CN1325556C - Large hole nano-composite resin material and its preparation method - Google Patents
Large hole nano-composite resin material and its preparation method Download PDFInfo
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Abstract
The present invention relates to macroporous nanometer composite resin material and a preparation method thereof, which mainly solves the problem that the prior art does not relate to ion exchange resin nanometer composite resin material and a preparation method thereof. The present invention has the technical scheme that the macroporous nanometer composite resin material is composed of monomer, co-monomer, nanometer material, initiator, first auxiliary agent and second auxiliary agent, the first auxiliary agent form solution A, the monomer, the co-monomer, the initiator and the second auxiliary agent form solution B, and the macroporous nanometer composite resin material is prepared by in-situ polymerization of the monomer on the surface of the nanometer material to solve the problems. The present invention can be used in industrial production of ethylene oxide catalytic hydration.
Description
Technical field
The present invention relates to a kind of large hole nano-composite resin material and preparation method thereof.
Background technology
With nano material especially carbon nanotube polymkeric substance is carried out mutual supplement with each other's advantages or the reinforcement that modification can realize group element material.Nano combined ion exchange resin is to improve traditional ion exchange resin material swelling property, an approach of thermostability.Carbon nanotube (CNTs) be the beginning of the nineties by Japanese scholar Iijima find (Iijima S., Nature, 1991.354 (7), 56-58).The polymer/carbon nano-tube matrix material has become focus (AjayanP.M., Stephan O., Colliex C., Tranth D.Science, 1994, the 265.1212-1215 of World Science research since reported first such as AJayan; Calvert P., Nature, 1999,399,210-211).With the compound mutual supplement with each other's advantages or the reinforcement that can realize group element material of nano material especially carbon nanotube and polymkeric substance, the most economical special performance that effectively utilizes carbon nanotube is the effective way of carbon nanotube stabilization.The polymer/carbon nano-tube matrix material has wide application prospect at aspects such as information material, bio-medical material, stealth material, catalyzer, high performance structures material, multifunctional materials.
Nano material/polymer composites is generally by solution, melting mixing and in-situ polymerization preparation.Stephen etc. add carbon nanotube in the toluene solution of PMMA, utilize ultra-sonic dispersion to make the suspension of homogeneous, and to apply and made thickness be the composite material film of 200 nanometers in rotation then.Utilize this method, PVA/CNTs, the matrix material of PSt/CNTs is made.Employings such as Jia Zhijie improve in-situ compositing and have prepared PA6/CNTs, the PMM/CNTs matrix material.
Polymkeric substance parcel carbon nanotube is an important channel improving and regulate and control the carbon nano tube surface characteristic, improves its consistency in different matrix.Coleman and Dalton etc. with solution mixing method prepared the carbon nano tube type of PmPV parcel matrix material (Dalton A, Stephan O.Coleman J, et al J.Phys.Chem., B 2000,104; 10012-10016).Wan Meixiang etc. are by carrying out home position polymerization reaction on carbon nanotube, prepared the polypyrrole parcel carbon nanotube (Fan J, WanM, Zhu D, et al J.Appl.Poly.Sci., 1999,74:2605-2610).Tang Benzhong etc. utilize situ aggregation method that MWNTs and phenylacetylene are carried out catalyzed polymerization, have obtained the MWNTs of polyphenylacetylene parcel, (Tang B Z, Xu XY.Macromolecules.1999,3:2569-2576).It is the important method of improving the carbon nano tube surface characteristic that carbon nanotube is carried out the graft modification processing.Jin etc. have reported the preparation of polyoxyethylene (PEO) grafting MWNTs matrix material.They utilize mixed strong acids (H
2SO
4+ HNO
3) carbon nanotube carried out purifying after, obtain the carbon nanotube that carboxyl (COOH) contained on the surface.Utilize thionyl chloride that carboxyl is changed into acyl chlorides, the end group with PEO reacts then, has obtained the PEO grafting carbon nanotube.
Summary of the invention
One of technical problem to be solved by this invention is the problem that does not relate to the amberlite resin nano composite material in the conventional art, and a kind of new large hole nano-composite resin material is provided.Two of technical problem to be solved by this invention is the preparation methods that do not relate to the amberlite resin nano composite material in the conventional art, and a kind of preparation method of new large hole nano-composite resin material is provided.Have with this preparation method and can realize the in-situ polymerization of monomer at nano-material surface, realize the stabilization and compoundization of nano material, solve nano material compound in the ion exchange resin matrix, make the characteristics of high-performance nano combination ion exchange resin material.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of large hole nano-composite resin material comprises following component by weight percentage:
(1) monomer 20～50%;
(2) comonomer 3～20%;
(3) nano material 0.1～10%;
(4) initiator 0.1～2%;
(5) auxiliary agent one 0.1～2%;
(6) auxiliary agent 2 20～60%;
Wherein monomer is selected from least a in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, divinyl, vinylbenzene or the vinyl cyanide; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT (carbon nano-tube), nano magnesia or the nano zine oxide; Initiator is selected from least a in benzoyl peroxide or the Diisopropyl azodicarboxylate; Auxiliary agent one is selected from least a in polyvinyl alcohol, wilkinite, lime carbonate or the gelatin; Auxiliary agent two is selected from least a in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or the paraffin.
The monomer preferred version is selected from vinylbenzene in the technique scheme, and the comonomer preferred version is selected from divinylbenzene, and the nano material preferred version is selected from CNT (carbon nano-tube), and the initiator preferred version is selected from benzoyl peroxide, and auxiliary agent one preferred version is selected from polyvinyl alcohol.Auxiliary agent two preferred versions are selected from polystyrene or gasoline.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of large hole nano-composite resin material may further comprise the steps:
(1) auxiliary agent one being made into weight percent concentration is 2～5% water solution A;
(2) with monomer, comonomer and initiator and auxiliary agent two, wiring solution-forming B;
(3) solution A and solution B are mixed, reacted 0～8 hour down at 70～90 ℃; Add nano material, reacted 2～8 hours down at 70～90 ℃; Be warming up to 90～100 ℃ of reactions 2～8 hours, after reaction finished, inclining supernatant liquid, washed with water, filtered then, dry compound pearl body, and wherein the nano material in above-mentioned reaction mixture adds wiring solution-forming B in step (2); Perhaps add reaction system after 0～8 hour in solution A and solution B hybrid reaction;
(4) 100～500% of the compound pearl body weight of adding chloromethyl ether and 20～70% zinc chloride catalyzer in compound pearl body, under 30～50 ℃, compound pearl body is carried out Friedel-crafts reaction, reaction times is 8～20 hours, 20～70% of the compound pearl body weight of adding ethylene dichloride after the suction strainer washing, 70～200% trimethylamine hydrochloride and 60～180% sodium hydroxide, 25～40 ℃ of reactions 5～20 hours, reaction finishes back adding sodium hydroxide and makes the transition, be washed to neutrality then, promptly get composite resin material, wherein monomer is selected from methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, divinyl, at least a in vinylbenzene or the vinyl cyanide; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT (carbon nano-tube), nano magnesia or the nano zine oxide; Initiator is selected from least a in benzoyl peroxide or the Diisopropyl azodicarboxylate; Auxiliary agent one is selected from least a in polyvinyl alcohol, wilkinite, lime carbonate or the gelatin; Auxiliary agent two is selected from least a in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or the paraffin.
Carbon nanotube among the present invention is multi-walled carbon nano-tubes (MWNTs), is prepared by chemical Vapor deposition process.Matrix material is obtained by situ aggregation method or improvement in-situ compositing by liposoluble carbon nanotube and monomer.Carbon nanotube also can adopt Single Walled Carbon Nanotube (SWNTs), and composite material and preparation method thereof also can adopt arc process, solid-phase pyrolysis etc.
The suspension copolymerzation with cross-linking is the polyreaction that is used to prepare a kind of uniqueness of ion exchange resin skeleton multipolymer.Mostly anionite-exchange resin is that with vinylbenzene-divinylbenzene copolymerization spheroid be skeleton, introduces by chloromethylation and amination that quaternary ammonium group or other amine groups make, and the basic synthetic route of the nano composite material among the present invention is:
The present invention utilize nano material especially liposoluble carbon nanotube dispersive is simultaneously in organic medium, realized the in-situ polymerization of monomer at nano-material surface, solved the compound problem of nano material in the ion exchange resin matrix, make high performance nano-composite resin material simultaneously, obtained better technical effect.
The invention will be further elaborated below by embodiment.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified, can not be interpreted as limiting the scope of the invention.
Embodiment
[embodiment 1]
In 500 milliliters of there-necked flasks, add 200 ml distilled waters and 0.9 gram gelatin, start the stirring intensification polyvinyl alcohol is all dissolved.Stop to stir, cold slightly back adds monomer mixture solution (29.2 gram vinylbenzene, 5.8 gram divinylbenzenes (weight content 40%), 1.2 gram carbon nanotubes, 35.6 grams 200 that contain initiator
#Gasoline, 0.35 gram benzoyl peroxide), start stirring, be warming up to 85 ℃, reacted 4 hours.Be warming up to 95 ℃ about 2 hours.After reaction finished, inclining supernatant liquid, with 85 ℃ of hot washes several times, more several times, filter then with cold wash, drying, weigh compound pearl body A.
[embodiment 2]
In 1000 milliliters of there-necked flasks, add 400 ml waters and dissolve 1.9 polyvinyl alcohol that restrain.0.5 gram benzoyl peroxide is dissolved in 80.6 gram vinylbenzene and 16.8 gram divinylbenzenes (weight content 40%), 98.3 grams 200
#In the mixed solution of gasoline, be added to then in the there-necked flask, start stirring, heat up, solution is mixed, be warming up to 80 ℃ in 1 hour, kept 0.5 hour, add 3.5 gram carbon nanotubes, rise to 90 ℃ and kept 4 hours, 100 ℃ were boiled ball 6 hours.Then ball is leached, use hot wash, dry, sieve, collect the compound pearl body B of qualified particle diameter.
[embodiment 3]
In 500 milliliters of there-necked flasks, add 200 ml distilled waters and 0.4 gram polyvinyl alcohol (or adding 35 milliliters of the 5% weight polyvinyl aqueous solution), start the stirring intensification polyvinyl alcohol is all dissolved.Stop to stir, cold slightly back adds monomer mixture solution (the 40.2 gram vinylbenzene that contain initiator, 11.2 gram divinylbenzene (weight content 40%), 49.1 the gram polystyrene, 0.25 gram benzoyl peroxide), start stirring, be warming up to 80 ℃, reacted 1 hour, and added 1.7 gram carbon nanotubes, reacted 3.5 hours.Be warming up to 95 ℃ about 2 hours.After reaction finished, inclining supernatant liquid, with 80 ℃ of hot washes several times, more several times, filter then with cold wash, drying, weigh the compound pearl body of matrix material C.
[embodiment 4]
The functionalization of compound pearl body: in 500 milliliters of there-necked flasks, add the 20.6 compound pearl body A of gram and 80 milliliters of chloromethyl ethers, start to stir and be warmed up to 30 ℃, adding 8 gram zinc chloride is catalyzer, under 39～40 ℃, compound pearl body A is carried out Friedel-crafts reaction, reaction times is 10 hours, and suction strainer is with washings such as acetone.Add 8.5 grams, two oxidative ethanes, 18.5 gram trimethylamine hydrochlorides, 75 milliliters of 20% weight sodium hydroxides, reaction is about 12 hours about 30 ℃.After reaction finished, progressively thin up to proportion equaled at 1.0 o'clock, washing, and hydro-oxidation sodium is washed to neutrality after transition, promptly gets composite resin material A.The resin mean pore size is 30.3 nanometers after measured.
[embodiment 5]
The functionalization of compound pearl body: in 500 milliliters of there-necked flasks, add the 30.2 compound pearl body B of gram and 90 milliliters of chloromethyl ethers, start to stir and be warmed up to 30 ℃, adding 7.6 gram zinc chloride is catalyzer, under 50 ℃, compound pearl body B is carried out Friedel-crafts reaction, reaction times is 15 hours, and suction strainer is with washings such as acetone.Add 9.5 grams, two oxidative ethanes, 48.5 gram trimethylamine hydrochlorides, 200 milliliters of 20% weight sodium hydroxides, reaction is about 8 hours about 40 ℃.After reaction finished, progressively thin up to proportion equaled at 1.0 o'clock, washing, and hydro-oxidation sodium is washed to neutrality after transition, promptly gets composite resin material B.The resin mean pore size is 28.2 nanometers after measured.
[embodiment 6]
The functionalization of compound pearl body: in 500 milliliters of there-necked flasks, add the 41.8 compound pearl body C of gram and 60 milliliters of chloromethyl ethers, start to stir and be warmed up to 30 ℃, adding 25 gram zinc chloride is catalyzer, under 25 ℃, compound pearl body C is carried out Friedel-crafts reaction, reaction times is 18 hours, and suction strainer is with washings such as acetone.Add 24.3 grams, two oxidative ethanes, 81.2 gram trimethylamine hydrochlorides, 130 milliliters of 20% weight sodium hydroxides, reaction is about 20 hours about 35 ℃.After reaction finished, progressively thin up to proportion equaled at 1.0 o'clock, washing, and hydro-oxidation sodium is washed to neutrality after transition, promptly gets composite resin material C.The resin mean pore size is 31.5 nanometers after measured.
[embodiment 7]
Above-mentioned composite resin material C24 milliliter is incorporated in one 300 milliliters the stainless steel gap reactor, adds 4.9 moles of raw waters and 0.48 moles of ethylene oxide.Reacting system pressure is 1.2MPa, 120 ℃ of temperature of reaction, and the reaction times is 2 hours, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography.The oxyethane transformation efficiency is 99.2%, and glycol selectivity is 87.8%.
Claims (8)
1, a kind of large hole nano-composite resin material comprises following component by weight percentage:
(1) monomer 20～50%;
(2) comonomer 3～20%;
(3) nano material 0.1～10%;
(4) initiator 0.1～2%;
(5) auxiliary agent one 0.1～2%;
(6) auxiliary agent 2 20～60%;
Wherein monomer is selected from least a in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, divinyl, vinylbenzene or the vinyl cyanide; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT (carbon nano-tube), nano magnesia or the nano zine oxide; Initiator is selected from least a in benzoyl peroxide or the Diisopropyl azodicarboxylate; Auxiliary agent one is selected from least a in polyvinyl alcohol, wilkinite, lime carbonate or the gelatin; Auxiliary agent two is selected from least a in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or the paraffin.
2,, it is characterized in that monomer is selected from vinylbenzene according to the described large hole nano-composite resin material of claim 1.
3,, it is characterized in that comonomer is selected from divinylbenzene according to the described large hole nano-composite resin material of claim 1.
4,, it is characterized in that nano material is selected from CNT (carbon nano-tube) according to the described large hole nano-composite resin material of claim 1.
5,, it is characterized in that initiator is selected from benzoyl peroxide according to the described large hole nano-composite resin material of claim 1.
6,, it is characterized in that auxiliary agent one is selected from polyvinyl alcohol according to the described large hole nano-composite resin material of claim 1.
7,, it is characterized in that auxiliary agent two is selected from polystyrene or gasoline according to the described large hole nano-composite resin material of claim 1.
8, a kind of preparation method of large hole nano-composite resin material may further comprise the steps:
(1) auxiliary agent one being made into weight percent concentration is 2～5% water solution A;
(2) with monomer, comonomer and initiator and auxiliary agent two, wiring solution-forming B;
(3) solution A and solution B are mixed, reacted 0～8 hour down at 70～90 ℃; Add nano material, reacted 2～8 hours down at 70～90 ℃; Be warming up to 90～100 ℃ of reactions 2～8 hours, after reaction finished, inclining supernatant liquid, washed with water, filtered then, dry compound pearl body, and wherein the nano material in above-mentioned reaction mixture adds wiring solution-forming B in step (2); Perhaps add reaction system after 0～8 hour in solution A and solution B hybrid reaction;
(4) 100～500% of the compound pearl body weight of adding chloromethyl ether and 20～70% zinc chloride catalyzer in compound pearl body, under 30～50 ℃, compound pearl body is carried out Friedel-crafts reaction, reaction times is 8～20 hours, 20～70% of the compound pearl body weight of adding ethylene dichloride after the suction strainer washing, 70～200% trimethylamine hydrochloride and 60～180% sodium hydroxide, 25～40 ℃ of reactions 5～20 hours, reaction finishes back adding sodium hydroxide and makes the transition, be washed to neutrality then, promptly get composite resin material, wherein monomer is selected from methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, divinyl, at least a in vinylbenzene or the vinyl cyanide; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT (carbon nano-tube), nano magnesia or the nano zine oxide; Initiator is selected from least a in benzoyl peroxide or the Diisopropyl azodicarboxylate; Auxiliary agent one is selected from least a in polyvinyl alcohol, wilkinite, lime carbonate or the gelatin; Auxiliary agent two is selected from least a in aliphatic hydrocarbon, polystyrene, gasoline, lipid acid or the paraffin.
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