CN103289092A - Preparation method of A2+B'B2+B2 type hyperbranched polyimide resin - Google Patents
Preparation method of A2+B'B2+B2 type hyperbranched polyimide resin Download PDFInfo
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Abstract
The invention relates to a preparation method of A2+B'B2+B2 type hyperbranched polyimide resin. The preparation method comprises the following steps of: performing polycondensation on a dianhydride monomer, a triamine monomer and a diamine monomer to obtain a polyamic acid solution; and then carrying out imidizing reaction to obtain the product. According to the preparation method, a diamine comonomer is introduced into a hyperbranched molecular chain so that the mechanical performance of the hyperbranched polyimide is improved, the filming capacity is improved and the brittleness is reduced; the molar ratio of a branched monomer to a comonomer is changed, thus the length and the degree of branching of a linear chain section of the macromolecular can be adjusted; the B'B2 type triamine monomers being different in amino activity are adopted to avoid the generation of gel in reaction, so that the production cost is reduced, and a new application prospect is developed for the hyperbranched polyimide in the emerging field.
Description
Technical field
The invention belongs to technical field of macromolecules, be specifically related to a kind of A
2+ B ' B
2+ B
2The preparation method of type super-branched polyimide resin.
Background technology
Nineteen fifty-two, Flory has proposed the concept of hyperbranched polymer first, (Kim Y H such as nineteen ninety Kim and Webster, Wester O W.J.Am.Chem.Soc.1990,112,4592-4593.) prepared the first highly branched polymkeric substance with bromophenyl boric acid as monomer, started the upsurge of one research hyperbranched polymer.This base polymer has three-dimensional spherical three-dimensional arrangement, and spheroid is with a large amount of terminal functionality outward.The chain entanglement that hyperbranched polymer is lower and the periphery of functional group distribute, and can make it have high functionally active, good solubility energy and lower melt viscosity, thereby enjoy the common concern of scientific circles and industry member.
As everyone knows, polyimide is a kind of important high-performance polymer material, has excellent thermostability, chemical stability, mechanical property and lower advantages such as specific inductivity, and it is had a wide range of applications in fields such as aerospace, electronic industries.
(Thompson D such as Thompson in 1999, Moore J S, Markoski L J.Macromolecules, 1999,32 (15): 4764-4768.) begun the research of super-branched polyimide (HBPIs), this polymkeric substance combines the advantage of hyperbranched polymer and polyimide and physicochemical property with a series of uniquenesses, as there is not a chain entanglement, be difficult to or non-crystallizable, solvability is good, low solution and melt viscosity, and it is splendid heat-resisting, anti-solvent and high dielectric property are now in gas delivery, fields such as proton exchange have obtained paying close attention to widely and studying.
The preparation method of super-branched polyimide mainly contains AB
2And A
2+ B
3And A
2+ B ' B
2Three kinds.Yet the super-branched polyimide that these three kinds of methods are synthetic is because have lower chain entanglement and molecular weight, and its mechanical property is relatively poor, and because the difficult too greatly and film forming of fragility, this has limited its application greatly.
Summary of the invention
The technical problem that solves
For fear of the deficiencies in the prior art part, the present invention proposes a kind of A
2+ B ' B
2+ B
2The preparation method of type super-branched polyimide resin, by in the super branched molecule chain, introducing the diamines monomer, improve the distance between the branched chain, thereby the branched chain that makes rigidity has higher handiness, thereby increased physical entanglement between the chain, improved the mechanical property of super-branched polyimide.By changing the mol ratio of branched monomer and comonomer, can regulate macromolecular linear chain segment length and degree of branching thereof.
Technical scheme
A kind of A
2+ B ' B
2+ B
2The preparation method of type super-branched polyimide resin is characterized in that step is as follows:
Step 1: in the straight four-hole boiling flask that water trap is housed of complete drying, add B ' B
2Type three amine monomers, B
2Type diamine monomer and strong polar aprotic solvent, at room temperature and N
2Protection is stirred the strong polar aprotic solvent of adding and A after 5～10 minutes down
2The type dianhydride monomer continued stirring reaction 40～48 hours; Described B ' B
2Type three amine monomers are triaminopyrimidine TAP;
Described B ' B
2Type three amine monomers and B
2Type diamine monomer and A
2The mol ratio of type dianhydride monomer is 1:1～1:2;
Described B ' B
2Type three amine monomers and B
2The ratio of type diamine monomer is arbitrary proportion;
Step 2: be warmed up to 150～160 ℃, add azeotropy dehydrant, reacted 5～7 hours, utilize the azeotropic of azeotropy dehydrant and water to remove the water that produces in the imidization process;
Step 3: behind the cool to room temperature, above-mentioned solution is poured in the washings, after washings washing, suction filtration three times, obtained faint yellow subject polymer A in 5～7 hours in 100～～150 ℃ of following vacuum-dryings
2+ B ' B
2+ B
2Type super-branched polyimide resin.
Described strong polar aprotic solvent is N, any or combination among dinethylformamide DMF, N,N-dimethylacetamide DMAc, N-Methyl pyrrolidone NMP or the dimethyl sulfoxide (DMSO) DMSO.
Described A
2The type dianhydride monomer is hexafluorodianhydride 6FDA, pyromellitic dianhydride PMDA, biphenyl dianhydride BPDA, diketone acid anhydride BTDA or diether acid anhydride ODPA.
Described azeotropy dehydrant is any or combination in toluene, the dimethylbenzene.
Described washings is any or combination in ethanol, the methyl alcohol.
Beneficial effect
A kind of A that the present invention proposes
2+ B ' B
2+ B
2The preparation method of type super-branched polyimide resin, by dianhydride monomer, three amine monomers, diamine monomer carry out polycondensation and form polyamic acid solution, then carry out imidization reaction and form; By in the super branched molecule chain, introducing the diamines monomer, improve the mechanical property of super-branched polyimide, and improved its film forming ability, reduced fragility; By changing the mol ratio of branched monomer and comonomer, can regulate macromolecular linear chain segment length and degree of branching thereof; By using amino active different B ' B
2Type three amine monomers are avoided the formation of gel in the reaction process, have reduced to become to produce cost, and this is super-branched polyimide and has opened up new application prospect in the application of emerging field.
Embodiment
Now in conjunction with the embodiments the present invention is further described:
B ' B that the embodiment of the invention adopts
2The type monomer is triaminopyrimidine (TAP), and its structural formula is:
Because three amino active differences can be avoided the formation of gel in the reaction process in this monomer, improved monomer concentration, reduced production cost, this is conducive to realize the scale operation of super-branched polyimide.
The A that the embodiment of the invention adopts
2Monomer is common dianhydride monomer, B
2Comonomer is common diamine monomer.
Embodiment 1:
(1) in the straight four-hole boiling flask of the 150mL that water trap is housed of complete drying, add 0.2344g2,4,6-Triaminopyrimidine (TAP), 3.4g diaminodiphenyl oxide (ODA) and 55gN, N-N,N-DIMETHYLACETAMIDE (DMAc) is at 25 ℃, mechanical stirring and N
2Protection is down stirred adding 8.88g hexafluorodianhydride (6FDA) monomer after 5 minutes, and with 15g DMAc washing bottle wall.Continue stirring reaction 48h.
(2) above-mentioned solution is warmed up to 160 ℃, adds 20g dimethylbenzene, reaction 6h utilizes the azeotropic of dimethylbenzene and water to remove the water that produces in the imidization process.
(3) be cooled to room temperature after, above-mentioned solution is poured in the ethanol, after washing with alcohol, suction filtration three times, obtain super-branched polyimide in 150 ℃ of following vacuum-drying 6h.
Embodiment 2:
(1) in the straight four-hole boiling flask of the 150mL that water trap is housed of complete drying, adds 0.4688g TAP, 2.8g ODA and 50g DMAc, at 25 ℃, mechanical stirring and N
2Protection is down stirred adding 8.88g6FDA monomer after 5 minutes, and with 13g DMAc washing bottle wall.Continue stirring reaction 48h.
(2) above-mentioned solution is warmed up to 160 ℃, adds 20g dimethylbenzene, reaction 6h utilizes the azeotropic of dimethylbenzene and water to remove the water that produces in the imidization process.
(3) be cooled to room temperature after, above-mentioned solution is poured in the ethanol, after washing with alcohol, suction filtration three times, obtain super-branched polyimide in 150 ℃ of following vacuum-drying 6h.
Embodiment 3:
(1) in the straight four-hole boiling flask of the 150mL that water trap is housed of complete drying, adds 0.7031g TAP, 2.2g ODA and 42g DMAc, at 25 ℃, mechanical stirring and N
2Protection is down stirred adding 8.88g6FDA monomer after 5 minutes, and with 15g DMAc washing bottle wall.Continue stirring reaction 48h.
(2) above-mentioned solution is warmed up to 160 ℃, adds 20g dimethylbenzene, reaction 6h utilizes the azeotropic of dimethylbenzene and water to remove the water that produces in the imidization process.
(3) be cooled to room temperature after, above-mentioned solution is poured in the ethanol, after washing with alcohol, suction filtration three times, obtain super-branched polyimide in 150 ℃ of following vacuum-drying 6h.
Embodiment 4:
(1) in the straight four-hole boiling flask of the 150mL that water trap is housed of complete drying, adds 0.9375g TAP, 1.6g ODA and 40g DMAc, at 25 ℃, mechanical stirring and N
2Protection is down stirred adding 8.88g6FDA monomer after 5 minutes, and with 10g DMAc washing bottle wall.Continue stirring reaction 48h.
(2) above-mentioned solution is warmed up to 160 ℃, adds 20g dimethylbenzene, reaction 6h utilizes the azeotropic of dimethylbenzene and water to remove the water that produces in the imidization process.
(3) be cooled to room temperature after, above-mentioned solution is poured in the ethanol, after washing with alcohol, suction filtration three times, obtain super-branched polyimide in 150 ℃ of following vacuum-drying 6h.
Embodiment 5:
(1) in the straight four-hole boiling flask of the 150mL that water trap is housed of complete drying, adds 1.1719g TAP, 1.0g ODA and 35g DMAc, at 25 ℃, mechanical stirring and N
2Protection is down stirred adding 8.88g6FDA monomer after 5 minutes, and with 10g DMAc washing bottle wall.Continue stirring reaction 48h.
(2) above-mentioned solution is warmed up to 160 ℃, adds 20g dimethylbenzene, reaction 6h utilizes the azeotropic of dimethylbenzene and water to remove the water that produces in the imidization process.
(3) be cooled to room temperature after, above-mentioned solution is poured in the ethanol, after washing with alcohol, suction filtration three times, obtain super-branched polyimide in 150 ℃ of following vacuum-drying 6h.
Claims (5)
1. A
2+ B ' B
2+ B
2The preparation method of type super-branched polyimide resin is characterized in that step is as follows:
Step 1: in the straight four-hole boiling flask that water trap is housed of complete drying, add B ' B
2Type three amine monomers, B
2Type diamine monomer and strong polar aprotic solvent, at room temperature and N
2Protection is stirred the strong polar aprotic solvent of adding and A after 5～10 minutes down
2The type dianhydride monomer continued stirring reaction 40～48 hours; Described B ' B
2Type three amine monomers are triaminopyrimidine TAP;
Described B ' B
2Type three amine monomers and B
2Type diamine monomer and A
2The mol ratio of type dianhydride monomer is 1:1～1:2;
Described B ' B
2Type three amine monomers and B
2The ratio of type diamine monomer is arbitrary proportion;
Step 2: be warmed up to 150～160 ℃, add azeotropy dehydrant, reacted 5～7 hours, utilize the azeotropic of azeotropy dehydrant and water to remove the water that produces in the imidization process;
Step 3: behind the cool to room temperature, above-mentioned solution is poured in the washings, after washings washing, suction filtration three times, obtained faint yellow subject polymer A in 5～7 hours in 100～～150 ℃ of following vacuum-dryings
2+ B ' B
2+ B
2Type super-branched polyimide resin.
2. according to the described A of claim 1
2+ B ' B
2+ B
2The preparation method of type super-branched polyimide resin is characterized in that:
Described strong polar aprotic solvent is N, any or combination among dinethylformamide DMF, N,N-dimethylacetamide DMAc, N-Methyl pyrrolidone NMP or the dimethyl sulfoxide (DMSO) DMSO.
3. according to the described A of claim 1
2+ B ' B
2+ B
2The preparation method of type super-branched polyimide resin is characterized in that:
Described A
2The type dianhydride monomer is hexafluorodianhydride 6FDA, pyromellitic dianhydride PMDA, biphenyl dianhydride BPDA, diketone acid anhydride BTDA or diether acid anhydride ODPA.
4. according to the described A of claim 1
2+ B ' B
2+ B
2The preparation method of type super-branched polyimide resin is characterized in that:
Described azeotropy dehydrant is any or combination in toluene, the dimethylbenzene.
5. according to the described A of claim 1
2+ B ' B
2+ B
2The preparation method of type super-branched polyimide resin is characterized in that:
Described washings is any or combination in ethanol, the methyl alcohol.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153699A (en) * | 2015-07-31 | 2015-12-16 | 江苏省电力公司泰州供电公司 | Preparation method of hyper branched copolymerized polyimide/zinc oxide (ZnO) hybrid insulated film |
| CN105461924A (en) * | 2015-12-30 | 2016-04-06 | 西北工业大学 | Preparation method for hyperbranched polymide film with low dielectric constant |
| CN106519673A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BPDA type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106519682A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | HQDA type bisphenol A tetramine branched polyimide resin film and preparation method thereof |
| CN106519677A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BTDA-type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106519680A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | PMDA type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106519683A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA type 14BDAPB branched polyimide resin film and preparation method thereof |
| CN106519678A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA-type bisphenol A tetramine branched polyimide resin film and preparation method thereof |
| CN106633867A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | BTDA-type 14BDAPB branched polyimide resin thin film and preparation method thereof |
| CN106633875A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | HQDA type 14BDAPB branched polyimide resin film and preparation method thereof |
| CN108911992A (en) * | 2018-07-31 | 2018-11-30 | 湖南工业大学 | A kind of Triamine monomer and its preparation method and application |
| CN111393644A (en) * | 2020-04-03 | 2020-07-10 | 深圳市华星光电半导体显示技术有限公司 | Polyimide, preparation method of polyimide film and flexible display panel |
| CN111471212A (en) * | 2020-06-01 | 2020-07-31 | 陕西科技大学 | Chemical-coordination double-crosslinking polyimide aerogel and preparation method thereof |
| CN114133565A (en) * | 2021-12-08 | 2022-03-04 | 江苏艾森半导体材料股份有限公司 | Hyperbranched polyimide resin and preparation method and application thereof |
| CN115181269A (en) * | 2022-07-20 | 2022-10-14 | 中国航空工业集团公司济南特种结构研究所 | Preparation method of hyperbranched nanopore alkynyl polyimide resin |
| CN116731557A (en) * | 2023-07-26 | 2023-09-12 | 江苏唐彩新材料科技股份有限公司 | High-water-resistance polyamide printing ink and preparation method thereof |
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| CN105153699A (en) * | 2015-07-31 | 2015-12-16 | 江苏省电力公司泰州供电公司 | Preparation method of hyper branched copolymerized polyimide/zinc oxide (ZnO) hybrid insulated film |
| CN105461924A (en) * | 2015-12-30 | 2016-04-06 | 西北工业大学 | Preparation method for hyperbranched polymide film with low dielectric constant |
| CN106633867A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | BTDA-type 14BDAPB branched polyimide resin thin film and preparation method thereof |
| CN106519682A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | HQDA type bisphenol A tetramine branched polyimide resin film and preparation method thereof |
| CN106519677A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BTDA-type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106519680A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | PMDA type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106519683A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA type 14BDAPB branched polyimide resin film and preparation method thereof |
| CN106519678A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA-type bisphenol A tetramine branched polyimide resin film and preparation method thereof |
| CN106519673A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BPDA type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106633875A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | HQDA type 14BDAPB branched polyimide resin film and preparation method thereof |
| CN108911992A (en) * | 2018-07-31 | 2018-11-30 | 湖南工业大学 | A kind of Triamine monomer and its preparation method and application |
| CN111393644A (en) * | 2020-04-03 | 2020-07-10 | 深圳市华星光电半导体显示技术有限公司 | Polyimide, preparation method of polyimide film and flexible display panel |
| CN111471212A (en) * | 2020-06-01 | 2020-07-31 | 陕西科技大学 | Chemical-coordination double-crosslinking polyimide aerogel and preparation method thereof |
| CN111471212B (en) * | 2020-06-01 | 2022-08-23 | 陕西科技大学 | Chemical-coordination double-crosslinking polyimide aerogel and preparation method thereof |
| CN114133565A (en) * | 2021-12-08 | 2022-03-04 | 江苏艾森半导体材料股份有限公司 | Hyperbranched polyimide resin and preparation method and application thereof |
| CN115181269A (en) * | 2022-07-20 | 2022-10-14 | 中国航空工业集团公司济南特种结构研究所 | Preparation method of hyperbranched nanopore alkynyl polyimide resin |
| CN115181269B (en) * | 2022-07-20 | 2023-05-23 | 中国航空工业集团公司济南特种结构研究所 | Preparation method of hyperbranched nano-pore alkynyl polyimide resin |
| CN116731557A (en) * | 2023-07-26 | 2023-09-12 | 江苏唐彩新材料科技股份有限公司 | High-water-resistance polyamide printing ink and preparation method thereof |
| CN116731557B (en) * | 2023-07-26 | 2024-03-05 | 江苏唐彩新材料科技股份有限公司 | High-water-resistance polyamide printing ink and preparation method thereof |
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Application publication date: 20130911 |