CN100540527C - A kind of triamido monomer and synthetic method thereof and application - Google Patents
A kind of triamido monomer and synthetic method thereof and application Download PDFInfo
- Publication number
- CN100540527C CN100540527C CNB200710055205XA CN200710055205A CN100540527C CN 100540527 C CN100540527 C CN 100540527C CN B200710055205X A CNB200710055205X A CN B200710055205XA CN 200710055205 A CN200710055205 A CN 200710055205A CN 100540527 C CN100540527 C CN 100540527C
- Authority
- CN
- China
- Prior art keywords
- monomer
- triamido
- dianhydride
- reaction
- trifluoromethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A kind of triamido monomer of the present invention and synthetic method thereof and application belong to polymeric material field.Said triamido monomer is exactly 1,3, and 5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer is a kind of polymkeric substance of brand new.Preparation method's the first step reaction: Phloroglucinol elder generation and salt of wormwood salify, toluene band water back flow reaction makes the trinitro-monomer with 3-trifluoromethyl-4-chloronitrobenzene reaction then; The reaction of second step: with the trinitro-monomer, iron powder, HCl are raw material, and ethanol, water, acetone are done the solvent refluxing reaction and obtained head product, and recrystallization obtains yellow triamido monomer.The application of triamido monomer is to be the synthesizing branched polyimide polymer material of raw material with it.The present invention prepares a series of excellent optical properties of branched polyimide that has, in great prospect such as photoetching, gas-premeable film, optical fields.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of 1,3, the synthetic method of 5-three (2-trifluoromethyl-4 amido phenoxy group) benzene, this triamido monomer and by triamido monomer synthetic branched polyimide polymkeric substance.
Background technology
Linear polyimide material is because it is poorly soluble, there is higher double refraction to make it in application, be subjected to certain restriction when using as waveguide material, the branched polyimide melt viscosity is low, be easy to processing, its terminal functional group is modified the polymkeric substance that can obtain higher fluorine content, simultaneously this branched structure can reduce the double refraction of material, and the optical communication field material in future is had good application prospects.
The prior art close with the present invention is that one piece of exercise question that is published on Journal of Membrane Science 182 (2001) 245-256 is the article of " Gas permeation properties of hyperbranched polyimidemembrane ", disclosed polymeric system is with a kind of three amine monomers---three (4-amino-benzene) amine (TAPA) and acid anhydrides obtain super-branched polyimide with the two-step approach polymerization, the author applies it to the gas-premeable film, obtains good effect.
Summary of the invention
The technical problem to be solved in the present invention is, 1 of a kind of brand new is provided, 3, the preparation method of 5-three (2-trifluoromethyl-4 amido phenoxy group) benzene and this triamido monomer, and carry out polycondensation by this triamido monomer and other industrialized anhydride monomers, prepare a series of excellent optical properties of branched polyimide that has.
Based on some above thoughts, in that to consider that linear polyimide is done the waveguide material double refraction big, and the more high factor of cost, the present invention has designed and synthesized the fluorine-containing branched polyimide of a series of height.
The said triamido monomer of the present invention is exactly 1,3, and 5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer is a kind of polymkeric substance of brand new.
Synthetic 1,3 of the present invention, 5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer structure is as follows:
This 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer synthetic method is as follows:
The first step reaction: with Phloroglucinol and 3-trifluoromethyl-4-chloronitrobenzene in molar ratio 1: (3～4) put into there-necked flask, Phloroglucinol elder generation and salt of wormwood salify, toluene band water back flow reaction 1.5～2.5 hours, then with N, the N dimethyl formamide is made solvent, reacts 7～9 hours under 150 ℃ of conditions with 3-trifluoromethyl-4-chloronitrobenzene, makes trinitro-monomer 1,3,5-three (2-trifluoromethyl-4 nitro-phenoxy) benzene.Discharging is in deionized water, and productive rate is 98%.
The reaction of second step: with the trinitro-monomer, iron powder, HCl 1: 18: 3 in molar ratio were raw material, ethanol, water, acetone 1: (1～2): (1～2) makees solvent, back flow reaction 4～5 hours, product with deionized water repetitive scrubbing oily matter, obtains head product through heat filtering, use the dehydrated alcohol recrystallization, obtain xanchromatic 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer.Productive rate 60-70%, total molar yield 60～70%.
Be 1,3 below, the building-up reactions formula of 5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer:
In the building-up reactions formula: DMF is N, and dinethylformamide, ethanol are ethanol, and acetone is an acetone.
As the application of triamido monomer of the present invention, be the synthesizing branched polyimide polymer material of raw material with it.Said branched polyimide polymer materials comprises end capped branched polyimide polymkeric substance of acid anhydrides and the end capped branched polyimide polymer materials of amine.
Can be by 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer, promptly industrial dianhydride monomer such as triamido monomer and triphen two ether dianhydrides or biphenyl dianhydride carries out amidate action, and preparation has acid anhydrides end-blocking or amido end-blocking branched polyimide polymer materials.
The end capped branched polyimide polymkeric substance of acid anhydrides synthetic chemistry reaction formula is as follows:
In the chemical equation, X represents dianhydride monomer, has 7 kinds, is respectively: pyromellitic dianhydride, biphenyl dianhydride, triphen two ether dianhydrides, diphenyl sulfone dianhydride, hexafluorodianhydride, ether ketone dianhydride, monoether dianhydride.
The synthetic chemistry reaction formula of the end capped branched polymer of amine is as follows:
The concrete building-up process of the end capped branched polyimide polymkeric substance of acid anhydrides is:
Dianhydride monomer is dissolved in the meta-cresol solvent, makees catalyzer with isoquinoline 99.9, with toluene as azeotropy dehydrant, 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene and dianhydride monomer mol ratio are 1: 2, progressively join in the dianhydride monomer solution, refluxed 6～7 hours, and got rid of azeotropy dehydrant, heat up and continue reaction 12～16 hours, the polymers soln that obtains is separated out in dehydrated alcohol, through washing, drying obtains acid anhydrides end-blocking branched polyimide polymkeric substance.
The concrete building-up process of the end capped branched polymer of amine is:
Triamido monomer (1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene) is dissolved in the meta-cresol solvent, make catalyzer with isoquinoline 99.9, as azeotropy dehydrant, dianhydride monomer and triamine monomer mole ratio are that 1: 1 amount progressively joins in the triamido monomer solution, reflux 6～7 hours with toluene, get rid of azeotropy dehydrant, heat up and continue reaction 12-16 hour, the polymers soln that obtains is separated out in dehydrated alcohol, through washing, drying obtains amine end-blocking branched polyimide polymkeric substance.
In above-mentioned two kinds of building-up processes, the dianhydride monomer that is applied to is a kind of in pyromellitic dianhydride, biphenyl dianhydride, triphen two ether dianhydrides, diphenyl sulfone dianhydride, hexafluorodianhydride, ether ketone dianhydride, the monoether dianhydride; Applied solvent is a meta-cresol; Catalyzer is an isoquinoline 99.9, and the azeotropy dehydrant that is applied to is a toluene.
In above-mentioned two kinds of building-up processes, by 1,3, the structural formula of a part of polymkeric substance of 5-three (2-trifluoromethyl-4 amido phenoxy group) benzene preparation is as follows:
The end capped branched polyimide polymer architecture of acid anhydrides formula:
More than, used dianhydride monomer difference provides 7 kinds of end capped polymkeric substance of acid anhydrides.Wherein, R is 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene, and n is the chain hop count.
The end capped branched polyimide polymer architecture of amine formula:
More than, used dianhydride monomer difference provides 7 kinds of end capped polymkeric substance of amine.
In order to improve fluorine content, to reduce the absorption that C-H causes in the near-infrared region on the phenyl ring in the material, simultaneously in order further to improve the thermal characteristics of material, application as triamido monomer of the present invention, can also with the triamido monomer raw material, after the end capped branched polyimide polymkeric substance of synthetic acid anhydrides, resynthesis goes out 3, and 5-two 5-trifluoromethylanilines are or/and the end capped branched polyimide polymer materials of 3-alkynyl aniline.
3,5-two 5-trifluoromethylanilines are or/and the synthetic method of the end capped branched polyimide polymkeric substance of 3-alkynyl aniline is as follows:
With dianhydride monomer, triamido monomer, 3,5-two 5-trifluoromethylanilines, 3-ethynyl aniline 2: 1 in molar ratio: x: (1-x) react, wherein 0＜x＜1; Triamido monomer is added dropwise to the N of dianhydride monomer, in N-dimethyl pyrrolidone (NMP) solution, and room temperature reaction 12h, add 3-ethynyl aniline, room temperature reaction 4h continues to add 3,5-two 5-trifluoromethylaniline room temperature reaction 12h, add triethylamine and acetic anhydride then, triethylamine and acetic anhydride mass ratio 1: 3, room temperature reaction 2h, temperature is elevated to 40 ℃ continues reaction 10h, discharging is in ethanol, and synthetic 3,5 two 5-trifluoromethylanilines are or/and the end capped branched polyimide polymkeric substance of 3-alkynyl aniline.
In the above-mentioned synthetic method, dianhydride monomer, triamido monomer, 3,5-two 5-trifluoromethylanilines fed intake by 2: 1: 1, with the end capped branched polymer of acid anhydrides and 3, the reaction of 5-two 5-trifluoromethylanilines, can obtain end group is 3, the branched polyimide of 5-two 5-trifluoromethylanilines, and the synthesis step reaction formula is as follows:
By 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene preparation by 3, the end capped branched polyimide polymkeric substance of 5-two 5-trifluoromethylanilines, its structural formula is as follows:
In the above-mentioned synthetic method, dianhydride monomer, triamido monomer, 3,5-two 5-trifluoromethylanilines, 3-ethynyl aniline were by 2: 1: x: (1-x) (0＜x＜1) mol ratio feeds intake, and can make 3, the end capped branched polyimide polymkeric substance of 5-two 5-trifluoromethylanilines and 3-alkynyl aniline.
Introducing alkynes carries out crosslinked to material, in the good solubility-resistence that improves material, improve the mechanical property of material greatly.The synthesis step reaction formula is as follows:
By 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene preparation by 3, the end capped branched polyimide polymkeric substance of 5-two 5-trifluoromethylanilines and 3-alkynyl aniline, its structural formula is as follows:
The invention belongs to 1,3, the synthetic technology of 5-three (2-trifluoromethyl-4 amido phenoxy group) benzene and utilize its synthetic a series of branched polyimide polymkeric substance.This monomeric introducing improves the fluorine content of branched polyimide, specific inductivity, thermostability, solvability, surface energy and optical property that can impact polymer, super-branched polyimide has low melt viscosity and thermostability, its unique branched structure and more capping group can carry out the end-blocking modification simultaneously, make it in great prospect such as a lot of for example photoetching of field, gas-premeable film, optical fields.
Specific implementation method:
Embodiment 1:
1. with Phloroglucinol 12.6g (0.1mol), 3-trifluoromethyl-4-chloronitrobenzene 22.55g (0.3mol), salt of wormwood 24.84g (0.18mol) and 100ml N, N dimethyl formamide (DMF), 20ml toluene are put into the there-necked flask refluxing toluene that mechanical stirring, thermometer, nitrogen port and reflux condensing tube are housed and were reacted 2-3 hour, get rid of toluene, be warmed up to 150 ℃ and continue reaction 8 hours.Discharging is in the deionization frozen water, and precipitation is washed 4～6 times with (95%) ethanol, obtains white powder precipitation 1,3,5-three (2-trifluoromethyl-4 nitro-phenoxy) benzene, and productive rate is 98%, fusing point is 163 ℃.
2. with the product 13.88g (0.02mol) of previous step gained, iron powder 26.16g (0.36mol), 40ml ethanol, 40ml water, mechanical stirring is equipped with in the adding of 48ml acetone, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl 1ml is diluted in 10ml water and the 10ml alcohol mixed solution was added drop-wise in the there-necked flask with two hours, drip and continued back flow reaction 2～3 hours, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain xanchromatic 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer.Total molar yield 60～70%, fusing point is 183 ℃.
Embodiment 2:
1. method is with embodiment 1, the charging capacity of Phloroglucinol is expanded as 63g (0.5mol), 3-trifluoromethyl-4-chloronitrobenzene 112.75g (1.5mol), salt of wormwood 124.2g (0.9mol) and 500mlN, N dimethyl formamide (DMF), 90ml toluene are put into the there-necked flask toluene band water back flow reaction 2～3 hours that mechanical stirring, thermometer, nitrogen port and reflux condensing tube are housed, get rid of toluene, be warmed up to 150 ℃ and continue reaction 8 hours.Discharging is in the deionization frozen water, and precipitation is washed 4～6 times with (95%) ethanol, obtains white powder precipitation 1,3,5-three (2-trifluoromethyl-4 nitro-phenoxy) benzene, and productive rate is 98%, fusing point is 163 ℃.
2. with the product 64.4g (0.1mol) of previous step gained, iron powder 130.8g (1.8mol), 200ml ethanol, 200ml water, mechanical stirring is equipped with in the adding of 240ml acetone, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl5ml is diluted in 50ml water and the 50ml alcohol mixed solution was added drop-wise in the there-necked flask with two hours, drip and continued back flow reaction 2～3 hours, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain xanchromatic 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer.Total molar yield 60～70%, fusing point is 183 ℃.
Embodiment 3:
With triphen two ether dianhydride 0.804g (2mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, with embodiment 1 or 2 make 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol) is dissolved into the 10mol m-cresol solution, splash in the there-necked flask in the 2h, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter, washing, drying obtains the terminated hyperbranched polyimide of white powder triphen two ether dianhydrides, 210 ℃ of DSC tested glass transition temperatures.
Embodiment 4:
With hexafluoropropane dianhydride (6FDA) 0.888g (2mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, with embodiment 1 or 2 make 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol) is dissolved in the 10mol m-cresol solution 2h and is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain the terminated hyperbranched polyimide of white powder hexafluoropropane dianhydride, 220 ℃ of DSC tested glass transition temperatures.
Embodiment 5:
With biphenyl dianhydride (BPDA) 0.588g (2mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, with embodiment 1 or 2 make 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol) is dissolved in the 10mol m-cresol solution 2h and is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain the terminated hyperbranched polyimide of white powder biphenyl dianhydride, 226 ℃ of DSC tested glass transition temperatures.
Embodiment 6:
With equal benzene tertacarbonic acid's dianhydride (PMDA) 0.64g (2mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, with embodiment 1 or 2 make 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol) is dissolved in the 10mol m-cresol solution 2h and is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain the terminated hyperbranched polyimide of the equal benzene tertacarbonic acid's dianhydride of white powder, 234 ℃ of DSC tested glass transition temperatures.
Embodiment 7:
With diphenyl sulfone dianhydride (DSDA) 0.716g (2mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, with embodiment 1 or 2 make 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol) is dissolved in the 10mol m-cresol solution 2h and is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain the terminated hyperbranched polyimide of white powder diphenyl sulfone dianhydride, 214 ℃ of DSC tested glass transition temperatures.
Embodiment 8:
With monoether dianhydride (ODPA) 0.62g (2mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, with embodiment 1 or 2 make 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol) is dissolved in the 10mol m-cresol solution 2h and is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain the terminated hyperbranched polyimide of white powder monoether dianhydride, 200 ℃ of DSC tested glass transition temperatures.
Embodiment 9:
With ether ketone dianhydride (BTDA) 0.644g (2mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, to have that aforesaid method makes 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol) is dissolved in the 10mol m-cresol solution 2h and is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain the terminated hyperbranched polyimide of white powder ether ketone dianhydride, 208 ℃ of DSC tested glass transition temperatures.
Embodiment 10:
With 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, triphen two ether dianhydrides (BTDA) 0.402g (1mmol) are dissolved in the 10mol m-cresol solution 2h are added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter, washing, drying obtains 216 ℃ of white powder amine end-blocking (triphen two ether dianhydride bases) super-branched polyimides.
Embodiment 11:
With 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, hexafluoropropane dianhydride (6FDA) 0444g (1mmol) is dissolved in the 10mol m-cresol solution 2h is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain white powder amine end-blocking (hexafluoropropane dianhydride base) super-branched polyimide, 220 ℃ of DSC tested glass transition temperatures.
Embodiment 12:
With 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, biphenyl dianhydride (BPDA) 0.294g (1mmol) is dissolved in the 10mol m-cresol solution 2h is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain white powder amine end-blocking (biphenyl dianhydride base) super-branched polyimide, 236 ℃ of DSC tested glass transition temperatures.
Embodiment 13:
With 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, equal benzene tertacarbonic acid's dianhydride (PMDA) 0.32g (1mmol) is dissolved in the 10mol m-cresol solution 2h is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain white powder amine end-blocking (all benzene tertacarbonic acid's dianhydride bases) super-branched polyimide, 240 ℃ of DSC tested glass transition temperatures.
Embodiment 14:
With 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, diphenyl sulfone dianhydride (DSDA) 0.358g (1mmol) is dissolved in the 10mol m-cresol solution 2h is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain white powder amine end-blocking (diphenyl sulfone dianhydride base) super-branched polyimide, 225 ℃ of DSC tested glass transition temperatures.
Embodiment 15:
With 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, monoether dianhydride (ODPA) 0.31g (1mmol) is dissolved in the 10mol m-cresol solution 2h is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain white powder amine end-blocking (monoether dianhydride base) super-branched polyimide, 200 ℃ of DSC tested glass transition temperatures.
Embodiment 16:
With 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol), water-taker is equipped with in 10ml m-cresol solution and the adding of 15ml toluene solution, the nitrogen port, in the 100ml four-hole bottle of thermometer and dropping funnel, be warmed up to refluxing toluene, ether ketone dianhydride (BTDA) 0.322g (1mmol) is dissolved in the 10mol m-cresol solution 2h is added dropwise in the there-necked flask, continue backflow 6h then, get rid of toluene, be warmed up to 200 ℃, continue reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain white powder amine end-blocking (ether ketone dianhydride base) super-branched polyimide, 220 ℃ of DSC tested glass transition temperatures.
Embodiment 17:
With hexafluoropropane dianhydride (6FDA) 0.888g (2mmol), 1 0mlNMP solution adds dress nitrogen port, in the 100ml there-necked flask of thermometer and dropping funnel, will by embodiment 1 or 2 make 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol) is dissolved in the 10molNMP solution 2h and is added dropwise in the there-necked flask, continue reaction 12h then, solution becomes sticky, add 3,5-two 5-trifluoromethylaniline 0.229g (1mmol), continue reaction 12h, add the 1g triethylamine then, the 3g acid anhydrides, clasp reaction 12h, polymers soln is separated out in the 150ml dehydrated alcohol, filter washing, drying, obtain white powder trifluoromethyl end-blocking (hexafluoropropane dianhydride base) super-branched polyimide, 226 ℃ of DSC tested glass transition temperatures.
Embodiment 18:
With hexafluoropropane dianhydride (6FDA) 0.888g (2mmol), 10mlNMP solution adds dress nitrogen port, in the 100ml there-necked flask of thermometer and dropping funnel, will by embodiment 1 or 2 make 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene 0.604g (1mmol) is dissolved in the 10molNMP solution 2h and is added dropwise in the there-necked flask, continue reaction 12h then, solution becomes sticky, add 3-alkynyl aniline and 3,5-two 5-trifluoromethylanilines 1mmol altogether continue reaction 12h, add the 1g triethylamine then, the 3g acid anhydrides, clasp reaction 12h separates out polymers soln in the 150ml dehydrated alcohol, filter, washing, drying obtains white powder alkynyl and trifluoromethyl end-blocking (hexafluoropropane dianhydride base) super-branched polyimide, crosslinked preceding 210 ℃ of DSC tested glass transition temperature, crosslinked back 267 ℃.
3-alkynyl aniline and 3,5-two 5-trifluoromethylanilines are than being (1-x): x, (0＜x＜1) can obtain trifluoromethyl and the end capped super-branched polyimide of alkynyl different ratios.
Claims (8)
1, a kind of triamido monomer is characterized in that, said triamido monomer is 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer, and structure is as follows:
2, a kind of preparation method of triamido monomer of claim 1 is characterized in that,
The first step reaction: Phloroglucinol and 3-trifluoromethyl-4-chloronitrobenzene 1: 3 in molar ratio～4 are put into there-necked flask, Phloroglucinol elder generation and salt of wormwood salify, toluene band water back flow reaction 1.5～2.5 hours, with N, dinethylformamide is made solvent then, reacts 7～9 hours under 150 ℃ of conditions with 3-trifluoromethyl-4-chloronitrobenzene, make trinitro-monomer 1,3,5-three (2-trifluoromethyl-4 nitro-phenoxy) benzene, discharging is in deionized water;
The reaction of second step: with the trinitro-monomer, iron powder, HCl 1: 18: 3 in molar ratio were raw material, ethanol, water, acetone 1: 1～2: 1～2 is made solvent, back flow reaction 4～5 hours, product with deionized water repetitive scrubbing oily matter, obtains head product through heat filtering, use the dehydrated alcohol recrystallization, obtain xanchromatic 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene monomer.
3, a kind of application of triamido monomer of claim 1 is characterized in that, is the synthesizing branched polyimide polymer material of raw material with the triamido monomer.
4, according to the application of the described triamido monomer of claim 3, it is characterized in that, said synthesizing branched polyimide polymer material is to carry out amidate action by triamido monomer and dianhydride monomer, and preparation has acid anhydrides end-blocking or amido end-blocking branched polyimide polymer materials; Said dianhydride monomer is a kind of in pyromellitic dianhydride, biphenyl dianhydride, triphen two ether dianhydrides, diphenyl sulfone dianhydride, hexafluorodianhydride, ether ketone dianhydride, the monoether dianhydride.
5, application according to claim 3 or 4 described triamido monomers, it is characterized in that, the process of said synthesizing branched polyimide polymer is, dianhydride monomer is dissolved in the meta-cresol solvent, make catalyzer with isoquinoline 99.9, with toluene as azeotropy dehydrant, 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene and dianhydride monomer are 1: 2 in molar ratio, progressively join in the dianhydride monomer solution, reflux 6～7 hours, get rid of azeotropy dehydrant, heat up and continue reaction 12～16 hours, the polymers soln that obtains is separated out in dehydrated alcohol, through washing, drying obtains acid anhydrides end-blocking branched polyimide polymkeric substance.
6, application according to claim 3 or 4 described triamido monomers, it is characterized in that, the process of said synthesizing branched polyimide polymer is, with 1,3,5-three (2-trifluoromethyl-4 amido phenoxy group) benzene is dissolved in the meta-cresol solvent, makees catalyzer with isoquinoline 99.9, with toluene as azeotropy dehydrant, dianhydride monomer and 1: 1 in molar ratio amount of three amine monomers progressively join in the triamido monomer solution, refluxed 6～7 hours, and got rid of azeotropy dehydrant, heat up and continue reaction 12～16 hours, the polymers soln that obtains is separated out in dehydrated alcohol, through washing, drying obtains amine end-blocking branched polyimide polymkeric substance.
7, according to the application of claim 3 or 4 described triamido monomers, it is characterized in that, said synthesizing branched polyimide polymer material, be after the end capped branched polyimide polymkeric substance of synthetic acid anhydrides, resynthesis 3,5-two 5-trifluoromethylanilines are or/and the end capped branched polyimide polymer materials of 3-alkynyl aniline.
8, according to the application of the described triamido monomer of claim 7, it is characterized in that, said synthetic 3,5-two 5-trifluoromethylanilines or/and the process of the end capped branched polyimide polymer materials of 3-alkynyl aniline be, with dianhydride monomer, triamido monomer, 3,5-two 5-trifluoromethylanilines, 3-ethynyl aniline 2: 1 in molar ratio: x: 1-x reacts, wherein 0＜x＜1; Triamido monomer is added dropwise to the N of dianhydride monomer, in the N-dimethyl pyrrolidone solution, and room temperature reaction 12h, add 3-ethynyl aniline, room temperature reaction 4h continues to add 3,5-two 5-trifluoromethylaniline room temperature reaction 12h, add triethylamine and acetic anhydride then, triethylamine and acetic anhydride mass ratio 1: 3, room temperature reaction 2h, temperature is elevated to 40 ℃ continues reaction 10h, discharging synthesizes 3 in ethanol, 5-two 5-trifluoromethylanilines are or/and the end capped branched polyimide polymkeric substance of 3-alkynyl aniline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710055205XA CN100540527C (en) | 2007-01-04 | 2007-01-04 | A kind of triamido monomer and synthetic method thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710055205XA CN100540527C (en) | 2007-01-04 | 2007-01-04 | A kind of triamido monomer and synthetic method thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN100999476A CN100999476A (en) | 2007-07-18 |
| CN100540527C true CN100540527C (en) | 2009-09-16 |
Family
ID=38258312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200710055205XA Expired - Fee Related CN100540527C (en) | 2007-01-04 | 2007-01-04 | A kind of triamido monomer and synthetic method thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100540527C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659610B (en) * | 2012-06-01 | 2014-07-23 | 吉林大学 | Diamino monomer as well as synthesis method and application thereof |
| CN104529839B (en) * | 2014-12-17 | 2016-08-17 | 吉林大学 | 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-aminophenoxyl) phenoxy group] diphenyl sulphone (DPS) and its preparation method and application |
| CN105037724A (en) * | 2015-07-07 | 2015-11-11 | 吉林大学 | Hyperbranched polyimide containing alkynyl group, and preparation method and application thereof |
| CN106700070A (en) * | 2015-07-31 | 2017-05-24 | 中科院广州化学有限公司南雄材料生产基地 | Soluble polyimides containing phenolic hydroxyl group and preparation method and application thereof |
| CN105566127B (en) * | 2016-03-02 | 2018-02-13 | 吉林大学 | A kind of Triamine monomer and its preparation method and application |
| CN106674520B (en) * | 2017-02-09 | 2019-03-26 | 吉林大学 | The preparation and application of super-branched polyimide containing non-isoreactivity Triamine monomer |
| CN109232892B (en) * | 2018-08-24 | 2020-11-06 | 吉林大学 | Cross-linkable hyperbranched polyimide and preparation method and application thereof |
| CN111423607B (en) * | 2020-05-21 | 2022-02-08 | 西南科技大学 | Preparation method of double-branched sulfonated polyimide membrane |
-
2007
- 2007-01-04 CN CNB200710055205XA patent/CN100540527C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN100999476A (en) | 2007-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100540527C (en) | A kind of triamido monomer and synthetic method thereof and application | |
| CN101200822B (en) | Polyimide fibre containing benzimidazole structure and preparation method thereof | |
| CN106008185A (en) | Tetramine monomer and preparation method and application thereof | |
| CN102267940B (en) | Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof | |
| CN113511980B (en) | Aromatic polyimide with main chain containing benzonorbornene structure and preparation method thereof | |
| CN103289091A (en) | Preparation method of hyperbranched polyimide with adjustable branching degree | |
| CN103289092A (en) | Preparation method of A2+B'B2+B2 type hyperbranched polyimide resin | |
| CN108530304B (en) | Aromatic diamine and polyimide containing tolyl and non-coplanar structure and preparation method thereof | |
| CN113388109B (en) | Polyimide with main chain containing benzonorbornene structure and preparation method thereof | |
| CN112275147B (en) | Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof | |
| CN101514164A (en) | Polyalkyl-substituted aromatic diamine monomer and preparation and application thereof | |
| CN101085833B (en) | Soluble fluorine-containing aromatic polyimide and synthetic method thereof | |
| Liu et al. | Synthesis and properties of novel soluble fluorinated polyamides containing pyridine and sulfone moieties | |
| CN103524738A (en) | Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure | |
| CN101709515B (en) | Polyimide fiber containing amido link structure and preparation method thereof | |
| CN113277950A (en) | Asymmetric aromatic diamine monomer containing terphenyl large-substitution side group and polyimide | |
| CN113480442A (en) | Cross-linkable diamine monomer, preparation method and application thereof in preparation of polyimide | |
| CN109833784A (en) | A kind of Silicone Containing Polyimides gas separation membrane and preparation method | |
| CN101921396A (en) | Semi-aryl poly (phenylene sulfide amide) and preparation method thereof | |
| CN101921403A (en) | Synthesizing method of polyimide material | |
| CN115557848B (en) | Diamine monomer, low CTE, high permeability polyimide and preparation method thereof | |
| CN103113309A (en) | Bipyrimidyl dibenzene/diether/diamine and synthesis method thereof | |
| CN104356383B (en) | Polyimide containing four substituent pendant groups and distorted non-coplanar structure synchronously and preparation method thereof | |
| JP2001181393A (en) | Triarylphosphine oxide derivative having fluorine- containing substituent | |
| CN102086181A (en) | Synthesis method of 2,2'-diaryl-4,4',5,5'-biphenyl tetraacid dianhydride monomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090916 Termination date: 20130104 |