monomers or bisphenol-A dianhydride, the adding of bisphenol-A monomer, can obviously improve the molecular weight of fluorinated polyimide, improved its molecular weight distribution (dispersion degree＜1.3), obviously improve the film forming of material, obviously improve the pliability of fluorinated polyimide film, breaking elongation does not more contain the polymer with bis phenol A imide membrane increases an order of magnitude.The glass temperature height of polymkeric substance (＞200 ℃), thermal stability is good.
(3) adopt that the fluorinated polyimide film of whirl coating preparation has that optical loss is low, thermal stability is high, good mechanical property, refractive index advantage such as adjustable in 1.5～1.6 scopes, be suitable for making the polymer plane waveguide.
Embodiment 1
Respectively with 5,5 '-(hexafluoro isopropyl)-two-(2-amino-phenol) be (3mmol) (6FHP), 4,4 '-hexafluoroisopropyli,ene-phthalic anhydride (6FDA) (1.5mmol) is dissolved among the 5mLDMF with bisphenol-A dianhydride (1.5mmol), then under blanket of nitrogen, the solution of 6FHP solution with 6FDA and bisphenol-A dianhydride is mixed, room temperature reaction 24h, the dimethylbenzene after the adding 8mL dried over mgso is warming up to 160 ℃, continue reaction 3～10h, water generation reaction and dimethylbenzene azeotropic steam.After being cooled to room temperature, reacted solution being dropped among the mixed solution 200mL of methanol (1: 1) and 2N HCl (2mL) and separate out precipitation after filtration, obtain the fluorinated polyimide crude product.The fluorinated polyimide crude product is dissolved in the 10mL tetrahydrofuran, again this tetrahydrofuran solution is added drop-wise among the mixed solution 200mL of methanol (1: 1) and 2N HCl (2mL) and separates out precipitation, after the filtration, in cable type extractor according with the methanol eddy sediment of purifying, the extract rotary evaporation is to doing, 60 ℃ of following vacuum drying 24h get fluorinated polyimide a after the cooling.
Embodiment 2
Respectively 6FDA (3mmol), 6FHP (1.5mmol) and bisphenol-A diamines (1.5mmol) are dissolved among the 5mLDMF, then under blanket of nitrogen, 6FDA solution is mixed with 6FHP and bisphenol-A two amine aqueous solutions, room temperature reaction 24h, dimethylbenzene after the adding 8mL dried over mgso, be warming up to 160 ℃, continue reaction 3～10h, water generation reaction and dimethylbenzene azeotropic steam.After being cooled to room temperature, reacted solution being dropped among the mixed solution 200mL of methanol (1: 1) and 2N HCl (2mL) and separate out precipitation after filtration, obtain the fluorinated polyimide crude product.The fluorinated polyimide crude product is dissolved in the 10mL tetrahydrofuran, again this tetrahydrofuran solution is added drop-wise among the mixed solution 200mL of methanol (1: 1) and 2N HCl (2mL) and separates out precipitation, after the filtration, in cable type extractor according with the methanol eddy sediment of purifying, the extract rotary evaporation is to doing, 60 ℃ of following vacuum drying 24h get fluorinated polyimide b after the cooling.
Embodiment 3
Respectively 6FHP (3mmol), 6FDA (1.5mmol) and fluorine-containing bisphenol-A dianhydride (1.5mmol) are dissolved among the 5mL DMF.Under blanket of nitrogen, the solution of 6FHP solution with 6FDA and fluorine-containing bisphenol-A dianhydride is mixed then, room temperature reaction 24h, the dimethylbenzene after the adding 8mL dried over mgso is warming up to 160 ℃, continues reaction 3～10h, and water generation reaction and dimethylbenzene azeotropic steam.After being cooled to room temperature, reacted solution being dropped among the mixed solution 200mL of methanol (1: 1) and 2N HCl (2mL) and separate out precipitation after filtration, obtain the fluorinated polyimide crude product.The fluorinated polyimide crude product is dissolved in the 10mL tetrahydrofuran, again this tetrahydrofuran solution is added drop-wise among the mixed solution 200mL of methanol (1: 1) and 2N HCl (2mL) and separates out precipitation, after the filtration, in cable type extractor according with the methanol eddy sediment of purifying, the extract rotary evaporation is to doing, 60 ℃ of following vacuum drying 24h get fluorinated polyimide c after the cooling.
Embodiment 4
Respectively 6FDA (1.5mmol), 6FHP (3mmol) and fluorine-containing bisphenol-A diamines (1.5mmol) are dissolved among the 5mL DMF.Under blanket of nitrogen, the solution of 6FDA solution with 6FHP and fluorine-containing bisphenol-A diamines is mixed then, room temperature reaction 24h, the dimethylbenzene after the adding 8mL dried over mgso is warming up to 160 ℃, continues reaction 3～10h, and water generation reaction and dimethylbenzene azeotropic steam.After being cooled to room temperature, reacted solution being dropped among the mixed solution 200mL of methanol (1: 1) and 2N HCl (2mL) and separate out precipitation after filtration, obtain the fluorinated polyimide crude product.The fluorinated polyimide crude product is dissolved in the 10mL tetrahydrofuran, again this tetrahydrofuran solution is added drop-wise among the mixed solution 200mL of methanol (1: 1) and 2N HCl (2mL) and separates out precipitation, after the filtration, in cable type extractor according with the methanol eddy sediment of purifying, the extract rotary evaporation is to doing, 60 ℃ of following vacuum drying 24h get fluorinated polyimide d after the cooling.
Respectively with the fluorinated polyimide (a of above-mentioned preparation, b, c, d) be dissolved in N-Methyl pyrrolidone (NMP) (after NMP stirs 12 hours with CaH2 before using, carry out decompression distillation) in, making concentration is the fluorinated polyimide nmp solution of 5wt%～30wt%, and filter through the polytetrafluoroethylene filter of 0.2 μ m, the refractive index that adopts twin polishing is that 1.449 piezoid (2*2cm) is as base substrate (piezoid cleans 2～5 times with deionized water, ethanol, acetone respectively before using repeatedly, dries).The piezoid of cleaning is adsorbed on the even glue sucker central authorities of sol evenning machine, then this fluorinated polyimide nmp solution is added drop-wise to substrate center, and covers most surfaces, spin-coating film then.After the film forming, the substrate room temperature that will have thin polymer film is placed 0.5h, moves to the drying glue platform then and toasts 1h down at 60 ℃, 70 ℃ of vacuum drying chamber 4～10h move to the drying glue platform at last and solidify the fluorinated polyimide membraneous material (a after obtaining solidifying at 110 ℃ of baking 1h then, b, c, d).The performance of fluorinated polyimide optical waveguide material is:
Fluorinated polyimide membraneous material a: optical loss hangs down 0.316dB/cm; 216 ℃ of glass temperatures; The good film-forming property of material, breaking elongation more do not contain order of magnitude of polymer with bis phenol A imide membrane increase and reach 252.500%; 1550nm place refractive index is 1.5447.
Fluorinated polyimide membraneous material b: optical loss 0.325dB/cm; 224 ℃ of glass temperatures; The good film-forming property of material, breaking elongation more do not contain order of magnitude of polymer with bis phenol A imide membrane increase and reach 235.870%; 1550nm place refractive index is 1.5162.
Fluorinated polyimide membraneous material c: optical loss hangs down 0.250dB/cm; 230 ℃ of glass temperatures, filming performance is good, and breaking elongation does not more contain order of magnitude of polymer with bis phenol A imide membrane increase and reaches 220.24%; 1550nm place refractive index is 1.5865.
Fluorinated polyimide membraneous material d: optical loss hangs down 0.255dB/cm; 226 ℃ of glass temperatures; The good film-forming property of material, breaking elongation more do not contain order of magnitude of polymer with bis phenol A imide membrane increase and reach 214.65%; 1550nm place refractive index is 1.5799.
Claims (5)
1, a kind of fluorinated polyimide optical waveguide material, it is characterized in that this material is obtained by three monomer condenses copolymerization, promptly by two diamine monomers and a dianhydride monomer condensation copolymerization or by two dianhydride monomers and a diamine monomer condensation copolymerization, the general structure of gained fluorinated polyimide optical waveguide material is:
Wherein, diamine monomer is:
In one or both potpourri, the mol ratio that two kinds of diamine monomers mix during mixing is 1: 1～1: 10; Dianhydride monomer is:
In one or both potpourri, the mol ratio that two kinds of dianhydride monomers mix during mixing is 1: 1～1: 10; Wherein, m, n are the degree of polymerization, and m is 1～1000, and n is 1～1000, and F is a fluorine atom.
2, a kind of preparation method of fluorinated polyimide optical waveguide material as claimed in claim 1 is characterized in that its preparation method is:
1.) respectively diamine monomer and dianhydride monomer are dissolved in N, making concentration in the dinethylformamide is diamine monomer solution and the dianhydride monomer solution of 5wt%～50wt%, then under blanket of nitrogen, by the total amine of moles such as adding and total acid anhydride, two diamine monomer solution are mixed with a dianhydride monomer solution or mix with a diamine monomer solution by two dianhydride monomer solution, behind room temperature reaction 12～72h, by the diamine monomer and the dianhydride monomer general assembly (TW) that add, every gram monomer adds 5～10mL dimethylbenzene, be warming up to 140～200 ℃, continue reaction 3～10h, water generation reaction and dimethylbenzene azeotropic steam;
2.) be cooled to room temperature after, reacted solution is dropped in the mixed solution of methanol and 2N HCl, the amount of required mixed solution is by the diamine monomer and the dianhydride monomer general assembly (TW) that add, required 200～500mL the mixed solution of every gram monomer, separate out precipitation, after filtration, obtain the fluorinated polyimide crude product;
3.) by the diamine monomer and the dianhydride monomer general assembly (TW) that add, every gram fluorinated polyimide crude product is dissolved in 5～10mL tetrahydrofuran, again this tetrahydrofuran solution is added drop-wise in the mixed solution of methanol and 2N HCl, the amount of required mixed solution is by the diamine monomer and the dianhydride monomer general assembly (TW) that add, required 200～500mL the mixed solution of every gram monomer, separate out precipitation, after the filtration, in cable type extractor according with the methanol eddy sediment of purifying, the extract rotary evaporation is to doing, 30～100 ℃ of following vacuum drying 12～36h get fluorinated polyimide after the cooling;
4.) fluorinated polyimide is dissolved in makes the fluorinated polyimide solution that concentration is 5wt%～30wt% in the N-Methyl pyrrolidone, this drips of solution is added in substrate center, spin-coating film then, after the film forming, the substrate room temperature that will have thin polymer film is placed 0.5～1h, moves to the drying glue platform then and toasts 1～5h, 50～100 ℃ of vacuum drying chamber 4～10h down at 60～100 ℃, move to the drying glue platform at last and solidify the fluorinated polyimide membraneous material after obtaining solidifying at 80～150 ℃ of baking 1～5h.
3, the preparation method of fluorinated polyimide optical waveguide material as claimed in claim 2, thickness＜5 μ the m that it is characterized in that prepared fluorinated polyimide optical waveguide material film, the glass temperature of film＞200 ℃, film is at the optical loss＜0.6dB/cm at optical communication wave band 1550nm place, film in the refractive index at 1550nm place 1.5～1.6.
4, the preparation method of fluorinated polyimide optical waveguide material as claimed in claim 2, it is characterized in that step 1.) and step 3.) described in the mixed solution of methanol and 2NHCl, the volume ratio of methanol is 1: 1～1: 3, the volume of 2NHCl accounts for 1% of mixed solution cumulative volume, wherein step 1.) in the mol ratio of total amount of the total amount of the dianhydride monomer that adds of reaction and diamine monomer be 1: 1.
5, the preparation method of fluorinated polyimide optical waveguide material as claimed in claim 2 is characterized in that step 2.) in the 3rd monomer be bisphenol-A diamines or bisphenol-A dianhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101910714A CN100561257C (en) | 2007-12-07 | 2007-12-07 | A kind of fluorinated polyimide optical waveguide material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101910714A CN100561257C (en) | 2007-12-07 | 2007-12-07 | A kind of fluorinated polyimide optical waveguide material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101246222A true CN101246222A (en) | 2008-08-20 |
| CN100561257C CN100561257C (en) | 2009-11-18 |
Family
ID=39946787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101910714A Expired - Fee Related CN100561257C (en) | 2007-12-07 | 2007-12-07 | A kind of fluorinated polyimide optical waveguide material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100561257C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831074A (en) * | 2010-04-30 | 2010-09-15 | 辽宁科技大学 | New type fluorine-containing copolyimide and preparation method thereof |
| JP2011202059A (en) * | 2010-03-26 | 2011-10-13 | Toray Ind Inc | Resin and positive photosensitive resin composition |
| CN102504255A (en) * | 2011-11-01 | 2012-06-20 | 东南大学 | Soluble fluorinated polyimide material and preparation method thereof |
| CN102559204A (en) * | 2010-12-13 | 2012-07-11 | 财团法人工业技术研究院 | Method and apparatus for purifying alignment solution |
| CN102659610A (en) * | 2012-06-01 | 2012-09-12 | 吉林大学 | Diamino monomer as well as synthesis method and application thereof |
| CN103092008A (en) * | 2011-11-07 | 2013-05-08 | 上海华虹Nec电子有限公司 | Non-photosensitive polyimide photo-etching process |
| CN103592721A (en) * | 2013-11-11 | 2014-02-19 | 华南师范大学 | Method for manufacturing all-polymer plane optical path |
| CN105218814A (en) * | 2015-09-24 | 2016-01-06 | 苏州华辉材料科技有限公司 | Fluorine-containing copolyimide and preparation method thereof |
| CN107337796A (en) * | 2016-05-03 | 2017-11-10 | 吉林师范大学 | A kind of organic polymer optical waveguide material and preparation method thereof |
| CN107450125A (en) * | 2017-08-03 | 2017-12-08 | 河北科技大学 | A kind of preparation method and applications of low dimensional organic optical diode material |
| CN111909378A (en) * | 2020-08-01 | 2020-11-10 | 淮南师范学院 | Fluorinated polyurethane imide electro-optic waveguide material |
| CN114779400A (en) * | 2022-04-13 | 2022-07-22 | 华中科技大学 | Preparation method and application of film with photonic device structure |
-
2007
- 2007-12-07 CN CNB2007101910714A patent/CN100561257C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011202059A (en) * | 2010-03-26 | 2011-10-13 | Toray Ind Inc | Resin and positive photosensitive resin composition |
| CN101831074A (en) * | 2010-04-30 | 2010-09-15 | 辽宁科技大学 | New type fluorine-containing copolyimide and preparation method thereof |
| CN102559204B (en) * | 2010-12-13 | 2014-03-12 | 财团法人工业技术研究院 | Method and apparatus for purifying alignment solution |
| CN102559204A (en) * | 2010-12-13 | 2012-07-11 | 财团法人工业技术研究院 | Method and apparatus for purifying alignment solution |
| CN102504255A (en) * | 2011-11-01 | 2012-06-20 | 东南大学 | Soluble fluorinated polyimide material and preparation method thereof |
| CN103092008A (en) * | 2011-11-07 | 2013-05-08 | 上海华虹Nec电子有限公司 | Non-photosensitive polyimide photo-etching process |
| CN103092008B (en) * | 2011-11-07 | 2015-04-08 | 上海华虹宏力半导体制造有限公司 | Non-photosensitive polyimide photo-etching process |
| CN102659610A (en) * | 2012-06-01 | 2012-09-12 | 吉林大学 | Diamino monomer as well as synthesis method and application thereof |
| CN103592721A (en) * | 2013-11-11 | 2014-02-19 | 华南师范大学 | Method for manufacturing all-polymer plane optical path |
| CN105218814A (en) * | 2015-09-24 | 2016-01-06 | 苏州华辉材料科技有限公司 | Fluorine-containing copolyimide and preparation method thereof |
| CN107337796A (en) * | 2016-05-03 | 2017-11-10 | 吉林师范大学 | A kind of organic polymer optical waveguide material and preparation method thereof |
| CN107337796B (en) * | 2016-05-03 | 2019-11-22 | 吉林师范大学 | A kind of organic polymer optical waveguide material and preparation method thereof |
| CN107450125A (en) * | 2017-08-03 | 2017-12-08 | 河北科技大学 | A kind of preparation method and applications of low dimensional organic optical diode material |
| CN107450125B (en) * | 2017-08-03 | 2018-08-07 | 河北科技大学 | A kind of preparation method and applications of low dimensional organic optical diode material |
| CN111909378A (en) * | 2020-08-01 | 2020-11-10 | 淮南师范学院 | Fluorinated polyurethane imide electro-optic waveguide material |
| CN111909378B (en) * | 2020-08-01 | 2022-08-19 | 淮南师范学院 | Fluorinated polyurethane imide electro-optic waveguide material |
| CN114779400A (en) * | 2022-04-13 | 2022-07-22 | 华中科技大学 | Preparation method and application of film with photonic device structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100561257C (en) | 2009-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100561257C (en) | A kind of fluorinated polyimide optical waveguide material and preparation method thereof | |
| CN103044916B (en) | Flexible transparent polyimide thin film and preparation method thereof | |
| Liaw et al. | Advanced polyimide materials: Syntheses, physical properties and applications | |
| Liu et al. | Highly refractive and transparent polyimides derived from 4, 4 ‘-[m-Sulfonylbis (phenylenesulfanyl)] diphthalic anhydride and various sulfur-containing aromatic diamines | |
| CN101195682B (en) | Method for producing flexible transparent polyimide film material | |
| CN103788650A (en) | Colorless and transparent polyimide film and preparation method thereof | |
| CN111040164B (en) | Colorless transparent non-fluorine polyimide film with low thermal expansion coefficient and preparation method and application thereof | |
| CN101796105A (en) | Polyimide film | |
| US20100279131A1 (en) | Polyimide film with improved thermal stability | |
| CN101831074A (en) | New type fluorine-containing copolyimide and preparation method thereof | |
| CN102634022A (en) | Colorless highly-transparent polyimide film as well as preparation method and application thereof | |
| Guo et al. | Organosoluble semi-alicyclic polyimides derived from 3, 4-dicarboxy-1, 2, 3, 4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride and aromatic diamines: Synthesis, characterization and thermal degradation investigation | |
| Kobzar et al. | Fluorinated polybenzoxazines as advanced phenolic resins for leading-edge applications | |
| CN106046373B (en) | A kind of solvable polyimide film and preparation method with anti-flammability | |
| CN112646182B (en) | Colorless transparent polyimide film material containing pyridine ring structure and preparation method thereof | |
| CN112500567A (en) | High-modulus transparent polyimide film material containing amide structure and preparation method thereof | |
| CN104558605A (en) | Transparent polyimide film and preparation method thereof | |
| CN108587163B (en) | High-transparency low-expansion polyimide film and preparation method and application thereof | |
| CN112062988A (en) | White polyimide optical film and preparation method thereof | |
| CN106832278A (en) | One class high transparency copoly type fluorine-containing polyimide film material and preparation method thereof | |
| CN104804189A (en) | Semi-alicyclic polyimide containing phenolic hydroxyl groups, and preparation method and application thereof | |
| CN110841493B (en) | Polyaryletherketone separation membrane or sulfonated polyaryletherketone separation membrane with adjustable pore diameter and preparation method thereof | |
| CN105218814A (en) | Fluorine-containing copolyimide and preparation method thereof | |
| CN101831075B (en) | Modified polyimide film | |
| CN106496557A (en) | A kind of preparation method of high transparency high temperature resistant fluorinated polyimide resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091118 Termination date: 20121207 |