CN102049243B - Cross-linking adsorbent resin with ultrahigh magnetic property and preparation method thereof - Google Patents
Cross-linking adsorbent resin with ultrahigh magnetic property and preparation method thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 101
- 229920005989 resin Polymers 0.000 title claims abstract description 101
- 238000004132 cross linking Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003463 adsorbent Substances 0.000 title abstract 5
- 239000006249 magnetic particle Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 230000005415 magnetization Effects 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000012071 phase Substances 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000004088 foaming agent Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011968 lewis acid catalyst Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- 229910001566 austenite Inorganic materials 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- -1 C22 alkanes Chemical class 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000010558 suspension polymerization method Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000007265 chloromethylation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 241001566735 Archon Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229940094933 n-dodecane Drugs 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001650 tertiary alcohol group Chemical group 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The invention discloses a magnetic ultrahigh cross-linking adsorbent resin and a preparation method thereof, belonging to the field of magnetic resin. The ultrahigh cross linking adsorbent resin provided by the invention is formed by a framework and magnetic particles wrapped in the framework, wherein the resin framework has the following basic structural formula that the saturation magnetization intensity of the resin is 0.1-10e mu/g; and the average particle size of the resin is 60-300 mu m. The resin provided by the invention is synthesized by adopting a suspension polymerization method and a reaction system comprises an oil phase, magnetic particles and a water phase, wherein the magnetic particles are wrapped in a double layer mode through a coupling agent and a dispersing agent, thereby enhancing the acid-resistant property and oil-phase dispersing property of the magnetic particles; chloromethyl styrene is adopted as a monomer to be synthesized into magnetic chlorine balls by adopting a one-step method; and then, a cross-linking reaction is carried out on the magnetic chlorine balls under the condition of nitrogen protection and in the presence of a buffer agent, thereby preparing the magnetic ultrahigh cross-linking adsorbent resin. The magnetic ultrahigh cross-linking adsorbent resin prepared by the invention can be applied to the elimination of organic pollutants in water, in particular to micro-pollution organic matters, and has wide application prospects in the fields of biological engineering, chemical analysis and the like.
Description
Technical field:
The invention discloses a kind of magnetic super high cross-linked adsorbing resin and preparation method thereof, super high cross-linked adsorbing resin of the internal package of saying so more specifically magnetic-particle and preparation method thereof
Background technology:
In recent years, the magnetic polymer material is widely used in a plurality of fields such as biological medicine engineering, the little pollution removal of environment and quick SPE because of its good separating property.In these were used, primary key problem in technology was to guarantee that the magnetic polymer material has stronger affinity and higher adsorption capacity to object, and existing synthetic technology is to realize through carrying out functionalizing on its surface mostly.And on the other hand, the increase of specific area can significantly improve adsorption capacity equally, and the super high cross-linked adsorbing resin that for example we were familiar with relies on its high-specific surface area (to surpass 1000m just
2/ g) and the abundant microporous structure, in aspect extensive uses such as the processing of bioengineering, chemical analysis, waste water and resources.For this reason, the present invention is intended to develop a kind of high-specific surface area superhigh cross-linking resin material with magnetic, makes it possess high-adsorption-capacity and the advantage that is easy to separate simultaneously.
How the synthetic imperfection still technically at present of magnetic super high cross-linked adsorbing resin, main difficult point are stable being scattered in the resin matrix of magnetic particle, and make resin magnetic in the cross-linking process of back, be able to keep.Traditional super high cross-linked adsorbing resin is that polystyrene back cross-linking reaction under the Louis acid catalysis effect makes; But in the chloromethylation and back cross-linking process of Archon; Reaction system is in the very strong sour environment, and the chloromethylation of magnetic Archon and crosslinked being difficult to of back are realized.Some research proofs use 1-chloro-4-methyl-benzene to replace styrene as monomer in the recent period, can prepare super high cross-linked adsorbing resin (Jou-Hyeon Ahn, Jin-Eon Jang; Chang-Gun Oh; Son-Ki Ihm, Jamie Cortez, and David C.Sherrington; Macromolecules, 39 (2006) 627).1-chloro-4-methyl-benzene was applied in synthesizing of magnetic super high cross-linked adsorbing resin, direct synthesizing magnetic chlorine ball, although avoided the chloromethylation process, the maintenance of back cross-linking process magnetic still is a difficult problem.Therefore, stability that magnetic particle disperses in the resin matrix and acid resistance thereof become the synthetic main restricting factor of magnetic super high cross-linked adsorbing resin.
Summary of the invention:
1, invents the technical problem that will solve
Stability and acid resistance thereof that the magnetic particle that causes to the problem of saying existence in the existing magnetic super high cross-linked adsorbing resin preparation disperses are not strong; The invention provides a kind of magnetic super high cross-linked adsorbing resin and preparation method thereof; Adopt simple method that magnetic particle is carried out preliminary treatment; Strengthen its antiacid performance, and it is evenly disperseed in resin matrix; Adopt new monomer one-step method to prepare the chlorine ball, simplify the synthesis step of chlorine ball; Change the crosslinked reaction environment in back, the synthetic of magnetic super high cross-linked adsorbing resin is achieved.
2, technical scheme
Magnetic super high cross-linked adsorbing resin provided by the present invention is that the magnetic-particle that new monomer of employing and process are modified prepares the chlorine ball, prepares through the back cross-linking reaction then.
A kind of magnetic super high cross-linked adsorbing resin, its super high cross-linked adsorbing resin skeleton and the magnetic-particle that is wrapped in wherein constitute, and resin matrix basic structure formula wherein is following:
its specific saturation magnetization is 0.1-10emu/g, and the resin average grain diameter is 60-300 μ m.
Above-mentioned magnetic super high cross-linked adsorbing resin, specific area is: 300-1200m
2/ g, the resin average grain diameter is 60-300 μ m, is preferably 80-200 μ m.
The magnetic-particle of being mentioned is meant the Fe with coupling agent double wrapped such as dispersants such as oleic acid, ethyl orthosilicate, neopelex and VTES, vinyltrimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane
3O
4, γ-Fe
2O
3, stainless steel powder, iron-nickel alloy particle etc., its particle diameter is 0.01～10 μ m, is preferably 0.1～5 μ m.
The preparation method of magnetic super high cross-linked adsorbing resin the steps include:
(a) be equipped with water, it is 0.1%～4% dispersant that aqueous phase adds the mass percent that accounts for water;
The dispersant that is adopted in the step (a) is selected from a kind of or its mixture in gelatin, polyvinyl alcohol, the hydroxyethylcellulose;
(b) be equipped with oil phase, oil phase is made up of reactant, pore-foaming agent, initator, and the mass ratio of reactant and pore-foaming agent is 1: 0.5～1: 2, and the mass percent that initator accounts for oil phase is 0.5～2%; Wherein reactant is made up of monomer and crosslinking agent, and the mass ratio of monomer and crosslinking agent is 1: 0.05～1: 0.2;
The monomer that is adopted in the step (b) is a 1-chloro-4-methyl-benzene, and crosslinking agent is a divinylbenzene;
Employed pore-foaming agent main component is monomer or its mixture of C4～C22 alkanes, C4～C22 alkane chain alcohol or saturated aromatic compound in the step (b), is preferably in toluene, xylenes, isobutanol, n-butanol, n-hexane, normal heptane, normal octane, n-dodecane, hexadecane, the atoleine one or more;
Employed initator is meant a kind of or its mixture in benzoyl peroxide, the azodiisobutyronitrile etc. in the step (b);
(c) the preliminary modification of magnetic particle; Organic solvent, magnetic-particle are mixed with the coupling agent ethyl orthosilicate; Wherein the mass ratio of organic solvent and magnetic-particle is 1: 1～5: 1; The mass ratio of ethyl orthosilicate and magnetic-particle is 0.1: 1～1: 1, reacts 3～24h, washed with methanol down at 40～65 ℃;
Employed organic solvent is selected from methyl alcohol, ethanol, acetone etc. in the step (c);
Employed magnetic-particle is selected from Fe in the step (c)
3O
4, γ-Fe
2O
3, stainless steel powder, iron-nickel alloy particle etc.;
(d) bilayer of magnetic particle is modified; With step (c) gained magnetic-particle and dispersant, methanol mixed; Wherein the mass ratio of methyl alcohol and magnetic-particle is 1: 1～5: 1; The mass ratio of dispersant and magnetic-particle is 0.1: 1～1: 1, at 40～65 ℃ of following reaction 3～24h, and oven dry after the washed with methanol 5 times;
Employed dispersant is selected from oleic acid, VTES, vinyltrimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, neopelex etc. in the step (d);
(e) the chlorine ball is synthetic, and the magnetic-particle that obtains in the step (d) is mixed with oil phase, and the mass percent that magnetic-particle accounts for reactant is 3～50%.The oil phase that will contain magnetic-particle is mixed with water, and mixing speed is 200～400rpm, and temperature rises to 70～80 ℃, reacts after 2～8 hours to be incubated 1～15 hour down in 85～95 ℃;
(f) with the resin centrifugation that obtains in the step (e), difference water, ethanol, washing with acetone, 60 ℃ of following vacuum drying;
(g) back cross-linking reaction; The resin that step (f) obtains adds sodium carbonate and lewis acid catalyst with solvent swell 6 hours, under the condition that feeds nitrogen; Insert reaction system in the concentrated base outward; 80 ℃～90 ℃ reactions 12～16 hours, sodium carbonate amount was 50～100% of a resin quality, and catalyst amount is 20～80% of a resin quality;
The solvent of the employed swelling resin of step (f) is dichloroethanes, nitrobenzene, n-hexane or normal heptane;
The employed lewis acid catalyst of step (f) is selected from iron chloride, zinc chloride or aluminium chloride;
(h) ethanol, washing with acetone are used in the resin centrifugation that step (g) is obtained respectively, air-dry after, 60 ℃ of following vacuum drying obtain the magnetic super high cross-linked adsorbing resin.
2, beneficial effect
The invention provides a kind of magnetic super high cross-linked adsorbing resin and preparation method thereof; Adopt coupling agent and dispersant that magnetic particle is carried out bilayer and modify, strengthened its acid resistance greatly, realized the successful preparation of magnetic super high cross-linked adsorbing resin; Its processing step is simple, and method is simple.The resulting magnetic super high cross-linked adsorbing resin of the present invention has absorption, desorption kinetic performance preferably, and is convenient to separate, and helps improving treatment effeciency, reduces processing cost.
Description of drawings
The FT-IR collection of illustrative plates of the magnetic superhigh cross-linking resin that Fig. 1 prepares for the present invention, as can be seen from the figure, this superhigh cross-linking resin has certain tertiary alcohol structure, and this mainly is to be contributed by silane coupler.Therefrom can judge 817cm according to list of references (R.V.Law, D.C.Sherrington, C.E.Snape, I.Ando, H.Korosu, Macromolecules1996,29,6284.)
-1And 1511cm
-1Two strong absworption peaks at place have proved and have existed a large amount of methylene bridge structures to see Fig. 2 (a) between the phenyl ring that this and superhigh cross-linking resin structure coincide.Simultaneously at 756cm
-1About do not have the mono-substituted absworption peak of phenyl ring, explain that phenyl ring at least all is two replacements in this material.
Fig. 2 is superhigh cross-linking resin structure figure, wherein (a) methylene bridge structure; (b) dimethylene bridge construction.
Fig. 3 is that same prescription does not add the synthetic superhigh cross-linking resin of magnetic particle
13C NMR collection of illustrative plates is for further proving the structure of this material, according to list of references (R.V.Law, D.C.Sherrington; C.E.Snape, I.Ando, H.Korosu, Macromolecules 1996; 29,6284.), peak area can compare phenyl ring carbon Ar in this material from nuclear magnetic resonance map
Total: alkane chain carbon Al
Total=1.78: 1, if the superhigh cross-linking resin all is the structure among Fig. 2 (a), then theoretical value should be 2.4: 1, proves the methylene bridge structure that there are other modes in it, infers its structure such as Fig. 2 (b).
The specific embodiment
Adopt 20g ethyl orthosilicate and 20g oleic acid to 40g γ-Fe
2O
3Carry out double wrapped.Oil phase is made up of 60g 1-chloro-4-methyl-benzene, 4g divinylbenzene, 17g normal heptane, 17g toluene, 2g benzoyl peroxide.2g gelatin, 3g polyvinyl alcohol be dissolved in the 500g water be made into water.Oil phase and 40g magnetic particle are added in the three-necked bottle, stir fast, add water simultaneously.Be warming up to 70 ℃ of initiation reactions, polymerization 6h progressively is warming up to 95 ℃ again, reaction 6h.With the chlorine ball centrifugation that obtains, water, ethanol, washing with acetone, dry back adds the dichloroethanes swelling; Under the condition of nitrogen protection and external alkali lye; Drop into the sodium carbonate of resin quality 60% and 80% iron chloride, reacted 12 hours down in 80 ℃, ethanol, washing with acetone get finished product.
The resin particle diameter is 150～200 μ m, and specific saturation magnetization is 8.3emu/g; Use the nitrogen adsorption method to record the BET specific area and be 481m
2/ g.According to analyzing in Fig. 1～3, prepared the magnetic super high cross-linked adsorbing resin skeleton that obtains is
Adopt 35g ethyl orthosilicate and 35g vinyltrimethoxy silane to 35g Fe
3O
4Carry out double wrapped.Oil phase is made up of 40g 1-chloro-4-methyl-benzene, 8g divinylbenzene, 25g normal heptane, 25g atoleine, 2g azodiisobutyronitrile.10g gelatin, 3g hydroxyethylcellulose be dissolved in the 500g water be made into water.Oil phase and 35g magnetic particle are added in the three-necked bottle, stir fast, add water simultaneously.Be warming up to 70 ℃ of initiation reactions, polymerization 2h progressively is warming up to 95 ℃ again, reaction 2h.With the chlorine ball centrifugation that obtains, water, ethanol, washing with acetone, dry back adds the dichloroethanes swelling; Under the condition of nitrogen protection and external alkali lye; Drop into the sodium carbonate of resin quality 80% and 50% iron chloride, reacted 15 hours down in 80 ℃, ethanol, washing with acetone get finished product.
The resin particle diameter is 60～140 μ m, and specific saturation magnetization is 4.3emu/g; Use the nitrogen adsorption method to record the BET specific area and be 532m
2/ g.The prepared magnetic super high cross-linked adsorbing resin skeleton that obtains is with embodiment 1.
Embodiment 3
Adopt 3g ethyl orthosilicate and 3g neopelex that the 3g stainless steel powder is carried out double wrapped.Oil phase is made up of 50g 1-chloro-4-methyl-benzene, 8g divinylbenzene, 20g normal heptane, 20g isobutanol, 1g azodiisobutyronitrile, 1g benzoyl peroxide.6g gelatin, 6g hydroxyethylcellulose be dissolved in the 500g water be made into water.Oil phase and 3g magnetic particle are added in the three-necked bottle, stir fast, add water simultaneously.Be warming up to 75 ℃ of initiation reactions, polymerization 4h progressively is warming up to 85 ℃ again, reaction 1h.With the chlorine ball centrifugation that obtains, water, ethanol, washing with acetone, dry back adds the nitrobenzene swelling; Under the condition of nitrogen protection and external alkali lye; Drop into the sodium carbonate of resin quality 60% and 40% aluminium chloride, reacted 12 hours down in 85 ℃, ethanol, washing with acetone get finished product.
The resin particle diameter is 180～240 μ m, and specific saturation magnetization is 0.1emu/g; Use the nitrogen adsorption method to record the BET specific area and be 1200m
2/ g.The prepared magnetic super high cross-linked adsorbing resin skeleton that obtains is with embodiment 1.
Embodiment 4
Adopt 20g ethyl orthosilicate and 20g VTES that 25g iron-nickel alloy particle is carried out double wrapped.Oil phase is made up of 35g 1-chloro-4-methyl-benzene, 7g divinylbenzene, 56.5g normal heptane, 1.5g azodiisobutyronitrile.5g polyvinyl alcohol, 10g hydroxyethylcellulose be dissolved in the 500g water be made into water.Oil phase and 25g magnetic particle are added in the three-necked bottle, stir fast, add water simultaneously.Be warming up to 70 ℃ of initiation reactions, polymerization 5h progressively is warming up to 85 ℃ again, reaction 4h.With the chlorine ball centrifugation that obtains, water, ethanol, washing with acetone, dry back adds the nitrobenzene swelling; Under the condition of nitrogen protection and external alkali lye; Drop into the sodium carbonate of resin quality 70% and 30% aluminium chloride, reacted 14 hours down in 90 ℃, ethanol, washing with acetone get finished product.
The resin particle diameter is 210～300 μ m, and specific saturation magnetization is 7.9emu/g; Use the nitrogen adsorption method to record the BET specific area and be 901m
2/ g.The prepared magnetic super high cross-linked adsorbing resin skeleton that obtains is with embodiment 1.
Embodiment 5
Adopt 25g ethyl orthosilicate and 25g vinyl three ('beta '-methoxy ethyoxyl) silane to 30g Fe
3O
4Carry out double wrapped.Oil phase is made up of 49g 1-chloro-4-methyl-benzene, 10g divinylbenzene, 20g xylenes, 20g n-dodecane, 1g benzoyl peroxide.The 20g gelatin is dissolved in the 500g water is made into water.Oil phase and 30g magnetic particle are added in the three-necked bottle, stir fast, add water simultaneously.Be warming up to 75 ℃ of initiation reactions, polymerase 17 h progressively is warming up to 90 ℃ again, reaction 2h.With the chlorine ball centrifugation that obtains, water, ethanol, washing with acetone, dry back adds the dichloroethanes swelling; Under the condition of nitrogen protection and external alkali lye; Drop into the sodium carbonate of resin quality 100% and 20% zinc chloride, reacted 15 hours down in 80 ℃, ethanol, washing with acetone get finished product.
The resin particle diameter is 130～220 μ m, and specific saturation magnetization is 6.4emu/g; Use the nitrogen adsorption method to record the BET specific area and be 658m
2/ g.The prepared magnetic super high cross-linked adsorbing resin skeleton that obtains is with embodiment 1.
Embodiment 6
Adopt 15g ethyl orthosilicate and 2g vinyltrimethoxy silane that the 20g stainless steel powder is carried out double wrapped.Oil phase is made up of 60g 1-chloro-4-methyl-benzene, 1.5g divinylbenzene, 17.5g n-hexane, 20g n-butanol, 0.5g benzoyl peroxide, 0.5g azodiisobutyronitrile.The 15g polyvinyl alcohol is dissolved in the 500g water is made into water.Oil phase and 20g magnetic particle are added in the three-necked bottle, stir fast, add water simultaneously.Be warming up to 70 ℃ of initiation reactions, polymerization 8h progressively is warming up to 90 ℃ again, reaction 6h.With the chlorine ball centrifugation that obtains, water, ethanol, washing with acetone, dry back adds the dichloroethanes swelling; Under the condition of nitrogen protection and external alkali lye; Drop into the sodium carbonate of resin quality 80% and 30% aluminium chloride, reacted 12 hours down in 80 ℃, ethanol, washing with acetone get finished product.
The resin particle diameter is 60～170 μ m, and specific saturation magnetization is 3.1emu/g; Use the nitrogen adsorption method to record the BET specific area and be 772m
2/ g.The prepared magnetic super high cross-linked adsorbing resin skeleton that obtains is with embodiment 1.
Embodiment 7
Adopt 5g ethyl orthosilicate and 25g VTES that 50g iron-nickel alloy particle is carried out double wrapped.Oil phase is made up of 50g 1-chloro-4-methyl-benzene, 8g divinylbenzene, 20g normal heptane, 10g toluene, 10g isobutanol, 1.5g benzoyl peroxide, 0.5g azodiisobutyronitrile.The 20g hydroxyethylcellulose is dissolved in the 500g water is made into water.Oil phase and 50g magnetic particle are added in the three-necked bottle, stir fast, add water simultaneously.Be warming up to 70 ℃ of initiation reactions, polymerization 6h progressively is warming up to 95 ℃ again, reaction 15h.With the chlorine ball centrifugation that obtains, water, ethanol, washing with acetone, dry back adds the nitrobenzene swelling; Under the condition of nitrogen protection and external alkali lye; Drop into the sodium carbonate of resin quality 50% and 70% normal heptane, reacted 14 hours down in 85 ℃, ethanol, washing with acetone get finished product.
The resin particle diameter is 90～200 μ m, and specific saturation magnetization is 9.3emu/g; Use the nitrogen adsorption method to record the BET specific area and be 300m
2/ g.The prepared magnetic super high cross-linked adsorbing resin skeleton that obtains is with embodiment 1.
Embodiment 8
Adopt 5g ethyl orthosilicate and 5g VTES to 5g Fe
3O
4Carry out double wrapped.Oil phase is made up of 60g 1-chloro-4-methyl-benzene, 1.5g divinylbenzene, 17.5g n-hexane, 20g n-butanol, 0.5g benzoyl peroxide, 0.5g azodiisobutyronitrile.The 15g polyvinyl alcohol is dissolved in the 500g water is made into water.Oil phase and 5g magnetic particle are added in the three-necked bottle, stir fast, add water simultaneously.Be warming up to 70 ℃ of initiation reactions, polymerization 8h progressively is warming up to 85 ℃ again, reaction 12h.With the chlorine ball centrifugation that obtains, water, ethanol, washing with acetone, dry back adds the dichloroethanes swelling; Under the condition of nitrogen protection and external alkali lye; Drop into the sodium carbonate of resin quality 70% and 40% aluminium chloride, reacted 12 hours down in 80 ℃, ethanol, washing with acetone get finished product.
The resin particle diameter is 60～170 μ m, and specific saturation magnetization is 0.8emu/g; Use the nitrogen adsorption method to record the BET specific area and be 1036m
2/ g.The prepared magnetic super high cross-linked adsorbing resin skeleton that obtains is with embodiment 1.
Claims (9)
1. a magnetic super high cross-linked adsorbing resin is characterized in that its super high cross-linked adsorbing resin skeleton and the magnetic-particle that is wrapped in wherein constitute, and resin matrix basic structure formula wherein is following:
(a) be equipped with water, it is 0.1%～4% dispersant that aqueous phase adds the mass percent that accounts for water;
(b) be equipped with oil phase, oil phase is made up of reactant, pore-foaming agent, initator, and the mass ratio of reactant and pore-foaming agent is 1: 0.5～1: 2, and the mass percent that initator accounts for oil phase is 0.5～2%; Wherein reactant is made up of monomer and crosslinking agent, and the mass ratio of monomer and crosslinking agent is 1: 0.05～1: 0.2;
(c) the preliminary modification of magnetic particle; Organic solvent, magnetic-particle are mixed with the coupling agent ethyl orthosilicate; Wherein the mass ratio of organic solvent and magnetic-particle is 1: 1～5: 1; The mass ratio of ethyl orthosilicate and magnetic-particle is 0.1: 1～1: 1, reacts 3～24h, washed with methanol 5 times down at 40～65 ℃;
(d) bilayer of magnetic particle is modified; With step (c) gained magnetic-particle and dispersant, methanol mixed; Wherein the mass ratio of methyl alcohol and magnetic-particle is 1: 1～5: 1; The mass ratio of dispersant and magnetic-particle is 0.1: 1～1: 1, at 40～65 ℃ of following reaction 3～24h, and oven dry after the washed with methanol 5 times;
(e) the chlorine ball is synthetic, and the magnetic-particle that obtains in the step (d) is mixed with oil phase, and the mass percent that magnetic-particle accounts for reactant is 3～50%; The oil phase that will contain magnetic-particle is mixed with water, and mixing speed is 200～400rpm, and temperature rises to 70～80 ℃, reacts after 2～8 hours to be incubated 1～15 hour down in 85～95 ℃;
(f) with the resin centrifugation that obtains in the step (e), difference water, ethanol, washing with acetone, 60 ℃ of following vacuum drying;
(g) back cross-linking reaction, the resin that step (f) obtains be with solvent swell 6 hours, adding sodium carbonate and lewis acid catalyst; Under the condition that feeds nitrogen; Reaction system is inserted outward in the concentrated base, and 80 ℃～90 ℃ reactions 12～16 hours, the mass percent of solvent load and resin was 3: 1～8: 1; Sodium carbonate amount is 50～100% of a resin quality, and catalyst amount is 20～80% of a resin quality;
(h) ethanol, washing with acetone are used in the resin centrifugation that step (g) is obtained respectively, air-dry after, 60 ℃ of following vacuum drying obtain the magnetic super high cross-linked adsorbing resin.
2. a kind of magnetic super high cross-linked adsorbing resin according to claim 1 is characterized in that its specific area is: 300-1200m
2/ g.
3. the preparation method of a magnetic super high cross-linked adsorbing resin the steps include:
(a) be equipped with water, it is 0.1%～4% dispersant that aqueous phase adds the mass percent that accounts for water;
(b) be equipped with oil phase, oil phase is made up of reactant, pore-foaming agent, initator, and the mass ratio of reactant and pore-foaming agent is 1: 0.5～1: 2, and the mass percent that initator accounts for oil phase is 0.5～2%; Wherein reactant is made up of monomer and crosslinking agent, and the mass ratio of monomer and crosslinking agent is 1: 0.05～1: 0.2;
(c) the preliminary modification of magnetic particle; Organic solvent, magnetic-particle are mixed with the coupling agent ethyl orthosilicate; Wherein the mass ratio of organic solvent and magnetic-particle is 1: 1～5: 1; The mass ratio of ethyl orthosilicate and magnetic-particle is 0.1: 1～1: 1, reacts 3～24h, washed with methanol 5 times down at 40～65 ℃;
(d) bilayer of magnetic particle is modified; With step (c) gained magnetic-particle and dispersant, methanol mixed; Wherein the mass ratio of methyl alcohol and magnetic-particle is 1: 1～5: 1; The mass ratio of dispersant and magnetic-particle is 0.1: 1～1: 1, at 40～65 ℃ of following reaction 3～24h, and oven dry after the washed with methanol 5 times;
(e) the chlorine ball is synthetic, and the magnetic-particle that obtains in the step (d) is mixed with oil phase, and the mass percent that magnetic-particle accounts for reactant is 3～50%; The oil phase that will contain magnetic-particle is mixed with water, and mixing speed is 200～400rpm, and temperature rises to 70～80 ℃, reacts after 2～8 hours to be incubated 1～15 hour down in 85～95 ℃;
(f) with the resin centrifugation that obtains in the step (e), difference water, ethanol, washing with acetone, 60 ℃ of following vacuum drying;
(g) back cross-linking reaction, the resin that step (f) obtains be with solvent swell 6 hours, adding sodium carbonate and lewis acid catalyst; Under the condition that feeds nitrogen; Reaction system is inserted outward in the concentrated base, and 80 ℃～90 ℃ reactions 12～16 hours, the mass percent of solvent load and resin was 3: 1～8: 1; Sodium carbonate amount is 50～100% of a resin quality, and catalyst amount is 20～80% of a resin quality;
(h) ethanol, washing with acetone are used in the resin centrifugation that step (g) is obtained respectively, air-dry after, 60 ℃ of following vacuum drying obtain the magnetic super high cross-linked adsorbing resin.
4. the preparation method of a kind of magnetic super high cross-linked adsorbing resin according to claim 3, the dispersant that it is characterized in that step (a) is a kind of or its mixture in gelatin, polyvinyl alcohol, the hydroxyethylcellulose.
5. the preparation method of a kind of magnetic super high cross-linked adsorbing resin according to claim 4, the monomer that it is characterized in that step (b) is a 1-chloro-4-methyl-benzene; Crosslinking agent is a divinylbenzene; The pore-foaming agent of step (b) is monomer or its mixture of C4～C22 alkanes, C4～C22 alkane chain alcohol or saturated aromatic compound.
6. according to the preparation method of claim 4 or 5 described a kind of magnetic super high cross-linked adsorbing resins, it is characterized in that the initator of step (b) is elected benzoyl peroxide, azodiisobutyronitrile or its mixture as.
7. according to the preparation method of claim 4 or 5 described a kind of magnetic super high cross-linked adsorbing resins, the magnetic-particle that it is characterized in that step (c) is Fe
3O
4, γ-Fe
2O
3, stainless steel powder or iron-nickel alloy particle; Organic solvent is methyl alcohol, ethanol or acetone.
8. according to the preparation method of claim 4 or 5 described a kind of magnetic super high cross-linked adsorbing resins, it is characterized in that the dispersant of step (d) is meant oleic acid, VTES, vinyltrimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, neopelex.
9. according to the preparation method of claim 4 or 5 described a kind of magnetic super high cross-linked adsorbing resins, it is characterized in that the solvent of step (g) is elected dichloroethanes, nitrobenzene, n-hexane or normal heptane as, lewis acid catalyst is iron chloride, zinc chloride or aluminium chloride.
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