CN102372830B - Strongly basic carbon nanotube composite resin and its preparation method - Google Patents
Strongly basic carbon nanotube composite resin and its preparation method Download PDFInfo
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Abstract
The invention relates to strongly basic carbon nanotube composite resin and its preparation method, and mainly aims to solve the problems of poor heat resistance and swelling resistance of ion exchange resin involved in previous technologies. The composite resin of the invention comprises: (1) 75-90% of a monomer; (2) 5-15% of a comonomer; (3) 0.1-5% of a nano-material; (4) 0.1-10% of an initiator. Specifically, the monomer is at least one of p-chloromethyl styrene, 4-(3-chloropropyl) styrene, 4-(3-bromopropyl) styrene, 4-(4-chlorobutyl) styrene, 4-(4-brombutyl) styrene, 4-(5-chloropentyl) styrene or 4-(5-bromopentyl) styrene; the comonomer is at least one of glycol dimethacrylate, 2-propenylbenzene, divinyl phenylmethane, and divinylbenzene;the nano-material is at least one of a multi-walled carbon nanotube, a single-walled carbon nanotube, C60 or C70 etc. fullerene; and the initiator is at least one of benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide, and cumene hydroperoxide. The composite resin and its preparation method of the invention well solves the above problems, and can be used in the industrial production of oxirane catalytic hydration.
Description
Technical field
The present invention relates to a kind of strong basicity carbon nanotube compound resin and preparation method thereof.
Background technology
Carbon nanotube is a kind of emerging material, and since carbon nanotube came to light, its particular structure and performance had caused one research boom (Iijima, S. in scientific circles; Ichihashi, T.Nature 1993,363,603-605; Wang, C.C.; Guo, Z.X.; Fu, S.K.; Wu, W.; Zhu, D.B.Progress in Polymer Science 2004,29,1079-1141.).Because the structure of carbon nanotube and polymkeric substance is close; Have good mechanics again, performances such as electricity are carried out carbon nanotube and polymkeric substance compound; Can obtain having the polymer nanocomposites of advantages such as specific tenacity height, designability is strong, anti-fatigue performance good, moulding process is simple; Realize both mutual supplement with each other's advantages, thereby effectively utilize carbon nanotube excellent mechanical property, thermostability and conductivity, develop multiple new function matrix material.
The purpose of the synthetic design of polymer nanocomposites is with the simplest, and the technology of shortcut obtains the homodisperse matrix material of nano-scale particle.It mainly depends on the fully dispersion of nano particle in polymeric matrix, and does not destroy its The Nomenclature Composition and Structure of Complexes.The method that realizes nano particle good distribution in polymeric matrix generally has physical blending method-solution blended process and melt-blending process, situ aggregation method, chemical modification method, electrical spinning method and tensio-active agent auxiliary law.
In-situ polymerization is based in polymerization single polymerization monomer and the carbon nanotube hybrid system, the polymerization of initiator trigger monomer, the π key of carbon tube-surface and chain polymerization reaction.This method can be grafted to the polymeric long chain on the carbon pipe sidewall, can mix with multiple polymers simultaneously, almost can be used for all polymer composites preparations.I.J.Chung etc. utilize in-situ emulsion polymerization to prepare PS/SMNTs matrix material (Hyeong Taek Ham; Yeong Suk Choi, Mu Guen Chee, In JaeChungJournal of Polymer Science Part a-Polymer Chemistry 2006; 44,573-584); Liu's generation is brave to be waited through under the gamma-rays effect, carrying out home position polymerization reaction; PS polymeric long chain is grafted on the multi-walled carbon nano-tubes, has prepared PS/MWNTs matrix material (Hangxun Xu, Xingbo Wang; Yanfeng Zhang; Shiyong Liu.Chem.Mater.2006,18,2929-2934); Kaminsky etc. utilize metallocene catalyst; Vestolen PP 7052/carbon nanofiber and carbon nano tube compound material (PP/CNF, PP/CNT) (Katharina Wiemann, Walter Kaminsky have been prepared through in-situ polymerization; FlorianH.Gojny; Karl Schulte.Macromol.Chem.Phys.2005,206,1472-1478).Mu Sang Lee etc. utilizes the in-situ chemical oxidative polymerization, has prepared Polythiophene/carbon nanotube (PTh/SWNTs) composite conductive polymer of Polythiophene carbon coated pipe.
Usually strongly basic anion exchange resin is on the basis of chloromethyl resin, makes through amination reaction.Though this method of normal employing in the industry, the reaction raw materials chloromethyl ether and the dichlormethyl ether of synthetic chloromethyl resin have the intensive carcinogenesis.Simultaneously there are problems such as polysubstituted and crosslinked in chloromethylation, makes the structure complicated of chloromethyl resin.
Summary of the invention
One of technical problem to be solved by this invention is that the resistance toheat that exists of the strong basic ion exchange resin of prior art is poor; The problem that anti swelling can differ from; A kind of new strong basicity carbon nanotube compound resin is provided, and it is good that this resin has resistance toheat, the characteristics that anti swelling can be good.Two of technical problem to be solved by this invention provides preparation method a kind of and one of technical solution problem corresponding strong basicity carbon nanotube compound resin.
For one of solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of preparation method of strong basicity carbon nanotube composite resin material comprises following component by weight percentage:
(1) 75～90% monomer;
(2) 5～15% comonomer;
(3) 0.1～5% nano material;
(4) 0.1～10% initiators;
Wherein monomer is selected from least a in p-chloromethyl styrene, 4-(3-chloropropyl) vinylbenzene, 4-(3-bromopropyl) vinylbenzene, 4-(4-chlorobutyl) vinylbenzene, 4-(4-brombutyl) vinylbenzene, 4-(5-chlorine amyl group) vinylbenzene or 4-(the 5-bromine amyl group) vinylbenzene; Comonomer is selected from least a in methacrylate glycol ester, diallyl benzene, divinyl phenylmethane, the Vinylstyrene; Nano material is selected from multi-walled carbon nano-tubes, single armed carbon nanotube, C
60Or C
70At least a Deng in the soccerballene; Initiator is selected from least a in Lucidol, Diisopropyl azodicarboxylate, lauroyl peroxide, the isopropyl benzene hydroperoxide.
The monomer preferred version is selected from p-chloromethyl styrene in the technique scheme, and the comonomer preferred version is selected from Vinylstyrene, and the nano material preferred version is selected from multi-walled carbon nano-tubes, and the initiator preferred version is selected from Lucidol.
For solve the problems of the technologies described above two, the technical scheme that the present invention adopts is following: a kind of preparation method of strong basicity carbon nanotube composite resin material may further comprise the steps:
(1) auxiliary agent of aequum being made into weight percent concentration is 0.3～2.5% water solution A;
(2) monomer, comonomer, nano material and the initiator with aequum is mixed into solution B;
(3) with solution B 60～75 ℃ of prepolymerizations 0.5～2.5 hour; Solution B is mixed with solution A,, reacted 5～15 hours, be warming up to 90～100 ℃ then at 70～90 ℃; Reacted 5～15 hours, and after reaction finishes, toppled over and supernatant liquid, through washing; Filter, drying is sieved, the complex microsphere of collection cut size scope 0.35～0.60mm;
(4) in complex microsphere, add the ethylene dichloride that is equivalent to complex microsphere weight 20～70%; 70～200% trimethylamine hydrochloride and 60～180% sodium hydroxide; Reacted about 5～30 hours down at 25～45 ℃, after reaction finishes, through washing; Adding sodium hydroxide makes the transition; Washing is to neutral again, strong basicity carbon nanotube compound resin, wherein monomer is selected from least a in p-chloromethyl styrene, 4-(3-chloropropyl) vinylbenzene, 4-(3-bromopropyl) vinylbenzene, 4-(4-chlorobutyl) vinylbenzene, 4-(4-brombutyl) vinylbenzene, 4-(5-chlorine amyl group) vinylbenzene or 4-(the 5-bromine amyl group) vinylbenzene; Comonomer is selected from least a in methacrylate glycol ester, diallyl benzene, divinyl phenylmethane, the Vinylstyrene; Nano material is selected from multi-walled carbon nano-tubes, single armed carbon nanotube, C
60Or C
70At least a Deng in the soccerballene; Initiator is selected from least a in Lucidol, Diisopropyl azodicarboxylate, lauroyl peroxide, the isopropyl benzene hydroperoxide; Auxiliary agent is selected from least a in Z 150PH, gelatin, starch, methylcellulose gum, wilkinite, the lime carbonate.
Nano material among the present invention is multi-walled carbon nano-tubes (MWNTs), is prepared by chemical Vapor deposition process.Matrix material is obtained through postponing situ aggregation method by liposoluble carbon nanotube and monomer.Nano material can also be single armed carbon nanotube (SWNTs), or C
60, C
70Deng soccerballene.
Suspension copolymerization is the polymerization method commonly used that is used for the crosslinked skeleton of ion exchange resin.The crosslinked skeleton that relates among the present invention is p-chloromethyl styrene-Vinylstyrene interpolymer, introduces quaternary ammonium group through amination reaction then.
The present invention is in the dispersion that utilizes nano material in organic medium; Realize the polymer in situ functionalization of nano material, solved the compound problem of nano material in the ion exchange resin matrix, utilized particular monomers-p-chloromethyl styrene simultaneously; Solved the chloromethylation problem that runs in the resins process in the past; Chloromethyl through monolithic design, is introduced directly in the crosslinked polymer network, has obtained good effect.
Through embodiment the present invention is done further elaboration below.Be necessary to be pointed out that at this following examples only are used for further specifying of the present invention, can not be interpreted as restriction protection domain of the present invention.
Embodiment
[embodiment 1]
In 250 milliliters of there-necked flasks, add 42.0 gram p-chloromethyl styrenes, 2.6 gram Vinylstyrenes and 0.3 gram Lucidol initiator stirred 1.5 hours down in 60 ℃; Add 1.4 gram multi-walled carbon nano-tubes then, continue stirring and carried out prepolymerization in 1 hour.Add the 130 ml deionized water solution that have been dissolved with 1.3 gram Z 150PH.Regulate stirring velocity, progressively be warming up to 80 ℃ simultaneously, reacted 5 hours; Be warmed up to 90 ℃ again, reacted 5 hours, be warming up to 98 ℃ at last, reacted 6 hours.After reaction finishes, topple over and supernatant liquid, use hot wash, 80 ℃ of oven dry of baking oven are put in filtration then, sieve the complex microsphere A of collection cut size in 0.35～0.60mm scope.
In 250 milliliters of there-necked flasks, add 30.0 gram complex microsphere A, 60 milliliters of ethylene dichloride are adjusted into 30 ℃ with bath temperature, let complex microsphere swelling 3 hours under this temperature.Add 27.0 gram trimethylamine hydrochlorides then, weight fraction is 200 milliliters of 20% sodium hydroxide solutions, and reaction is about 6 hours about 30 ℃.After reaction finishes; Progressively thin up to proportion equals at 1.0 o'clock; Washing, hydro-oxidation sodium are after transition, and washing is to neutral; Promptly get composite resin material A, its aperture is
The last handling process of catalyzer is following: get above-mentioned resin material A50 milliliter, soak the back with 200 milliliters methyl alcohol and wash with 700 ml deionized water.Packing into then has the glass column of Sha Xin, uses the deionized water wash resin, and the deionized water flow velocity is 5 ml/min, and the treatment time is 30 minutes; With the HCl solution washing resin of 0.75 mol, flow velocity is 2 ml/min, and the treatment time is 90 minutes; Use the deionized water wash resin to be neutrality then until elutant; With the NaOH solution washing resin of 0.3 mol, flow velocity is 1.7 ml/min, and the treatment time is 200 minutes; Use the deionized water wash resin to be neutrality then, under 25 ℃ of room temperatures, dry moisture and process catalyst A until elutant.
It is 10 millimeters that 10 milliliters of catalyst A are filled in a diameter, in long 350 millimeters the stainless steel fixed-bed reactor, is that 10: 1 water and oxyethane is delivered to reactive system through volume pump with mol ratio.Reaction pressure is 1.2 MPas, and temperature is 87～93 ℃, and the liquid air speed is 3 hours
-1, product is analyzed through the HP5890 gc, and appraisal result is listed in table 1.
[embodiment 2]
In 500 milliliters of there-necked flasks, add 4.6 gram Z 150PH and 300 ml deionized water, begin to stir intensification Z 150PH is all dissolved.Stop to stir, cold slightly back adds 63.0 gram p-chloromethyl styrenes, 6.0 gram Vinylstyrenes and 0.5 gram Lucidol initiator, and the mixed solution of 4.9 gram multi-walled carbon nano-tubes.Regulate stirring velocity, progressively heat up simultaneously, reacted 5 hours down at 80 ℃; Be warmed up to 88 ℃ again, continue reaction 5 hours, heat up at last and reacted 6 hours down at 100 ℃.After reaction finishes, topple over and supernatant liquid, use hot wash, 80 ℃ of oven dry of baking oven are put in filtration, sieve the complex microsphere B of collection cut size in 0.35～0.60mm scope.
In 250 milliliters of there-necked flasks, add 20.0 gram complex microsphere B, 50 milliliters of ethylene dichloride are adjusted into 35 ℃ with bath temperature, let complex microsphere swelling 1 hour under this temperature.Add 20.0 gram trimethylamine hydrochlorides then, weight fraction is 150 milliliters of 20% sodium hydroxide solutions, and reaction is about 4 hours about 40 ℃.After reaction finishes; Progressively thin up to proportion equals at 1.0 o'clock; Washing, hydro-oxidation sodium are after transition, and washing is to neutral; Promptly get composite resin material B, its aperture is
Post-processing step and condition according to catalyzer among the embodiment 1 prepare catalyst B, and check and rate according to identical condition.Its appraisal result is listed in table 1.
[embodiment 3]
In 1000 milliliters of there-necked flasks, add 140 gram p-chloromethyl styrenes, 17.5 gram Vinylstyrenes and 1.4 restrain the Lucidol initiators, and 5.2 gram multi-walled carbon nano-tubes, stir down in 65 ℃ and carry out prepolymerization in 1.5 hours.Add the 500 ml deionized water solution that have been dissolved with 5.0 gram Z 150PH then.Regulate stirring velocity, in one hour, be warming up to 80 ℃, successive reaction 5 hours; Be warmed up to 90 ℃ again, reacted 5 hours, be warming up to 98 ℃ at last, reacted 6 hours.After reaction finishes, topple over and supernatant liquid, use hot wash, 80 ℃ of oven dry of baking oven are put in filtration then, sieve the complex microsphere C of collection cut size in 0.35～0.60mm scope.
In 500 milliliters of there-necked flasks, add 50.0 gram complex microsphere C, 150 milliliters of ethylene dichloride are adjusted into 35 ℃ with bath temperature, let complex microsphere swelling 5 hours under this temperature.Add 27.0 gram trimethylamine hydrochlorides then, weight fraction is 200 milliliters of 20% sodium hydroxide solutions, and reaction is about 3 hours about 35 ℃.After reaction finishes; Progressively thin up to proportion equals at 1.0 o'clock; Washing, hydro-oxidation sodium are after transition, and washing is to neutral; Promptly get composite resin material C, its aperture is
Post-processing step and condition according to catalyzer among the embodiment 1 prepare catalyzer C, and check and rate according to identical condition.Its appraisal result is listed in table 1.
[embodiment 4]
In 250 milliliters of there-necked flasks, add 31.0 gram p-chloromethyl styrenes, 5.6 gram Vinylstyrenes and 0.2 gram Lucidol initiator stirred 1.5 hours down in 60 ℃; Add 2.7 gram multi-walled carbon nano-tubes then, continue stirring and carried out prepolymerization in 1 hour.Add the 140 ml deionized water solution that have been dissolved with 1.3 gram Z 150PH.Regulate stirring velocity, progressively be warming up to 80 ℃ simultaneously, reacted 5 hours; Be warmed up to 90 ℃ again, reacted 5 hours, be warming up to 98 ℃ at last, reacted 6 hours.After reaction finishes, topple over and supernatant liquid, use hot wash, 80 ℃ of oven dry of baking oven are put in filtration then, sieve the complex microsphere D of collection cut size in 0.35～0.60mm scope.
In 250 milliliters of there-necked flasks, add 30.0 gram complex microsphere D, 70 milliliters of ethylene dichloride are adjusted into 30 ℃ with bath temperature, let complex microsphere swelling 3 hours under this temperature.Add 30.0 gram trimethylamine hydrochlorides then, weight fraction is 180 milliliters of 20% sodium hydroxide solutions, and reaction is about 5 hours about 35 ℃.After reaction finishes; Progressively thin up to proportion equals at 1.0 o'clock; Washing, hydro-oxidation sodium are after transition, and washing is to neutral; Promptly get composite resin material D, its aperture is
Post-processing step and condition according to catalyzer among the embodiment 1 prepare catalyzer D, and check and rate according to identical condition.Its appraisal result is listed in table 1.
The appraisal result that table 1 different catalysts catalytic epoxyethane water closes
Claims (6)
1. the preparation method of a strong basicity carbon nanotube composite resin material, said strong basicity carbon nanotube composite resin material comprises following component by weight percentage:
(1) 75～90% monomer;
(2) 5～15% comonomer;
(3) 0.1～5% nano material;
(4) 0.1～10% initiators;
Wherein monomer is selected from least a in p-chloromethyl styrene, 4-(3-chloropropyl) vinylbenzene, 4-(3-bromopropyl) vinylbenzene, 4-(4-chlorobutyl) vinylbenzene, 4-(4-brombutyl) vinylbenzene, 4-(5-chlorine amyl group) vinylbenzene or 4-(the 5-bromine amyl group) vinylbenzene; Comonomer is selected from least a in methacrylate glycol ester, diallyl benzene, divinyl phenylmethane, the Vinylstyrene; Nano material is selected from least a in multi-walled carbon nano-tubes, single armed carbon nanotube, the soccerballene; Initiator is selected from least a in Lucidol, Diisopropyl azodicarboxylate, lauroyl peroxide, the isopropyl benzene hydroperoxide; May further comprise the steps:
(1) auxiliary agent of aequum being made into weight percent concentration is 0.3～2.5% water solution A;
(2) monomer, comonomer, nano material and the initiator with aequum is mixed into solution B;
(3) with solution B 60～75 ℃ of prepolymerizations 0.5～2.5 hour; Solution B is mixed with solution A, be warming up to 70～90 ℃, reacted 5～15 hours, be warming up to 90～100 ℃ then; Reacted 5～15 hours, and after reaction finishes, toppled over and supernatant liquid, through washing; Filter, drying is sieved, the complex microsphere of collection cut size scope 0.35～0.60mm;
(4) in complex microsphere, add the ethylene dichloride that is equivalent to complex microsphere weight 20～70%; 70～200% trimethylamine hydrochloride and 60～180% sodium hydroxide reacted 5～30 hours down at 25～45 ℃, after reaction finishes; Through washing; Adding sodium hydroxide makes the transition, and washing gets strong basicity carbon nanotube compound resin to neutral again; Auxiliary agent is selected from least a in Z 150PH, gelatin, starch, methylcellulose gum, wilkinite, the lime carbonate.
2. according to the preparation method of the said strong basicity carbon nanotube of claim 1 composite resin material, it is characterized in that said soccerballene is C
60Or C
70
3. according to the preparation method of claim 1 or 2 said strong basicity carbon nanotube composite resin materials, it is characterized in that monomer is selected from p-chloromethyl styrene.
4. according to the preparation method of claim 1 or 2 said strong basicity carbon nanotube composite resin materials, it is characterized in that comonomer selection Vinylstyrene.
5. according to the preparation method of claim 1 or 2 said strong basicity carbon nanotube composite resin materials, it is characterized in that nano material selection multi-walled carbon nano-tubes.
6. according to the preparation method of claim 1 or 2 said strong basicity carbon nanotube composite resin materials, it is characterized in that initiator selection Lucidol.
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| CN104558360B (en) * | 2013-10-28 | 2017-06-20 | 中国石油化工股份有限公司 | Strong basicity combination ion exchange resin material and preparation method thereof |
| CN104558359A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of strong basic graphene composite resin material |
| CN105367700B (en) * | 2014-08-27 | 2018-02-13 | 中国石油化工股份有限公司 | Metallic graphite carbon alkene ion exchange resin material of strong basicity tri compound and preparation method thereof |
| CN111100255B (en) * | 2018-10-25 | 2022-11-01 | 中国石油化工股份有限公司 | Carbon nano tube-styrene derivative compound, preparation method and application |
| CN114433230B (en) * | 2020-10-20 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for alkylene oxide catalytic hydration reaction, preparation method and application thereof |
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| CN1752134A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Large hole nano-composite resin material and its preparation method |
| CN101708475A (en) * | 2009-12-22 | 2010-05-19 | 南京大学 | Magnetic styrene alkali anion exchange microsphere resin and preparation method thereof |
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| CN1752134A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Large hole nano-composite resin material and its preparation method |
| CN101708475A (en) * | 2009-12-22 | 2010-05-19 | 南京大学 | Magnetic styrene alkali anion exchange microsphere resin and preparation method thereof |
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