CN1151334A - Preparation method of macroporous strong acid type cation exchange resin catalyst - Google Patents
Preparation method of macroporous strong acid type cation exchange resin catalyst Download PDFInfo
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- CN1151334A CN1151334A CN 95112259 CN95112259A CN1151334A CN 1151334 A CN1151334 A CN 1151334A CN 95112259 CN95112259 CN 95112259 CN 95112259 A CN95112259 A CN 95112259A CN 1151334 A CN1151334 A CN 1151334A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002253 acid Substances 0.000 title claims description 12
- 239000004088 foaming agent Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 241001566735 Archon Species 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 3
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 150000002605 large molecules Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000003044 adaptive effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000006266 etherification reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 125000000542 sulfonic acid group Chemical group 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- MQGIBEAIDUOVOH-UHFFFAOYSA-N 1-[2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOCCOCCCC MQGIBEAIDUOVOH-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000008961 swelling Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a macroporous cation exchange resin catalyst, which takes a C3-C4 low-carbon alcohol compound as a pore-foaming agent, and adopts a polymer compound which is adaptive to the pore-foaming agent as a dispersing agent and an auxiliary dispersing agent to make styrene and a polyvinyl monomer undergo suspension copolymerization to prepare copolymer white balls with reasonable pore structure and uniform particle size. And then the white balls are dynamically treated by high-temperature deionized water, and the treated white balls are directly subjected to sulfonation reaction without being subjected to hole expanding by an organic solvent, so that the production efficiency can be improved, the production cost can be reduced, and the environmental pollution can be reduced. The prepared resin has the advantages of high exchange capacity, high catalytic activity, long service life and the like, and can be widely applied to organic catalytic reactions such as etherification and the like.
Description
The present invention relates to a kind of preparation method of catalyst of large porous strong acid cation exchange resin, relating to a kind of organic catalytic reactions such as etherificate that are used for specifically, is that the pore-foaming agent synthesizing styrene is the method for catalyst of large porous strong acid cation exchange resin with the low-carbon alcohols compounds.
The polystyrene large porous strong acid cation exchange resin is widely used in the organic catalytic reactions such as etherificate, esterification, hydrolysis, and the quality of pore structure directly influences activity of such catalysts and selectivity.Suitable catalyst is this area research personnel's the common objective of the struggle how to prepare pore structure, and the processing of the selection of pore-foaming agent and preparation technology's central hole structure is the key that reaches this target in the polymerization formula.
The technology of traditional preparation process large hole cation exchanger resin is divided into polymerization and sulfonation two parts.
Promptly in the presence of pore-foaming agent, styrene and multi-vinyl monomer suspension polymerisation generate the technology of macroporous copolymer Archon to polymeric part, and the pore-foaming agent that adopts divides following several usually:
(1) can dissolve each other with polymerization single polymerization monomer and the organic solvent of swollen polymer not, claim poor solvent, as gasoline, C
5～C
6Alkane, C
5～C
12Fatty alcohol etc.The resin aperture of adopting such pore-foaming agent to make is big, specific area is less.
(2) can dissolve each other with polymerization single polymerization monomer and organic solvent that can swollen polymer, claim good solvent, as benzene and homologue thereof etc.The resin aperture of making is less, specific area is bigger.
(3) linear polymer of mono-vinyl monomer, as polystyrene etc., the resin pore structure of making is more even, but that pore-foaming agent is difficult to extracting is clean, and the extraction process more complicated.
(4) in order to adjust pore structure, good solvent and poor solvent are used.
Use above-mentioned pore-foaming agent in the polymerization,, all will carry out the swelling reaming to Archon before the sulfonation with organic solvents such as chlorohydrocarbons though can make the Archon of required pore structure.So just, need increase the operation that a chlorohydrocarbon reclaims, not only operating process is loaded down with trivial details, and used chlorohydrocarbon toxicity is bigger, can produce harmful effect to operating environment.
After polymerization technique finished, traditional method was generally all dry with the Archon washing, directly uses chlorohydrocarbon reaming, sulfonation.In fact, the small organic molecule impurity that also residual a part of pore-foaming agent, dispersant and polymerization single polymerization monomer carry in the Archon duct, simply wash with water, be difficult to it is removed clean, they are attached on the hole wall, sulfonating reaction is formed one deck barrier, hinder combining of carbon atom on sulfonic acid group and the phenyl ring, cause the resin exchange capacity reduction.Simultaneously some small molecular weight impurity can be sulfonated equally, forms unsettled active constituent, cause resin in use active constituent constantly run off, influence catalytic effect.
Chinese patent CN1032017A proposes the synthetic making large-pore white balls used method of the part or all of replace organic solvent of water, can save the reaming step of back, but the Archon intensity of making is too low, is used for organic catalytic reaction after the sulfonation, anti-breaking capacity is too poor, can not satisfy the catalytic reaction requirement well.
Chinese patent CN1076385A proposes a kind of method of purifying copolymer structure, can slow down the loss of resin active constituent, promptly uses C
1～C
4Halogenated hydrocarbons was with copolymer swelling 0.5～5.0 hour, again the copolymer after the swelling is moved in the benzene series solvent of 1.5～4.0 times of volumes, handled 3～20 hours in 0.1～5.0MPa and 130 ℃～200 ℃, handled 3～20 hours down in similarity condition with absolute ethyl alcohol, washing is dry at last.This processing method not only can be disposed organic impurities in the hole, also the linear molecule chain in the polymer is all extracted simultaneously, has changed the original grid structure of polymer.Therefore this processing method has also played the effect that increases hole and reaming, and the polymer that the degree of cross linking is low is more handled its pore structure of back and changed more greatly.But this processing method operating process more complicated, and can cause the loss of benzene series solvent and ethanol to a certain extent.
The objective of the invention is the problem at above-mentioned existence, a kind of simple economy is provided, preparation has greater activity and optionally, is used for the method for the catalyst of large porous strong acid cation exchange resin of organic catalytic reaction.
For achieving the above object, technical scheme of the present invention is: 1. make pore-foaming agent by employing low-carbon alcohols compounds, and adopt the dispersion that adapts with it, make the polymer Archon; 2. with the high temperature deionized water 1. product is carried out purified treatment, impurity is removed; 3. with conventional method 2. product is carried out sulfonation.
The dispersion that said method is mentioned in 1. is made up of dispersant, dispersion aids and electrolyte, its action principle is: owing to adopt the low-carbon alcohols compounds to make pore-foaming agent in polymerization process, reduced the surface tension of organic facies in water, if adopt conventional dispersion, can make the copolymer Archon size distribution that makes inhomogeneous, reduce the yield of qualified polymer.And adopt dispersion of the present invention, make dispersion aids by in conventional dispersion, adding a kind of high molecular polymer, can increase the surface tension of organic facies effectively at aqueous phase, thereby make Archon epigranular that polymerization obtains, be of moderate size, qualified polymer yield can be increased to more than 90%.
The process of the purification Archon pore structure that the foregoing invention method is mentioned in 2. is a kind of physical process, can under the prerequisite that does not change the polymer three-dimensional grid structure contaminant removal in the Archon hole be fallen.The method of the purifying copolymer structure that proposes among the method for this purification Archon pore structure and the Chinese patent CN1076385 has the difference of essence, and the latter is a kind of chemical process, in the Purge holes structure, the linear polymer in the polymer is all extracted.
Detailed process of the present invention is as follows:
1. the macroporous copolymer Archon is synthetic:
In the presence of low-carbon (LC) alcohols pore-foaming agent and the dispersion that adapts, make styrene and multi-vinyl monomer suspension copolymerization, the macroporous copolymer Archon that generation has required pore structure.The each component proportioning is as follows in the whole polymerization system: (if no specified otherwise, hereinafter shown in umber be weight portion) oil phase: 70～90 parts of styrene are preferably 75～85 parts
30～10 parts of multi-vinyl monomers are preferably 25～15 parts
0.5～5 part of initator is preferably 1.0～1.2 parts
40～150 parts of pore-foaming agents (low-carbon (LC) alcohols) are preferably 60～75 parts of waters: 1～5 part of dispersant is preferably 2.2～2.6 parts
0.1～5 part of dispersion aids is preferably 0.1～0.2 part
10～50 parts in electrolyte is preferably 18～22 parts
0.01～1 part of polymerization inhibitor is preferably 0.03～0.04 part
200～1000 parts in decentralized medium (deionized water) is preferably 350～450 parts
Multi-vinyl monomer in the above-mentioned prescription can adopt divinylbenzene, divinyl dimethylbenzene, divinyl toluene etc.; Initator can adopt benzoyl peroxide, azodiisobutyronitrile etc.; Pore-foaming agent can adopt the alcohols of C3～C4, as isopropyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, isobutanol etc.; Dispersant can adopt gelatin, polyvinyl alcohol etc.; Dispersion aids can adopt polyacrylamide (Mw=10 ten thousand～3,000,000), PDDA (Mw=10 ten thousand～3,000,000), ammonium polystyrene-maleic anhydride (Mw=8 ten thousand～2,000,000) etc.; Electrolyte can be used sodium chloride, ammonium chloride etc.; The water polymerization inhibitor can be used methylene blue.
Take by weighing deionized water in reactor by above-mentioned prescription, add the water auxiliary agent, adding thermal agitation dissolves it fully, be warming up to 40 ℃～70 ℃ then, the oil phase component that adding takes by weighing by above-mentioned prescription stirs and is warming up to 60 ℃～95 ℃, reacts 6～12 hours, product is filtered, obtain even-grained macroporous copolymer Archon with perfect apertures structure.
2. the purification of Archon pore structure.
Making large-pore white balls usedly place the going of 2～10 times of volumes with what above-mentioned copolymerization obtained, under 70 ℃～100 ℃, decompression or normal pressure, boiled 3～8 hours from water, then with hot wash, filter and dry, the impurity in the Archon hole is just removed.
3. the sulfonation of Archon.
Be not higher than under 85 ℃ and the stirring condition, to through dripping 10%～20% oleum in the copolymer Archon of purified treatment, to add sulfuric acid weight be 4～8 times of Archon weight, be warming up to 85 ℃～100 ℃ then, kept 2～5 hours, and be warming up to 105 ℃～140 ℃ again, reacted 3～8 hours.Reaction finishes, and adds the dilute sulfuric acid dilute reaction solution in reactor, makes its concentration reduce to 30%～40%, and extremely neutral with big water gaging flushing again, centrifugal filtration just obtains Hydrogen ion exchange resin.
Its granularity of resin made from the inventive method is 0.3mm～1.2mm, and average pore radius is 15nm～60nm, and specific area is 40～80m2/g, specific pore volume 0.25～0.65ml/g, exchange capacity 〉=4.6mmol/g, wear-resisting rate 〉=85%.
The outstanding advantage of the inventive method shows: 1. polymerization stage adopts the low-carbon (LC) alcohols to make pore-foaming agent, the polymer Archon of making just can carry out sulfonation without reaming, saved the operation of using the reaming of chlorohydrocarbon swelling in the traditional handicraft, not only can enhance productivity, reduce production costs, also can overcome by distillation and reclaim the environmental pollution that expanding agent brings.2. adopt simple effective method that pore structure is cleared up, can improve resin exchange capacity, reduce the loss of active group, thus the service life of having improved resin catalyst.3. the resin pore size of making is moderate, is evenly distributed, and pore volume and specific area are bigger, thereby (see Table 2 and 3, table 2 is listed carbon tetraether activity rating result to have higher activity and selectivity in organic catalytic reaction; Table 3 is listed carbon pentaether activity rating result).
In order to illustrate in greater detail method of the present invention, list following each embodiment, but the present invention is not limited to each embodiment.
Example 1.
Polymerization: in having 10 liters of stainless steel stirred tanks of reflux condensate device, add 4500g water, the 28.3g gelatin, 2.1g ammonium polystyrene-maleic anhydride (Mw=40 ten thousand), 240g sodium chloride and 0.4g methine orchid add thermal agitation, and interior each auxiliary agent of still is dissolved fully.Be warming up to 70 ℃, add again by 770g styrene (styrene-content 〉=99%), 430g divinylbenzene (divinylbenzene content 50%), the mixture of organic phase that 780g sec-butyl alcohol and 12g benzoyl peroxide are formed stirs and is warming up to 86 ℃, reacts 10 hours.
Pore structure purifies: product is filtered, and the polymer Archon that obtains places 90 ℃ of deionized waters, and decompression was boiled 6 hours under the pressure of 0.07MPa, spent deionised water again 2 times, and room temperature is dried, and obtains the 1180g Archon.It is 0.28mm～1.00mm that 92% particle size range is wherein arranged.
Sulfonation: in 10 liters of enamel stirred tanks, add the polymer Archon of 700g drying, drip 20% oleum 4200g under stirring condition, the control temperature in the kettle is lower than 70 ℃, is warming up to 90 ℃ then, reacts 2 hours; Be warming up to 105 ℃, reacted 4 hours; Be warming up to 115 ℃, reacted 4 hours, cooling, dilute product in the still by following step:
1. stirring and temperature is lower than under 40 ℃ the condition, Dropwise 5 0% dilute sulfuric acid 5000g dropwises in still, the interior dilute sulfuric acid of sucking-off still, just cover the resin top to liquid level till.
2. stirring and temperature is lower than under 40 ℃ the condition, in still, dripping 30% dilute sulfuric acid 5000g, dropwising the interior dilute sulfuric acid of sucking-off still.
3. slowly drip 30% dilute sulfuric acid 5000g again according to 2. step.
4. stirring and temperature is lower than under 40 ℃ the condition, drip deionized water in still, the while is with certain speed sucking-off liquid from still, be neutrality to liquid till.
With product centrifugal filtration in the still, just can obtain Hydrogen ion exchange resin, its main physical parameter sees Table 1.
The sulfonic acid group estimation of stability: get above-mentioned resin 50g, normal pressure boiled 500 hours in isopropyl alcohol, and temperature is 82.5 ℃ ± 2.5 ℃, has boiled taking-up, and test cross changes capacity and sulfonic acid group falling speed, the results are shown in Table 1, and table 1 is listed the main physical parameter of various resins.
Carbon tetraether catalytically active assessment: get above-mentioned fresh resin catalyst 20ml, carry out the methyl tertiary butyl ether(MTBE) synthetic reaction in the fixed bed reactors of pack into internal diameter 12mm, long 300mm.Reaction condition: alcohol/alkene=1.05 (mol ratio), reaction pressure 1.5MPa, reaction result sees Table 2.
Carbon pentaether catalytically active assessment: get above-mentioned fresh resin catalyst 20ml, the internal diameter 12mm that packs in the fixed bed reactors of long 300mm, carries out the tert amyl methyl ether(TAME) synthetic reaction.Reaction condition: alcohol/alkene=1.05 (mol ratio), reaction pressure 1.2MPa, reaction result sees Table 3.
Example 2.
Polymerization: in the stirred tank identical with example 1, add 5400g water, 31.2g gelatin, 1.8g PDDA (Mw=120 ten thousand), 240g sodium chloride and 0.4g methylene blue, be warming up to 70 ℃, add by 570g styrene (styrene-content 〉=99%) 630g divinylbenzene (divinylbenzene content 50%), the mixture of organic phase that 800g sec-butyl alcohol and 12g benzoyl peroxide are formed again, stirring is warming up to 86 ℃, reacts 10 hours.
The purification of pore structure: product is filtered, and the polymer Archon that obtains places 100 ℃ of deionized waters, and normal pressure boiled 4 hours, again with 80 ℃ of deionized water washings 2 times, room temperature is dried, and obtains the 1160g Archon, and it is 0.28mm～1.00mm that 90.5% particle size range is wherein arranged.
Method of sulfonating and sulfonic acid group method for estimating stability are identical with example 1, and the main physical parameter of resin and the exfoliation rates of sulfonic acid group see Table 1.
Carbon four, carbon pentaether catalytically active assessment method are identical with example 1, and evaluation result sees Table 2 and 3.
Example 3
In polymerization formula, remove and adopt 1.4g ammonium phenylethylene-maleic anhydride to make dispersion aids, to do outside the pore-foaming agent with the 750g tert-butyl alcohol, additive method is identical with example 1.Obtain the 1180g Archon, it is 0.28mm～1.00mm that 93.2% particle size range is wherein arranged.Main physical parameter of the resin that obtains after the sulfonation and sulfonic acid group exfoliation rates see Table 1.Carbon four, carbon pentaether catalytically active assessment the results are shown in Table 2, table 3.
Comparative example 1
The copolymer Archon made from the method identical with example 1, without the pore structure purified treatment, directly washing, drying use the method identical with example 1 to carry out sulfonation again, and its exchange capacity data of the ion exchange resin of making see Table 1.Adopt the method identical with example 1, carry out the sulfonic acid group estimation of stability and test, the sulfonic acid group exfoliation rates sees Table 1.
Comparative example 2
The every physical parameter of resin catalyst Amberlyst-15 that U.S. Rohm and Hass company produces is tested, and used the method identical that it is carried out the test of sulfonic acid group estimation of stability, the results are shown in Table 1 with example 1.Carry out carbon four, the test of carbon pentaether catalytically active assessment with the method identical, the results are shown in Table 2, table 3 with example 1.Table 1
Table 2
Table 3
Claims (6)
1. earlier by styrene and multi-vinyl monomer, there is the low suspension copolymerization in the preparation method of a catalyst of large porous strong acid cation exchange resin at pore-foaming agent and dispersant, make into the macroporous copolymer Archon, through hole purification, sulfonation, make resin catalyst again, its feature comprises:
(1) with C
3～C
4The low-carbon alcohols compounds make pore-foaming agent, and adopt the high-molecular weight compounds adapt with it to make dispersant and dispersion aids prepares the copolymer Archon, whole each set of dispense of polymerization system is such as (by weight) down:
Oil phase: 70～90 parts of styrene
30～10 parts of multi-vinyl monomers
0.5～5 part of initator
40～150 parts of pore-foaming agents (low-carbon (LC) alcohols)
Water: 1～5 part of dispersant
0.1～5 part of dispersion aids
10～50 parts in electrolyte
0.01～1 part of polymerization inhibitor
200～1000 parts in decentralized medium (water)
(2) product with step (1) places deionized water, boils processing under decompression or the normal pressure, uses hot wash, filtration, drying then;
(3) product with step (2) carries out sulfonation.
2. according to the preparation method of the described catalyst of large porous strong acid cation exchange resin of claim 1, it is characterized in that each set of dispense of polymerization system than (by weight) is:
Oil phase: 75～85 parts of styrene
25～15 parts of multi-vinyl monomers
1.0～1.2 parts of initators
60～75 parts of pore-foaming agents (low-carbon (LC) alcohols)
Water: 2.2～2.6 parts of dispersants
0.1～0.2 part of dispersion aids
18～22 parts in electrolyte
0.03～0.04 part of polymerization inhibitor
350～450 parts in decentralized medium (deionized water)
3. according to the preparation method of claim 1 or 2 described catalyst of large porous strong acid cation exchange resin, it is characterized in that described multi-vinyl monomer is divinylbenzene, divinyl dimethylbenzene, divinyl toluene.
4. according to the preparation method of claim 1 or 2 described catalyst of large porous strong acid cation exchange resin, it is characterized in that described pore-foaming agent is isopropyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, isobutanol.
5. according to the preparation method of claim 1 or 2 described catalyst of large porous strong acid cation exchange resin, it is characterized in that described dispersant is gelatin, polyvinyl alcohol; Described dispersion aids can be polyacrylamide (Mw=10～3,000,000), PDDA (Wm=10～3,000,000), ammonium polystyrene-maleic anhydride (Mw=8～2,000,000).
6. according to the preparation method of the described catalyst of large porous strong acid cation exchange resin of claim 1, it is characterized in that the copolymer Archon that makes being placed 2～10 times deionized water, under 70 ℃～100 ℃ decompressions or normal pressure, boiled 3～8 hours.
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