CN104140536B - A kind of hyperbranched modified diphenyl diimide and preparation method thereof - Google Patents
A kind of hyperbranched modified diphenyl diimide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of hyperbranched modified diphenyl diimide and preparation method thereof.This hyperbranched modified diphenyl diimide, is prepared via a method which to obtain: take the trialkoxy silane containing epoxy radicals, trialkoxy silane containing vinyl and dehydrated alcohol, mixing, N240 70 DEG C it are warming up under protection, reflux condensation mode, add distilled water, add sodium hydroxide controlling system pH is 9 11, stirring insulation 25 hours, and decompression distillation obtains the hyperbranched system of mixed hydrolysis；Taking the hyperbranched system of mixed hydrolysis, and add dehydrated alcohol, stirring forms uniform solution, adds the ethanol solution containing diphenyl diimide, reacts 10 72 hours at 40 70 DEG C, reactant liquor decompression distillation, obtains hyperbranched modified diphenyl diimide.The hyperbranched modified diphenyl diimide of the present invention, on the basis of keeping the good photochromic properties of diphenyl diimide, contain substantial amounts of active reactive group simultaneously, for the most modified with apply, the aspect such as the research and development of new material has huge application prospect.
Description
Technical field
The invention belongs to materials synthesis field, relate to a kind of hyperbranched modified diphenyl diimide and preparation method thereof.
Background technology
Diphenyl diimide is a kind of compound with typical chromophores, and along with the change of external condition, structure can occur
As change.Azo chromophore can occur reversible cis-trans isomerism to react under the effect of light, brings the most photic to polymeric material
The characteristics such as dichroism, photic phase transformation and photodecomposition protonatomic mass migration, can be used for photoswitch, optical storage, electrooptic modulator and
Integrated optoelectronics material etc..Due to the using value that it is potential, a large amount of about diphenyl diimide being incorporated into the research of macromolecular chain
Work is carried out in succession, and achieves good experiment and application effect.Azobenzene polymer material is as important optical information function
Material gets the attention.
The chromophore high-molecular optical switching material containing diphenyl diimide reported the earliest is to mix general by diphenyl diimide chromophore compound
The doping body formed in logical macromolecule.But, in doping system, when the doping content of diphenyl diimide is higher, system easily produces
It is separated, reduces the stability of system, diphenyl diimide chromophore is bonded on macromolecule by chemical bond and then can overcome
This shortcoming.In recent years, polymer optical switch material becomes the focus of research.Chinese scholars was launched a large amount of to diphenyl diimide in recent years
The result of research shows, the high molecular multifunctional dough of azobenzene, multifunction remain to be further improved, with satisfied modern work
The industry demand to functional material.Therefore, the modification of diphenyl diimide becomes the important content of diphenyl diimide research and development.
Before the present invention makes, Chinese invention patent (CN101225504B) discloses a kind of 2, and the hydrogenation of 2 '-dichloro is even
The preparation method of pyridine, it is in the presence of beta-schardinger dextrin-, 2-chloronitrobenzene and sodium hydroxide is heated the most in aqueous instead
Should, then obtain product 2,2 '-dichlorohydrazobenzene through simple post processing.
Chinese invention patent (CN1810771A) discloses the synthetic method of a kind of azobenzene compound.It as a means of
The asymmetric hydrogenation diphenyl diimide of matter is raw material, with K3Fe(CN)6/ NaOH is oxidant, with CH2Cl2For solvent, taken off by oxidation
Hydrido has become a series of azobenzene compound.
Chinese invention patent (CN1680288A) discloses a kind of novel end alkyne compound containing diphenyl diimide, its molecule
Containing terminal acetylene groups and azobenzene group in formula.
Chinese invention patent (CN87100778A) discloses a kind of azoic diphenylamine yellow dispering dye, the dyestuff of synthesis
Structure is 4-(2,4-dinitro) benzene imines-4 '-hydroxyazobenzene, this dyestuff has every fastness and the dyeability of excellence
Can, bright in color light, there is the highest dye uptake.
By above-mentioned prior art it will be seen that current diphenyl diimide modification technology can only introduce substantially in chain type macromolecule
Azobenzene group, and it is difficult to use simple and efficient preparation method, keep the original good light of diphenyl diimide basic
On the basis of mutagens color, it is simultaneously introduced substantial amounts of active reactive group.Therefore, develop hyperbranched modified diphenyl diimide and have important
Meaning and using value.
Summary of the invention
It is an object of the invention to the above-mentioned deficiency for prior art, it is provided that a kind of hyperbranched modified diphenyl diimide.
It is a further object of the present invention to provide the preparation method of this hyperbranched modified diphenyl diimide.
The purpose of the present invention can be achieved through the following technical solutions:
(1) taking the trialkoxy silane containing epoxy radicals, trialkoxy silane containing vinyl and dehydrated alcohol, mixing is stirred
Mix, N240-70 DEG C it is warming up under protection, reflux condensation mode, it is added dropwise over distilled water, and add sodium hydroxide to control system pH to be 9-
11, high-speed stirred is incubated 2-5 hour, after reaction terminates, and decompression distillation, obtain the hyperbranched system of mixed hydrolysis, wherein containing epoxy
The trialkoxy silane of base: the trialkoxy silane containing vinyl: dehydrated alcohol: distilled water=(20～30) g:(15～25) g:
(40～60) mL:(4～6) g；
(2) taking the hyperbranched system of mixed hydrolysis, and add dehydrated alcohol, stirring forms uniform solution, is added dropwise over molten
Have at the ethanol solution of diphenyl diimide, 40-70 DEG C and react 10-72 hour, after question response terminates, by reactant liquor decompression distillation,
Obtain hyperbranched modified diphenyl diimide；In the wherein said ethanol solution dissolved with diphenyl diimide, the concentration of diphenyl diimide is
0.025g/mL～0.125g/mL；The hyperbranched system of mixed hydrolysis: dehydrated alcohol: dissolved with the ethanol solution=(8-of diphenyl diimide
14) g:(22-32) mL:(12-20) mL.
Wherein, the described trialkoxy silane containing epoxy radicals is selected from 3-glycydoxy trimethoxy silicon
Alkane, 2-(3,4-7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silane, 2-(3,4-7-oxa-bicyclo[4.1.0 alkyl) ethyl triethoxy silicane
The combination of any one or more in alkane；The described trialkoxy silane containing vinyl is selected from vinyl trimethoxy silicon
In alkane, VTES, vinyl three tert-butoxy silane, 3-methacryloxypropyl trimethoxy silane
The combination of any one or more.
The hyperbranched system of described mixed hydrolysis mainly comprises the trialkoxy silane containing epoxy radicals and three containing vinyl
The product of alkoxy silane mixed hydrolysis.
Described diphenyl diimide appointing in 4-aminoazabenzol, P-aminoazobenzene, symmetrical diphenyl azo carbonyl hydrazides
Anticipate one or more combination.
The preparation method of hyperbranched modified diphenyl diimide of the present invention, comprises the steps of:
(1) taking the trialkoxy silane containing epoxy radicals, trialkoxy silane containing vinyl and dehydrated alcohol, mixing is stirred
Mix, N240-70 DEG C it is warming up under protection, reflux condensation mode, it is added dropwise over distilled water, and add sodium hydroxide to control system pH to be 9-
11, high-speed stirred is incubated 2-5 hour, after reaction terminates, and decompression distillation, obtain the hyperbranched system of mixed hydrolysis, wherein containing epoxy
The trialkoxy silane of base: the trialkoxy silane containing vinyl: dehydrated alcohol: distilled water=(20～30) g:(15～25) g:
(40～60) mL:(4～6) g；
(2) taking the hyperbranched system of mixed hydrolysis, and add dehydrated alcohol, stirring forms uniform solution, is added dropwise over molten
Have at the ethanol solution of diphenyl diimide, 40-70 DEG C and react 10-72 hour, after question response terminates, by reactant liquor decompression distillation,
Obtain hyperbranched modified diphenyl diimide；In the wherein said ethanol solution dissolved with diphenyl diimide, the concentration of diphenyl diimide is
0.025g/mL～0.125g/mL；The hyperbranched system of mixed hydrolysis: dehydrated alcohol: dissolved with the ethanol solution=(8-of diphenyl diimide
14) g:(22-32) mL:(12-20) mL.
Wherein, the described trialkoxy silane containing epoxy radicals is selected from 3-glycydoxy trimethoxy silicon
Alkane, 2-(3,4-7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silane, 2-(3,4-7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane
In the combination of any one or more.
The described trialkoxy silane containing vinyl is selected from vinyltrimethoxy silane, vinyl triethoxyl silicon
Any one or more in alkane, vinyl three tert-butoxy silane, 3-methacryloxypropyl trimethoxy silane
Combination.
The hyperbranched system of described mixed hydrolysis mainly comprises the trialkoxy silane containing epoxy radicals and three containing vinyl
The product of alkoxy silane mixed hydrolysis.
Described diphenyl diimide is in 4-aminoazabenzol, p-diaminoazobenzene, symmetrical diphenyl azo carbonyl hydrazides
The combination of any one or more.
The inventive method stirs preferred magnetic agitation；The preferred rotating speed of described high-speed stirred is at 100～200 revs/min
Magnetic agitation.
Reaction in preparation method of the present invention can be carried out in there-necked flask, more also may be used in amplification test or industrialized production
Select corresponding reactor.
Hyperbranched modified diphenyl diimide prepared by the present invention, can be used for preparing there is the material of photochromism, erasable rewrites
Type optical storage media, improve macromolecular material orientation stability and mechanical property, be simultaneously introduced epoxy radicals, vinyl isoreactivity anti-
Answer group, optimize modification for it further and lay the foundation.
Compared with prior art, provide the benefit that acquired by the present invention:
1, the diphenyl diimide of anamorphic zone dissaving structure of the present invention, utilizes the hydrolysis of siloxanes that multiple diphenyl diimide is divided
Son is connected by branched structure.
2, mixed hydrolysis is hyperbranched existence gives modified diphenyl diimide to be had in substantial amounts of active reactive group quantity and doubles,
Have huge for the further modified of diphenyl diimide and application, the research and development of new material, modification and high performance, the aspect such as multiple functionalized
Big application prospect.
3, the preparation method of the hyperbranched modified diphenyl diimide that the present invention provides has that operating procedure is simple, raw material sources is rich
Feature rich, that the suitability is wide.
Accompanying drawing explanation
Fig. 1 is the diphenyl diimide of the embodiment of the present invention 1 offer, the hyperbranched system of mixed hydrolysis, hyperbranched modified diphenyl diimide
Infrared spectrum.
Fig. 2 is diphenyl diimide in the embodiment of the present invention 1, the ultra-violet absorption spectrum of hyperbranched modified diphenyl diimide.
Fig. 3 is diphenyl diimide in the embodiment of the present invention 1, the hyperbranched system of mixed hydrolysis, hyperbranched modified diphenyl diimide1H-
NMR。
Fig. 4 is the hyperbranched system of mixed hydrolysis in the embodiment of the present invention 1, hyperbranched modified diphenyl diimide29Si-NMR。
Fig. 5 is the structural representation of the hyperbranched system of mixed hydrolysis in the embodiment of the present invention 1.
Fig. 6 is the structural representation of hyperbranched modified diphenyl diimide in the embodiment of the present invention 1.
Fig. 7 is the infrared of hyperbranched modified diphenyl diimide and acrylate copolymer emulsion and comparative example in the embodiment of the present invention 1
Collection of illustrative plates.
Fig. 8 is hyperbranched modified diphenyl diimide and the structural representation of acrylate copolymer in the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, technical solution of the present invention will be further described.
Embodiment 1
1, in there-necked flask, 27.5g3-glycydoxy trimethoxy silane, 23.6g3-methyl-prop are added
Alkene acryloxypropylethoxysilane trimethoxy silane, 55mL dehydrated alcohol, magnetic agitation, N265 DEG C it are warming up to, at such a temperature under protection
Reflux condensation mode.Being added dropwise over 5.82g distilled water, and add a certain amount of sodium hydroxide to control system pH to be 11, rotating speed is 150
Rev/min stirring insulation 4.5 hours.After reaction terminates, at 80 DEG C, decompression distillation, obtains the hyperbranched system of mixed hydrolysis, structure
Formula is shown in Fig. 5, wherein
2, weigh the hyperbranched system of 13.5g mixed hydrolysis to add in there-necked flask, and add the dehydrated alcohol of 31mL, magnetic force
Stirring forms uniform solution, is added dropwise over the 18mL ethanol solution dissolved with 1.4g4-aminoazabenzol, reacts at 60 DEG C
68 hours.After question response terminates, by decompression distillation at reactant liquor 60 DEG C, obtaining hyperbranched modified diphenyl diimide, structural formula is shown in Fig. 6,
Wherein
3, hyperbranched modified diphenyl diimide reacts with acrylic ester copolymer
Using pre-emulsification technology, emulsion polymerization is equipped with condensing tube, mechanical agitator, the 500ml tetra-of constant pressure funnel
Carrying out in mouth bottle, nitrogen is protected, and bath temperature controls at 80 DEG C.Take 7.1g methyl methacrylate, 20.5g butyl acrylate,
0.6g sodium lauryl sulphate, 0.6g alkylphenol polyoxyethylene (OP-10), the hyperbranched modified diphenyl diimide of 0.3g, 60mL go from
Sub-water, pre-emulsification in constant temperature blender with magnetic force, weigh 0.12g Ammonium persulfate., be made into the aqueous solution of 0.012g/mL.Pre-emulsification
After half an hour, take pre-emulsion and ammonium persulfate solution each 1/4 adds four-hole bottle, react under stirring.Residue pre-emulsion
High speed shear is disperseed 3 minutes, and rotating speed is 6000r/min.When in four-hole bottle, blue light occurs in solution, continuing reaction 15min, dropping is surplus
Remaining pre-emulsion and ammonium persulfate solution, drip off for about 1 hour, and reactant liquor is incubated 5 hours, finally takes out four-hole bottle, is down to
Room temperature, filters discharging, obtains hyperbranched modified diphenyl diimide and acrylate copolymer emulsion, and structural formula is shown in Fig. 8, wherein
Take a certain amount of emulsion and put in glass apparatus film forming under room temperature.
Comparative example
Using pre-emulsification technology, emulsion polymerization is equipped with condensing tube, mechanical agitator, the 500ml tetra-of constant pressure funnel
Carrying out in mouth bottle, nitrogen is protected, and bath temperature controls at 80 DEG C.Take 7.1g methyl methacrylate, 20.5g butyl acrylate,
0.6g sodium lauryl sulphate, 0.6g alkylphenol polyoxyethylene (OP-10), 60mL deionized water, in constant temperature blender with magnetic force
Upper pre-emulsification, with weighing 0.12g Ammonium persulfate., wiring solution-forming.After pre-emulsification half an hour, take pre-emulsion and ammonium persulfate solution
Each 1/4 adds four-hole bottle, reacts under stirring.Residue pre-emulsion high speed shear is disperseed 3 minutes, and rotating speed is 6000r/min.
When in four-hole bottle, blue light occurs in solution, continue reaction 15min, drip remaining monomer and ammonium persulfate solution, within about 1 hour, drip
Complete, reactant liquor is incubated 5 hours, finally takes out four-hole bottle, is down to room temperature, filters discharging.Take a certain amount of emulsion and put into glass apparatus
Film forming under middle room temperature.
Seeing accompanying drawing 1, it is the diphenyl diimide of the embodiment of the present invention 1 offer, the hyperbranched system of mixed hydrolysis, hyperbranched modification
The infrared spectrum of diphenyl diimide；In diphenyl diimide, 1501cm-1It is the absworption peak of phenyl ring, 3470cm-1And 3380cm-1Bimodal be primary
The absworption peak of amino；In the hyperbranched system of mixed hydrolysis, 2800-2900cm-1The absworption peak at place is 3-glycidyl ether epoxide
-CH in propyl trimethoxy silicane and 3-methacryloxypropyl trimethoxy silane2-and-CH3Characteristic peak,
1040-1120cm-1Locating relatively broad peak is Si-O-Si characteristic peak, 1720cm-1The characteristic peak at place is carbonyl characteristic peak, 950cm-1Place
Characteristic peak is epoxy characteristic peak, and above phenomenon shows that the hyperbranched system of mixed hydrolysis successfully synthesizes；Modified diphenyl diimide has azo
The characteristic peak of benzene, the newest characteristic peak, show that hyperbranched modified diphenyl diimide successfully synthesizes.
Seeing accompanying drawing 2, it is diphenyl diimide in the embodiment of the present invention 1, the ultra-violet absorption spectrum of hyperbranched modified diphenyl diimide.By
Figure understands, and the ultraviolet spectra of diphenyl diimide has two absorption bands, first absorption band to be positioned at 248nm, and second absorption band is positioned at
384nm；Compared with diphenyl diimide, the absorbing wavelength of the absorption band that two intensity of modified diphenyl diimide are higher be respectively 251nm and
390nm.Absorption band red shift shows that hyperbranched modified diphenyl diimide successfully synthesizes.
Seeing accompanying drawing 3, it is diphenyl diimide in the embodiment of the present invention 1, the hyperbranched system of mixed hydrolysis, hyperbranched modified azo
Benzene1H-NMR(nuclear magnetic resonance, NMR).As seen from the figure, in diphenyl diimide, chemical shift is benzene ring hydrogen at 7.4-7.8ppm,
It is the hydrogen on amino at 6.1ppm, is the hydrogen of ortho position carbon on the phenyl ring being connected with amino at 6.7ppm.Hyperbranched at mixed hydrolysis
In system, it is the hydrogen on the α carbon being connected with Si at 0.6ppm；It is the hydrogen on the C being connected with N after open loop and 3-methyl at 1.1ppm
Methyl hydrogen in acryloxypropyl trimethoxy silane；It is the hydrogen on the β carbon being connected with Si at 1.6ppm；At 1.8ppm it is
The hydrogen in double bond being connected with carbonyl；It is the hydrogen being connected with O at 3.1-3.8ppm；It is to be connected with hydroxyl after open loop at 4.3ppm
Hydrogen on C；It is the hydrogen on the hydroxyl generated after open loop at 5.0ppm；5.6, at 6.0ppm it is 3-methacryloxypropyl three
Hydrogen on remaining double bond in methoxy silane.Hyperbranched modified diphenyl diimide remains hydrogen signal both substantially, shows idol
Pyridine has been successfully connected in the hyperbranched system of mixed hydrolysis.
Seeing accompanying drawing 4, it is the hyperbranched system of mixed hydrolysis in the embodiment of the present invention 1, hyperbranched modified diphenyl diimide29Si-NMR spectrogram.There it can be seen that in the hyperbranched system of mixed hydrolysis chemical displacement value be respectively-60.91ppm ,-
52.32ppm and-44.32ppm place occur in that three peaks, and they represent branched chain link, linear chain link and end-blocking chain link respectively.And
Hyperbranched modified diphenyl diimide remains above signal, shows that, by ring-opening reaction, diphenyl diimide has been successfully connected to dissaving structure
On.
According to data above it can be seen that compared with diphenyl diimide, hyperbranched modified diphenyl diimide prepared by the present invention has ball
The feature of shape structure, has multiple labile functional groups simultaneously, has a extensive future.
Seeing accompanying drawing 7, it is comparative example and the infrared spectrum of embodiment 1 emulsion polymerization products therefrom.With do not add diphenyl diimide
The spectrogram of emulsion polymeric product compare, in embodiment 1, spectrogram is at 3400cm-1There is absworption peak in place, shows that diphenyl diimide is the most successful
Introduce in polymer.
Compared with the ultraviolet-visible light spectrogram of the emulsion polymeric product not adding diphenyl diimide, the spectrogram in embodiment 1 occurs bright
Aobvious change, shows that the UV-Visible absorption of embodiment 1 products therefrom occurs obvious red shift, and its reason is copolymer emulsion
In diphenyl diimide sensual pleasure group 386nm at generation π-π energy level electron transition, it is seen then that the photochromism that copolymer emulsion has
Energy.
Embodiment 2
1, in there-necked flask, 20g2-(3,4-7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silane, 15g vinyl three are added
Methoxy silane, 40mL dehydrated alcohol, magnetic agitation, N240 DEG C it are warming up to, reflux condensation mode at such a temperature under protection.Dropwise add
Entering 4g distilled water, and add a certain amount of sodium hydroxide to control system pH to be 9, rotating speed is 200 revs/min of stirring insulations 2 hours.
After reaction terminates, at 80 DEG C, decompression distillation, obtains the hyperbranched system of mixed hydrolysis, and structural formula is shown in Fig. 5, wherein
2, weighing the hyperbranched system of 8g mixed hydrolysis to add in there-necked flask, and add the dehydrated alcohol of 22mL, magnetic force stirs
Mix the uniform solution of formation, be added dropwise over the 12mL ethanol solution dissolved with 0.5g p-diaminoazobenzene, react 72 at 40 DEG C little
Time.After question response terminates, by decompression distillation at reactant liquor 65 DEG C, obtaining hyperbranched modified diphenyl diimide, structural formula is shown in Fig. 6, wherein
Embodiment 3
1, in there-necked flask, 30g3-glycydoxy trimethoxy silane, 25g3-methacryl are added
Epoxide propyl trimethoxy silicane, 60mL dehydrated alcohol, magnetic agitation, N2It is warming up to 70 DEG C under protection, refluxes at such a temperature
Condensation.Being added dropwise over 6g distilled water, and add a certain amount of sodium hydroxide to control system pH to be 11, rotating speed is 100 revs/min and stirs
Mix insulation 5 hours.After reaction terminates, at 70 DEG C, decompression distillation, obtains the hyperbranched system of mixed hydrolysis, and structural formula is shown in Fig. 5, wherein
2, weighing the hyperbranched system of 14g mixed hydrolysis to add in there-necked flask, and add the dehydrated alcohol of 32mL, magnetic force stirs
Mix the uniform solution of formation, be added dropwise over the 20mL ethanol solution dissolved with 1.5g symmetry diphenyl azo carbonyl hydrazides, anti-at 70 DEG C
Answer 10 hours.After question response terminates, by decompression distillation at reactant liquor 60 DEG C, obtaining hyperbranched modified diphenyl diimide, structural formula is shown in figure
6, wherein
Embodiment 4
1, in there-necked flask, 23.6g3-glycydoxy trimethoxy silane, 16.9g vinyl three are added
Ethoxysilane, 45mL dehydrated alcohol, magnetic agitation, N260 DEG C it are warming up to, reflux condensation mode at such a temperature under protection.Dropwise add
Entering 4.21g distilled water, and add a certain amount of sodium hydroxide to control system pH to be 10, rotating speed is 200 revs/min of stirring insulations 4
Hour.After reaction terminates, at 85 DEG C, decompression distillation, obtains the hyperbranched system of mixed hydrolysis, and structural formula is shown in Fig. 5, wherein
2, weighing the hyperbranched system of 10g mixed hydrolysis to add in there-necked flask, and add the dehydrated alcohol of 25mL, magnetic force stirs
Mix the uniform solution of formation, be added dropwise over the 15mL ethanol solution dissolved with 0.72g4-aminoazabenzol, react 48 at 55 DEG C little
Time.After question response terminates, distillation that reactant liquor is reduced pressure at 65 DEG C, obtain hyperbranched modified diphenyl diimide, structural formula is shown in Fig. 6, its
In
Embodiment 5
1, in there-necked flask, 28.8g2-(3,4-7-oxa-bicyclo[4.1.0 alkyl) ethyl triethoxysilane, 20g ethylene are added
Base tri-tert silane, 50mL dehydrated alcohol, magnetic agitation, N260 DEG C it are warming up to, reflux condensation mode at such a temperature under protection.By
Being added dropwise to 4.32g distilled water, and add a certain amount of sodium hydroxide to control system pH to be 10, rotating speed is that 150 revs/min of stirrings are protected
Temperature 3 hours.After reaction terminates, at 70 DEG C, decompression distillation, obtains the hyperbranched system of mixed hydrolysis, and structural formula is shown in Fig. 5, wherein
2, weighing the hyperbranched system of 10g mixed hydrolysis to add in there-necked flask, and add the dehydrated alcohol of 30mL, magnetic force stirs
Mix the uniform solution of formation, be added dropwise over the 20mL ethanol solution dissolved with 1g4 aminoazabenzol, react 24 hours at 65 DEG C.Treat
After reaction terminates, by decompression distillation at reactant liquor 70 DEG C, obtaining hyperbranched modified diphenyl diimide, structural formula is shown in Fig. 6, wherein
Claims (8)
1. a hyperbranched modified diphenyl diimide, it is characterised in that be prepared via a method which to obtain:
(1) trialkoxy silane containing epoxy radicals, trialkoxy silane containing vinyl and dehydrated alcohol, mix and blend, N are taken2Protect
Protect down and be warming up to 40-70 DEG C, reflux condensation mode, it is added dropwise over distilled water, and add sodium hydroxide to control system pH to be 9-11, at a high speed
Stirring insulation 2-5 hour, after reaction terminates, decompression distillation, obtain the hyperbranched system of mixed hydrolysis, wherein three alkane containing epoxy radicals
TMOS: the trialkoxy silane containing vinyl: dehydrated alcohol: distilled water=(20 ~ 30) g:(15 ~ 25) g:(40 ~ 60) mL:
(4 ~ 6) g；
(2) taking the hyperbranched system of mixed hydrolysis, and add dehydrated alcohol, stirring forms uniform solution, is added dropwise over dissolved with idol
The ethanol solution of pyridine, reacts 10-72 hour at 40-70 DEG C, after question response terminates, by reactant liquor decompression distillation, obtains
Hyperbranched modified diphenyl diimide；In the wherein said ethanol solution dissolved with diphenyl diimide the concentration of diphenyl diimide be 0.025g/ml ~
0.125 g/ml；The hyperbranched system of mixed hydrolysis: dehydrated alcohol: dissolved with ethanol solution=(8-14) g:(22-of diphenyl diimide
32) mL:(12-20) mL.
Hyperbranched modified diphenyl diimide the most according to claim 1, it is characterised in that the described tri-alkoxy containing epoxy radicals
Silane is selected from 3-glycydoxy trimethoxy silane, 2-(3,4-7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silicon
The combination of any one or more in alkane, 2-(3,4-7-oxa-bicyclo[4.1.0 alkyl) ethyl triethoxysilane；Described containing second
The trialkoxy silane of thiazolinyl is selected from vinyltrimethoxy silane, VTES, vinyl tri-tert silicon
The combination of any one or more in alkane, 3-methacryloxypropyl trimethoxy silane.
Hyperbranched modified diphenyl diimide the most according to claim 1, it is characterised in that the hyperbranched system of described mixed hydrolysis
Mainly comprise the product of the trialkoxy silane containing epoxy radicals and the trialkoxy silane mixed hydrolysis containing vinyl.
Hyperbranched modified diphenyl diimide the most according to claim 1, it is characterised in that described diphenyl diimide is even selected from 4-amino
The combination of any one or more in pyridine, symmetrical diphenyl azo carbonyl hydrazides.
5. the preparation method of the hyperbranched modified diphenyl diimide described in claim 1, it is characterised in that comprise the steps of: (1) takes
Trialkoxy silane containing epoxy radicals, the trialkoxy silane containing vinyl and dehydrated alcohol, mix and blend, N2Protection is lower to heat up
To 40-70 DEG C, reflux condensation mode, it is added dropwise over distilled water, and add sodium hydroxide to control system pH to be 9-11, high-speed stirred is incubated
2-5 hour, after reaction terminates, decompression distillation, obtain the hyperbranched system of mixed hydrolysis, wherein the tri-alkoxy silicon containing epoxy radicals
Alkane: the trialkoxy silane containing vinyl: dehydrated alcohol: distilled water=(20 ~ 30) g:(15 ~ 25) g:(40 ~ 60) mL:(4 ~ 6) g；
(2) taking the hyperbranched system of mixed hydrolysis, and add dehydrated alcohol, stirring forms uniform solution, is added dropwise over dissolved with idol
The ethanol solution of pyridine, reacts 10-72 hour at 40-70 DEG C, after question response terminates, by reactant liquor decompression distillation, obtains
Hyperbranched modified diphenyl diimide；In the wherein said ethanol solution dissolved with diphenyl diimide, the concentration of diphenyl diimide is 0.025g/mL
~0.125 g/mL；The hyperbranched system of mixed hydrolysis: dehydrated alcohol: dissolved with ethanol solution=(8-14) g:(22-of diphenyl diimide
32) mL:(12-20) mL.
The preparation method of hyperbranched modified diphenyl diimide the most according to claim 5, it is characterised in that described containing epoxy radicals
Trialkoxy silane selected from 3-glycydoxy trimethoxy silane, 2-(3,4-7-oxa-bicyclo[4.1.0 base) ethyl three
The combination of any one or more in methoxy silane, 2-(3,4-7-oxa-bicyclo[4.1.0 alkyl) ethyl triethoxysilane；Institute
The trialkoxy silane containing vinyl stated is selected from vinyltrimethoxy silane, VTES, vinyl three
The combination of any one or more in tert-butoxy silane, 3-methacryloxypropyl trimethoxy silane.
The preparation method of hyperbranched modified diphenyl diimide the most according to claim 5, it is characterised in that described mixed hydrolysis
Hyperbranched system mainly comprises the product of the trialkoxy silane containing epoxy radicals and the trialkoxy silane mixed hydrolysis containing vinyl
Thing.
The preparation method of hyperbranched modified diphenyl diimide the most according to claim 5, it is characterised in that described diphenyl diimide choosing
The combination of any one or more in 4-aminoazabenzol, symmetrical diphenyl azo carbonyl hydrazides.
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