CN101085744A - Fluorine-containing aromatic diaminomonomer and synthetic method thereof - Google Patents
Fluorine-containing aromatic diaminomonomer and synthetic method thereof Download PDFInfo
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Abstract
The invention relates to a kind of fluorine- containing aromatic diamido monomer and the synthesis method, belonging to field of organic chemical compound. It discloses four kinds of diamino monomers such as 1, 4- (4- amnio- 2- trifluoromethyl- phenoxy)- 2- (3'-methyl phenyl)benzene containing fluorine, ether linkage and benzene side chain. The method comprises following steps: taking diphenol and 3- trifluoromethyl- 4- chloronitrobenzene as raw material, salt precipitating for diphenol and potash, refluxing with water- containing toluene, reacting with 3- trifluoromethyl- 4- chloronitrobenzene and getting dinitro monomer; taking dinitro monomer, ferro powder and HCl as raw material, ethanol and water as disslovant for refluxing and ethanol recrystallization, getting fluorine- containing aromatic diamido monomer. The product meets requirement for medlin ploymer synthesis, which can be used for optical waveguide material.
Description
Technical field
The invention belongs to the technical field of organic compound and preparation method thereof, be specifically related to four kinds of diaminomonomer and synthetic methods thereof that contain fluorine, big side group and ehter bond novel the time.
Background technology
Polyimide is a kind of high performance material, be widely used in a lot of fields, but because it is poorly soluble, shortcoming in ultraviolet region light transmission difference, make it at light, fields such as electricity are used and are restricted, if introduce big side group and ehter bond, can improve the solvability of polyimide material, the introducing of trifluoromethyl can improve the light transmission of material, reduce specific inductivity, particularly be applied to optical waveguide material, can reduce the absorption loss of material at communication band, and the introducing of side group can reduce the birefringence value of polyimide material in the past greatly, thereby can further reduce the polarization loss that material in use brings.
The prior art close with the present invention is one piece and is published in Journal of Polymer Science:PartA:Polymer Chemistry, Vol.43, on the 3018-3029 (2005), exercise question is the article of " Synthesis andCharacterization of Organosoluble Ditrifluoromethylated AromaticPolyimides ", disclosed diaminomonomer is 1,4-two (4-phenoxy group)-2-[(3 ', 5 '-two trifluoromethyls) phenyl] benzene and 1,4-two [2 '-cyano group-3 ' (4 "-the amido phenoxy group) phenoxy group]-2-[(3 ', 5 '-two trifluoromethyls) phenyl] benzene.By these two kinds of amine monomers synthetic polymkeric substance by higher thermostability and good light transmittance.
Summary of the invention
The technical problem to be solved in the present invention is: for solvability, the light transmission that improves polyimide material, reduce the birefringence value of material, synthetic have trifluoromethyl, big benzene lateral group and a special construction diaminomonomer of ehter bond.So four kinds of diaminomonomers of the present invention design synthetic for the polyimide material that satisfies above-mentioned performance.
A kind of fluorine-containing aromatic diamine base monomer, it is characterized in that, diaminomonomer is fluorine-containing, ehter bond and benzene lateral group, concrete is 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene (a), 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene (b), 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 ', 5 '-two trifluoromethyls) benzene (c) and 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl-4 ' chloro phenyl) benzene (d); Their structure is respectively:
These four kinds of fluorine-containing aromatic diamine base monomer synthetic methods are as follows:
The first step reaction: with (3 '-methylbenzene)-1, the 4-Resorcinol, (3 '-trifluoromethylbenzene)-1, the 4-Resorcinol, (3 ', 5 '-two trifluoromethylbenzenes)-1,4-Resorcinol or (3 '-trifluoromethyl-4 '-chlorobenzene)-1,4-Resorcinol and 3-trifluoromethyl-4-chloronitrobenzene 1: 2 in molar ratio～2.3 is made raw material, earlier with above-mentioned diphenol and salt of wormwood salify, toluene band water back flow reaction 2～3 hours, with comprising N, dinethylformamide is made solvent then, reacts 7～9 hours under 150～170 ℃ of conditions with 3-trifluoromethyl-4-chloronitrobenzene, make the dinitrobenzene monomer, discharging is in deionized water.
Second step reaction: with the dinitrobenzene monomer, iron powder, HCl 1: 10 in molar ratio～13: 2～3 is a raw material, the second alcohol and water is made solvent, back flow reaction 4～5 hours, and product is through heat filtering, use deionized water wash oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain fluorine-containing aromatic diamine base monomer.
Said dinitrobenzene monomer is: 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene, 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene, 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 ', 5 '-two trifluoromethyls) benzene or 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl-4 ' chloro phenyl) benzene.
Four kinds of xanchromatic diaminomonomers that obtain at last are respectively: 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene (a), 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene (b), 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 ', 5 '-two trifluoromethyls) benzene (c), 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl-4 ' chloro phenyl) benzene (d).
In the first step reaction, solvent can also be N,N-dimethylacetamide or N-Methyl pyrrolidone.In the reaction of second step, second alcohol and water 1～2: 1 mixing is by volume made solvent.
Be diaminomonomer building-up reactions formula below:
Wherein Ar is
In the building-up reactions formula: DMF is N, and dinethylformamide, EtOH are ethanol.
Four kinds of diaminomonomers of synthetic all contain trifluoromethyl, flexible ehter bond and big benzene lateral group group, the introducing of these three kinds of groups all can destroy monomeric regularity, when diamine monomer and anhydride monomers synthetic polymer, wherein flexible ehter bond and big benzene lateral group can make polymkeric substance carry out non-copline and arrange, thereby also produce the big problem of double refraction owing to the orientation of main chain phenyl ring with regard to reducing material, the free volume that trifluoromethyl is big can reduce the specific inductivity of polymer materials, and three kinds of groups all can play in the saboteur in polymkeric substance and intermolecular reactive force, thereby improve the solvability and the photopermeability of material, and can guarantee the excellent heat stability of material.Simultaneously, these diaminomonomers have different fluorine contents, two amidos and certain acid anhydrides with different fluorine contents carry out copolymerization, and the fluorine content of telomerized polymer can further be regulated the specific refractory power of material, and this just provides a kind of new application promptly to can be applicable to optical waveguide material to material.
Description of drawings
Fig. 1 is 1, the infrared spectra of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene (a).
Fig. 2 is 1, the infrared spectra of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene (b).
Fig. 3 is 1, the infrared spectra of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 ', 5 '-two trifluoromethyls) benzene (c).
Fig. 4 is 1, the infrared spectra of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl-4 '-chloro phenyl) benzene (d).
Fig. 5 is 1, the mass spectrum of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene (a).
Fig. 6 is 1, the mass spectrum of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene (b).
Fig. 7 is 1, the mass spectrum of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 ', 5 '-two trifluoromethyls) benzene (c).
Fig. 8 is 1, the mass spectrum of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl-4 '-chloro phenyl) benzene (d).
Fig. 9 is 1, the nuclear-magnetism of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene (a)
1The H-NNR analysis of spectra.
Figure 10 is 1, the nuclear-magnetism of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene (b)
1The H-NNR analysis of spectra.
Figure 11 is 1, the nuclear-magnetism of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 ', 5 '-two trifluoromethyls) benzene (c)
1The H-NNR analysis of spectra.
Figure 12 is 1, the nuclear-magnetism of 4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl-4 '-chloro phenyl) benzene (d)
1The H-NNR analysis of spectra.
Specific implementation method:
Following implementation method is to further specify of the present invention, rather than limits the scope of the invention
Embodiment 1:
With (3 '-methylbenzene)-1,4-Resorcinol 20g (0.1mol), 3-trifluoromethyl-4-chloronitrobenzene 49.61g (0.22mol), salt of wormwood 16.56 (0.12mol) and 100mL N, dinethylformamide (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 hours, get rid of toluene, be warmed up to 150 ℃ and continue reaction 7 hours.Discharging is in the deionization frozen water, and precipitation is washed 4-6 time with (95%) ethanol, obtains yellow powder precipitation 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene, productive rate 90%.
With the above-mentioned yellow powder product 57.8g (0.1mol) that obtains, iron powder 67.2g (1.2mol), mechanical stirring is equipped with in the adding of 75mL ethanol 75mL water, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl 5.5mL is diluted in 50mL water and the 50mL alcohol mixed solution, be added drop-wise in the there-necked flask with 2 hours, drip and continued back flow reaction 3 hours, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain yellow 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene monomer.Total molar yield 60-70%, fusing point is 136 ℃.Fig. 1: 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene (a) infrared spectra.
Fig. 1 is the infrared spectrum of this diaminomonomer, as can be seen from Figure 1 has two tangible N-H to absorb vibration peak in 3350～3500 intervals, proves the monomeric existence of amido; Fig. 5 is the mass spectrum of this diaminomonomer, and the molecular weight that can prove institute's synthon from Fig. 5 is 518 to conform to calculated value; Fig. 9 is the nuclear magnetic spectrogram of this diaminomonomer, and intact ownership has been carried out in all the hydrogen positions to diaminomonomer among Fig. 9, has proved that by above three kinds of tests monomer is a target product.
With (3 '-trifluoromethylbenzene)-1,4-Resorcinol 25.4g (0.1mol), 3-trifluoromethyl-4-chloronitrobenzene 47.36g (0.21mol), salt of wormwood 15.18 (0.11mol) and 100mL N, dinethylformamide (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 2.5 hours, get rid of toluene, be warmed up to 155 ℃ and continue reaction 7.5 hours.Discharging is in the deionization frozen water, and precipitation is washed 4-6 time with (95%) ethanol, obtains yellow powder precipitation 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene, productive rate 92%.
With the above-mentioned yellow powder product 63.2g (0.1mol) that obtains, iron powder 56g (1.mol), mechanical stirring is equipped with in the adding of 75mL ethanol 75mL water, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl 4.5mL is diluted in 50mL water and the 50mL alcohol mixed solution, be added drop-wise in the there-necked flask with 2 hours, drip and continued back flow reaction 2.5 hours, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain yellow 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene monomer.Total molar yield 60-70%, fusing point is 128 ℃.
Fig. 2 is the infrared spectrum of this diaminomonomer, as can be seen from Figure 2 has two tangible N-H to absorb vibration peak in 3350～3500 intervals, proves the monomeric existence of amido; Fig. 6 is the mass spectrum of this diaminomonomer, can prove that from Fig. 6 the molecular weight 572 of institute's synthon conforms to calculated value; Figure 10 is the nuclear magnetic spectrogram of this diaminomonomer, and intact ownership is carried out in all the hydrogen positions to diaminomonomer among Figure 10, has proved that by above three kinds of tests monomer is a target product.
With (3 ' 5 '-two trifluoromethylbenzenes)-1,4-Resorcinol 32.2g (0.1mol), 3-trifluoromethyl-4-chloronitrobenzene 51.86g (0.23mol), salt of wormwood 16.56 (0.12mol) and 100mL N, dinethylformamide (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 3 hours, get rid of toluene, be warmed up to 155 ℃ and continue reaction 7 hours.Discharging is in the deionization frozen water, and precipitation is washed 4-6 time with (95%) ethanol, obtains yellow powder precipitation 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 ' 5 '-two trifluoromethyls) benzene, productive rate 92%.
With the above-mentioned yellow powder product 70g (0.1mol) that obtains, iron powder 61.6g (1.1mol), mechanical stirring is equipped with in the adding of 75mL ethanol 75mL water, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl 5mL is diluted in 50mL water and the 50mL alcohol mixed solution, be added drop-wise in the there-necked flask with 2 hours, drip and continued back flow reaction 2.5 hours, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain yellow 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 ' 5 '-two trifluoromethyls) benzene monomer.Total molar yield 50%, fusing point is 154 ℃.
Fig. 3 is the infrared spectrum of this diaminomonomer, as can be seen from Figure 3 has two tangible N-H to absorb vibration peak in 3350～3500 intervals, proves the monomeric existence of amido; Fig. 7 is the mass spectrum of this diaminomonomer, can prove that from Fig. 7 the molecular weight 640 of institute's synthon conforms to calculated value; Figure 11 is the nuclear magnetic spectrogram of this diaminomonomer, among Figure 11 intact ownership has been carried out in monomeric all hydrogen positions, has proved that by above three kinds of tests monomer is a target product.
With (3 '-trifluoromethyl-4 '-chlorobenzene)-1,4-Resorcinol 28.8g (0.1mol), 3-trifluoromethyl-4-chloronitrobenzene 54.12g (0.2mol), salt of wormwood 16.56 (0.12mol) and 100mL N, dinethylformamide (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 hours, get rid of toluene, be warmed up to 150 ℃ and continue reaction 9 hours.Discharging is in the deionization frozen water, and precipitation is washed 4-6 time with (95%) ethanol, obtains yellow powder precipitation 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl 4 '-chloro-phenyl-) benzene, productive rate 94%.
With the above-mentioned yellow powder product 66.7g (0.1mol) that obtains, iron powder 67.2g (1.2mol), mechanical stirring is equipped with in the adding of 75mL ethanol 75mL water, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl 5mL is diluted in 50mL water and the 50mL alcohol mixed solution, be added drop-wise in the there-necked flask with 2 hours, drip and continued back flow reaction 2-3 hour, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain xanchromatic 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl 4 '-chloro-phenyl-) benzene monomer.Total molar yield 50%, fusing point is 142 ℃.
Fig. 4 is the infrared spectrum of this diaminomonomer, as can be seen from Figure 4 has two tangible N-H to absorb vibration peak in 3350～3500 intervals, proves the monomeric existence of amido; Fig. 8 is the mass spectrum of this diaminomonomer, can prove that from Fig. 8 the molecular weight 606 of institute's synthon conforms to calculated value; Figure 12 is the nuclear magnetic spectrogram of this diaminomonomer, among Figure 12 intact ownership has been carried out in monomeric all hydrogen positions, has proved that by above three kinds of tests monomer is a target product.
With (3 '-methylbenzene)-1,4-Resorcinol extensive magnitude 100g (0.5mol), 3-trifluoromethyl-4-chloronitrobenzene 225.5g (1mol), salt of wormwood 82g (0.6mol) and 500mL N, dinethylformamide (DMF), 100mL 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 3 hours, 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 time with (95%) ethanol, obtains yellow powder precipitation 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene, productive rate 90%.
Product extensive magnitude 29g (0.5mol) with the above-mentioned yellow powder that obtains, iron powder 308g (5.5mol), mechanical stirring is equipped with in the adding of 375mL ethanol 375mL water, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl25mL is diluted in 250mL water and the 250mL alcohol mixed solution, be added drop-wise in the there-necked flask with two hours, drip and continued back flow reaction 3 hours, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain yellow 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene monomer.Total molar yield 60-70%, fusing point is 136 ℃.
With (3 '-trifluoromethylbenzene)-1,4-Resorcinol extensive magnitude 127g (0.5mol), 3-trifluoromethyl-4-chloronitrobenzene 270.6g (1.2mol), salt of wormwood 82g (0.6mol) and 500mL N, dinethylformamide (DMF), 100mL 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 3.5 hours, get rid of toluene, be warmed up to 155 ℃ and continue reaction 9 hours.Discharging is in the deionization frozen water, and precipitation is washed 4-6 time with (95%) ethanol, obtains yellow powder precipitation 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene, productive rate 92%.
Product extensive magnitude 316g (0.5mol) with the above-mentioned yellow powder that obtains, iron powder 280g (5mol), mechanical stirring is equipped with in the adding of 375mL ethanol 375mL water, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl 23mL is diluted in 250mL water and the 250mL alcohol mixed solution, be added drop-wise in the there-necked flask with two hours, drip and continued back flow reaction 4 hours, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain yellow 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene monomer.Total molar yield 60-70%, fusing point is 128 ℃.
With (3 ' 5 '-two trifluoromethylbenzenes)-1,4 Resorcinol 161g (0.5mol), 3-trifluoromethyl-4-chloronitrobenzene 293g (1mol), salt of wormwood 82g (0.6mol) and 500mLN, dinethylformamide (DMF), 100mL 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 2.5 hours, get rid of toluene, be warmed up to 165 ℃ and continue reaction 7 hours.Discharging is in the deionization frozen water, and precipitation is washed 4-6 time with (95%) ethanol, obtains yellow powder precipitation 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 ' 5 '-two trifluoromethyls) benzene, productive rate 92%.
Product 350g (0.5mol) with the above-mentioned yellow powder that obtains, iron powder 336g (6mol), mechanical stirring is equipped with in the adding of 375mL ethanol 375mL water, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl 25mL is diluted in 250mL water and the 250mL alcohol mixed solution, be added drop-wise in the there-necked flask with two hours, drip and continued back flow reaction 2.5 hours, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain yellow 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 ' 5 '-two trifluoromethyls) benzene monomer.Total molar yield 50%, fusing point is 154 ℃.
With (3 '-trifluoromethyl-4 '-chlorobenzene)-1,4-Resorcinol 144g (0.5mol), 3-trifluoromethyl-4-chloronitrobenzene 112.75g (1mol), salt of wormwood 82g (0.6mol) and 500mL N, dinethylformamide (DMF), 100mL 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 3 hours, get rid of toluene, be warmed up to 160 ℃ and continue reaction 8 hours.Discharging is in the deionization frozen water, and precipitation is washed 4-6 time with (95%) ethanol, obtains yellow powder precipitation 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl-4 '-chloro-phenyl-) benzene, productive rate 94%.
With the above-mentioned yellow powder product 333.5g (0.5mol) that obtains, iron powder 336g (6mol), mechanical stirring is equipped with in the adding of 375mL ethanol 375mL water, dropping funnel, in the there-necked flask of nitrogen port and reflux condensing tube, HCl25mL is diluted in 250mL water and the 250mL alcohol mixed solution, be added drop-wise in the there-necked flask with two hours, drip and continued back flow reaction 2-3 hour, product is through heat filtering, with hot ethanol repetitive scrubbing oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain xanchromatic 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl 4 '-chloro-phenyl-) benzene monomer.Total molar yield 50%,, fusing point is 142 ℃.
Claims (4)
1, a kind of fluorine-containing aromatic diamine base monomer, it is characterized in that, diaminomonomer is fluorine-containing, ehter bond and benzene lateral group, concrete is 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene (a), 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene (b), 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 ', 5 '-two trifluoromethyls) benzene (c) and 1,4-(4-amido-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl-4 ' chloro phenyl) benzene (d); Their structure is respectively:
2, a kind of monomeric synthetic method of fluorine-containing aromatic diamine base of claim 1, react in two steps:
The first step reaction: with (3 '-methylbenzene)-1, the 4-Resorcinol, (3 '-trifluoromethylbenzene)-1, the 4-Resorcinol, (3 ', 5 '-two trifluoromethylbenzenes)-1,4-Resorcinol or (3 '-trifluoromethyl-4 '-chlorobenzene)-1,4-Resorcinol and 3-trifluoromethyl-4-chloronitrobenzene 1: 2 in molar ratio～3 is made raw material, earlier with above-mentioned diphenol and salt of wormwood salify, toluene band water back flow reaction 2～3 hours, with comprising N, dinethylformamide is made solvent then, reacts 7～9 hours under 150～170 ℃ of conditions with 3-trifluoromethyl-4-chloronitrobenzene, make the dinitrobenzene monomer, discharging is in deionized water;
Second step reaction: with the dinitrobenzene monomer, iron powder, HCl 1: 10 in molar ratio～13: 2～3 is a raw material, the second alcohol and water is made solvent, back flow reaction 4～5 hours, and product is through heat filtering, use deionized water wash oily matter, obtain head product, use the dehydrated alcohol recrystallization, obtain fluorine-containing aromatic diamine base monomer.
3, according to the monomeric synthetic method of the described fluorine-containing aromatic diamine base of claim 2, it is characterized in that, said dinitrobenzene monomer is: 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-aminomethyl phenyl) benzene, 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl) benzene, 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 ', 5 '-two trifluoromethyls) benzene or 1,4-(4-nitro-2-trifluoromethyl-phenoxy group)-2-(3 '-trifluoromethyl-4 ' chloro phenyl) benzene.
According to claim 2 or the monomeric synthetic method of 3 described fluorine-containing aromatic diamine bases, it is characterized in that 4, in the first step reaction, solvent comprises N,N-dimethylacetamide or N-Methyl pyrrolidone; In the reaction of second step, second alcohol and water 1～2: 1 mixing is by volume made solvent.
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| US20140184997A1 (en) * | 2011-09-19 | 2014-07-03 | Beijing Boe Display Technology Co. Ltd. | Prepolymer orientated film and method for preparing same, and liquid display device |
| CN104356383A (en) * | 2014-10-17 | 2015-02-18 | 常州大学 | Polyimide containing four substituent pendant groups and distorted non-coplanar structure synchronously and preparation method thereof |
| CN106496557A (en) * | 2016-11-02 | 2017-03-15 | 沈阳化工大学 | A kind of preparation method of high transparency high temperature resistant fluorinated polyimide resin |
| CN106543438A (en) * | 2016-11-07 | 2017-03-29 | 沈阳化工大学 | A kind of preparation method of chlorinated and fluorinated polyamide-imide resin |
| CN107043535A (en) * | 2017-04-25 | 2017-08-15 | 晶锋集团股份有限公司 | A kind of bismuth, manganese, cobalt, zinc oxide polyimide composite film of niobium doping and preparation method thereof |
-
2007
- 2007-07-11 CN CN 200710055866 patent/CN101085744A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20140184997A1 (en) * | 2011-09-19 | 2014-07-03 | Beijing Boe Display Technology Co. Ltd. | Prepolymer orientated film and method for preparing same, and liquid display device |
| CN103193674A (en) * | 2013-03-11 | 2013-07-10 | 吉林大学 | Multi-cyandiamine monomer and preparation and application thereof |
| CN103193674B (en) * | 2013-03-11 | 2015-08-26 | 吉林大学 | Many cyano group diamine monomer and preparation and application thereof |
| CN103420878A (en) * | 2013-07-16 | 2013-12-04 | 常州大学 | Aromatic diamine monomer containing multi-trifluoromethyl structure and preparation method of aromatic diamine monomer |
| CN103420878B (en) * | 2013-07-16 | 2014-12-17 | 常州大学 | Aromatic diamine monomer containing multi-trifluoromethyl structure and preparation method of aromatic diamine monomer |
| CN104356383A (en) * | 2014-10-17 | 2015-02-18 | 常州大学 | Polyimide containing four substituent pendant groups and distorted non-coplanar structure synchronously and preparation method thereof |
| CN104356383B (en) * | 2014-10-17 | 2017-01-18 | 常州大学 | Polyimide containing four substituent pendant groups and distorted non-coplanar structure synchronously and preparation method thereof |
| CN106496557A (en) * | 2016-11-02 | 2017-03-15 | 沈阳化工大学 | A kind of preparation method of high transparency high temperature resistant fluorinated polyimide resin |
| CN106543438A (en) * | 2016-11-07 | 2017-03-29 | 沈阳化工大学 | A kind of preparation method of chlorinated and fluorinated polyamide-imide resin |
| CN107043535A (en) * | 2017-04-25 | 2017-08-15 | 晶锋集团股份有限公司 | A kind of bismuth, manganese, cobalt, zinc oxide polyimide composite film of niobium doping and preparation method thereof |
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