CN102504255A - Soluble fluorinated polyimide material and preparation method thereof - Google Patents
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Abstract
本发明的一种可溶性氟化聚酰亚胺材料是由三单体缩合共聚得到，即按两个二酐单体的总摩尔数与一个含醚键二胺单体的摩尔数之比为1:1，将两个二酐单体与一个含醚键二胺单体进行缩合共聚而得，其中两个二酐单体的摩尔比为1:1～1:10；或按含醚键二胺单体与不含醚键二胺单体的总摩尔数和二酐的摩尔数之比为1:1，由一个含醚键二胺单体、一个不含醚键二胺单体与二酐单体进行缩合共聚而得，其中含醚键二胺单体与不含醚键二胺单体的摩尔比为1:1～1:10，其结构通式为：或。该材料具有良好的溶解性能、较低吸湿率、高热稳定性能和较低的吸收损耗。A kind of soluble fluorinated polyimide material of the present invention is obtained by condensation copolymerization of three monomers, that is, the ratio of the total number of moles of two dianhydride monomers to the number of moles of an ether bond-containing diamine monomer is 1 : 1, obtained by condensation and copolymerization of two dianhydride monomers and one ether bond-containing diamine monomer, wherein the molar ratio of the two dianhydride monomers is 1:1 to 1:10; The ratio of the total number of moles of amine monomers to the total number of moles of diamine monomers without ether bonds and the number of moles of dianhydrides is 1:1. It is obtained by condensation and copolymerization of anhydride monomers, wherein the molar ratio of diamine monomers containing ether bonds to diamine monomers without ether bonds is 1:1~1:10, and its general structural formula is:or. The material has good solubility, low moisture absorption, high thermal stability and low absorption loss.
Description
Technical field
The present invention relates to a kind of solubility and fluoridize polyimide material and preparation method thereof, belong to the preparation category of polymer materials in the photoelectric device.
Background technology
Along with developing rapidly of optical communication and all optical network,, basic design and development have also been obtained like light separator, optical multiplexer, photoswitch, photomodulator etc. based on the optical device of fiber waveguide device.Yet in required field of materials, but there is not victor completely.With glass, LiNbO
3, III-V family semiconductor material (GaAs or InP), Si base for the inorganic waveguide of representative since its cost an arm and a leg, shortcoming such as complete processing complicacy is restricted it in the application of optical-fiber network of future generation.Polymer materials then owing on specific function research and thin film preparation process method, obtained great advance, has obtained to use extremely widely at optical communication field.Trace it to its cause because polymkeric substance has the following advantages: (1) can realize big area, prepare waveguide device cheaply through simple spin coating technique, and manufacture craft is simple simultaneously, and compatible with traditional semiconductor technology.(2) polymkeric substance can be spin-coated on different base materials, helps integrated with other opto-electronic devices.(3) can obtain the uniform film of thickness through the concentration and the spin speed of controlling polymers.(4) polymer materials is of a great variety, and can synthesize the polymkeric substance with desired result through molecular designing, like good solvability, mechanical property etc.(5) use polymkeric substance to make the technological shortcut and simple of waveguide, can utilize mature technologies such as direct photoetching, soft lithographic to realize.Make the optical waveguides rete with polymkeric substance and start from nineteen seventies, at present, be used for the main polymethylmethacrylate of polymer materials (PMMA), PS (PS), polycarbonate (PC), urethane (PU), epoxy resin of optical waveguides etc.Yet most of traditional polymers are low because of its thermostability again, the absorption loss at communication band place greatly with and the matching of operation wavelength and silica fibre not good, restricted its application on optics greatly.Research shows through the thermostability that not only can improve polymkeric substance with the H atom in the F atom substituted polymer, reduces its absorption loss, can also solve the unmatched problem of its operation wavelength.Therefore fluorinated polymer just begins to get into scientific workers' the visual field.Wherein fluorinated polyimide is again because of it not only possesses character such as traditional polyimide material is high temperature resistant, corrosion-resistant, mechanical property is good, also has characteristics such as excellent solubility property, low-k, low water absorption, low thermal coefficient of expansion and receives much concern.Particularly with CF
3After group was introduced in the polyimide molecule chain, the coplanarity of polymer molecule and charge transfer structure obtained destroying, and the color of whole material will shoal, and the transparency will strengthen.In addition, its specific refractory power can accurately be regulated by monomeric proportioning, and the geometric parameter of making device is easy to control, helps the design and the making of various waveguide devices.CN1569995 disclose a kind of production have outstanding thermotolerance, chemical proofing, water-repellancy, insulativity, electrical property and optical property the fluorinated polyimide film method and be applicable to the rotary coating machine of this method; CN1550801 disclose have high heat resistance, high-clarity, low-loss polyimide light-guide material; Yet the preparation of the fluorinated polyimide material that these patents relate to is main with two monomer-polymers, seldom relates to the preparation of three monomeric fluoro polyimide.Three monomer polymerizations are the molecular weight and the MWD of telomerized polymer effectively; Reduce the ordered structure of polymkeric substance; The solubility property of further effective modulation fluorinated polyimide material, film forming properties, resistance toheat, specific refractory power etc.; Especially can improve the machining property of material, and then make the excellent more optical waveguides of over-all properties and use the fluorinated polyimide material.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of solubility and fluoridize polyimide material and preparation method thereof; Good, the easy processing of this material dissolves property, mechanical property and film forming properties are good; Have higher heat-resistant stability, low optical losses, low rate of moisture absorption, material carries out can be made into polymer optical wave guide after photoetching, the etching.
Technical scheme: solubility of the present invention is fluoridized polyimide material and is obtained by three monomer condenses copolymerization; Wherein, First kind is: carry out condensation copolymerization by two dianhydride monomers and an ether-containing key diamine monomer and get; The total mole number of two dianhydride monomers is 1: 1 with the ratio of the mole number of an ether-containing key diamine monomer, and the mol ratio of two dianhydride monomers is 1: 1～1: 10;
Second kind is: by one not the ether-containing key diamine monomer, one ether-containing key diamine monomer, a dianhydride monomer do not carry out condensation copolymerization and get; The ether-containing key diamine monomer and not the ratio of total mole number and the mole number of dianhydride monomer of ether-containing key diamine monomer be 1: 1; The ether-containing key diamine monomer is 1: 1～1: 10 with the mol ratio of ether-containing key diamine monomer not, and its general structure is:
Wherein, the ether-containing key diamine monomer is:
In a kind of;
The ether-containing key diamine monomer is not:
In a kind of;
Dianhydride monomer is:
In a kind of;
M, n are the polymerization degree, and m is 1～1000, and n is 1～1000.
The preparation method that solubility of the present invention is fluoridized polyimide material is:
A) be 1: 1 by the total mole number of two dianhydride monomers and the mole ratio of ether-containing key diamine monomer, wherein the mol ratio of two dianhydride monomers is 1: 1～1: 10, under nitrogen protection and condition of ice bath; With mass concentration respectively the N of two dianhydride monomers of 5wt%～50wt%; The N of the ether-containing key diamine monomer of dinethylformamide (DMF) solution and 5wt%～50wt%, dinethylformamide solution joins in the reaction kettle, room temperature reaction 12～72h behind the mixing; Total monomer quality by the polymerization single polymerization monomer that adds; Every gram polymerization single polymerization monomer total mass need add 5～10mL YLENE, is warming up to 140～200 ℃, continues reaction 3～10h; The water that reaction generates steams with YLENE formation azeotrope, obtains the solution that solubility is fluoridized polyimide material after being cooled to room temperature;
Or it is 1: 1 by the ratio of the mole number of the total mole number of ether-containing key diamine monomer and ether-containing key diamine monomer not and dianhydride; Wherein the ether-containing key diamine monomer is 1: 1～1: 10 with the mol ratio of ether-containing key diamine monomer not; With mass concentration respectively the N of the dianhydride monomer of 5wt%～50wt%, the N of the ether-containing key diamine monomer of dinethylformamide solution, 5wt%～50wt%, the N of the not ether-containing key diamine monomer of dinethylformamide solution and 5wt%～50wt%; Dinethylformamide solution joins in the reaction kettle; Room temperature reaction 12～72h behind the mixing, by the total monomer quality of the polymerization single polymerization monomer that adds, every gram polymerization single polymerization monomer total mass need add 5～10mL YLENE; Be warming up to 140～200 ℃; Continue reaction 3～10h, the water that reaction generates steams with YLENE formation azeotrope, obtains the solution that solubility is fluoridized polyimide material after being cooled to room temperature;
The total mass meter of the polymerization single polymerization monomer that b) adds in a) set by step; Every gram polymerization single polymerization monomer total mass needs the mixing solutions of 200～500mL methanol and 2N HCl; Under the room temperature, the drips of solution of the solubility that makes in the step a) being fluoridized polyimide material is added in the mixing solutions of methanol and 2N HCl, and throw out is separated out; Filter, obtain solubility and fluoridize the polyimide material bullion;
The total mass meter of the polymerization single polymerization monomer that c) adds in a) set by step, every gram polymerization single polymerization monomer total mass needs 5～10mL THF, under the room temperature; The solubility that makes in the step b) is fluoridized the polyimide material bullion be added in the THF and dissolve, need the mixing solutions of 200～500mL methanol and 2N HCl, the tetrahydrofuran solution of this bullion is added drop-wise in the mixing solutions of methanol and 2N HCl by every gram polymerization single polymerization monomer total mass; Throw out is separated out; Filter, with the methanol eddy throw out of purifying, the extracting solution rotary evaporation is to doing in cable type extractor according; 30～100 ℃ of following vacuum-drying 12～36h obtain solubility and fluoridize polyimide material after the cooling.
Wherein: the compound method of the mixing solutions of methanol described in step b) and the step c) and 2N HCl is: being 1: 1～1: 3 compounding methanol/water by volume with methyl alcohol and water earlier, will be to be mixed with the mixing solutions of methanol and 2N HCl in 1: 50～1: 100 then by the volume ratio of the volume of 2NHCl and methanol.
Beneficial effect: the present invention provides a kind of solubility to fluoridize polyimide material and preparation method thereof, and for solvability and the film-forming properties that improves polymer materials, selecting the ether-containing key diamine monomer for use is one of them diamine monomer; Adopt three monomer copolymerization methods further to reduce the regularity of polymer architecture simultaneously, thereby improve its solubility property; In order to reduce the absorption loss and the thermostability that improve material of polymkeric substance at the optical communication wave band; Can select degree of fluorination higher not ether-containing key diamine monomer and dianhydride monomer for use; Addition through regulating three kinds of different monomers can effectively be regulated the performance that solubility is fluoridized polyimide material, obtains the different solubility of a series of fluorine contents and fluoridizes polyimide material.Trifluoromethyl functional group and flexible link group have been introduced in the polyimide material owing to fluoridizing in solubility; Fluorinated polyimide has shown that good solubility can; Not only like N; Have the good solubility ability in the intensive polar solvents such as dinethylformamide and N-N-methyl-2-2-pyrrolidone N-, can also dissolve preferably like common solvent such as acetone, chloroform, methylene dichloride and ETHYLE ACETATE.This material also has lower rate of moisture absorption in addition, good thermal stability and lower absorption loss.
Embodiment
Solubility is fluoridized polyimide material and 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 integral molar quantity of the dianhydride monomer that adds when wherein reacting and the integral molar quantity of diamine monomer ratio be 1: 1.For solvability, film-forming properties, processing characteristics and the mechanical property that improves polymkeric substance, select the ether-containing key diamine monomer to be one of essential monomer of reaction; Simultaneously in order further to reduce the absorption loss and the thermostability that improve material of polymkeric substance at the optical communication wave band; Can select degree of fluorination higher not ether-containing key diamine monomer and dianhydride monomer for use; Addition through regulating three kinds of different monomers can effectively be regulated the performance that solubility is fluoridized polyimide material, obtains the different solubility of a series of fluorine contents and fluoridizes polyimide material.
The general structure that solubility is fluoridized polyimide material is:
Wherein, the ether-containing key diamine monomer is:
In a kind of;
The ether-containing key diamine monomer is not:
In a kind of;
Dianhydride monomer is:
In a kind of;
M, n are the polymerization degree, and m is 1～1000, and n is 1～1000.
The preparation method that this solubility is fluoridized the polyimide luminescent material is:
A) be 1: 1 by the total mole number of two dianhydride monomers and the mole ratio of ether-containing key diamine monomer, wherein the mol ratio of two dianhydride monomers is 1: 1～1: 10, under nitrogen protection and condition of ice bath; With mass concentration respectively the N of two dianhydride monomers of 5wt%～50wt%; The N of the ether-containing key diamine monomer of dinethylformamide solution and 5wt%～50wt%, dinethylformamide solution joins in the reaction kettle, room temperature reaction 12～72h behind the mixing; Total monomer quality by the polymerization single polymerization monomer that adds; Every gram polymerization single polymerization monomer total mass need add 5～10mL YLENE, is warming up to 140～200 ℃, continues reaction 3～10h; The water that reaction generates steams with YLENE formation azeotrope, obtains the solution that solubility is fluoridized polyimide material after being cooled to room temperature; Or it is 1: 1 by the ratio of the mole number of the total mole number of ether-containing key diamine monomer and ether-containing key diamine monomer not and dianhydride; Wherein the ether-containing key diamine monomer is 1: 1～1: 10 with the mol ratio of ether-containing key diamine monomer not; With mass concentration respectively the N of the dianhydride monomer of 5wt%～50wt%, the N of the ether-containing key diamine monomer of dinethylformamide solution, 5wt%～50wt%, the N of the not ether-containing key diamine monomer of dinethylformamide solution and 5wt%～50wt%; Dinethylformamide solution joins in the reaction kettle; Room temperature reaction 12～72h behind the mixing, by the total monomer quality of the polymerization single polymerization monomer that adds, every gram polymerization single polymerization monomer total mass need add 5～10mL YLENE; Be warming up to 140～200 ℃; Continue reaction 3～10h, the water that reaction generates steams with YLENE formation azeotrope, obtains the solution that solubility is fluoridized polyimide material after being cooled to room temperature;
B) under the room temperature; The drips of solution of the solubility that makes in the step a) being fluoridized polyimide material is added in the mixing solutions of methanol and 2NHCl; The total mass meter of the polymerization single polymerization monomer that adds in a) set by step, every gram polymerization single polymerization monomer total mass needs the mixing solutions of above-mentioned methanol of 200～500mL and 2N HCl, and deposition is separated out; Filter, obtain solubility and fluoridize the polyimide material bullion;
C) under the room temperature, the total mass meter of the polymerization single polymerization monomer that adds in a) set by step, every gram polymerization single polymerization monomer total mass adds the solubility that 5～10mL THF makes and fluoridizes in the polyimide material bullion in step b); After the dissolving, the tetrahydrofuran solution of this bullion is added drop-wise in the mixing solutions of methanol and 2N HCl, every gram polymerization single polymerization monomer total mass needs the mixing solutions of above-mentioned methanol of 200～500mL and 2N HCl; Deposition is separated out; Filter, with the methanol eddy throw out of purifying, the extracting solution rotary evaporation is to doing in cable type extractor according; 30～100 ℃ of following vacuum-drying 12～36h obtain solubility and fluoridize polyimide material after the cooling.
The compound method of mixing solutions that above-mentioned solubility is fluoridized preparing method's step b) and the methanol described in the step c) and the 2NHCl of polyimide material is: being 1: 1～1: 3 compounding methanol/water by volume with methyl alcohol and water earlier, will be to be mixed with the mixing solutions of methanol and 2N HCl in 1: 50～1: 100 then by the volume ratio of the volume of 2NHCl and methanol.
Embodiment 1
Respectively with dianhydride 4,4 '-(hexafluoro sec.-propyl)-phthalic acid (0.1111g, 0.25mmol; 6FDA), 4,4 '-(4,4 '-sec.-propyl-two-phenoxy) two (Tetra hydro Phthalic anhydride) (0.1301g; 0.25mmol, BPADA) with 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene (0.2140g of 4-; 0.5mmol, pBATB) be dissolved in N, in the dinethylformamide.Under nitrogen protection and condition of ice bath, with mass concentration respectively the N of two dianhydride monomers of 50wt%, 1 of dinethylformamide solution and 50wt%; The N of two (4-amino-2-4-trifluoromethylphenopendant) benzene of 4-, dinethylformamide solution joins in the reaction kettle, is reacting 24h under the room temperature; Add 2mL YLENE again; 165 ℃ of thermal cyclization reaction 6h are added drop-wise to reacted solution in the mixing solutions of methanol (volume ratio of methyl alcohol and water is 1: 1) and 1NHCl (2mL) of 150mL, separate out deposition; After carry out suction filtration, obtain solubility and fluoridize the polyimide material bullion.Solubility is fluoridized the polyimide material bullion be dissolved in the 10mL THF, this tetrahydrofuran solution is added drop-wise among the mixing solutions 200mL of methanol (volume ratio of methyl alcohol and water is 1: 1) and 2N HCl (2mL) separates out deposition again, filter; With the methanol eddy throw out of purifying, the extracting solution rotary evaporation is to doing 60 ℃ of following vacuum-drying 24h in cable type extractor according; Cooling back solubility is fluoridized polyimide material pFPI-1; This material has good thermostability, and its second-order transition temperature is 201.5 ℃, has lower rate of moisture absorption (0.54%); Have lower absorption loss at 1550nm, its optical loss is 1.5dB/cm.
Solubility is fluoridized the synthetic route of polyimide material pFPI-1
Embodiment 2
Respectively with dianhydride 4,4 '-(hexafluoro sec.-propyl)-phthalic acid (0.2222g, 0.5mmol; 6FDA), 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene (0.1070g, the 0.25mmol of 4-; PBATB) and 2,2 '-two [4-(4-amido phenoxy) phenyl] propane (0.1026g, 0.25mmol; BAPP) be dissolved in N, in the dinethylformamide.Obtain saturated solution.Under nitrogen protection and condition of ice bath, with mass concentration respectively the N of two diamine monomers of 50wt%, 4 of dinethylformamide solution and 50wt%; The N of 4 '-(hexafluoro sec.-propyl)-phthalic acid, dinethylformamide solution joins in the reaction kettle, is reacting 24h under the room temperature; Add 2mL YLENE again; 165 ℃ of thermal cyclization reaction 6h are added drop-wise to reacted solution in the mixing solutions of methanol (volume ratio of methyl alcohol and water is 1: 1) and 1NHCl (2mL) of 150mL, separate out deposition; After carry out suction filtration, obtain solubility and fluoridize the polyimide material bullion.Solubility is fluoridized the polyimide material bullion be dissolved in the 10mL THF, this tetrahydrofuran solution is added drop-wise among the mixing solutions 200mL of methanol (volume ratio of methyl alcohol and water is 1: 1) and 2N HCl (2mL) separates out deposition again, filter; With the methanol eddy throw out of purifying, the extracting solution rotary evaporation is to doing 60 ℃ of following vacuum-drying 24h in cable type extractor according; Cooling back solubility is fluoridized polyimide material pFPI-2; This material has good thermostability, and its second-order transition temperature is 233.3 ℃, has lower rate of moisture absorption (0.63%); Have lower absorption loss at 1550nm, its optical loss is 1.7dB/cm.
Solubility is fluoridized the synthetic route of polyimide material pFPI-2
Embodiment 3
Respectively with dianhydride 4,4 '-(hexafluoro sec.-propyl)-phthalic acid (0.2222g, 0.5mmol; 6FDA), 2,2 '-two (3-amino-4-hydroxy phenyl) HFC-236fa (0.09156g, 0.25mmol; 6FHP) with 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene (0.1070g, the 0.25mmol of 3-; PBATB) be dissolved in N, in the dinethylformamide.Under nitrogen protection and condition of ice bath, with mass concentration respectively the N of two diamine monomers of 50wt%, 4 of dinethylformamide solution and 50wt%; The N of 4 '-(hexafluoro sec.-propyl)-phthalic acid, dinethylformamide solution joins in the reaction kettle, is reacting 24h under the room temperature; Add 2mL YLENE again; 165 ℃ of thermal cyclization reaction 6h are added drop-wise to reacted solution in the mixing solutions of methanol (volume ratio of methyl alcohol and water is 1: 1) and 1NHCl (2mL) of 150mL, separate out deposition; After carry out suction filtration, obtain solubility and fluoridize the polyimide material bullion.Solubility is fluoridized the polyimide material bullion be dissolved in 10m L THF, this tetrahydrofuran solution is added drop-wise among the mixing solutions 200mL of methanol (volume ratio of methyl alcohol and water is 1: 1) and 2N HCl (2mL) separates out deposition again, filter; With the methanol eddy throw out of purifying, the extracting solution rotary evaporation is to doing 60 ℃ of following vacuum-drying 24h in cable type extractor according; Cooling back solubility is fluoridized polyimide material pFPI-3; This material has good thermostability, and its second-order transition temperature is 262.6 ℃, has lower rate of moisture absorption (0.75%); Have lower absorption loss at 1550nm, its optical loss is 0.5dB/cm.
Solubility is fluoridized the synthetic route of polyimide material pFPI-3
Embodiment 4
4,4 '-(4,4 '-sec.-propyl-two-phenoxy) two (Tetra hydro Phthalic anhydride) (0.2602g; 0.5mmol, BPADA), 2,2 '-two (3-amino-4-hydroxy phenyl) HFC-236fa (0.09156g; 0.25mmol, 6FHP) with 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene (0.1070g of 3-; 0.25mmol, pBATB) be dissolved in N, in the dinethylformamide.Under nitrogen protection and condition of ice bath, with mass concentration respectively the N of two diamine monomers of 50wt%, 4 of dinethylformamide solution and 50wt%; 4 '-(4,4 '-sec.-propyl-two-phenoxy) two (Tetra hydro Phthalic anhydrides) N, dinethylformamide solution joins in the reaction kettle; At reaction 24h, add 2mL YLENE again, 165 ℃ of thermal cyclization reaction 6h under the room temperature; Reacted solution is added drop-wise in the mixing solutions of methanol (volume ratio of methyl alcohol and water is 1: 1) and 1NHCl (2mL) of 150mL; Separate out deposition, after carry out suction filtration, obtain solubility and fluoridize the polyimide material bullion.Solubility is fluoridized the polyimide material bullion be dissolved in the 10mL THF, this tetrahydrofuran solution is added drop-wise among the mixing solutions 200mL of methanol (volume ratio of methyl alcohol and water is 1: 1) and 2NHCl (2mL) separates out deposition again, filter; With the methanol eddy throw out of purifying, the extracting solution rotary evaporation is to doing 60 ℃ of following vacuum-drying 24h in cable type extractor according; Cooling back solubility is fluoridized polyimide material pFPl-4; This material has good thermostability, and its second-order transition temperature is 211.3 ℃, has lower rate of moisture absorption (0.67%); Have lower absorption loss at 1550nm, its optical loss is 1.6dB/cm.
Solubility is fluoridized the synthetic route of polyimide material pFPI-4
Embodiment 5
Respectively with dianhydride 4,4 '-(hexafluoro sec.-propyl)-phthalic acid (0.1111g, 0.25mmol; 6FDA), 4,4 '-(4,4 '-sec.-propyl-two-phenoxy) two (Tetra hydro Phthalic anhydride) (0.1301g; 0.25mmol, BPADA) with 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene (0.2140g of 3-; 0.5mmol, pBATB) be dissolved in N, in the dinethylformamide.Under nitrogen protection and condition of ice bath, with mass concentration respectively the N of two dianhydride monomers of 50wt%, 1 of dinethylformamide solution and 50wt%; The N of two (4-amino-2-4-trifluoromethylphenopendant) benzene of 3-, dinethylformamide solution joins in the reaction kettle, is reacting 24h under the room temperature; Add 2mL YLENE again; 165 ℃ of thermal cyclization reaction 6h are added drop-wise to reacted solution in the mixing solutions of methanol (volume ratio of methyl alcohol and water is 1: 1) and 1NHCl (2mL) of 150mL, separate out deposition; After carry out suction filtration, obtain solubility and fluoridize the polyimide material bullion.Solubility is fluoridized the polyimide material bullion be dissolved in the 10mL THF, this tetrahydrofuran solution is added drop-wise among the mixing solutions 200mL of methanol (volume ratio of methyl alcohol and water is 1: 1) and 2N HCl (2mL) separates out deposition again, filter; With the methanol eddy throw out of purifying, the extracting solution rotary evaporation is to doing 60 ℃ of following vacuum-drying 24h in cable type extractor according; Cooling back solubility is fluoridized polyimide material mFPI-1; This material has good thermostability, and its second-order transition temperature is 209.5 ℃, has lower rate of moisture absorption (0.57%); Have lower absorption loss at 1550nm, its optical loss is 1.8dB/cm.
Solubility is fluoridized the synthetic route of polyimide material mFPI-1.
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| KR101912738B1 (en) | 2017-05-23 | 2018-10-30 | 주식회사 대림코퍼레이션 | High Transparency polyimide precursor resin composition having excellent Optical Characteristics and phase Retardation, method for manufacturing polyimide film using the same, and polyimide film thereof |
| WO2018216852A1 (en) * | 2017-05-23 | 2018-11-29 | 주식회사 대림코퍼레이션 | Polyimide precursor resin composition having excellent light characteristics and phase retardation characteristics and high transparency, method for manufacturing polyimide film using same, and polyimide film manufactured thereby |
| CN109337437A (en) * | 2018-10-12 | 2019-02-15 | 楼乐超 | A kind of preparation process of solubility environment-friendly ink |
| CN115490857A (en) * | 2022-09-26 | 2022-12-20 | 北京化工大学 | Fluorine-containing thermoplastic polyimide resin and preparation method and application thereof |
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