CN103524738A - Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure - Google Patents
Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure Download PDFInfo
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Abstract
The invention discloses a method for preparing soluble polyimide by use of aromatic diamine monomer containing a naphthaline and tertiary-butyl structure. The method comprises the following steps: in the presence of nitrogen, performing high-temperature one-step solution condensation reaction on raw materials, namely aromatic diamine monomer containing a naphthaline and tertiary-butyl structure, and an aromatic dianhydride monomer which have equal molar amount, thereby preparing the soluble polyimide containing a naphthaline and tertiary-butyl structure. The structural general formula of the soluble polyimide is shown in the specification, wherein Ar is an aromatic structure. The method is simple in technological operations and low in cost, has no special requirements on reaction equipment, and is suitable for industrial production, and the prepared soluble polyimide has good dissolubility, excellent heat resistance stability, superior optical performance and good dielectric property.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly a kind of aromatic diamine monomers containing naphthalene and tertiary butyl structure is prepared the method for soluble polyimide.
Background technology
Polyimide, as a kind of high temperature polymeric materials, has been widely used in aircraft industry, automotive industry, electric industry etc., especially in high-end technology field as microelectronics, rocket and space travel etc., be one of indispensable high temperature material.Polyimide (PI) is in molecular structure, to contain a class high-performance polymer of imide ring structure, tightly packed and intermolecular stronger interaction force due to its stiff backbone structure having, molecular chain, make the polyimide material to there is the shortcomings such as very high melt processing temperature, solubility property is poor, forming process is difficult, thereby further limited them in the application of association area.In order to overcome above-mentioned difficulties, prepare the polyimide material that solubility property is good, be easy to the excellent combination properties such as processing, related scientific research department has dropped into the R&D work that a large amount of human and material resources, financial resources are engaged in this respect.
Soluble polyimide is the focus of Recent study, wherein adopt the synthetic polyimide material with large space steric hindrance and non-coplanar structure, by destroying upright and outspoken chain structure and the intermolecular interaction force of main chain, thereby obtain highly soluble polyimide material.The advantages such as this method monomer is synthetic simply, price is cheap, material excellent combination property are generally to adopt one of method of synthesizing soluble polyimide at present.Such as people such as Zhang Yi, reported soluble functional polyimide based on fluorene structured and its preparation method and application (CN102352039); Yellow the people such as defends and has studied solvable polyimide luminous material containing naphthalene structure and preparation method thereof (CN1371932); Wang claims meaning to wait people to synthesize the method (CN101456954) of preparing polyimide containing pair assorted naphthalenone structures and trifluoromethyl substituted aroma diamine monomer.
By molecular designing, non-coplanar structure and substituted radical are induced one to prepare soluble polyimide in polyimide structures.Such polyimide material at room temperature not only can be dissolved in the conventional organic solvent of high boiling point completely, as DMF, DMAc, NMP,
m-Cresol etc., and wherein partial polymer can also be dissolved in low boiling point solvent, as CDCl
3, THF and acetone etc.This class material also has excellent thermal characteristics, optical property and dielectric properties etc. simultaneously.Aspect thermal characteristics, compare with commercial polyimide, although thermal characteristics reduction to a certain extent, its second-order transition temperature (
t g) still remain on 300 ℃ of above, heat decomposition temperatures (
t d) more than 500 ℃, this type of material is enough to meet its service requirements in Application Areass such as aerospace, microelectronics and photoelectrons.
Summary of the invention
The object of this invention is to provide a kind of aromatic diamine monomers containing naphthalene and tertiary butyl structure and prepare the method for soluble polyimide.
Thinking of the present invention: aromatic diamine monomers and the aromatic dianhydride monomer of take containing naphthalene and tertiary butyl structure are raw material, by high temperature " single stage method " solution polycondensation, react, prepare the soluble polyimide containing naphthalene and tertiary butyl structure, the preparation method who wherein contains the aromatic diamine monomers of naphthalene and tertiary butyl structure is documented in (application number: 2013104485149) in the previous patent application of contriver.
The general structure of the soluble polyimide that the inventive method makes is:
Wherein Ar is a kind of in following 11 kinds of aromatic structures:
The preparation method of above-mentioned soluble polyimide is:
(1), under nitrogen protection, will wait mole aromatic diamine monomers containing naphthalene and tertiary butyl structure and aromatic dianhydride monomer stirring and dissolving under 0 ~ 50 ℃ of environment in meta-cresol, and to add catalyzer isoquinoline 99.9; Then be warming up to 100 ~ 120 ℃ and carry out prepolymerization 10 ~ 12 hours; Be warming up to again 180 ~ 200 ℃ and carry out imidization dehydration reaction 18 ~ 24 hours, make the polymers soln of thickness.
(2) sticky polymers solution step (1) being made is cooled to room temperature, with precipitation agent, precipitate, then successively through filtering, dry, with DMF, be N, N'-dimethyl formamide dissolves again, redeposition, refilter and dry again, makes fibrous soluble polyimide.
The described aromatic diamines containing naphthalene and tertiary butyl structure is 3,3 ˊ-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane, and its structural formula is:
Described aromatic dianhydride is 3, 3 ˊ, 4, 4 ˊ-pyromellitic acid anhydride, 3, 3 ˊ, 4, 4 ˊ-bibenzene tetracarboxylic dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl ether tetraformic dianhydride, 3, 3 ˊ, 4, 4 ˊ-benzophenone tetracarboxylic dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl thio-ether tetrformate dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl sulfone tetraformic acid dianhydride, 2, 2-two (3, 4-dicarboxyl phenyl) hexafluoropropane dianhydride, 2, 2-two (3, 4-dicarboxyl phenyl) propane dianhydride, 2, 2-is two, and [4-(3, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 1, 4-two (3, 4-di carboxyl phenyloxy)-2, 2 ˊ, 3-Three methyl Benzene dianhydride and 1, 4-two (3, 4-di carboxyl phenyloxy)-2, a kind of in 3 ˊ-di-t-butyl benzene dianhydride.
The consumption of described meta-cresol is 9 times of two kinds of monomer total masses.
The consumption of described catalyzer is 0.5 ~ 2.5% of the quality that always feeds intake.
Described precipitation agent is methyl alcohol or ethanol.
The present invention has the following advantages:
(1) technological operation of the inventive method is simple, with low cost, simultaneously to conversion unit without particular requirement, be applicable to suitability for industrialized production.
(2) polyimide material that prepared by the present invention has good solubility energy, dissolve in conventional high boiling organic solvent N, N'-dimethyl formamide (DMF), N, N'-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) and meta-cresol (
m-Cresol) etc., wherein partial polymer can also be dissolved in low boiling point solvent THF, CHCl
3and in acetone, above-mentioned dissolution characteristics in low boiling point solvent, can realize low-temperature curing film-forming process, thereby material is widely used at microelectronic.
(3) polyimide material that prepared by the present invention has superior heat-resistant stability, second-order transition temperature (
t g) more than 300 ℃, thermolysis starting temperature (
t d) more than 500 ℃, carbon yield is more than 55%.
(4) polyimide material that prepared by the present invention has excellent optical property, and cutoff wavelength scope is 323 ~ 356 nanometers, wavelength 388 ~ 461 nanometers that transmitance is 80%.
(5) the polyimide material specific inductivity that prepared by the present invention is low, and specific inductivity is all between 1.80 ~ 3.00.
Accompanying drawing explanation
Fig. 1 is the general structure of the soluble polyimide prepared of the inventive method.
Fig. 2 is the structural formula of the soluble polyimide of the embodiment of the present invention 1 preparation.
Fig. 3 is the structural formula of the soluble polyimide of the embodiment of the present invention 2 preparations.
Fig. 4 is the structural formula of the soluble polyimide of the embodiment of the present invention 3 preparations.
Fig. 5 is the structural formula of the soluble polyimide of the embodiment of the present invention 4 preparations.
Fig. 6 is the structural formula of the soluble polyimide of the embodiment of the present invention 5 preparations.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention, should understand, these embodiment are only not used in and limit the scope of the invention for the present invention is described, in addition should understand, after having read the content of the present invention's instruction, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the appended claims limited range of the application equally.
embodiment 1:
(1) under nitrogen protection, by 1.0000 grams of (2.2920 mmoles) 3,3 ˊ-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane and 0.5000 gram of (2.2920 mmole) 3,3 ˊ, 4,4 ˊ-pyromellitic acid anhydride joins in 13.50 grams of meta-cresols under 25 ℃ of environment, and add 0.235 gram of catalyzer isoquinoline 99.9, stir 30 minutes; Then be heated to 50 ℃, the system of being stirred to is after homogeneous phase transparent, to be warming up to 100 ℃ to carry out prepolymerization 12 hours; Be warming up to again 195 ℃ and carry out imidization dehydration reaction 20 hours, obtain the polymers soln of thickness.
(2) after being cooled to room temperature, sticky polymers solution step (1) being made precipitates with ethanol, then successively through filtering, be dried, being N with DMF, N'-dimethyl formamide dissolves again, with ethanol redeposition, refilter and dry again, make fibrous polyimide, its structural formula is shown in Figure of description.
embodiment 2:
(1) under nitrogen protection, by 1.0000 grams of (2.2920 mmoles) 3,3 ˊ-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane and 0.6744 gram of (2.2920 mmole) 3,3 ˊ, 4,4 ˊ-bibenzene tetracarboxylic dianhydride joins in 15.07 grams of meta-cresols under 25 ℃ of environment, and add 0.25117 gram of catalyzer isoquinoline 99.9, stir 30 minutes; Then be heated to 50 ℃, the system of being stirred to is after homogeneous phase transparent, to be warming up to 100 ℃ to carry out prepolymerization 12 hours; Be warming up to again 200 ℃ and carry out imidization dehydration reaction 18 hours, obtain the polymers soln of thickness.
(2) after being cooled to room temperature, sticky polymers solution step (1) being made precipitates with ethanol, then successively through filtering, be dried, being N with DMF, N'-dimethyl formamide dissolves again, with ethanol redeposition, refilter and dry again, make fibrous polyimide, its structural formula is shown in Figure of description.
embodiment 3:
(1) under nitrogen protection, by 1.0000 grams of (2.2920 mmoles) 3,3 ˊ-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane and 0.7110 gram of (2.2920 mmole) 3,3 ˊ, 4,4 ˊ-diphenyl ether tetraformic dianhydride joins in 15.40 grams of meta-cresols under 25 ℃ of environment, and add 0.25667 gram of catalyzer isoquinoline 99.9, stir 30 minutes; Then be heated to 50 ℃, the system of being stirred to is after homogeneous phase transparent, to be warming up to 100 ℃ to carry out prepolymerization 12 hours; Be warming up to again 180 ℃ and carry out imidization dehydration reaction 24 hours, obtain the polymers soln of thickness.
(2) after being cooled to room temperature, sticky polymers solution step (1) being made precipitates with methyl alcohol, then successively through filtering, be dried, being N with DMF, N'-dimethyl formamide dissolves again, with methyl alcohol redeposition, refilter and dry again, make fibrous polyimide, its structural formula is shown in Figure of description.
embodiment 4:
(1) under nitrogen protection, by 1.0000 grams of (2.2920 mmoles) 3,3 ˊ-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane and 0.7386 gram of (2.2920 mmole) 3,3 ˊ, 4,4 ˊ-benzophenone tetracarboxylic dianhydride joins in 15.65 grams of meta-cresols under 25 ℃ of environment, and add 0.26083 gram of catalyzer isoquinoline 99.9, stir 30 minutes; Then be heated to 50 ℃, the system of being stirred to is after homogeneous phase transparent, to be warming up to 120 ℃ to carry out prepolymerization 10 hours; Be warming up to again 190 ℃ and carry out imidization dehydration reaction 21 hours, obtain the polymers soln of thickness.
(2) after being cooled to room temperature, sticky polymers solution step (1) being made precipitates with methyl alcohol, then successively through filtering, be dried, being N with DMF, N'-dimethyl formamide dissolves again, with methyl alcohol redeposition, refilter and dry again, make fibrous polyimide, its structural formula is shown in Figure of description.
embodiment 5:
(1) under nitrogen protection, by 1.0000 grams of (2.2920 mmoles) 3,3 ˊ-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane and 0.7442 gram of (2.2920 mmole) 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride joins in 15.70 grams of meta-cresols under 25 ℃ of environment, and adds 0.26166 gram of catalyzer isoquinoline 99.9, stirs 30 minutes; Then be heated to 50 ℃, the system of being stirred to is after homogeneous phase transparent, to be warming up to 110 ℃ to carry out prepolymerization 11 hours; Be warming up to again 185 ℃ and carry out imidization dehydration reaction 22 hours, obtain the polymers soln of thickness.
(2) after being cooled to room temperature, sticky polymers solution step (1) being made precipitates with ethanol, then successively through filtering, be dried, being N with DMF, N'-dimethyl formamide dissolves again, with ethanol redeposition, refilter and dry again, make fibrous polyimide, its structural formula is shown in Figure of description.
Claims (1)
1. containing the aromatic diamine monomers of naphthalene and tertiary butyl structure, prepare a method for soluble polyimide, it is characterized in that concrete steps are:
(1), under nitrogen protection, will wait mole aromatic diamine monomers containing naphthalene and tertiary butyl structure and aromatic dianhydride monomer stirring and dissolving under 0 ~ 50 ℃ of environment in meta-cresol, and to add catalyzer isoquinoline 99.9; Then be warming up to 100 ~ 120 ℃ and carry out prepolymerization 10 ~ 12 hours; Be warming up to again 180 ~ 200 ℃ and carry out imidization dehydration reaction 18 ~ 24 hours, make the polymers soln of thickness;
(2) sticky polymers solution step (1) being made is cooled to room temperature, with precipitation agent, precipitate, then successively through filtering, be dried, being N with DMF, N'-dimethyl formamide dissolves again, redeposition, refilter and dry again, make fibrous soluble polyimide, its general structure is:
Wherein Ar is a kind of in following 11 kinds of aromatic structures:
The described aromatic diamines containing naphthalene and tertiary butyl structure is 3,3 ˊ-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane, and its structural formula is:
；
Described aromatic dianhydride is 3, 3 ˊ, 4, 4 ˊ-pyromellitic acid anhydride, 3, 3 ˊ, 4, 4 ˊ-bibenzene tetracarboxylic dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl ether tetraformic dianhydride, 3, 3 ˊ, 4, 4 ˊ-benzophenone tetracarboxylic dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl thio-ether tetrformate dianhydride, 3, 3 ˊ, 4, 4 ˊ-diphenyl sulfone tetraformic acid dianhydride, 2, 2-two (3, 4-dicarboxyl phenyl) hexafluoropropane dianhydride, 2, 2-two (3, 4-dicarboxyl phenyl) propane dianhydride, 2, 2-is two, and [4-(3, 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 1, 4-two (3, 4-di carboxyl phenyloxy)-2, 2 ˊ, 3-Three methyl Benzene dianhydride and 1, 4-two (3, 4-di carboxyl phenyloxy)-2, a kind of in 3 ˊ-di-t-butyl benzene dianhydride,
The consumption of described meta-cresol is 9 times of two kinds of monomer total masses;
The consumption of described catalyzer is 0.5 ~ 2.5% of the quality that always feeds intake;
Described precipitation agent is methyl alcohol or ethanol.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356386A (en) * | 2014-11-11 | 2015-02-18 | 桂林理工大学 | Soluble polyimide containing fluorine and isopropyl structure and preparation method thereof |
| CN104387586A (en) * | 2014-11-11 | 2015-03-04 | 桂林理工大学 | Soluble transparent fluorine-containing polyimide material and preparation method thereof |
| CN104447351A (en) * | 2014-11-11 | 2015-03-25 | 桂林理工大学 | Fluorine-containing diamine monomer with large side group and non-coplanar structure and preparation method of fluorine-containing diamine monomer |
| 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 |
| CN104987506A (en) * | 2015-06-29 | 2015-10-21 | 桂林理工大学 | Soluble polyimide containing tert-butyl and benzofuran structure and preparation method of soluble polyimide |
| CN105601919A (en) * | 2016-01-12 | 2016-05-25 | 湖南工业大学 | Polyimide nanocomposite of naphthalene-containing structure and preparation method and application of polyimide nanocomposite |
| CN112275147A (en) * | 2020-09-01 | 2021-01-29 | 中国科学院山西煤炭化学研究所 | Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356386A (en) * | 2014-11-11 | 2015-02-18 | 桂林理工大学 | Soluble polyimide containing fluorine and isopropyl structure and preparation method thereof |
| CN104387586A (en) * | 2014-11-11 | 2015-03-04 | 桂林理工大学 | Soluble transparent fluorine-containing polyimide material and preparation method thereof |
| CN104447351A (en) * | 2014-11-11 | 2015-03-25 | 桂林理工大学 | Fluorine-containing diamine monomer with large side group and non-coplanar structure and preparation method of fluorine-containing diamine monomer |
| 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 |
| CN104987506A (en) * | 2015-06-29 | 2015-10-21 | 桂林理工大学 | Soluble polyimide containing tert-butyl and benzofuran structure and preparation method of soluble polyimide |
| CN104987506B (en) * | 2015-06-29 | 2017-12-12 | 桂林理工大学 | Soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof |
| CN105601919A (en) * | 2016-01-12 | 2016-05-25 | 湖南工业大学 | Polyimide nanocomposite of naphthalene-containing structure and preparation method and application of polyimide nanocomposite |
| CN105601919B (en) * | 2016-01-12 | 2018-03-27 | 湖南工业大学 | A kind of polyimide nano-composite material containing naphthalene structure and its preparation method and application |
| CN112275147A (en) * | 2020-09-01 | 2021-01-29 | 中国科学院山西煤炭化学研究所 | Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof |
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