CN106397766A - Preparation and application of 1,8-diamino-p-methane hyperbranched polyether amine and its hybrid hydrogel - Google Patents
Preparation and application of 1,8-diamino-p-methane hyperbranched polyether amine and its hybrid hydrogel Download PDFInfo
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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- C08J2479/02—Polyamines
Abstract
The invention discloses preparation and application of 1,8-diamino-p-methane hyperbranched polyether amine and its hybrid hydrogel; the hyperbranched polyether amine is prepared from 1,8-diamino-p-methane via one-pot method; terminal amino groups of the 1,8-diamino-p-methane hyperbranched polyether amine are functionally modified with double bonds introduced, the double bonds and 3-mercaptopropyltrimethoxysilane are then subjected to 'click chemical' reaction to introduce organic silicon groups, and the 1,8-diamino-p-methane hyperbranched polyether amine hybrid hydrogel is prepared by crosslinking of silicon-oxygen bonds in water. The A2B4 type hyperbranched polyether amine is prepared through one-pot method, the method is simple, expensive equipment and complex operations are not required, the product contains mass hydroxyl radicals, facilitating further functional modification and application; the prepared hydrogel is applicable to the adsorption of water-soluble dyes and modification of polyacrylamide hydrogels; reaction conditions are simple, operating is simple, additional catalysts are not required, and post-treatment is simple.
Description
Technical field：
Present invention design is a kind of hyper-branched polymer polymer and the method synthesizing this polymer, specifically 1,8-
Synthetic method to Meng's diamidogen hyperbranched polyetheramine and 1,8- to the preparation of Meng's diamidogen hyperbranched polyetheramine hybridized hydrogel with should
With
Background technology
1,8- is the alicyclic binary primary amine with tetra functional to Meng's diamidogen, is a kind of important monoterpenes compound pinane
The derivant of alkene.1,8- is connected on two tertiary carbon atoms to two amidos of Meng's diamidogen, and structure is as follows.
Due to its special six-membered ring structure, its reactivity is slightly below the binary primary amine of linear chain structure, therefore its reaction is easily
In control.1,8- to Meng's diamidogen 20th century mid-term synthesis and industrialized production, Feng Zhi bravely wait (Feng Zhiyong, Zhao Zhendong. Oleum Terebinthinae
The property of derivant (Lv Meng) diamidogen and its applied research progress [J]. chemistry of forest product and industry, 2005,25 (S1):168-
170.) review 1,8- to property and the application of Meng's diamidogen it can be seen that its main purposes is the solidification as epoxy resin
Agent, separately has the raw material that small part purposes is as synthesis antibacterial, auxiliary agent, cross-linking agent etc..
In recent years, developing rapidly with functional polymer and nanometer new material, 1,8- to Meng's diamidogen in new material
Application has obtained expanding further.(Wei K, the Zhu G, Tang Y, et al.Shape-memory effects of such as Wei
a hydro-epoxy resin system[J].Journal of Polymer Research,2013,20(5):1-7.) will
1,8- is used for the preparation of shape-memory material to Meng's diamidogen, reacts a kind of memory material obtaining with AL-3040 and PPGDGE, its
Shape recovery ratio is close to 100%.
(Jiang X, the Wang R, Ren Y, et al.Responsive polymer nanoparticles such as Jiang Xuesong
formed by poly(ether amine)containing coumarin units and a poly(ethylene
oxide)short chain[J].Langmuir,2009,25(17):9629-9632.) using two degrees of functionality Piperazine anhydrous with
Coumarin diglycidyl ether reacts, and has obtained the multiple sensitivity polyetheramine nanoparticle of linear structure, can be to light, temperature
Degree, the change of pH value respond.(Ren Y, the Jiang X, Liu R, et al.Multistimuli such as Ren Yanrong
responsive grafted poly(ether tert-amine)(gPEA):Synthesis,characterization
and controlled morphology in aqueous solution[J].Journal of Polymer Science
Part A:Polymer Chemistry,2009,47(23):6353-6361.) Piperazine anhydrous, Jeffamine L100 is then used to gather
Ethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether reaction have obtained graft polyether amine.
Dissaving polymer is a kind of novel high molecular polymer developed in recent years, and it is by continuously hyperbranched
Repetitives are constituted.Compared with linear macromolecule, there is good dissolubility, relatively low viscosity, extremely low molecular entanglement journey
Degree, molecule internal cavity and a large amount of functional end-group, the features such as higher chemical reactivity；Compared with amine dendrimer,
The building-up process of dissaving polymer is simple, such as can pass through AB2Type monomer or " A2+B3" (A and B is the sense of mutually reactive
Group) monomer is to one-step synthesis method (Gao C, Yan D.Hyperbranched polymers:from synthesis to
applications[J].Progress in Polymer Science,2004,29(3):183-275.), course of reaction letter
List, it is not necessary to the purge process of complexity, this reduces the preparation cost of material, makes dissaving polymer in coating, rheology helps
Agent, biomaterial, photoelectric material numerous areas all show potential using value.
A kind of hyperbranched polyetheramine nanometer with multiple sensitivity can be obtained by polyamine and epoxy-capped polyether reactant
Particle.(Yu B, the Jiang X, Yin G, et al.Multistimuli-responsive hyperbranched such as Yu Bing
poly(ether amine)s[J].Journal of Polymer Science Part A:Polymer Chemistry,
2010,48(19):4252-4261.) use three-functionality-degree NEED and polyethyleneglycol diglycidylether and polypropylene glycol
Diglycidyl ether reaction has obtained hyperbranched polyetheramine, and the change of light, temperature, pH value can be responded.Hyperbranched poly
Substantial amounts of functional end-group, such as amido is contained, hydroxyl etc. is it is easy to carry out functional modification to it in ether amines.As precious in Lee (Li B,
Jiang X,Yin J.Multi-responsive microgel of hyperbranched poly(ether amine)
(hPEA-mGel)for the selective adsorption and separation of hydrophilic
fluorescein dyes[J].Journal of Materials Chemistry,2012,22(34):17976-17983.)
React the over-expense obtaining Deng to NEED with polyethyleneglycol diglycidylether and polypropylene glycol diglycidyl ether
The terminal amido changing polyetheramine is modified, and introduces four (3- mercaptopropionic acid) tetramethylolmethane ester group by two-step reaction, obtains
Intelligent microgel based on polyethers amine structure.Hu Lihua (Hu Lihua, Wei Qin, Wang Xiaodong, etc. one kind is used for heavy metal and dyestuff
The hyperbranched polyetheramine of absorption is grafted preparation and the application of GO adsorbent:ZL201510011093.2 [P] .2015.06.17) etc.
Disclose a kind of method is simple for heavy metal and dye adsorption hyperbranched polyetheramine is grafted the preparation method of GO adsorbent,
Adsorbance is high and can reuse.
In document report with regard to hyperbranched polyetheramine functional modification, amine monomers used were N- ethyl second two in the past
Amine, there is not yet 1,8- to the hyperbranched polyetheramine of Meng's diamidogen preparation and its report of functional modification aspect.The present invention is with 1,8-
For raw material, hyperbranched polyetheramine is prepared to Meng's diamidogen and its terminal amido carried out with functional modification introduces double bond, then pass through
Double bond and (3- mercaptopropyi) trimethoxy silane click chemistry under ultraviolet light react access organosilicon radical, logical in water
The crosslinking crossing siliconoxygen bond is obtained 1,8- to Meng's diamidogen hyperbranched polyetheramine hybridized hydrogel.
Content of the invention
The invention discloses a kind of preparation and application to Meng's diamidogen hyperbranched polyetheramine and its hybridized hydrogel for 1, the 8-, lead to
Cross one kettle way and obtain A2B4Type hyperbranched polyetheramine, then to the terminal amido of Meng's diamidogen hyperbranched polyetheramine, function is carried out to 1,8-
Change modified introduce double bond, then double bond and 3-mercaptopropyi trimethoxy silane carried out " click chemistry " under ultraviolet light react drawing
Enter organosilicon radical, finally in water, 1,8- is obtained to Meng's diamidogen hyperbranched polyetheramine hydridization water-setting by the crosslinking of siliconoxygen bond
Glue.Reaction condition is gentle, simple to operate it is not necessary to extra catalyst, post processing is simple.
The technical scheme is that：A kind of 1,8- Meng's alkane diamidogen hyperbranched polyetheramine, chemical constitution is：
The method to Meng's diamidogen hyperbranched polyetheramine for 1 described, the 8- of synthesis, poly- to Meng's diamidogen and bis-epoxy end-blocking with 1,8-
Ether is raw material, carries out as follows：1,8- is dissolved in organic solvent to Meng's diamidogen, under nitrogen protection, drips in reactant liquor
Plus bis-epoxy end capped polyether solution is reacted, carry out vacuum distillation after reaction fully and remove organic solvent, sink through sedimentation solvent
Fall, the white paste obtaining, vacuum dried, as hyperbranched polyetheramine.
Described epoxy-capped polyethers includes polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, bisphenol-A
One of diglycidyl ether or the mixture of any two compositions.
1,8- is 1: 2-4 to the ratio of Meng's diamidogen and the amount of the material of bis-epoxy end capped polyether, and reaction temperature is 50-120 DEG C.
Described organic solvent include ethanol, propanol, 1,4- dioxane, oxolane, in N,N-dimethylformamide
Any one；Described sedimentation solvent includes petroleum ether, normal hexane, any one in ether.
1,8- using the organosilicon grafting of described 1,8- Meng's alkane diamidogen hyperbranched polyetheramine preparation overspends to Meng's diamidogen
Change polyetheramine hydrogel, 1,8- Meng's diamidogen hyperbranched polyetheramine is reacted with allyl glycidyl ether obtain double bond block 1,
8- is to Meng's diamidogen hyperbranched polyetheramine；The 1,8- of double bond end-blocking exists in ultraviolet initiator to Meng's diamidogen hyperbranched polyetheramine again
Lower and (3- mercaptopropyi) trimethoxy silane reaction obtains the 1,8- of trimethoxy silane grafting to Meng's diamidogen hyperbranched polyether
Amine, then hydrolytic crosslinking obtains hyperbranched polyetheramine hydrogel in ultra-pure water.
To Meng's diamidogen hyperbranched polyetheramine hydrogel, step is 1,8- of the described organosilicon grafting of preparation：(1) double bond envelope
The preparation of 1,8- Meng's alkane diamidogen hyperbranched polyetheramine at end：1,8- is dissolved in organic solvent to Meng's diamidogen hyperbranched polyetheramine,
Under nitrogen protective condition, react with allyl glycidyl ether, vacuum distillation removes organic solvent, through petroleum ether sedimentation, obtain
White paste be vacuum dried again, thus obtain double bond end-blocking 1,8- to Meng's diamidogen hyperbranched polyetheramine；
(2) preparation of 1,8- Meng's alkane diamidogen hyperbranched polyetheramine hydrogel of organosilicon grafting：The 1,8- that double bond is blocked
Meng's diamidogen hyperbranched polyetheramine is dissolved in organic solvent, adds ultraviolet initiator and (3- mercaptopropyi) trimethoxy silicon
Alkane, reacts under uviol lamp, and vacuum distillation removes organic solvent, obtains white paste through petroleum ether sedimentation and is trimethoxy
To Meng's diamidogen hyperbranched polyetheramine, 1, the 8- that trimethoxy silane is grafted is to Meng's diamidogen hyperbranched polyether for 1,8- of Silane Grafted
Amine is dissolved in ultra-pure water, and hydrolytic crosslinking obtains hyperbranched polyetheramine hybridized hydrogel.
1,8- is 0.5-10: 1 to the mass ratio of Meng's diamidogen hyperbranched polyetheramine and allyl glycidyl ether, and double bond is sealed
The 1,8- at end is 0.5-10: 1 to the mass ratio of Meng's diamidogen hyperbranched polyetheramine and (3- mercaptopropyi) trimethoxy silane.
The ultraviolet initiator being adopted is I-907, any one in 1173,184.
1,8- Meng's alkane diamidogen hyperbranched polyetheramine hydrogel of described organosilicon grafting is in absorption organic dyestuff and modification
Application in polyacrylamide hydrophilic gel.
Beneficial effect:
1st, the present invention adopts the alicyclic binary primary amine 1 of tetra functional, and 8- synthesizes A to Meng's diamidogen as amine monomers2B4Type
Hyperbranched polyetheramine, not only can improve the degree of branching of polyetheramine, and the great amount of hydroxy group generating in polyetheramine also can be further
Implement functional modification, expand the application to Meng's diamidogen in dissaving polymer field for 1, the 8-.
2nd, a kind of 1,8- of the present application to Meng's diamidogen hyperbranched polyetheramine and uses tetra functional cycloalphatic diamine
1,8- is heated to reflux preparing this hyperbranched poly by one kettle way to Meng's diamidogen and the epoxy-capped polyethers of two degrees of functionality in a solvent
The method of ether amines.Reaction without catalyst it is only necessary to be heated to reflux a period of time, reaction condition gently, reaction process and after
Processing procedure is simple.
3rd, the present invention is also prepared for a kind of 1,8- of organosilicon grafting to Meng's diamidogen in hyperbranched polyetheramine hydrogel, and should
For adsorbing water-soluble dye and modified polyacrylamide hydrogel.
4th, solvent for use is nontoxic or the ethanol of low toxicity etc., reusable, green, economy, environmental protection, easy and simple to handle easily
OK.
5th, reaction condition is gentle, and reaction process and last handling process are simple.
Brief description
Fig. 1 is the infrared spectrogram of embodiment 3 gained hyperbranched polyetheramine.In figure, 3418cm-1Locate to shake for hydroxyl (- OH)
Dynamic peak.1108cm-1The vibration peak at place is the stretching vibration of ehter bond (C-O-C) in hyperbranched polyetheramine strand.2872cm-1Place
Stretching vibration peak absworption peak for C-H.
Fig. 2 is gpc analysis spectrogram and its molecular mass determination data of embodiment 1 gained hyperbranched polyetheramine.In figure, RT
For chromatographic peak retention time, MnFor number-average molecular weight, MwFor weight average molecular weight, MPFor peak molecular weight, MzFor z average molecular weight, Mw/
MnFor molecular weight distributing index (i.e. dispersion polymerization).
Fig. 3 is macro morphology figure and the scanning electricity of the organosilicon grafted and modified hyperbranched polyetheramine hydrogel of embodiment 9 gained
Mirror figure.In figure (A) is the macro morphology figure of hydrogel；(B) it is hydrogel surface surface sweeping electron microscope in embodiment 9；(C), (D) is
Hydrogel inner scanning electron microscope in embodiment 9.
Specific embodiment
The invention discloses a kind of 1,8- prepares this over-expense to Meng's diamidogen hyperbranched polyetheramine and by 1,8- to Meng's diamidogen
The method changing polyetheramine.Reaction equation is as follows.
Comprise the following steps that：1,8- is dissolved in organic solvent to Meng's diamidogen, under conditions of nitrogen protection, in reactant liquor
The polyether solutions of Deca bis-epoxy end-blocking, reaction mass total concentration in the solution is 0.1-0.8g/mL, reacts in 50-120 DEG C
6-72h, carries out vacuum distillation under the conditions of vacuum is for 0.08-0.1MPa and removes organic solvent, through organic solvent sedimentation, obtains
White paste 2-24h is dried under vacuum is for 0.09MPa, you can obtain hyperbranched polyetheramine.
Above-mentioned amine is tetra functional cycloalphatic diamine 1,8- to Meng's diamidogen；Organic solvent is ethanol, propanol, 1,4- dioxy
Six rings, oxolane, DMF etc., preferably for ethanol；Reaction mass total concentration in the solution is 0.1-
0.8g/mL；Reaction temperature is 50-120 DEG C；Response time is 6-72h；Sedimentation solvent is petroleum ether, normal hexane, in ether
A kind of；Vacuum drying time is 2-24h, and vacuum is 0.09MPa.
A kind of preparation method and application to Meng's diamidogen hyperbranched polyetheramine hydrogel for 1,8- of organosilicon grafting, reaction side
Formula is as follows.
Comprise the following steps that：
(1) preparation to Meng's diamidogen hyperbranched polyetheramine for the 1,8- of double bond end-blocking
1,8- is dissolved in organic solvent to Meng's diamidogen hyperbranched polyetheramine, under nitrogen protective condition, drips in reactant liquor
Plus allyl glycidyl ether, the mass ratio of reactant is (0.5-10): 1, react 16-24h in 80-120 DEG C, in vacuum
Carry out vacuum distillation under the conditions of 0.1MPa and remove organic solvent, through petroleum ether sedimentation, the white paste obtaining exists in vacuum
It is vacuum dried 12h, thus obtaining 1,8- of double bond end-blocking to Meng's diamidogen hyperbranched polyetheramine under 0.09MPa
(2) preparation to Meng's diamidogen hyperbranched polyetheramine hydrogel for the 1,8- of organosilicon grafting
1, the 8- that double bond is blocked is dissolved in organic solvent to Meng's diamidogen hyperbranched polyetheramine, adds micro ultraviolet light to draw
Send out agent and (3- mercaptopropyi) trimethoxy silane, 1,8- of double bond end-blocking is to Meng's diamidogen hyperbranched polyetheramine and (3- sulfydryl third
Base) trimethoxy silane mass ratio be (0.5-10): 1, under uviol lamp react 4-10h, in vacuum 0.1MPa condition
Under carry out vacuum distillation remove organic solvent, through petroleum ether sedimentation obtain white paste be trimethoxy silane grafting 1,
8-, to Meng's diamidogen hyperbranched polyetheramine, takes the above-mentioned polymer of 1g, is dissolved in 2-4g ultra-pure water, hydrolytic crosslinking can be surpassed
Branch polyether aqueous amine gel.
The preparation to Meng's diamidogen hyperbranched polyetheramine for the 1,8-
Embodiment 1
Weigh 3.4g (0.02mol) 1,8- to Meng's diamidogen, add 8.5mL dehydrated alcohol, magnetic agitation, logical nitrogen half an hour
Afterwards.Weigh polyethyleneglycol diglycidylether (Mn=500) 20g (0.04mmol) and be dissolved in 50mL ethanol, be slowly dropped into reactant liquor
In, after completion of dropping, stir 24h, then heat to 85 DEG C of reaction 24h, the reactant liquor obtaining is 0.086MPa bar in vacuum
Carry out vacuum distillation under part and remove ethanol, then repeatedly settled with petroleum ether, abandon upper liquid, lower floor's paste in vacuum is
Hyperbranched polyetheramine is can get after carrying out under the conditions of 0.09MPa being vacuum dried 6h.As shown in Figure 2, product is surveyed through GPC
Fixed, GPC retention time RT of gained hyperbranched polyetheramine is 10.9min, and its equal molecular mass Mn of number is 3.8K, Weight-average molecular matter
Amount MwFor 7.8K, molecular weight distributing index (Mw/Mn) it is 2.1.
| RT | Mn | Mw | MP | Mz | Mw/Mn |
| 10.904 | 3779 | 7840 | 17126 | 12339 | 2.074623 |
Embodiment 2
Weigh 3.4g (0.02mol) 1,8- to Meng's diamidogen, add 8.5mL dehydrated alcohol, magnetic agitation, logical nitrogen half an hour
Afterwards.Weigh poly- propanol diglycidyl ether (Mn=640) 38.4g (0.06mol) and be dissolved in 64mL ethanol, be slowly dropped into reactant liquor
In, after completion of dropping, stir 24h, then heat to 80 DEG C of reaction 30h, the reactant liquor obtaining is 0.09MPa condition in vacuum
Under carry out vacuum distillation remove ethanol, then repeatedly settled with normal hexane, abandon upper liquid, lower floor's paste in vacuum is
Hyperbranched polyetheramine is can get after carrying out under the conditions of 0.09MPa being vacuum dried 6h.
Embodiment 3
Weigh 1.7g (0.01mol) 1,8- to Meng's diamidogen, add 10mL dehydrated alcohol, magnetic agitation, logical nitrogen half an hour
Afterwards.Weigh poly- propanol diglycidyl ether (Mn=640) 6.4g (0.01mol) and polyethyleneglycol diglycidylether (Mn=
500) 5g (0.01mol) is dissolved in 60mL ethanol, is slowly dropped in reactant liquor, after completion of dropping, stirs 24h, then heats to 85
DEG C reaction 24h, the reactant liquor obtaining carry out under the conditions of vacuum is for 0.09MPa vacuum distillation remove ethanol, then use just oneself
Alkane repeatedly settles, and abandons upper liquid, and lower floor's paste can get after carrying out being vacuum dried 4h under the conditions of vacuum is for 0.09MPa
Hyperbranched polyetheramine.
Embodiment 4
Weigh 5.1g (0.03mol) 1,8- to Meng's diamidogen, add the anhydrous Isosorbide-5-Nitrae-dioxane of 17mL, magnetic agitation, logical nitrogen
After gas half an hour.Weigh poly- propanol diglycidyl ether (Mn=640) (0.06mol) 57.6g and be dissolved in 128mL 1,4- dioxy six
Ring, is slowly dropped in reactant liquor, after completion of dropping, stirs 20h, then heats to 110 DEG C of reaction 16h, and the reactant liquor obtaining exists
Vacuum removes Isosorbide-5-Nitrae-dioxane for carrying out vacuum distillation under the conditions of 0.086MPa, is then repeatedly settled with petroleum ether, abandons
Layer liquid, lower floor's paste can get hyperbranched polyetheramine after carrying out being vacuum dried 6h under the conditions of vacuum is for 0.09MPa.
Embodiment 5
Weigh 5.1g (0.03mol) 1,8- to Meng's diamidogen, add the anhydrous Isosorbide-5-Nitrae-dioxane of 17mL, magnetic agitation, logical nitrogen
After gas half an hour.Weigh poly- propanol diglycidyl ether (Mn=640) (0.12mol) 76.8g and be dissolved in 128mL 1,4- dioxy six
Ring, is slowly dropped in reactant liquor, after completion of dropping, stirs 20h, then heats to 100 DEG C of reaction 16h, and the reactant liquor obtaining exists
Vacuum removes Isosorbide-5-Nitrae-dioxane for carrying out vacuum distillation under the conditions of 0.09MPa, is then repeatedly settled with petroleum ether, abandons upper strata
Liquid, lower floor's paste can get hyperbranched polyetheramine after carrying out being vacuum dried 8h under the conditions of vacuum is for 0.09MPa.
Embodiment 6
Weigh 3.4g (0.03mol) 1,8- to Meng's diamidogen, add the anhydrous DMF of 6mL, magnetic agitation, lead to
After nitrogen half an hour.Weigh PVOH diglycidyl ether (Mn=500) (0.09mol) 45g and be dissolved in 45mL N, N- dimethyl methyl
Amide, is slowly dropped in reactant liquor, after completion of dropping, stirs 20h, then heats to 120 DEG C of reaction 16h, the reactant liquor obtaining
Carry out vacuum distillation and remove DMF under the conditions of vacuum is for 0.09MPa, then repeatedly settled with ether, abandon
Upper liquid, lower floor's paste can get hyperbranched polyether after carrying out being vacuum dried 12h under the conditions of vacuum is for 0.09MPa
Amine.
The preparation of 1,8- Meng's alkane diamidogen hyperbranched polyetheramine hydrogel of organosilicon grafting
Embodiment 7
(1) weigh 1,8- Meng diamidogen hyperbranched polyetheramine 5g to be dissolved in ethanol, under nitrogen protective condition, to reactant liquor
Middle Deca 1g allyl glycidyl ether, reacts 24h at 90 DEG C, carries out vacuum distillation removing under the conditions of vacuum 0.1MPa
Ethanol, through petroleum ether sedimentation, the white paste obtaining is vacuum dried 12h in vacuum under 0.09MPa, thus obtaining double bond
The 1,8- of end-blocking is to Meng's diamidogen hyperbranched polyetheramine.
(2) 1, the 8- claiming 4g double bond end-blocking is dissolved in ethanol to Meng's diamidogen hyperbranched polyetheramine, adds micro ultraviolet light
Initiator I-907 and 1.2g (3- mercaptopropyi) trimethoxy silane, reacts 8h, in vacuum 0.1MPa condition under uviol lamp
Under carry out vacuum distillation remove ethanol, through petroleum ether sedimentation obtain trimethoxy silane grafting 1,8- to Meng's diamidogen hyperbranched poly
Ether amines, take the above-mentioned polymer of 1g, are dissolved in 3g ultra-pure water, hydrolytic crosslinking can get hyperbranched polyetheramine hydrogel.
Embodiment 8
(1) weigh 1,8- Meng diamidogen hyperbranched polyetheramine 6g to be dissolved in ethanol, under nitrogen protective condition, to reactant liquor
Middle Deca 1.2g allyl glycidyl ether, reacts 24h at 95 DEG C, carries out vacuum distillation and remove under the conditions of vacuum 0.1MPa
Remove ethanol, through petroleum ether sedimentation, the white paste obtaining is vacuum dried 12h in vacuum under 0.09MPa, thus obtaining double
The 1,8- of key end-blocking is to Meng's diamidogen hyperbranched polyetheramine.
(2) 1, the 8- claiming 3.8g double bond end-blocking is dissolved in ethanol to Meng's diamidogen hyperbranched polyetheramine, adds micro ultraviolet
Light trigger I-907 and 1g (3- mercaptopropyi) trimethoxy silane, reacts 6h, in vacuum 0.1MPa condition under uviol lamp
Under carry out vacuum distillation remove ethanol, through petroleum ether sedimentation obtain trimethoxy silane grafting 1,8- to Meng's diamidogen hyperbranched poly
Ether amines, take the above-mentioned polymer of 1g, are dissolved in 3.3g ultra-pure water, hydrolytic crosslinking can get hyperbranched polyetheramine hydrogel.
Embodiment 9
(1) weigh 1,8- Meng diamidogen hyperbranched polyetheramine 8g to be dissolved in ethanol, under nitrogen protective condition, to reactant liquor
Middle Deca 2g allyl glycidyl ether, reacts 12h at 100 DEG C, carries out vacuum distillation and remove under the conditions of vacuum 0.1MPa
Remove ethanol, through petroleum ether sedimentation, the white paste obtaining is vacuum dried 12h in vacuum under 0.09MPa, thus obtaining double
The 1,8- of key end-blocking is to Meng's diamidogen hyperbranched polyetheramine.
(2) 1, the 8- claiming 6g double bond end-blocking is dissolved in ethanol to Meng's diamidogen hyperbranched polyetheramine, adds micro ultraviolet light
Initiator I-907 and 2g (3- mercaptopropyi) trimethoxy silane, reacts 6h, in vacuum 0.1MPa condition under uviol lamp
Under carry out vacuum distillation remove ethanol, through petroleum ether sedimentation obtain trimethoxy silane grafting 1,8- to Meng's diamidogen hyperbranched poly
Ether amines, take the above-mentioned polymer of 1g, are dissolved in 2.6g ultra-pure water, hydrolytic crosslinking can get hyperbranched polyetheramine hydrogel.
Embodiment 4 organosilicon grafting hyperbranched polyetheramine hydrogel absorption water-soluble dye
5mL concentration is taken to be 100 μm of ol/L neutral red aqueous solutions, the gel after adding 20mg to dry.At 25 DEG C, after 72h
Survey absorbance under its maximum absorption wavelength for the neutral red solution with ultraviolet spectrophotometer, concentration is calculated to obtain according to standard curve
ct, according to formulaCalculate its saturated extent of adsorption (Qe).Being computed the red clearance of centering is 96.23%, inhales
Attached amount is 24.06 μm of ol/g.
Embodiment 10 organosilicon is grafted hyperbranched polyetheramine hydrogel modified polyacrylamide hydrogel
Weigh 1g acrylamide and 0.02g N,N methylene bis acrylamide in 10g ultra-pure water, be added thereto to 1g
Unhydrolysed organosilicon is grafted hyperbranched polyetheramine, is sufficiently stirred for making it mix all, then adds 0.02g mistake in mixed liquor
Ammonium sulfate and 0.015g N, N, N ', N '-tetramethylethylenediamine, ultrasonic degasification rapidly, at normal temperatures hydrolytic crosslinking 48h surpassed
Branch polyether amine/polyacrylamide composite aquogel.The incompressible mechanical property carrying out gel on omnipotent mechanical test instrument is surveyed
Examination, compression speed is 3mm/min, until gel breaks.The incompressible intensity of gel calculates according to formula CS=F/S, and this is combined
The incompressible intensity of hydrogel is 198.7kPa.
Claims (10)
1. one kind 1,8- is, chemical constitution is to Meng's diamidogen hyperbranched polyetheramine, its characteristic：
2. 1,8- described in synthesis claim 1 to the method for Meng's diamidogen hyperbranched polyetheramine it is characterised in that with 1,8- to Meng
Diamidogen and bis-epoxy end capped polyether are raw material, carry out as follows：1,8- is dissolved in organic solvent to Meng's diamidogen, protects in nitrogen
Under shield, in reactant liquor, Deca bis-epoxy end capped polyether solution is reacted, and carries out vacuum distillation removing organic after reaction fully
Solvent, through sedimentation solvent sedimentation, the white paste obtaining, vacuum dried, as hyperbranched polyetheramine.
3. synthesis as claimed in claim 21,8- to the method for Meng's diamidogen hyperbranched polyetheramine it is characterised in that described ring
Oxygen end capped polyether include polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, in bisphenol A diglycidyl ether
A kind of or any two composition mixture.
4. synthesis as claimed in claim 21,8- to the method for Meng's diamidogen hyperbranched polyetheramine it is characterised in that 1,8- to Meng
Diamidogen is 1: 2-4 with the ratio of the amount of the material of bis-epoxy end capped polyether, and reaction temperature is 50-120 DEG C.
5. synthesis as claimed in claim 21,8- to the method for Meng's diamidogen hyperbranched polyetheramine it is characterised in that described has
Machine solvent includes ethanol, propanol, 1,4- dioxane, oxolane, any one in N,N-dimethylformamide；Described
Sedimentation solvent includes petroleum ether, normal hexane, any one in ether.
6. adopt 1,8- Meng's alkane two that the organosilicon that the 1,8- described in claim 1 is prepared is grafted to Meng's diamidogen hyperbranched polyetheramine
Amine hyperbranched polyetheramine hydrogel is it is characterised in that 1,8- is anti-with allyl glycidyl ether to Meng's diamidogen hyperbranched polyetheramine
1,8- Meng's alkane diamidogen hyperbranched polyetheramine of double bond end-blocking should be obtained；The 1,8- of double bond end-blocking is to Meng's diamidogen hyperbranched polyetheramine again
Obtain the 1,8- of trimethoxy silane grafting with the reaction of (3- mercaptopropyi) trimethoxy silane in the presence of ultraviolet initiator
To Meng's diamidogen hyperbranched polyetheramine, then hydrolytic crosslinking obtains hyperbranched polyetheramine hydrogel in ultra-pure water.
7. to Meng's diamidogen hyperbranched polyetheramine hydrogel, its feature exists 1,8- of the organosilicon grafting described in preparation claim 6
In step is：(1) preparation to Meng's diamidogen hyperbranched polyetheramine for the 1,8- of double bond end-blocking：By 1,8- to Meng's diamidogen hyperbranched poly
Ether amines are dissolved in organic solvent, under nitrogen protective condition, react with allyl glycidyl ether, and vacuum distillation removes organic molten
Agent, through petroleum ether sedimentation, the white paste obtaining is vacuum dried again, thus 1, the 8- obtaining double bond end-blocking overspends to Meng's diamidogen
Change polyetheramine；
(2) preparation to Meng's diamidogen hyperbranched polyetheramine hydrogel for the 1,8- of organosilicon grafting：The 1,8- that double bond is blocked is to Meng
Diamidogen hyperbranched polyetheramine is dissolved in organic solvent, adds ultraviolet initiator and (3- mercaptopropyi) trimethoxy silane,
React under uviol lamp, vacuum distillation removes organic solvent, obtain white paste through petroleum ether sedimentation and be trimethoxy silane
, to Meng's diamidogen hyperbranched polyetheramine, 1, the 8- that trimethoxy silane is grafted is molten to Meng's diamidogen hyperbranched polyetheramine for 1,8- of grafting
In ultra-pure water, hydrolytic crosslinking obtains hyperbranched polyetheramine hydrogel.
8. 1, the 8- preparing organosilicon grafting as claimed in claim 7 is to Meng's diamidogen hyperbranched polyetheramine hydrogel, its feature
It is, 1,8- is 0.5-10: 1 to the mass ratio of Meng's diamidogen hyperbranched polyetheramine and allyl glycidyl ether, and double bond blocks
1,8- be 0.5-10: 1 to the mass ratio of Meng's diamidogen hyperbranched polyetheramine and (3- mercaptopropyi) trimethoxy silane.
9. 1, the 8- preparing organosilicon grafting as claimed in claim 7 is to Meng's diamidogen hyperbranched polyetheramine hydrogel, its feature
It is, the ultraviolet initiator being adopted is I-907, any one in 1173,184.
10. the 1,8- of the organosilicon grafting described in claim 6 is being adsorbed with engine dyeing to Meng's diamidogen hyperbranched polyetheramine hydrogel
Application in material and modified polyacrylamide hydrogel.
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