CN106748963A - Polyamidoimide containing indane structural and preparation method thereof - Google Patents
Polyamidoimide containing indane structural and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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Abstract
The present invention provides a kind of polyamidoimide containing indane structural, and its general structure is：In formula, n=1~8.The present invention also proposes the described polyamidoimide containing indane structural by 220~380 DEG C of materials obtained after solidifying.And the polyamidoimide preparation method containing indane structural.The present invention has carried out subject study for the synthesis of polyimides and performance, with (4 aminophenyl) 1 of 5 (6) amino 1,3,3 trimethyl indanes prepare the thermosetting polyamide acid imide of different polymerization degree for monomer, to reduce the bulk density of molecule interchain and interact, increase Chain Flexibility, finally synthesize that dissolubility is excellent, the polyamide-imide resin of excellent heat resistance.
Description
Technical field
The invention belongs to field of organic polymer compound, and in particular to a kind of polyamideimide resin containing indane structural
And preparation method thereof.
Background technology
Aromatics Thermocurable polyimide (PI) resin is due to wide with excellent heat endurance and mechanical behavior under high temperature
It is general to be applied to every field.But the solubility in organic solvent of the imide resin after imidization is far below technological requirement, institute
With more than when prepreg is prepared, hot setting is molded in the form of amic acid, but resin can be produced during hot imidization
The small molecule product such as water, the problems such as cause the porosity of product high, making the processing of large scale product becomes difficult, and this is also to cause
The reason for limited one of polyimides application is extremely important.Therefore, it is solvable fusible and with excellent processability after exploitation imidization
The polyimides of energy increasingly attracts attention[1-2].Polyamide-imides (PAI) is regarded as polyimides and aromatic series polyamides
The alternate copolymer of amine, belongs to the transformed lines show of polyimides.Polyamide-imides molecular backbone is by two kinds of acid amides and acid imide
Construction unit is constituted, thus with heat resistance as polyimide, while its dissolubility and machinability are improved,
It is a kind of resin with excellent machinability[3-4]。
With 1,3,3- trimethyl -1- phenyl indans are raw material, can be obtained by nitrification, reduction reaction, 5 (6)-amino -1-
(4- aminophenyls) -1,3,3- trimethyl indanes (PIDA), obtained PIDA fusing points are relatively low and with ring-type indane structural, both drop
Low solidification temperature, hardening time is shortened, the heat resistance of composite is improve again[5].With 5 (6)-amino -1- (4- amino
Phenyl) -1,3,3- trimethyl indanes prepare the thermosetting polyamide-acid imide of different polymerization degree for monomer, can reduce point
Bulk density and interaction between subchain, increase Chain Flexibility.
Bibliography
[1] Yang Shiyong, Fan Lin, Chen Jiansheng, wait progress [J] thermosetting resins of high-performance polyimide materials,
2008,23:32-35。
[2] Yan Jingling, Meng Xiangsheng, Wang Zhen, wait Thermocurable polyimides progress [J] applied chemistries, 2015,32
(5):489-497。
[3]ShahramMehdipour-Ataei,Mehdi Hatami.Synthesis and characterization
of novel heat resistant poly(amide imide)s[J].European Polymer Journal 41
(2005)2010–2015。
[4] Chen Lijun, Zhang Xinya, Huang Hong, wait the preparation of polyamidoimides and its apply [J] insulating materials, and 2005,
5:61-64。
[5] Ji Qinglin, Wang Juhua, Cao Qinghua, wait .5 (6)-amino -1- (4- aminophenyls) -1,3,3- trimethyl indanes
Synthesis and its curing characteristics research [J] fiberglass/composite, 2011,4:9-13.
The content of the invention
In view of the shortcomings of the prior art, it is sub- the purpose of the present invention is to propose to a kind of polyamide containing indane structural-acyl
Amine.
Second object of the present invention is the material for proposing to be obtained after being solidified by the polyamide-imides.
Third object of the present invention is the preparation method for proposing the polyamide-imides.
Realize that above-mentioned purpose technical scheme of the present invention is：
A kind of polyamide-imides containing indane structural, its general structure is：
In formula, n=1~8.
Polyamide-imides containing indane structural of the present invention is by 220~380 DEG C of materials obtained after solidifying.
Polyamide-imides preparation method containing indane structural of the present invention, including step：
By 5 (6)-amino -1- (4- aminophenyls) -1,3,3- trimethyl indanes (PIDA) are dissolved in organic solvent to S1, plus
Enter triethylamine as acid binding agent, the solution that will be obtained is placed under gas shield；Gas for protecting is nitrogen, argon gas, helium
In one kind；
S2 adds dissolving Trimellitic Anhydride Chloride (TMAC) in organic solvent, reacts at room temperature.
4- phenylacetylene benzoic anhydrides (PEPA) are added S3 the reaction system obtained by S2, continue to react, and are obtained polyamic acid and (are repeated
Unit number is different, the light yellow clear shape product with certain viscosity).
S4 adds acetic anhydride and triethylamine to be dehydrated 1~8h, pours into a large amount of water, separates out product.
The reaction scheme of the preparation method is：
Further, 5 (6)-amino -1- (4- aminophenyls) -1,3,3- trimethyl indanes (PIDA), trimellitic acid
The molar ratio that acid anhydride acyl chlorides (TMAC), 4- phenylacetylene benzoic anhydrides (PEPA) are added is (n+1):n:2,
Organic solvent described in step S1 and S2 be 1-METHYLPYRROLIDONE (NMP), acetone, dimethylformamide (DMF),
One or more in dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO).PIDA can be obtained using means well known in the art.This
Invention herein proposes a kind of optimal technical scheme for preparing PIDA：
5 (6)-amino -1- (4- aminophenyls) -1,3,3- trimethyl indanes (PIDA) is by 5 (6)-nitro -1-
(4- nitrobenzophenones) -1,3,3- trimethyl indanes (PIDN) are obtained by hydrazine hydrate reduction, and palladium-carbon catalyst is added in reduction reaction.
Preferably, 5 (6)-nitro -1- (4- nitrobenzophenones) -1,3,3- trimethyl indanes (PIDN) are dissolved in solvent, with
The hydrazine hydrate solution of mass content 40~80% carries out reduction reaction, and the solvent is the one kind in ethanol, ethylene glycol, acetone；5
(6)-nitro -1- (4- nitrobenzophenones) -1,3,3- trimethyl indanes (PIDN) and palladium-carbon catalyst, the mass ratio of hydrazine hydrate solution
Example is 5：0.1~0.5：20~30.
The palladium-carbon catalyst is commercially available, and wherein the mass content of Pd is 3~10%.
Another optimal technical scheme of the invention is:5 (6)-nitro -1- (4- nitrobenzophenones) -1,3,3- trimethyls
Indane (PIDN) is that, by 1,3,3- trimethyl -1- phenyl indans are obtained with mixed acid solution reaction, and the mixed acid solution is the concentrated sulfuric acid
With concentrated nitric acid volume ratio 2~3：1 mixed solution.
Wherein, 1,3,3- trimethyl -1- phenyl indans are dissolved in organic solvent, are reacted at 0~5 DEG C with mixed acid solution,
Divide liquid to retain organic layer after completion of the reaction, washed with saturated sodium carbonate solution and/or saturated nacl aqueous solution, depressurize dense after drying
Contracting, adds petroleum ether, and solid is separated out after stirring.Reaction with mixed acid solution can be analyzed by TCL and determine reaction end.Can lead to
Cross and add anhydrous MgSO4Dry the organic phase after washing.
In polyamide-imides preparation method containing indane structural, 5 (6)-amino-1- (4- aminophenyls) in step S1-
The volume ratio that 1,3,3- trimethyl indanes (PIDA) are dissolved in organic solvent is 1:3~6, add triethylamine mass ratio be
1:0.1~3.
The step S2 reacts 1~3h at room temperature；The S3 adds 4- phenylacetylene benzoic anhydrides (PEPA) to continue to react 15 afterwards
~30h.
Wherein, product carries out suction filtration after separating out, then at 100~150 DEG C, is fully dried under 0~0.1MPa of vacuum.
The beneficial effects of the present invention are：
The present invention prepares different polymerization degree by monomer of 6- amino -1- (4- aminophenyls) -1,3,3- trimethyl indanes
Thermosetting polyamide-acid imide, to reduce the bulk density of molecule interchain and interact, increase Chain Flexibility, finally
Synthesize that dissolubility is excellent, the polyamide-imide resin of excellent heat resistance.
Inventor analyzes the knot of (DMA) to polymer with infrared spectrum (FT-IR), thermogravimetric analysis (TGA), dynamic thermomechanical
Structure and performance are characterized, and dissolubility and rheological property to polymer is inquired into.Result shows, contains indane knot
The polyamide-imide resin of structure has excellent dissolubility in organic solvent, and glass transition temperature exceedes after its solidification
330 DEG C, in atmosphere 5% thermal weight loss reach more than 450 DEG C, with good heat resistance.Additionally, PAI resin process windows
Width, lowest melt viscosity is up to 1.3Pas, and processing characteristics is excellent.
Brief description of the drawings
Fig. 1 is the infrared spectrum of TMAC.
Fig. 2 for PIDN hydrogen nuclear magnetic resonance (1H-NMR) figure.
Fig. 3 for PIDA hydrogen nuclear magnetic resonance (1H-NMR) figure.
Fig. 4 is the infrared spectrum of PIDN and PIDA.Fig. 5 is the infrared spectrum of 4~7PAI1-4 of embodiment.
Fig. 6 is the X ray diffracting spectrum of PAI1-4.
Fig. 7 is the viscosity with temperature variation diagram of performed polymer PAI1-4.
Fig. 8 is the hot weightless picture after performed polymer PAI1-4 solidifies 90min at 370 DEG C.
Fig. 9 is dynamic thermal analysis (DMA) curve of PAI-1 and PAI-2.
Specific embodiment
Following examples are used to illustrate the present invention, but are not used in restriction the scope of the present invention.
In embodiment unless otherwise instructed, the means for being used are technological means well known in the art.
The synthesis of the Trimellitic Anhydride Chloride of embodiment 1 (TMAC)
38g (0.2mol) trimellitic anhydride, 100ml thionyl chlorides are added to equipped with condensing unit, device for absorbing tail gas
There-necked flask in, be added dropwise 1~2 and drip DMF, 70 DEG C of heating reflux reaction 7h, reaction solution is changed into yellow clear liquid, and vacuum distillation goes out excess
After thionyl chloride, White crystalline solid is obtained after standing recrystallization, synthetic product is obtained after vacuum drying 12h.m.p：66-68
℃。
The infrared analysis of product is shown in Fig. 1, and the result of sign is as follows：
The synthesis of (6)-nitro -1- of embodiment 25 (4- nitrobenzophenones) -1,3,3- trimethyl indanes (PIDN)
In equipped with churned mechanically there-necked flask, by 1,3,3- trimethyls -1- phenyl indans 18.9g (0.08mol) are molten
In 60ml dichloromethane, as 0-5 DEG C of ice bath in, be slowly added dropwise proportioning the 33ml concentrated sulfuric acids it is molten with the nitration mixture of 14.5ml concentrated nitric acids
Liquid, TCL analyses determine reaction end.Divide liquid to retain organic layer after completion of the reaction, be washed till neutrality with saturated sodium carbonate solution, then use
Saturated nacl aqueous solution is washed, anhydrous MgSO4Dry, be concentrated under reduced pressure to give brown yellow oil liquid, petroleum ether is added, under low temperature
Stirring separates out solid, and absolute ethyl alcohol is recrystallized, and yield is 83%.mp:110-120℃.
Nuclear-magnetism detection collection of illustrative plates is shown in Fig. 2,1H-NMR(CDCl3, TMS, 500MHz), δ:8.25-7.95 (m, 4H, PhH), 7.38-
7.21 (m, 3H, PhH), 2.54-2.46 (dd, 1H, CH2), 2.39-2.32 (d, 1H, CH2), 1.80-1.74 (d, 3H), 1.45-
1.39(d,3H),1.14–1.06(d,3H).
The synthesis of (6)-amino -1- of embodiment 35 (4- aminophenyls) -1,3,3- trimethyl indanes (PIDA)
In the 250ml there-necked flasks for being connected with nitrogen equipped with mechanical agitation, PIDN 6g are dissolved in 120ml absolute ethyl alcohols, risen
Temperature adds 0.3g Pd/C to 80 DEG C, is slowly added dropwise the hydrazine hydrate solutions of 29ml 80%, and 0.4g activated carbons, 1h are added after reaction 7h
Filter while hot afterwards, filtrate decompression is concentrated to give brown oil liquid, be dissolved in 50ml 2mol/L watery hydrochloric acid, stir at room temperature to
It is completely dissolved, is extracted with ethyl acetate, remove organic layer, water layer saturation NaOH solution is adjusted pH to alkalescence, extracted with ethyl acetate
Take, be concentrated under reduced pressure to give brown oil, pour into and Light brown solid is obtained in the water being stirred continuously, yield is 63.7%.mp：
77-98℃。
1H-NMR(CDCl3, TMS, 500MHz), δ:7.13-6.89 (m, 3H), 6.70-6.43 (m, 4H), 4.10-3.40
(s, 4H), 2.38-2.29 (dd, 1H), 2.17-2,08 (dd, 1H) 1.66-1.57 (d, 3H), 1.34-1.26 (s, 3H), 1.10-
0.98(d,3H).Referring to Fig. 3.
The infared spectrum of PIDA and PIDN is shown in Fig. 4.From Fig. 4 infrared spectrums, PIDN by after reduction nitro it is infrared
Absworption peak (1344cm-1With 1519cm-1) disappear, there is the infrared absorption peak of new amino, while Fig. 3 nuclear-magnetisms figure similarly table
Bright reaction reduction generates target product DAPI.
The preparation of the polyamide acyl of embodiment 4-imines performed polymer
The 1.3 6- amino -1- (4- aminophenyls) -1 that will be measured, 3,3- trimethyl indanes (PIDA, diamine monomer) lead to
Stirring and dissolving is crossed in 4 times of volume NMP, (mass ratio for adding triethylamine is 1 to add 5% triethylamine:1) obtained as acid binding agent
Shallow yellow transparent solution, is placed in N2Under protective atmosphere；Respective amount Trimellitic Anhydride Chloride (TMAC) is dissolved in NMP, stirring is equal
Reaction bulb is poured into after even, 2h is reacted under room temperature (about 20 DEG C).Then 4- phenylacetylene benzoic anhydrides (PEPA) are added into reaction system, is continued
Reaction 20h.
In above-mentioned reaction, the molar ratio of PIDA, TMAC, PEPA is 1:2:2, obtain number of repeat unit n=1 with one
Determine the polyamic acid of the light yellow clear shape of viscosity.Labeled as PAI-1.
Then 70 DEG C of dehydration 5h of acetic anhydride and triethylamine are added in system, is poured into a large amount of water, separate out product.Then
Carry out suction filtration, product is fully dried to obtain under 120 DEG C of vacuum (vacuum 0.09MPa) lurid powdered polyamide-
Acid imide oligomer.
Embodiment 5
With embodiment 4 the step of precipitation, desciccate after synthetic reaction and reaction.The difference is that reactant ratio：PIDA、
The molar ratio of TMAC, PEPA is respectively 3:2:2, obtain the light yellow clear shape with certain viscosity of number of repeat unit n=2
Polyamic acid.Labeled as PAI2.
Embodiment 6
With embodiment 4 the step of precipitation, desciccate after synthetic reaction and reaction.The difference is that reactant ratio：PIDA、
The molar ratio of TMAC, PEPA is respectively 4:3:2, obtain the light yellow clear shape with certain viscosity of number of repeat unit n=3
Polyamic acid.Labeled as PAI3.
Embodiment 7
With embodiment 4 the step of precipitation, desciccate after synthetic reaction and reaction.The difference is that reactant ratio：PIDA、
The molar ratio of TMAC, PEPA is respectively 7:6:2, obtain the light yellow clear shape with certain viscosity of number of repeat unit n=6
Polyamic acid.Labeled as PAI6.
Infrared spectrum such as Fig. 5 before and after resin oligomers solidification obtained in embodiment 4~7, as seen from Figure 5
3430cm-1The broad peak at place is the stretching vibration absworption peak of acid amides N-H groups；1778cm-1And 1723cm-1Asia is respectively at wave number
The asymmetric and symmetrical stretching vibration peak of carbonyl (C=O) in amine ring；Imide ring C-N key mappings are in 1377cm-1Feature at wave number
Absworption peak, it can also be observed that acetylene bond is located at 2212cm-1Absworption peak at wave number, shows our prepared expected polyamides
Amine-acid imide performed polymer.
The preparation of the composite of embodiment 8
Resin obtained in weighing embodiment 5~7 is dissolved in acetone and obtains prepreg solution and is uniformly coated to (resin on T3OO carbon fibers
About 40%) mass fraction, obtains prepreg after drying.Mould is put into after prepreg to be tailored into the laying material of sizing, by such as
Lower program is solidified：240 DEG C insulation 2h, risen to after pressurization 370 DEG C solidification 1.5h, after be cooled to room temperature.Obtain 15 × 80mm
Batten.
The dissolubility of test example 1 is tested
Table 1 lists the solubility of the product of embodiment 4~7 in different solvents.
The dissolubility of the polyimide prepolymer of table 1
Note 1：Observed after (25 ± 2 DEG C) placement 20h at room temperature：++：It is completely dissolved；+：Only very small amount is undissolved；
+-：Have more undissolved；-：It is a large amount of undissolved；--：It is almost totally insoluble
The polyamide-imides of present invention synthesis, the distortion contained in PIDA or the structure of non-co-planar, can make
Polyamide-imides strand is distorted deformation, rather than regular direct linkage type structure, while containing amido link etc. in molecule
Flexible structure, so as to reduce the bulk density of molecule interchain, increased strand spacing, reduce the effect of molecule interchain
Power, therefore significantly increase PAI resins dissolubility in organic solvent.
The XRD spectrum of the polymer of test example 2
By can be seen that PAI1-4 is shown as disperse peak wide in Fig. 6, the polyamide-imides for illustrating synthesis is amorphous
Macromolecular structure, belongs to amorphous structure.
The research of the Resin Rheology of test example 3 energy
The rheological curve of performed polymer is tested with rotational rheometer, performed polymer powder is pressed into thickness about 2mm, it is a diameter of
The disk of 25mm, is tested in the range of 200~400 DEG C, and heating rate is 4 DEG C/min.
The viscosity of performed polymer PAI1-4 is as the curve of temperature change is as shown in fig. 7, the viscosity of performed polymer shows
First reduced as temperature is raised, a period of time is then kept at a relatively low viscosity, finally drastically elevated trend.Curve
The specific data of gained are listed in table 2.Understand, with the increase of molecular weight, the minimum melting viscosity increase that performed polymer shows
(PAI1, PAI2, PAI3 change to 7.1 again to 52.4Pa s from 1.2), keep narrowing compared with the land regions of low-viscosity (PAI1,
PAI2, PAI3 change to 60 DEG C from 128 DEG C again to 17 DEG C), process window narrows explanation performed polymer as molecular weight increases, molecule
Chain movement reduced capability；And the viscosity of performed polymer starts drastically elevated temperature spot and is more or less the same, at 320 DEG C or so, this master
If because the identical mass difference of their structures is not too big, and the crosslinking temperature of phenylacetylene group is just attached in the temperature
Closely.
The rheology testing result of the polyimide prepolymer of table 2
Thermogravimetic analysis (TGA) after the resin solidification of test example 4
According to the method for embodiment 8, after four kinds of performed polymers are solidified into 1.5h at 370 DEG C, in air atmosphere with 10
DEG C/min carries out thermal weight loss test in the range of 50~800 DEG C.
Result is as shown in Figure 8.Four kinds of PAI are respectively provided with preferable heat endurance, but are still below polyimides, and this is due to dividing
Backbone portion contains aliphatic structure in son.After solidification resin in air atmosphere 5% weightless temperature (T5%) at 480 DEG C
Left and right, this explanation T5% with crosslink density relation less, and depends primarily on the power of key.But for T10%, number of repeat unit
N=3,6 are better than n=1,2, and this is probably the volatile small molecule that molecular weight high is produced due to when temperature is less high
It is less.
The present invention introduces " circle " shape structure in the molecular structure, reduces the accumulation compactness of strand, is conducive to solvent
The infiltration of molecule, so as to increase the dissolubility of resin.This " circle " shape structure refers to that one of atom is connected on main chain
Ring, can not only increase the steric hindrance of sub-chain motion, so that resin possesses Tg and heat endurance higher, Er Qieyou after its introducing
Excellent processing characteristics.
The thermodynamic performance of the resin of test example 5
The ordinate on right side is dynamic mechanical loss tan Delta in Fig. 9.
By Fig. 9 it can be seen that, the glass of polyamide-imide resin PAI-1 (upper figure) after solidification and PAI-2 (figure below)
Change transition temperature up to more than 330 DEG C, this is due to containing the ring in certain rigid structure and indane in trimellitic anhydride
Shape structure increased the glass transition temperature that both steric hindrances of sub-chain motion effectively improve resin.Simultaneously can from figure
Know that the crosslink density of polymer declines as the increase molecular weight of number of repeat unit increases, turn the vitrifying after resin solidification
Temperature is gradually reduced.
Conclusion：
6- amino -1- (4- aminophenyls) -1,3,3- trimethyl indanes are introduced into polymer and is blocked by phenylacetylene base
The polyamide-imides for obtaining compared with common thermoset polyimide resin, at room temperature in low boilings such as acetone after dehydration
There is excellent dissolubility, its melt viscosity is minimum up to 1.2pas, with process window wider, it is shown that good in solvent
Good processing characteristics.Meanwhile, the glass transition temperature of resin reaches as high as 360 DEG C after solidification, and heat resistance is good.Thus may be used
See, such polyamide-imide resin has the combination property of relative good, there is good application prospect.
Embodiment above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is entered
Row is limited, and on the premise of design spirit of the present invention is not departed from, this area ordinary skill technical staff is to technical side of the invention
The all variations and modifications that case is made, all should fall into the protection domain of claims of the present invention determination.
Claims (10)
1. a kind of polyamide-imides containing indane structural, it is characterised in that its general structure is：
In formula, n=1~8.
2. the polyamide-imides containing indane structural described in claim 1 is by 220~380 DEG C of materials obtained after solidifying.
3. the polyamide-imides preparation method of indane structural is contained described in claim 1, it is characterised in that including step：
By 5 (6)-amino -1- (4- aminophenyls) -1,3,3- trimethyl indanes are dissolved in organic solvent to S1, add triethylamine to make
It is acid binding agent, the solution that will be obtained is placed under gas shield；Gas for protecting is the one kind in nitrogen, argon gas, helium；
S2 adds dissolving Trimellitic Anhydride Chloride in organic solvent, reacts at room temperature；
4- phenylacetylene benzoic anhydrides are added S3 the reaction system obtained by S2, continue to react, and obtain polyamic acid；
S4 adds acetic anhydride and triethylamine to be dehydrated 1~8h, pours into a large amount of water, separates out product.
4. preparation method according to claim 3, it is characterised in that 5 (6)-amino -1- (4- aminophenyls) -1,
3,3- trimethyl indanes:Trimellitic Anhydride Chloride:The molar ratio that 4- phenylacetylene benzoic anhydrides are added is (n+1):n:2；
Organic solvent described in step S1 and S2 is 1-METHYLPYRROLIDONE (NMP), acetone, dimethylformamide (DMF), diformazan
One or more in yl acetamide (DMAc), dimethyl sulfoxide (DMSO).
5. preparation method according to claim 3, it is characterised in that the 6- amino -1- (4- aminophenyls) -1,3,3-
Trimethyl indane is that 3,3- trimethyl indanes are obtained by hydrazine hydrate reduction, reduction reaction by 6- nitros -1- (4- nitrobenzophenones) -1
Middle addition palladium-carbon catalyst.
6. preparation method according to claim 5, it is characterised in that 5 (6)-nitro -1- (4- nitrobenzophenones) -1,3,3-
Trimethyl indane is dissolved in solvent, and reduction reaction is carried out with the hydrazine hydrate solution of mass content 40~80%, and the solvent is
One kind in ethanol, ethylene glycol, acetone；5 (6)-nitro -1- (4- nitrobenzophenones) -1,3,3- trimethyl indanes are catalyzed with palladium carbon
Agent, the ratio of hydrazine hydrate solution are 5g：0.1~0.5g：20~30mL.
7. preparation method according to claim 4, it is characterised in that 5 (6)-nitro -1- (4- nitrobenzophenones) -1,
3,3- trimethyl indanes are that, by 1,3,3- trimethyl -1- phenyl indans are obtained with mixed acid solution reaction, and the mixed acid solution is dense
Sulfuric acid and concentrated nitric acid volume ratio 2~3：The ratio of 1 mixed solution, 1,3,3- trimethyl -1- phenyl indans and mixed acid solution is
0.1mol：30~50mL.
8. preparation method according to claim 7, it is characterised in that 1,3,3- trimethyl -1- phenyl indans are dissolved in organic
In solvent, reacted at 0~5 DEG C with mixed acid solution, divide after completion of the reaction liquid retain organic layer, with saturated sodium carbonate solution and/
Or saturated nacl aqueous solution washing, it is concentrated under reduced pressure after drying, petroleum ether is added, solid is separated out after stirring.
9. preparation method according to claim 3, it is characterised in that in step S1,5 (6)-amino -1- (4- aminobenzenes
Base) -1,3,3- trimethyl indanes be dissolved in organic solvent ratio be 1:1~6, the mass ratio for adding triethylamine is 1:0.1
~3；
The step S2 reacts 1~3h at room temperature；The S3 continues to react 5~60h after adding 4- phenylacetylene benzoic anhydrides.
10. preparation method according to claim 3, it is characterised in that product carries out suction filtration after separating out, then 100~150
DEG C, fully dried under 0~0.1MPa of vacuum.
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| CN111484412A (en) * | 2020-05-26 | 2020-08-04 | 上海华谊树脂有限公司 | Method for synthesizing compound containing indan structure |
| CN111584851A (en) * | 2020-05-26 | 2020-08-25 | 苏州凌威新能源科技有限公司 | Positive electrode composite material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484412A (en) * | 2020-05-26 | 2020-08-04 | 上海华谊树脂有限公司 | Method for synthesizing compound containing indan structure |
| CN111584851A (en) * | 2020-05-26 | 2020-08-25 | 苏州凌威新能源科技有限公司 | Positive electrode composite material and preparation method thereof |
| CN111584851B (en) * | 2020-05-26 | 2021-10-26 | 苏州凌威新能源科技有限公司 | Positive electrode composite material and preparation method thereof |
| CN112409187A (en) * | 2020-11-30 | 2021-02-26 | 山东华夏神舟新材料有限公司 | Synthesis method of 6-amino-1- (4-aminophenyl) -1,3,3-trimethylindane |
| CN112409187B (en) * | 2020-11-30 | 2022-09-02 | 山东华夏神舟新材料有限公司 | Synthesis method of 6-amino-1- (4-aminophenyl) -1,3,3-trimethylindane |
| CN114436848A (en) * | 2021-12-30 | 2022-05-06 | 山东华夏神舟新材料有限公司 | Synthesis method of 5(6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane |
| CN114436848B (en) * | 2021-12-30 | 2024-03-22 | 山东华夏神舟新材料有限公司 | Synthesis method of 5 (6) -amino-1- (4-aminophenyl) -1, 3-trimethylindane |
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