CN1269873C - Thermosetting polyimide matrix resin, preparation and use thereof - Google Patents
Thermosetting polyimide matrix resin, preparation and use thereof Download PDFInfo
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- CN1269873C CN1269873C CN 200410034256 CN200410034256A CN1269873C CN 1269873 C CN1269873 C CN 1269873C CN 200410034256 CN200410034256 CN 200410034256 CN 200410034256 A CN200410034256 A CN 200410034256A CN 1269873 C CN1269873 C CN 1269873C
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Abstract
The present invention discloses a polyimide resin matrix with high temperature resistance, which is prepared by using aromatic dianhydride, multi-alkyl substituted organic diamine and reactive terminating agent as raw materials by adopting a PMR method. Resin solution is prepared and obtained from the aromatic dianhydride, the multi-alkyl substituted organic diamine and the reactive terminating agent for matrix resin by heating, reflux and mixing. The resin solution is molded after heat treatment so as to obtain a resin molded component. The polyimide resin which comprises the multi-alkyl substituted organic diamine (TMMDA) of the present invention can be used for preparing resin molded components and composite materials of the resin matrix. The prepared and obtained resin molded components and composite materials of the resin matrix can be used for the preparation of high-temperature resistant components for the fields of aviation, aerospace, precise machinery and petrochemical industry.
Description
Technical field
The present invention discloses a kind of thermosetting polyimide base resin and its production and use.
Background technology
1972, the people such as T.T.Serafini in U.S. NASA Lewis research centre (ThermallyStable Polyimide from Solutions of Monomeric Reactants, J.Appl.Polym.Sci., 1972,16:905; U.S.Patent 3,745,149) reported that high temperature resistant (316 ℃) carbon fiber of employing monomer reactant in-situ polymerization (Insitu Polymerization of Monomer Reactants) method preparation strengthens the matrix resin (PMR-15) of polyimide resin based composites.Simultaneously, Chinese Academy of Sciences chemistry also succeed in developing the method for preparing PMR type polyimid-base resin (KH-304).Different with PMR-15; the KH-304 matrix resin has adopted nontoxic, harmless lower boiling dehydrated alcohol to replace the primary solvent of anhydrous methanol as the resins process; not only can reduce environmental pollution, protection operator ' s health, can improve the building-up properties of matrix resin simultaneously.At present, PMR-15 and KH-304 have become the main matrix resin of the anti-316 ℃ of polymer matrix composites of preparation, lightening fire resistant structural part prepared therefrom or aggregated(particle) structure spare have been widely used in many high-technology fields such as Aeronautics and Astronautics, space technology, as main duct, by-pass air duct, high speed blade, the jet valve of aircraft engine; The empennage of cruise missile, instrument compartment section, housing etc.
But PMR-15 and KH-304 polyimid-base resin also exist some shortcomings, and this has influenced the process of its practical application to a certain extent.These shortcomings mainly comprise 1) one of the principal monomer (4,4-two amido ditanes) of preparation matrix resin has the potential carinogenicity; 2) impelling strength of matrix material prepared therefrom is relatively poor, requires further improvement; 3) be easy to generate fine fisssure etc. in the composite product military service process at high temperature.
1994, people such as R.H.Pater (the ThermosettingPolyimid-es.A Review in NASA Langley research centre, SAMPE Journal, v 30, n 5, Sept-Oct, 1994, p29) reported a kind of PMR type polyimid-base resin (LaRC-RP46), this matrix resin adopts 3,4 '-diamines yl diphenyl ether (3,4 '-ODA) substitutes 4 of PMR-15,4-two amido ditanes, less to environment and operator's harm, the impelling strength of prepared matrix material also obtains improvement to a certain degree.Nineteen ninety-five, people such as R.D.Vannucci (Low Cost Non-MDA Polyimide for HighTemperature Applications, SAMPE International Symposium, 40 (1), p277) reported a kind of polyimid-base resin (AMB-21), this matrix resin adopts 2,2-pair-4-phenoxy group-4-phenyl-propane (BAPP), has good forming process and gives birth to energy; Its shortcoming is that the second-order transition temperature of prepared polymer matrix composites is lower, has limited its use under hot environment to a certain extent.
2000, the people such as K.C.Chuang in NASA Glenn research centre (A High Tg PMRPolyimide Composites DMBZ-15, Journal of Advanced Materials.2001,33 (4): 33) report is a kind of by 2, the PMR type polyimid-base resin of 2 '-dimethyl-benzidine (DMBZ) preparation.Polymer matrix composites prepared therefrom have high glass transition and good mechanical property.
Summary of the invention
The object of the present invention is to provide a kind of thermosetting polyimide base resin.
Another object of the present invention is to provide a kind of method for preparing above-mentioned matrix resin.
For achieving the above object, thermosetting polyimide base resin provided by the invention is substituted with organic diamines and reactive end-capping reagent is formed by aromatic series tetracarboxylic dianhydride, many alkyl, its structure as shown in the formula:
N=2-10 wherein;
Described matrix resin each component is by weight: the aromatic series tetracarboxylic dianhydride is 100 parts, and it is 30-120 part that many alkyl are substituted with organic diamines, and end-capping reagent is 5-60 part.
The organic tetracarboxylic dianhydride of described aromatic series means 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4, the mixture of 4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides and arbitrary proportion thereof.
Described aromatic diamine is 3,3 ', 5,5 '-tetramethyl--4, and 4 '-diaminodiphenylmethane, its structural formula is:
Described end-capping reagent is the norbornylene dicarboxylic acid anhydride, and its structural formula is:
R
1=C
1-C
3Straight-chain paraffin
The method of the above-mentioned thermosetting polyimide base resin of preparation provided by the invention, key step is:
A) with the reactive end-capping reagent of 5-60 part reflux 1-5 hour generation corresponding carboxylic acid monoesters solution in 5-800 part organic solvent;
B) with 100 parts of aromatic series tetracarboxylic dianhydrides reflux 1-3 hour generation corresponding aroma family two acid diesters solution in 80-1800 part organic solvent;
C) under the protection of inert gas the many alkyl of 30-120 part being substituted with organic diamines is dissolved in 20-1000 part organic solvent;
D) with above-mentioned three kinds of solution under protection of inert gas, in 5-30 ℃ of stirring reaction 2-15 hour, obtain solution shape matrix resin.
Described organic solvent comprises the mixture of anhydrous methanol, dehydrated alcohol, Virahol, propyl carbinol and arbitrary proportion thereof.
Thermosetting polyimide base resin solution provided by the invention has characteristics such as solids content height, viscosity is low, stability in storage is good, is suitable for impregnation of carbon fibers, glass fibre or aramid fiber etc., can be made into high-quality prepreg (band or cloth).Prepared prepreg has good composite material forming processing characteristics, low, the fine heat-resisting performance of matrix material porosity that after 50-350 ℃ heat curing process moulding, obtains, the mechanical property height, as lightweight, high-temperature-resistant structure parts or aggregated(particle) structure parts, has the potential using value at high-technology fields such as space flight, aviation, space technologies.Table 1-4 lists the resistance toheat and the mechanical property of typical substrates resin solution, virgin resin molding and carbon fiber enhancement resin base composite material respectively.
The SOLUTION PROPERTIES of table 1PMR type polyimid-base resin
| Title | Fundamental property |
| Outward appearance | Red homogeneous phase solution |
| Solid content (wt%) | 20-60 |
| Solvent | The low-boiling point alcohol kind solvent |
| 25 ℃ of viscosity | 15-400Cp |
| Package stability | 20-25 ℃: 2 months, 0 ℃: December |
The thermal characteristics of the typical polyimide virgin resin of table 2 molding
| Title | Performance index |
| Crosslinking temperature ℃ | 270-350 |
| Weightless 5% temperature ℃ | 510 |
| Weightless 10% temperature ℃ | 560 |
| Second-order transition temperature ℃ | 380 |
| At 316 ℃/1atm/400hrs/N 2In thermal weight loss % | ＜3 |
| Thermal weight loss % in 316 ℃/1atm/400hrs/Air | ＜10 |
| At 343 ℃/1atm/400hrs/N 2In thermal weight loss % | ＜5 |
| At 343 ℃/1atm/400hrs/N 2In thermal weight loss % | ＜20 |
The thermal characteristics of the typical T-300 carbon fiber reinforced of table 3 matrix material
| Title | Performance index |
| Crosslinking temperature, ℃ | 270-350 |
| Weightless 5% temperature, ℃ | 520 |
| Weightless 10% temperature, ℃ | 570 |
| Second-order transition temperature, ℃ | 400 |
| At 316 ℃/1atm/400hrs/N 2In thermal weight loss % | ＜2 |
| At 316 ℃/1atm/400hrs/N 2In thermal weight loss % | ＜10 |
| At 343 ℃/1atm/400hrs/N 2In thermal weight loss % | ＜5 |
| At 343 ℃/1atm/400hrs/N 2In thermal weight loss % | ＜20 |
The typical T-300 carbon fiber of table 4 strengthens the mechanical property of composite polyimide material
| Mechanical property | Performance index |
| Flexural strength (MPa), 25 ℃ 288 ℃ 316 ℃ | 1430 869 740 |
| Modulus in flexure (GPa), 25 ℃ 288 ℃ 316 ℃ | 90.9 93.0 88.1 |
| Interlaminar shear strength (MPa), 25 ℃ 288 ℃ 316 ℃ | 89.2 43.3 39.3 |
Embodiment
Embodiment 1: with 3, and 3 ', 4,64 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) obtained corresponding aroma family two acid diesters solution (BTDE) in reflux 1-3 hour in 80 parts of ethanol.37 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 54 parts of ethanol.79 parts of organic diamine monomers (TMMDA) are dissolved in 50 parts of ethanol, and stirring adds the NE and the BTDE solution of above-mentioned preparation successively after half hour; This mixed solution stirred 2-15 hour down at 5-30 ℃, obtained the solution of polyimid-base resin of solid content 45%; Its absolute viscosity (25 ℃) is 25-40mPa.s.
This resin solution is removed the thick liquid that obtains behind most of solvent 60-80 ℃ of following underpressure distillation; Be heated oven dry (50-220 ℃) and obtain the resin mold molding powder.50g molding powder is put into mould, put in the press that is preheating to 250 ℃ and heat,, continued to be heated to 320-350 ℃ of pressurize 1-5 hour, remove pressure when waiting nature to cool to below 200 ℃, obtain the virgin resin molding at 270-300 ℃ of pressurization 1-10MPa.
Embodiment 2: with 3, and 3 ', 4,146 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) obtained corresponding aroma family two acid diesters solution (BTDE) in reflux 1-3 hour in 200 parts of ethanol.33 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 50 parts of ethanol.141 parts of diamine monomer TMMDA are dissolved in 130 parts of ethanol, and stirring adds prepared NE in front and BTDE solution after half hour successively, and this mixed solution stirred 2-15 hour down at 5-30 ℃, obtains the polyimide homogeneous phase resin solution of solid content 41%.Its absolute viscosity (25 ℃) is 20-40mPa.s.
This resin solution is removed the thick liquid that obtains behind most of solvent 60-80 ℃ of following underpressure distillation; Be heated oven dry (50-220 ℃) and obtain the resin mold molding powder.50g molding powder is put into mould, mould put in the press that is preheating to 250 ℃ heat,, continued to be heated to 320-350 ℃ of pressurize 1-5 hour at 270-300 ℃ of pressurization 1-10MPa, remove pressure when cooling to below 200 ℃ naturally, obtain the resin mold casting die.
Embodiment 3: with 3, and 3 ', 4,133 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) obtained corresponding aroma family two acid diesters solution (BTDE) in reflux 1-3 hour in 180 parts of ethanol.16 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 50 parts of ethanol.117 parts of diamine monomer TMMDA are dissolved in 150 parts of ethanol, and stirring adds NE and the BTDE solution for preparing previously after half hour successively, and this mixed solution stirred 2-15 hour down at 5-30 ℃, obtains the polyimide homogeneous phase resin solution of solid content 37%.Its absolute viscosity (25 ℃) is 15-35mPa.s.
This substrate resin solution is carried out compound preparation prepreg with carbon fiber on wrapping machine, behind most of solvent of waiting to volatilize, fold overlay as requested, the prepreg behind the layer of shop is made the prepreg (band or cloth) in B stage after 50-220 ℃ of temperature programming handled.The prepreg in B stage is put into and is preheating to 260 ℃ press, at 270-300 ℃ of pressure that applies 1-10MPa, be cured crosslinkedly then at 320-350 ℃ of heat-insulation pressure keeping 1-5 hour, die sinking obtains the veneer sheet of composite polyimide material when cooling to below 200 ℃ naturally.
Embodiment 4: with 3, and 3 ', 4,64 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) obtained corresponding aroma family two acid diesters solution (BTDE) in reflux 1-3 hour in 100 parts of methyl alcohol.37 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 60 parts of methyl alcohol.80 parts of diamine monomer TMMDA are dissolved in 100 parts of methyl alcohol, and stirring adds NE and the BTDE solution for preparing previously after half hour successively, and this mixed solution stirred 2-15 hour down at 5-30 ℃, obtains the polyimide homogeneous phase resin solution of solid content 37%.Its absolute viscosity (25 ℃) is 20-40mPa.s.
This substrate resin solution is carried out compound preparation prepreg with carbon fiber on wrapping machine, behind most of solvent of waiting to volatilize, fold overlay as requested, the prepreg behind the layer of shop is made the prepreg (band or cloth) in B stage after 50-220 ℃ of temperature programming handled.The prepreg in B stage is put into and is preheating to 260 ℃ press, at 270-300 ℃ of pressure that applies 1-10MPa, be cured crosslinkedly then at 320-350 ℃ of heat-insulation pressure keeping 1-5 hour, die sinking obtains the veneer sheet of composite polyimide material when cooling to below 200 ℃ naturally.
Embodiment 5: with 3,62 parts of 3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) obtained corresponding aroma family two acid diesters solution (ODPE) in reflux 1-3 hour in 120 parts of ethanol.36 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 50 parts of ethanol.79 parts of diamine monomer TMMDA are dissolved in 100 parts of ethanol, add NE and the ODPE solution for preparing previously successively after stirring half hour, this mixed solution stirred 2-15 hour down at 5-30 ℃, obtain the polyimide homogeneous phase resin solution of solid content 36%, its absolute viscosity (25 ℃) is 15-40mPa.s.
This substrate resin solution is carried out compound preparation prepreg with carbon fiber on wrapping machine, behind most of solvent of waiting to volatilize, fold overlay as requested, the prepreg behind the layer of shop is made the prepreg (band or cloth) in B stage after 50-220 ℃ of temperature programming handled.The prepreg in B stage is put into and is preheating to 260 ℃ press, at 270-300 ℃ of pressure that applies 1-10MPa, be cured crosslinkedly then at 320-350 ℃ of heat-insulation pressure keeping 1-5 hour, die sinking obtains the veneer sheet of composite polyimide material when cooling to below 200 ℃ naturally.
Embodiment 6: with 3,144 parts of 3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) obtained corresponding aroma family two acid diesters solution (ODPE) in reflux 1-3 hour in 150 parts of ethanol.33 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 40 parts of ethanol.143 parts of TMMDA are dissolved in 160 parts of ethanol, add NE and the ODPE solution for preparing previously successively after stirring half hour, this mixed solution stirred 2-15 hour down at 5-30 ℃, obtained the polyimide homogeneous phase resin solution of solid content 43%, and its absolute viscosity (25 ℃) is 25-40mPa.s.
This substrate resin solution is carried out compound preparation prepreg with carbon fiber on wrapping machine, behind most of solvent of waiting to volatilize, fold overlay as requested, the prepreg behind the layer of shop is made the prepreg (band or cloth) in B stage after 50-220 ℃ of temperature programming handled.The prepreg in B stage is put into and is preheating to 260 ℃ press, at 270-300 ℃ of pressure that applies 1-10MPa, be cured crosslinkedly then at 320-350 ℃ of heat-insulation pressure keeping 1-5 hour, die sinking obtains the veneer sheet of composite polyimide material when cooling to below 200 ℃ naturally.
Embodiment 7: with 4,247 parts of 4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) obtained corresponding aroma family two acid diesters solution (6FDE) in reflux 1-3 hour in 300 parts of ethanol.49 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 60 parts of ethanol.179 parts of diamine monomer TMMDA are dissolved in 200 parts of ethanol, add NE and the 6FDE solution for preparing previously successively after stirring half hour, this solution stirred 2-15 hour down at 5-30 ℃, obtain the polyimide homogeneous phase resin solution of solid content 41%, its absolute viscosity (25 ℃) is 20-40mPa.s.
This resin solution is removed the thick liquid that obtains behind most of solvent 60-80 ℃ of following underpressure distillation; Be heated oven dry (50-220 ℃) and obtain the resin mold molding powder.50g molding powder is put into mould, put in the press that is preheating to 250 ℃ and heat,, continued to be heated to 320-350 ℃ of pressurize 1-5 hour, remove pressure when waiting nature to cool to below 200 ℃, obtain the virgin resin molding at 270-300 ℃ of pressurization 1-10MPa.
Embodiment 8: with 4,178 parts of 4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) obtained corresponding aroma family two acid diesters solution (6FDE) in reflux 1-3 hour in 200 parts of ethanol.33 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 40 parts of ethanol.127 parts of diamine monomer TMMDA are dissolved in 150 parts of ethanol, and stirring adds NE and the 6FDE solution for preparing previously after half hour successively, and this solution stirred 2-15 hour down at 5-30 ℃, obtains the polyimide homogeneous phase resin solution of solid content 46%.Its absolute viscosity (25 ℃) is 25-45mPa.s.
This substrate resin solution is carried out compound preparation prepreg with carbon fiber on wrapping machine, behind most of solvent of waiting to volatilize, fold overlay as requested, the prepreg behind the layer of shop is made the prepreg (band or cloth) in B stage after 50-220 ℃ of temperature programming handled.The prepreg in B stage is put into and is preheating to 260 ℃ press, at 270-300 ℃ of pressure that applies 1-10.0MPa, be cured crosslinkedly then at 320-350 ℃ of heat-insulation pressure keeping 1-5 hour, die sinking obtains the veneer sheet of composite polyimide material when cooling to below 200 ℃ naturally.
Embodiment 9: with 3,3 ', 4,97 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) obtained corresponding aroma family two acid diesters solution (BTDE) in reflux 1-3 hour in 120 parts of ethanol, with 3,93 parts of 3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) obtained corresponding aroma family two acid diesters solution (ODPE) in reflux 1-3 hour in 150 parts of ethanol.98 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 120 parts of ethanol.229 parts of diamine monomer TMMDA are dissolved in 300 parts of ethanol, add NE, BTDE and the ODPE solution for preparing previously successively after stirring half hour, this solution stirred 2-15 hour down at 5-30 ℃, obtain the polyimide homogeneous phase resin solution of solid content 47%, its absolute viscosity (25 ℃) is 25-45mPa.s.
This resin solution is removed the thick liquid that obtains behind most of solvent 60-80 ℃ of following underpressure distillation; Be heated oven dry (50-220 ℃) and obtain the resin mold molding powder.50g molding powder is put into mould, put in the press that is preheating to 250 ℃ and heat,, continued to be heated to 320-350 ℃ of pressurize 1-5 hour, remove pressure when waiting nature to cool to below 200 ℃, obtain the virgin resin molding at 270-300 ℃ of pressurization 1-10MPa.
Embodiment 10: with 3,3 ', 4,64 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) obtained corresponding aroma family two acid diesters solution (BTDE) in reflux 1-3 hour in 100 parts of ethanol, with 3,124 parts of 3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) obtained corresponding aroma family two acid diesters solution (ODPE) in reflux 1-3 hour in 180 parts of ethanol.66 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 80 parts of ethanol.204 parts of diamine monomer TMMDA are dissolved in 250 parts of ethanol, add NE, BTDE and the ODPE solution for preparing previously successively after stirring half hour, this solution stirred 2-15 hour down at 5-30 ℃, obtain the polyimide homogeneous phase resin solution of solid content 43%, its absolute viscosity (25 ℃) is 20-40mPa.s.
This substrate resin solution is carried out compound preparation prepreg with carbon fiber on wrapping machine, behind most of solvent of waiting to volatilize, fold overlay as requested, the prepreg behind the layer of shop is made the prepreg (band or cloth) in B stage after 50-220 ℃ of temperature programming handled.The prepreg in B stage is put into and is preheating to 260 ℃ press, at 270-300 ℃ of pressure that applies 1-10MPa, be cured crosslinkedly then at 320-350 ℃ of heat-insulation pressure keeping 1-5 hour, die sinking obtains the veneer sheet of composite polyimide material when cooling to below 200 ℃ naturally.
Embodiment 11: with 3,3 ', 4,129 parts of 4 '-benzophenone tetracarboxylic dianhydrides (BTDA) obtained corresponding aroma family two acid diesters solution (BTDE) in reflux 1-3 hour in 200 parts of ethanol, with 4,178 parts of 4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) obtained corresponding aroma family two acid diesters solution (6FDE) in reflux 1-3 hour in 220 parts of ethanol, 88 parts on end-capping reagent NA acid anhydrides was obtained corresponding single acid monoester solution (NE) in reflux 1-5 hour in 110 parts of ethanol.271 parts of diamine monomer TMMDA are dissolved in 350 parts of ethanol, add NE, BTDE and the 6FDE solution for preparing previously successively after stirring half hour, this solution stirred 2-15 hour down at 5-30 ℃, obtain the polyimide homogeneous phase resin solution of solid content 43%, its absolute viscosity (25 ℃) is 20-40mPa.s.
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| US7994274B2 (en) | 2003-09-02 | 2011-08-09 | I.S.T. (Ma) Corporation | Two-stage cure polyimide oligomers |
| CN101412812B (en) * | 2008-10-28 | 2011-07-20 | 上海三普化工有限公司 | Method for aqueous phase synthesis of polyimides |
| CN102120820B (en) * | 2011-01-26 | 2016-03-30 | 上海三普化工有限公司 | A kind of method of performing aqueous synthesis of thermosetting polyimide |
| CN103980489B (en) * | 2014-04-30 | 2018-08-31 | 中国科学院化学研究所 | A kind of low melt viscosity thermoplastic polyimide material and its 3D printing forming method |
| CN105037725A (en) * | 2015-07-13 | 2015-11-11 | 长春理工大学 | Polyimide oligomer, and preparation method and application thereof |
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