CN101921403A - Synthesizing method of polyimide material - Google Patents
Synthesizing method of polyimide material Download PDFInfo
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- CN101921403A CN101921403A CN 201010288804 CN201010288804A CN101921403A CN 101921403 A CN101921403 A CN 101921403A CN 201010288804 CN201010288804 CN 201010288804 CN 201010288804 A CN201010288804 A CN 201010288804A CN 101921403 A CN101921403 A CN 101921403A
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- polyimide
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- ointment
- dianhydride
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Abstract
The invention discloses a synthesizing method of a polyimide material, comprising the following steps of: dissolving aromatic diamine and aromatic dianhydride into a molten salicylic acid solvent according to the mole ratio of 1:1.0-1:1.3 to form a solution with the mass concentration of 10-60 percent; adding a catalyst, and reacting for 1-4 hours at 160-210 DEG C to be polymerized into a polyimide solution; and precipitating the synthesized polyimide solution in methanol and deionized water to prepare polyimide powder or a polyimide film. The invention has safety without toxicity and green environmental protection by using a molten salicylic acid as the solvent, reduces the environmental pollution and the production cost because the salicylic acid is easy to recycle and has the advantages of easy and convenient operation, short polymerization time, easy product purification, high dissolvability and yield, stable property, excellent film forming property and wide application prospect, is suitable for industrialized production.
Description
Affiliated technical field
The present invention relates to the macromolecular material synthesis technical field, be specifically related to a kind of synthetic method of polyimide material.
Technical background
In technical field of polymer materials, polyimide material is a kind of high-performance polymer material with imide ring structural performance, have excellent thermotolerance, anti-irradiation, excellent mechanical property and electric property etc., be widely used in technical fields such as Aeronautics and Astronautics, automobile, petrochemical complex.The method of traditional synthesis of polyimides has two kinds: promptly one-step synthesis and two goes on foot synthesis methods, one-step synthesis is in high boiling solvent such as meta-cresol, para-chlorophenol, and next step becomes the ring direct polymerization to obtain polyimide in higher temperature (about 200 ℃) and catalyst action with dianhydride monomer by diamines; The shortcoming of this method is polymerization time long (about 18h), system concentration generally has only about 10%, the polymers soln that later stage obtains can not directly be used for being processed into polyimide material, and used solvent is poisonous carcinogenic in the building-up process, does not meet the demand for development of Green Chemistry now.Two step synthesis methods are to form polyamic acid by the reaction earlier in polar solvent such as N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP) of diamines and dianhydride monomer, and then thermal treatment or adding catalyst chemical Cheng Huan obtain polyimide material.Though the used solvent toxicity of two-step approach is less, polyamic acid instability, oxidation easily.Therefore, in the synthesis of polyimides material technology, how avoid the environmental pollution that causes because of solvent from the source, researching and developing a kind of technology that substitutes poisonous and harmful solvent synthesis of polyimides materials such as meta-cresol with green and environment-friendly solvent, have important social effect, also is current facing of the task in this area.
Summary of the invention
The purpose of this invention is to provide that a kind of environmental protection, production cost are low, easy and simple to handle, polymerization time short, solvability is strong, stable performance, film-forming properties is good, yield is high, be fit to the synthetic method of the polyimide material of suitability for industrialized production.
In order to achieve the above object, the present invention by the following technical solutions: a kind of synthetic method of polyimide material, its processing step is as follows:
A. prepare polyimide solution
Under nitrogen protection, at first Whitfield's ointment is fused under 160-210 ℃ temperature, after finishing, fusion keeps 10-30min, then aromatic diamine monomers under agitation is dissolved in the fusion Whitfield's ointment, after dissolving finishes, add aromatic dianhydride again, and add catalyzer, polyreaction continues 1-4h under continuously stirring, obtain the solution that mass concentration is 10%-60%; Aromatic diamines that adds and aromatic dianhydride example in molar ratio are 1: 1.0-1: 1.3;
B. prepare polyimide powder
The polyimide solution that step a. is obtained is cooled to 150-160 ℃ and pours in the methyl alcohol, mix the back and add deionized water, promptly separate out yellow mercury oxide, with methyl alcohol and deionized water repetitive scrubbing and carry out suction filtration, in vacuum drying oven,, get the xanchromatic polyimide powder at 60-150 ℃ of following dry 6-12h;
C. prepare Kapton
The polyimide solution that step a. is obtained is cooled to 150-160 ℃ and pours on the heat resistant glass plate, use the hot type flat membrane casting equipment 150-160 ℃ of following striking film forming, and the film forming glass plate placed fill the nitrogen baking oven in 200-350 ℃ of following evaporation Whitfield's ointment 4-8h, be cooled to room temperature then, carry out the poach demoulding, the film thickness of taking off from sheet glass is the Kapton of 20-80 μ m.
Above-mentioned described aromatic diamines is: 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa (Bis-AP-AF), 3 of 2-, 3 '-dimethyl-4,4 '-diphenylmethane diamine (DMMDA), 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (BAHFP) or 4 of 2-, 4 '-diaminodiphenyl oxide (ODA).
Above-mentioned described aromatic dianhydride is: 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride (HQDPA), 4,4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride (6FDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-BPDA (BPDA) or 1,2 ', 4,5 '-pyromellitic dianhydride (PMDA).
Above-mentioned described catalyzer is: isoquinoline 99.9, pyridine or triethylamine; Consumption is 0.01-0.5 a times of aromatic dianhydride monomer mass.
Above-mentioned processing step relates to various compositions in unit weight.
Used Whitfield's ointment is a kind of crystallization needle-like or meal of white among the present invention, and odorless is nontoxic, and the Whitfield's ointment fusing point is 157-159 ℃, and about 211 ℃ of boiling point is present in natural bark of willow, Gaultheria leaf and the sweet birch tree.In foodstuffs industry, Whitfield's ointment can be used as the sanitas and the anti-mycotic agent of food; In medicine industry, Whitfield's ointment itself is exactly the extremely wide disinfection preservative of a kind of purposes, also is the starting material of various medicines of preparation such as acetylsalicylic acid.Contain carboxyl and phenolic group in the Whitfield's ointment structural formula, it is similar to meta-cresol and phenylformic acid, but the acidity of Whitfield's ointment (acidity quotient pKa=2.97) far is better than meta-cresol (acidity quotient pKa=4.19)) and the acidity of phenylformic acid (acidity quotient pKa=10.09), therefore the present invention substitutes in the method for poisonous and harmful solvent synthesis of polyimides such as meta-cresol with Whitfield's ointment, salicylic dissolving power is stronger than conventional solvents such as meta-cresols, not only can increase concentration of reactants, reduce the Whitfield's ointment consumption, simultaneously can also shorten polymerization reaction time, thereby reduce production costs.
Beneficial effect of the present invention is: Whitfield's ointment is a kind of green and environment-friendly solvent, is solvent synthesis of polyimides material with the fusion Whitfield's ointment, the technological process safety non-toxic, and Whitfield's ointment is easy to recycling, not only reduces environmental pollution, and reduces production costs; In addition, this synthetic method is easy and simple to handle, and polymerization time is short, and product is easy to purifying, the yield height, and solvability is strong, stable performance, film-forming properties is good, is fit to suitability for industrialized production, has a extensive future.
Embodiment:
Below in conjunction with specific embodiment the present invention is described in further detail:
Embodiment 1:
Mechanical stirrer is being housed, thermometer, nitrogen is derived and is added 69.33g Whitfield's ointment solid in the dry four-hole boiling flask of pipe, fusion is the fusion Whitfield's ointment of 49.17mL under 200 ℃ temperature, after finishing, fusion keeps 10-30min, logical nitrogen protection, under mechanical stirring, add 2 of 9.16g (0.025mol), two (the 3-amino-4-hydroxy phenyl) HFC-236fa (Bis-AP-AF) of 2-, be stirred to fully add again after the dissolving 8.18g (1.015 * 0.025mol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), and adding 0.5g isoquinoline 99.9, dissolving back fully obtains polyimide solution at 200 ℃ of following polyreaction 2h; Synthetic hot polymerization imide solution is cooled to 150 ℃ to be poured in the methyl alcohol, mix the back and add deionized water, promptly separate out yellow mercury oxide, with methyl alcohol and deionized water repetitive scrubbing and carry out suction filtration, dry 8h gets the xanchromatic polyimide powder under 80 ℃ in vacuum drying oven, this product yield is 97%, dissolves in conventional solvents such as tetrahydrofuran (THF), chloroform.
Embodiment 2:
Present embodiment and specific embodiment 1 are different is that the temperature of reaction of synthesis of polyimides is 180 ℃, and other is identical with specific embodiment 1, finally makes the xanchromatic polyimide powder, and this product yield is 94%, dissolves in conventional solvents such as tetrahydrofuran (THF), chloroform.
Embodiment 3:
Mechanical stirrer is being housed, thermometer, nitrogen is derived and is added 69.33g Whitfield's ointment solid in the dry four-hole boiling flask of pipe, fusion is the fusion Whitfield's ointment of 49.17mL under 200 ℃ temperature, after finishing, fusion keeps 10-30min, logical nitrogen protection, under mechanical stirring, add 2 of 9.16g (0.025mol), two (the 3-amino-4-hydroxy phenyl) HFC-236fa (Bis-AP-AF) of 2-, be stirred to fully add again after the dissolving 8.18g (1.015 * 0.025mol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), and adding 0.5g isoquinoline 99.9, dissolving back reaction 2h under 200 ℃ fully obtains polyimide solution; Above-mentioned polyimide solution is cooled to 150 ℃ to be poured on the heat resistant glass plate, use the hot type flat membrane casting equipment 150 ℃ of following striking film forming, and the film forming glass plate placed fill the nitrogen baking oven in 275 ℃ of following evaporation Whitfield's ointment 6h, cool to room temperature then with the furnace, carry out the poach demoulding, promptly making thickness is 35 μ m Kaptons, and the second-order transition temperature of this Kapton is 277 ℃, tensile strength is 107MPa, and tensile modulus is 2.4GPa.
Embodiment 4:
What present embodiment and specific embodiment 3 were different is to add 40.44g Whitfield's ointment solid, other is identical with specific embodiment 3, and finally making thickness is 47 μ m Kaptons, and the second-order transition temperature of this Kapton is 267 ℃, tensile strength is 92MPa, and tensile modulus is 2.2GPa.
Embodiment 5:
Mechanical stirrer is being housed, thermometer, nitrogen is derived and is added 81.08g Whitfield's ointment solid in the dry four-hole boiling flask of pipe, fusion is the fusion Whitfield's ointment of 57.50mL under 200 ℃ temperature, after finishing, fusion keeps 10-30min, logical nitrogen protection, under mechanical stirring, add 2 of 9.16g (0.025mol), two (the 3-amino-4-hydroxy phenyl) HFC-236fa (Bis-AP-AF) of 2-, be stirred to fully and add 4 of 11.11g (0.025mol) again after the dissolving, 4 '-hexafluoro sec.-propyl Tetra hydro Phthalic anhydride (6FDA), and adding 0.6g isoquinoline 99.9, dissolving back fully obtains polyimide solution at 200 ℃ of following polyreaction 1.5h; Synthetic hot polymerization imide solution is cooled to 150 ℃ to be poured in the methyl alcohol, mix the back and add deionized water, promptly separate out yellow mercury oxide, with methyl alcohol and deionized water repetitive scrubbing and carry out suction filtration, dry 8h gets the xanchromatic polyimide powder under 80 ℃ in vacuum drying oven, this product yield is 95%, dissolves in conventional solvents such as tetrahydrofuran (THF), chloroform.
Embodiment 6:
Mechanical stirrer is being housed, thermometer, nitrogen is derived and is added 39.21g Whitfield's ointment solid in the dry four-hole boiling flask of pipe, fusion is the fusion Whitfield's ointment of 27.81mL under 180 ℃ temperature, after finishing, fusion keeps 10-30min, logical nitrogen protection, under mechanical stirring, add 4 of 5.01g (0.025mol), 4 '-diaminodiphenyl oxide (ODA), be stirred to fully and add 3 of 8.06g (0.025mol) again after the dissolving, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), and adding 0.3g isoquinoline 99.9, dissolving back reaction 2h under 180 ℃ fully obtains polyimide solution; Above-mentioned polyimide solution is cooled to 150 ℃ to be poured on the heat resistant glass plate, use the hot type flat membrane casting equipment 150 ℃ of following striking film forming, and the film forming glass plate placed fill the nitrogen baking oven in 300 ℃ of following evaporation Whitfield's ointment 6h, cool to room temperature then with the furnace, carry out the poach demoulding, promptly making thickness is 35 μ m Kaptons.The second-order transition temperature of this Kapton is 271 ℃, and tensile strength is 78MPa, and tensile modulus is 1.9GPa.
Claims (4)
1. the synthetic method of a polyimide material, its processing step is as follows:
A. prepare polyimide solution
Under nitrogen protection, at first Whitfield's ointment is fused under 160-210 ℃ temperature, after finishing, fusion keeps 10-30min, then aromatic diamine monomers under agitation is dissolved in the fusion Whitfield's ointment, after dissolving finishes, add aromatic dianhydride again, and add catalyzer, polyreaction continues 1-4h under continuously stirring, obtain the solution that mass concentration is 10%-60%; Aromatic diamines that adds and aromatic dianhydride example in molar ratio are 1: 1.0-1: 1.3;
B. prepare polyimide powder
The polyimide solution that step a. is obtained is cooled to 150-160 ℃ and pours in the methyl alcohol, mix the back and add deionized water, promptly separate out yellow mercury oxide, with methyl alcohol and deionized water repetitive scrubbing and carry out suction filtration, in vacuum drying oven,, get the xanchromatic polyimide powder at 60-150 ℃ of following dry 6-12h;
C. prepare Kapton
The polyimide solution that step a. is obtained is cooled to 150-160 ℃ and pours on the heat resistant glass plate, use the hot type flat membrane casting equipment 150-160 ℃ of following striking film forming, and the film forming glass plate placed fill the nitrogen baking oven in 200-350 ℃ of following evaporation Whitfield's ointment 4-8h, be cooled to room temperature then, carry out the poach demoulding, the film thickness of taking off from sheet glass is the Kapton of 20-80 μ m.
2. according to the synthetic method of the described polyimide material of claim 1, it is characterized in that: described aromatic diamines is: 2, two [the 3 amino-4-hydroxy phenyl] HFC-236fa, 3 of 2-, 3 '-dimethyl-4,4 '-diphenylmethane diamine, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa or 4 of 2-, 4 '-diaminodiphenyl oxide.
3. according to the synthetic method of the described polyimide material of claim 1, it is characterized in that: described aromatic dianhydride is: 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 4,4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA or 1,2 ', 4,5 '-pyromellitic dianhydride.
4. according to the synthetic method of the described polyimide material of claim 1, it is characterized in that: described catalyzer is: isoquinoline 99.9, pyridine or triethylamine, its consumption are 0.01-0.5 times of aromatic dianhydride monomer mass.
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| CN 201010288804 CN101921403A (en) | 2010-09-21 | 2010-09-21 | Synthesizing method of polyimide material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418163A (en) * | 2011-11-10 | 2012-04-18 | 东华大学 | Preparation method of polyimide fiber |
| CN102492320A (en) * | 2011-12-05 | 2012-06-13 | 北方涂料工业研究设计院 | Quick-curing polyimide coating for high-temperature-resistant optical fiber |
| CN103183824A (en) * | 2011-12-30 | 2013-07-03 | 财团法人工业技术研究院 | Polyimide |
| US8883956B2 (en) | 2011-12-30 | 2014-11-11 | Industrial Technology Research Institute | Polyimides |
| CN112958094A (en) * | 2021-02-05 | 2021-06-15 | 山东省分析测试中心 | Catalyst for efficiently catalyzing and degrading sulfonamide antibiotics and preparation method and application thereof |
| CN113912848A (en) * | 2021-12-02 | 2022-01-11 | 王植源 | One-step method for preparing polyimide by using organic aromatic acid as reaction medium |
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| CN101112677A (en) * | 2007-06-22 | 2008-01-30 | 清华大学 | Method for preparing fluorinated polyimide film for separating arene/alkane through permeating and steaming |
| CN101700474A (en) * | 2009-11-30 | 2010-05-05 | 北京市射线应用研究中心 | Polyimide gas separation membrane with high molecular weight and preparation method thereof |
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2010
- 2010-09-21 CN CN 201010288804 patent/CN101921403A/en active Pending
Patent Citations (2)
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|---|---|---|---|---|
| CN101112677A (en) * | 2007-06-22 | 2008-01-30 | 清华大学 | Method for preparing fluorinated polyimide film for separating arene/alkane through permeating and steaming |
| CN101700474A (en) * | 2009-11-30 | 2010-05-05 | 北京市射线应用研究中心 | Polyimide gas separation membrane with high molecular weight and preparation method thereof |
Non-Patent Citations (2)
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| 《Polymer》 20080106 Fatima Hasanain et al New one-step synthesis of polyimides in salicylic acid p831-835 1-4 第49卷, 2 * |
| 《化学进展》 20090131 汪称意 聚酰亚胺研究新进展 p174-181 1-4 第21卷, 第1期 2 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418163A (en) * | 2011-11-10 | 2012-04-18 | 东华大学 | Preparation method of polyimide fiber |
| CN102418163B (en) * | 2011-11-10 | 2014-04-23 | 东华大学 | Preparation method of polyimide fiber |
| CN102492320A (en) * | 2011-12-05 | 2012-06-13 | 北方涂料工业研究设计院 | Quick-curing polyimide coating for high-temperature-resistant optical fiber |
| CN102492320B (en) * | 2011-12-05 | 2014-01-15 | 中昊北方涂料工业研究设计院有限公司 | Quick-curing polyimide coating for high-temperature-resistant optical fiber |
| CN103183824A (en) * | 2011-12-30 | 2013-07-03 | 财团法人工业技术研究院 | Polyimide |
| US8883956B2 (en) | 2011-12-30 | 2014-11-11 | Industrial Technology Research Institute | Polyimides |
| CN103183824B (en) * | 2011-12-30 | 2015-10-28 | 财团法人工业技术研究院 | Polyimide |
| CN112958094A (en) * | 2021-02-05 | 2021-06-15 | 山东省分析测试中心 | Catalyst for efficiently catalyzing and degrading sulfonamide antibiotics and preparation method and application thereof |
| CN113912848A (en) * | 2021-12-02 | 2022-01-11 | 王植源 | One-step method for preparing polyimide by using organic aromatic acid as reaction medium |
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