CN103910882A - High-Tg soluble polyimide and preparation method thereof - Google Patents
High-Tg soluble polyimide and preparation method thereof Download PDFInfo
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- CN103910882A CN103910882A CN201310738658.8A CN201310738658A CN103910882A CN 103910882 A CN103910882 A CN 103910882A CN 201310738658 A CN201310738658 A CN 201310738658A CN 103910882 A CN103910882 A CN 103910882A
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Abstract
The invention discloses a high-Tg soluble polyimide and a preparation method thereof. Tert-butylbiphenyl-type diamine monomer and an aromatic dianhydride monomer undergo one-step condensation polymerization reaction in a phenol solvent in the presence of an isoquinoline or quinoline catalyst to produce the high-Tg soluble polyimide. The high-Tg soluble polyimide has good heat resistance (generally greater than 330 DEG C), has good solubility and can be molded at a low temperature (of a room temperature to 70 DEG C).
Description
Technical field
The present invention relates to polyimide technical field, be specifically related to a kind of high T
gsoluble polyimide and preparation method thereof.
Background technology
Polyimide is the family macromolecule material that thermotolerance is the highest, owing to having excellent over-all properties, has application very widely in every field such as Aeronautics and Astronautics, electric, mechanical, chemical industry, microelectronics.Traditional fragrant polyimide, owing to having the backbone structure of rigidity, is insoluble in most organic solvent, and very high its decomposition temperature that even exceedes of fusing point, is therefore difficult to by conventional forming method processing.In industrial production, polyimide adopts " two-step approach " synthetic conventionally at present, i.e. the polyamic acid intermediate of first synthesizing soluble, obtains corresponding polyimide goods through high temperature imidization after machine-shaping again.But polyamic acid intermediate is conventionally stable not, be difficult to long-term preservation, and aftertreatment bothers.Therefore, exploitation can be processed by ordinary method, and can keep the polyimide of high heat resistance and good mechanical properties to become challenging research topic.
Exploitation easily processing polyimide main method has two kinds: one, improve its solvability; Two, improve its thermoplasticity.Generally speaking, improve the thermoplastic approach of polyimide and often cause its second-order transition temperature to reduce, thereby make the yet corresponding reduction of its use temperature, therefore the method is not suitable for high T
gthe exploitation of polyimide.So, improve solvability and just become the high T of exploitation
gcan process the important method of polyimide.At present, improving polyimide deliquescent Main Means comprises: introduce fatty segment, cycloaliphatic ring structure, flexibly connect group, fluorine atom and large side group etc.Wherein, fatty segment, cycloaliphatic ring structure, flexibly connect the introducing of group, also can cause its T
greduce; The introducing of fluorine atom will cause polyimide cost significantly to rise.And introduce large side group and not only can reduce the interaction of polyimide molecule interchain, change their accumulation mode, increase substantially the solvability of polyimide, simultaneously, large side group also can hinder the rotation of polyimide molecule chain, improves its second-order transition temperature and thermostability.
2005, Der-Jang Liaw etc. reported a kind of biphenyl type diamine monomer containing large side group (1-naphthyl) and corresponding polyimide (Macromolecules, 2005,38,4024-4029) thereof, and this polyimide has following repeated structural unit:
Should be containing naphthyl diamine monomer and 4,4 '-(hexafluoro isopropylidene) two anhydride phthalic acids, 3,3 ', 4, the prepared polyimide of 4 '-diphenylsulfone acid dianhydride dissolves in the strong polar aprotic solvent such as NMP, DMAc and DMF; And be only partially soluble in NMP with the prepared polyimide of 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, and completely insoluble in DMAc, DMF.
As one of large side group, the tertiary butyl is also often introduced in aromatic diamine monomers.Chinese invention patent CN01112809.7 discloses a kind of polyimide based on containing tertiary butyl aromatic diamine monomers, and it has following repeated structural unit:
The solvability that this quasi-polyimide is extremely excellent, dissolves in the low boiling point organic solvents such as chloroform, but the relatively low (T under normal circumstances of its second-order transition temperature
g<300 ℃).
Summary of the invention
Based on above-mentioned technical background, the present invention adopts and has a kind ofly prepared a series of new type polyimide resins that contain large side group containing tertiary butyl biphenyl type diamine monomer and extensive stock aromatic dianhydride monomer, and such polyimide resin not only has good resistance toheat (T under normal circumstances
g>330 ℃), also possess good solubility simultaneously, can descend machine-shaping in lower temperature (room temperature～70 ℃), and technique is simple, cost is lower.
Technical scheme of the present invention is as follows:
A kind of high T
gsoluble polyimide, this high T
gsoluble polyimide has following repeated structural unit:
Wherein: 10<n<1000, Ar refers to aromatic structure.
Wherein in specific embodiments more of the present invention, described high T
garomatic structure Ar in the repeated structural unit of soluble polyimide is selected from one or more in following chemical structure unit:
The present invention also provides a kind of above-mentioned high T simultaneously
gthe preparation method of soluble polyimide, this preparation method is take phenol solvent as solvent, take a small amount of isoquinoline 99.9 or quinoline as catalyzer, by react the high T described in generating containing tertiary butyl biphenyl type diamines and aromatic dianhydride by single stage method
gsoluble polyimide, the wherein said mol ratio containing tertiary butyl biphenyl type diamines and aromatic dianhydride is 1:0.95～1.05.
Preferably, above-mentioned high T
gthe preparation method of soluble polyimide comprises the steps:
A) at ℃ temperature of room temperature～100, by phenol solvent, a small amount of isoquinoline 99.9 or quinoline, add reaction in reactor to obtain polyamic acid solution containing tertiary butyl biphenyl type diamines and aromatic dianhydride; The content of catalyzer is common catalytic amount, can be 1～5 in common laboratory reaction, and concrete consumption can be determined according to common experience and this area general knowledge by those skilled in the art;
B) by steps A) gained polyamic acid solution be warming up to 120 ℃～150 ℃ reaction 5～12h; Then be warming up to 180～220 ℃ of continuation reaction 12～24h and obtain soluble polyimide solution; Wherein, the process that polyamic acid solution is warming up to 120 ℃～150 ℃ reaction 5～12h can be temperature reaction process or repeatedly temperature reaction process;
C) by step B) polyimide in gained polyimide solution is precipitated out, and separates dry.Wherein, intermediate processing can be: by gained polyimide solution dilution and slowly pour in alcohols precipitation agent, separate out fibrous polyimide, through suction filtration vacuum-drying to constant weight.Wherein, described precipitation agent can be the alcohols such as methyl alcohol or ethanol.
Wherein, described is as follows 3 containing tertiary butyl biphenyl type diamines, 3 '-di-t-butyl-4, and 4 '-benzidine:
This raw material is prepared by contriver, and its preparation method is take 2-tertiary butyl aniline as raw material, under sodium bicarbonate exists, water as solvent, with Iod R 5～6 hours, obtains the 2-tertiary butyl-4-Iodoaniline under normal temperature, then the 2-tertiary butyl-4-Iodoaniline is under 5% palladium catalyst action, using DMF/water as solvent, Tetrabutyl amonium bromide is as phase-transfer catalyst, under sodium carbonate exists, there is linked reaction, 6～8 hours reaction times, 115 ℃ of temperature; After reaction finishes, be extracted with ethyl acetate, oil reservoir anhydrous sodium sulfate drying, column chromatography, last dehydrated alcohol recrystallization can obtain 3,3 '-di-t-butyl-4,4 '-benzidine.The details such as the design parameter of not mentioning in more than describing can be determined according to general knowledge or limited number of time experiment by those skilled in the art.Figure of description Fig. 1 be contriver prepare 3,3 '-di-t-butyl-4, the nucleus magnetic hydrogen spectrum figure of 4 '-benzidine, the chemical structure that each characteristic peak is corresponding is indicated in the drawings.As can be seen from Figure 1, contriver has successfully prepared following raw material of the present invention: 3, and 3 '-di-t-butyl-4,4 '-benzidine.
In specific embodiments more of the present invention, described aromatic dianhydride is selected from 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 4,4 '-(hexafluoro isopropylidene) two anhydride phthalic acids (6FDA), Bisphenol A Type Diether Dianhydride (BPADA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) or 1,2, one or both in the commercialization aromatic dianhydride such as the equal benzene tertacarbonic acid's dianhydride of 4,5-(PMDA).
In preferred embodiments more of the present invention, in above-mentioned preparation method, steps A) in the solid content of polyamic acid solution be 5wt%～20wt%.
The present invention provides a kind of above-mentioned high T simultaneously
gsoluble polyimide is for the preparation of the application of polyimide goods, by described polyimide at room temperature～70 ℃, be dissolved in DMAc, DMF, NMP, chloroform, tetrahydrofuran (THF), meta-cresol isopolarity organic solvent and be mixed with solution, and casting film or directly application.
In above-mentioned application method, preferably, the solid content of described polyimide solution is 0.5wt%～10wt%.
Compared with prior art, beneficial effect of the present invention is as follows:
The first, the present invention has prepared high T by suitable preparation method (single stage method)
gsoluble polyimide;
The second, the high T of gained of the present invention
gsoluble polyimide not only has good resistance toheat (T under normal circumstances
g>330 ℃), also possess good solubility simultaneously, can be in the lower machine-shaping of lower temperature (room temperature～70 ℃).
Certainly, implement arbitrary product of the present invention and might not need to reach above-described all advantages simultaneously.
Accompanying drawing explanation
Fig. 1 is that the present invention of preparing of contriver is raw materials used 3,3 '-di-t-butyl-4, the nucleus magnetic hydrogen spectrum figure of 4 '-benzidine;
Fig. 2 is the infrared spectrogram of the embodiment of the present invention one;
Fig. 3 is the infrared spectrogram of the embodiment of the present invention two;
Fig. 4 is the infrared spectrogram of the embodiment of the present invention three.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be appreciated that, these embodiment are only for the present invention is described, and are not intended to limit the scope of the invention.Those skilled in the art make according to the present invention in actual applications improvement and adjustment, still belong to protection scope of the present invention.
In the present invention, for the preparation of high T
gthe aromatic dianhydride monomer of soluble polyimide is not particularly limited, and any suitable commercialization aromatic dianhydride all can be used for preparing high T of the present invention
gsoluble polyimide, described aromatic dianhydride monomer can for but be not limited to mention in following examples 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 3,3 ', 4, one or both in 4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 4,4 '-(hexafluoro isopropylidene) two anhydride phthalic acids (6FDA) and Bisphenol A Type Diether Dianhydride (BPADA).
Following examples Raw, catalyzer and aromatic dianhydride monomer are commercially available, and 3,3 '-di-t-butyl-4,4 '-benzidine is laboratory self-control, its preparation method illustrates in summary of the invention part.
In following examples, the performance test methods of each embodiment gained sample is as follows:
Its molecular weight and molecular weight distribution detect (test condition: employing DMF is eluent on the PE Series200GPC instrument of being furnished with differential refractive index detector (RI), 25 ℃ of column temperatures, flow velocity 1.0mL/min, take polymethylmethacrylate (PMMA) as standard specimen);
Its second-order transition temperature (T
g) adopt TA Q2000 differential scanning calorimeter (DSC) measure (test condition: under nitrogen atmosphere, temperature rise rate is 20 ℃/min, temperature range is 40 ℃～430 ℃, test result obtains from eliminate the secondary temperature elevation curve thermal history;
Its thermostability adopts TA Q5000IR thermogravimetric analyzer (TGA) to detect (test condition: carry out respectively, temperature rise rate is 20 ℃/min, 50 ℃～800 ℃ of temperature ranges, the temperature (T while selecting the weightless 5wt% of being under nitrogen or air atmosphere
5wt%) as its decomposition temperature).
Embodiment mono-(PI-1's is synthetic):
Preparation principle and the process of the PI-1 of the present embodiment are as follows:
The preparation method of the polyimide of the present embodiment is as follows:
Under nitrogen protection; by 500mg(1.69mmol) compound 1 adds in tri-mouthfuls of round-bottomed flasks of 100mL; then add successively 15mL meta-cresol and 496.2mg(1.69mmol) BPDA; splash into two isoquinoline 99.9; stirring reaction 12h at 85 ℃; generate polyamic acid solution, then be warming up to successively 120 ℃, 150 ℃ respectively stirring reaction 5h, be finally warming up to 220 ℃ and continue stirring reaction 15h.Reaction solution is cooled to after room temperature, adds the dilution of 20mL chloroform, more slowly pours in the methyl alcohol of 300mL rapid stirring, separates out white fiber shape solid.Obtain PI-1 resin through suction filtration and at 150 ℃ of vacuum-drying 24h.
At 70 ℃, a certain amount of PI-1 resin is dissolved in to (solid content is 6wt%) in NMP, then at clean sheet glass (3 × 6cm
2) top casting film forming.Finally vacuum-drying 12h at 150 ℃, can obtain faint yellow PI-1 film.The infrared spectrogram that accompanying drawing 2 is this polymeric film, wherein 1779cm
-1and 1721cm
-1the absorption peak at place is the charateristic avsorption band of carbonyl on imide ring in polyimide, illustrates that the present embodiment successfully prepared the soluble polyimide PI-1 in above-mentioned reaction formula.
Measure through aforesaid method, the number-average molecular weight of PI-1 is 1.27 × 10
5, molecular weight distribution (M
w/ M
n) be 4.19; Second-order transition temperature (T
g) be 375.4 ℃; Decomposition temperature (T in nitrogen
5wt%) be 523.1 ℃.The solvability of this PI-1 resin sees the following form 1.
Embodiment bis-(PI-2's is synthetic):
Preparation principle and the process of the PI-2 of the present embodiment are as follows:
The preparation method of the polyimide of the present embodiment is as follows:
Under nitrogen protection; by 500mg(1.69mmol) compound 1 adds in tri-mouthfuls of round-bottomed flasks of 100mL; then add successively 15mL meta-cresol and 523.2mg(1.69mmol) ODPA; splash into two isoquinoline 99.9; stirring reaction 12h at 85 ℃; generate polyamic acid solution, then be warming up to successively 120 ℃, 150 ℃ respectively stirring reaction 5h, be finally warming up to 220 ℃ and continue stirring reaction 15h.Reaction solution is cooled to after room temperature, adds the dilution of 20mL chloroform, more slowly pours in the methyl alcohol of 300mL rapid stirring, separates out white fiber shape solid.Obtain PI-2 resin through suction filtration and at 150 ℃ of vacuum-drying 24h.
At room temperature, a certain amount of PI-2 resin is dissolved in to (solid content is 6wt%) in NMP, then at clean sheet glass (3 × 6cm
2) top casting film forming.Finally vacuum-drying 12h at 150 ℃, can obtain faint yellow PI-2 film.The infrared spectrogram that accompanying drawing 3 is this polymeric film, wherein 1780cm
-1and 1724cm
-1the absorption peak at place is the charateristic avsorption band of carbonyl on imide ring in polyimide, illustrates that the present embodiment successfully prepared the soluble polyimide PI-2 in above-mentioned reaction formula.
Measure through aforesaid method, the number-average molecular weight of PI-2 is 8.06 × 10
4, molecular weight distribution (M
w/ M
n) be 3.31; Second-order transition temperature (T
g) be 332.0 ℃; Decomposition temperature (T in nitrogen
5wt%) be 513.6 ℃.The solvability of this PI-2 resin is in table 1.
Embodiment tri-(PI-3's is synthetic):
Preparation principle and the process of the PI-3 of the present embodiment are as follows:
The preparation method of the polyimide of the present embodiment is as follows:
Under nitrogen protection; by 541.7mg(1.827mmol) compound 1 adds in tri-mouthfuls of round-bottomed flasks of 100mL; then add successively 12mL meta-cresol and 811.8mg(1.827mmol) 6FDA; splash into two isoquinoline 99.9; stirring reaction 12h at 85 ℃; generate polyamic acid solution, then be warming up to successively 120 ℃, 150 ℃ respectively stirring reaction 5h, be finally warming up to 220 ℃ and continue stirring reaction 15h.Reaction solution is cooled to after room temperature, adds the dilution of 20mL chloroform, more slowly pours in the methyl alcohol of 300mL rapid stirring, separates out white fiber shape solid.Obtain PI-3 resin through suction filtration and at 150 ℃ of vacuum-drying 24h.
At room temperature, a certain amount of PI-3 resin is dissolved in to (solid content is 6wt%) in NMP, then at clean sheet glass (3 × 6cm
2) top casting film forming.Finally vacuum-drying 12h at 150 ℃, can obtain colourless PI-3 film.The infrared spectrum that accompanying drawing 4 is this polymeric film, wherein 1788cm
-1and 1729cm
-1the absorption peak at place is the charateristic avsorption band of carbonyl on imide ring in polyimide, illustrates that the present embodiment successfully prepared the soluble polyimide PI-3 in above-mentioned reaction formula.
Measure through aforesaid method, the number-average molecular weight of PI-3 is 1.05 × 10
5, molecular weight distribution (M
w/ M
n) be 2.78; Second-order transition temperature (T
g) be 336.8 ℃; Decomposition temperature (T in nitrogen
5wt%) be 515.1 ℃.The solvability of this PI-3 resin is in table 1.
In the above embodiment 1-3, the solvability test result of synthetic each polyimide resin can see the following form 1; Wherein, deliquescent concrete testing method is: take 10mg sample and be placed in the corresponding solvent of 1mL, add stirrer in room temperature or 60 ℃ of stirring 0.5-12h, observe its dissolution degree.
The solvability test chart of table 1 polyimide
| ? | PI-1 | PI-2 | PI-3 |
| m-cresol | (++) | ++ | ++ |
| DMAc | (++) | ++ | ++ |
| DMSO | (+) | ++ | ++ |
| DMF | (+) | (++) | ++ |
| THF | - | (+) | ++ |
| Toluene | - | (+) | (++) |
| CDCl 3 | - | (+) | ++ |
| NMP | (++) | ++ | ++ |
Note: ++ represent to dissolve completely under room temperature, (++) is illustrated at 60 ℃ and dissolves completely, and (+) is illustrated at 60 ℃ and is partly dissolved ,-represent not dissolve.
As can be seen from Table 1, the polyimide of above embodiment 1～3 gained in the present invention greatly can be at a lower temperature (normal temperature or 60 ℃) is dissolved in the middle of some solvent, especially the polyimide of embodiment bis-and embodiment tri-gained, dissolve respectively or be partially dissolved in above-mentioned all solvents of listing, being convenient to process.
Under the instruction of the present invention and above-described embodiment, those skilled in the art are easy to predict, cited or the each raw material that exemplifies of the present invention or its are equal to alternative, each working method or its and are equal to alternative and can realize the present invention, and parameter bound value, the interval value of each raw material and working method can realize the present invention, do not enumerate embodiment at this.
Claims (10)
1. a high T
gsoluble polyimide, is characterized in that, this high T
gsoluble polyimide has following repeated structural unit:
Wherein: 10<n<1000.
2. high T as claimed in claim 1
gsoluble polyimide, is characterized in that, the Ar in described repeated structural unit is selected from one or more in following chemical structure unit:
3. the high T described in any one in a claim 1 or 2
gthe preparation method of soluble polyimide, is characterized in that, take phenol solvent as solvent, take a small amount of isoquinoline 99.9 or quinoline as catalyzer, by react the high T described in generating containing tertiary butyl biphenyl type diamines and aromatic dianhydride by single stage method
gsoluble polyimide, the wherein said mol ratio containing tertiary butyl biphenyl type diamines and aromatic dianhydride is 1:0.95～1.05.
4. high T according to claim 3
gthe preparation method of soluble polyimide, is characterized in that, comprises the steps:
A) at ℃ temperature of room temperature～100, by phenol solvent, a small amount of isoquinoline 99.9 or quinoline, add reaction in reactor to obtain polyamic acid solution containing tertiary butyl biphenyl type diamines and aromatic dianhydride;
B) by steps A) gained polyamic acid solution be warming up to 120 ℃～150 ℃ reaction 5～12h; Then be warming up to 180～220 ℃ of continuation reactions and obtain soluble polyimide solution;
C) by step B) polyimide in gained polyimide solution is precipitated out, and separates dry.
5. according to the high T described in claim 3 or 4
gthe preparation method of soluble polyimide, is characterized in that, described is as follows 3 containing tertiary butyl biphenyl type diamines, 3 '-di-t-butyl-4, and 4 '-benzidine:
6. according to the high T described in claim 3 or 4
gthe preparation method of soluble polyimide, is characterized in that, described aromatic dianhydride is selected from 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 4,4 '-(hexafluoro isopropylidene) two anhydride phthalic acids, Bisphenol A Type Diether Dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride or 1, one or both in the equal benzene tertacarbonic acid's dianhydride of 2,4,5-.
7. high T according to claim 4
gthe preparation method of soluble polyimide, is characterized in that, steps A) in the solid content of polyamic acid solution be 5wt%～20wt%.
8. high T according to claim 4
gthe preparation method of soluble polyimide, is characterized in that, step B) in, the process that polyamic acid solution is warming up to 120 ℃～150 ℃ reaction 5～12h can be temperature reaction process or repeatedly temperature reaction process.
9. the high T described in any one in a claim 1 or 2
gsoluble polyimide, for the preparation of the application of polyimide goods, is characterized in that, described polyimide, at room temperature～70 ℃, is dissolved in and in polar organic solvent, is mixed with solution casting film or directly application.
10. high T according to claim 9
gsoluble polyimide, for the preparation of the application of polyimide goods, is characterized in that, the solid content of described polyimide solution is 0.5wt%～10wt%.
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| CN104130408A (en) * | 2014-07-15 | 2014-11-05 | 上海交通大学 | Hight-Tg soluble polyimide containing fluorene and tertiary butyl and preparation method thereof |
| CN104725636A (en) * | 2015-02-02 | 2015-06-24 | 上海交通大学 | Soluble polyimide containing ether bond and tertiary butyl and preparation method thereof |
| CN104861162A (en) * | 2015-05-20 | 2015-08-26 | 上海交通大学 | Soluble polyimide with tert-butyl and triphenylamine structure and preparation method of soluble polyimide |
| CN106046376A (en) * | 2016-06-16 | 2016-10-26 | 上海交通大学 | Tert-butyl B'B2-containing triamine monomer, hyperbranched polyimide thereof and preparation method |
| CN113402709A (en) * | 2021-05-07 | 2021-09-17 | 苏州予信天材新材料应用技术有限公司 | High-temperature-resistant polyimide soluble in o-diallyl bisphenol A and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130408A (en) * | 2014-07-15 | 2014-11-05 | 上海交通大学 | Hight-Tg soluble polyimide containing fluorene and tertiary butyl and preparation method thereof |
| CN104725636A (en) * | 2015-02-02 | 2015-06-24 | 上海交通大学 | Soluble polyimide containing ether bond and tertiary butyl and preparation method thereof |
| CN104861162A (en) * | 2015-05-20 | 2015-08-26 | 上海交通大学 | Soluble polyimide with tert-butyl and triphenylamine structure and preparation method of soluble polyimide |
| CN106046376A (en) * | 2016-06-16 | 2016-10-26 | 上海交通大学 | Tert-butyl B'B2-containing triamine monomer, hyperbranched polyimide thereof and preparation method |
| CN106046376B (en) * | 2016-06-16 | 2019-02-22 | 上海交通大学 | The B of the B ' containing tert-butyl2Type Triamine monomer and its super-branched polyimide and preparation method |
| CN113402709A (en) * | 2021-05-07 | 2021-09-17 | 苏州予信天材新材料应用技术有限公司 | High-temperature-resistant polyimide soluble in o-diallyl bisphenol A and preparation method thereof |
| CN113402709B (en) * | 2021-05-07 | 2022-09-16 | 苏州予信天材新材料应用技术有限公司 | High-temperature-resistant polyimide soluble in o-diallyl bisphenol A and preparation method thereof |
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