CN108794662A - A kind of preparation method and applications of macropore strong acid resin - Google Patents
A kind of preparation method and applications of macropore strong acid resin Download PDFInfo
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- CN108794662A CN108794662A CN201810507489.XA CN201810507489A CN108794662A CN 108794662 A CN108794662 A CN 108794662A CN 201810507489 A CN201810507489 A CN 201810507489A CN 108794662 A CN108794662 A CN 108794662A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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Abstract
The present invention relates to a kind of preparation method and applications of macropore strong acid resin, the macropore strong acid resin is with p-nitrophenyl ethylene for main raw material monomer, divinylbenzene is crosslinking agent, with dispersant, initiator, pore-foaming agent etc. together coreaction, the microballoon of p-nitrophenyl ethylene-divinylbenzene is made, macropore strong acid resin has been made in sulfonating reaction through chlorosulfonic acid again.Prepared macropore strong acid resin has good thermal stability, can be used as the effective catalyst of following system：It is catalyzed iso-amylene and methanol reacts synthesizing methyl tert-amyl ether（TAME）, iso-amylene and ethanol synthesis synthesize tertiary amyl ethyl ether（ETBE）, cyclopentene reacted with methanol synthesis cyclopentyl methyl ether（CPME）；And there is high catalytic activity to reactions such as the synthesis of the precursor of loxoprofen sodium-loxoprofen acid.In addition, the recyclable rear recycling of macropore strong acid resin after catalysis reaction, is a kind of environmentally protective efficient catalytic material.
Description
Technical field
The invention belongs to polymer resin technology fields, and in particular to a kind of macropore strong acid process for preparing resins and its answer
With.
Background technology
Ion exchange resin is widely used in Treatment of Industrial Water, medicine food industry, pesticide, dyestuff, coating, detergent etc.
The fields such as Fine Chemical, ore dressing and environmental protection.In organic synthesis field, strong-acid ion exchange resin can be used as epoxy
Change the catalyst of the organic reactions such as reaction, addition reaction and esterification.In Zhou Jie, appoint the paper celebrated victory etc. and delivered《Ce4+It is modified
The research of catalyzing cation exchange resin epoxidation reaction》（Zhou Jie appoints and celebrates victory, and Pan Jingjing waits Ce4+Modified cation is handed over
Change research [J] ion exchanges and absorption, 2015 (4) of resin catalysis epoxidation reaction:359-369.）In, disclose one kind
Ce4+Modified cation-exchange resin be used for catalysis biological diesel oil epoxy reaction, for replace traditional industry produce in frequently with
The liquid acid catalysts such as the concentrated sulfuric acid, phosphoric acid, the catalyst have that environmentally protective, catalytic activity is high, the advantages such as cheap, catalysis
The epoxide number of the epoxy methyl esters of synthesis is up to 5.85%.
With the continuous progress of research, macropore strong acid ion-exchange resin gradually exposes some problems.With phenyl ring
Connected sulfonic group is easy to fall off at relatively high temperatures, and thermal stability is poor.In the paper that graceful, Zhu Zhihua of bear etc. is delivered《Esterification
The deactivation mechanism of reaction cation exchange resin catalyst is studied》（Xiong Ting, Zhu Zhihua, Zhang Jingjing wait esterifications to use
The deactivation mechanism of cation exchange resin catalyst studies [J] Industrial Catalysis, 2012,20 (5):36-40.）It is middle to use by force
Acid type cation exchange resin is catalyzed the esterification of acetic acid and isopropanol at 60 DEG C, and research finds the stream of active sulfonic acid group
Mistake is to lead to the principal element of catalyst activity reduction.The use of macropore strong acid ion exchange resin currently on the market can only be
140 DEG C hereinafter, easily losing sulfonic acid group at 140 DEG C~150 DEG C and inactivating, this just greatly limits such ion exchange resin
It uses.For some need the reaction carried out at relatively high temperatures, this fall off can cause catalytic activity to decline, required
Reaction time extend or even catalyst is entirely ineffective, while it is also possible to cause the pollution to reaction system, raffinate after reaction
Last handling process it is complicated, three wastes discharge amount is big.In the master thesis that the villages Zuo Cun deliver《Ion-exchange resin catalyzed esterification
Continuously generating methyl acetate by reactive distillation》（The Hunan the villages Zuo Cun ion-exchange resin catalyzed esterification reaction rectification production methyl acetate [D]
Pool university, 2015.）In, it for the polymer that polymerized monomer, divinylbenzene are crosslinking agent is substrate to use styrene, through dense sulphur
Obtain that there is main cation exchange groups sulfonic group after acid or oleum sulfonation（-SO3H）Strong-acid ion exchange resin.Due to
Sulfonated reagent using the concentrated sulfuric acid or oleum as resin, and the concentrated sulfuric acid and SO therein3The sulfonating reaction of participation is fierce,
Hot-spot, oxidation easily occurs and phenomena such as coking, by-product is more in reaction process.
The stability of C-S keys determines the thermal stability of polystyrene resin between sulfonic acid group and aromatic ring, if can be
Electron-withdrawing group is introduced on polystyrene resin, the bond energy between phenyl ring and sulfonic group is increased, between phenyl ring and sulfonic group
C-S keys will become more to consolidate, to improve the temperature in use of phenylethylene resin series.
Making sulfonating agent into chlorosulfonic acid then by the concentrated sulfuric acid has many advantages, such as.In Mu Li, bends and learn the paper delivered such as thrifty《It is novel
Order mesoporous sulfonated phenolic resin FDU-16-SO3The synthesis of H and acid catalytic property》（Mu Li, Qu Xuejian, Wang Chun are gorgeous, and is new
The order mesoporous sulfonated phenolic resin FDU-16-SO of type3The synthesis of H and acid catalytic property [J] Chemical Journal of Chinese Universities,
2010, 31(8):1643-1646.）In pass through chlorosulfuric acid ordered mesoporous phenolic resin（FDU-16）It is prepared for novel orderly
Mesoporous solid acid catalyst FDU-16-SO3H, by the experimental results showed that, the solid acid catalyst after sulfonation is still kept
High-sequential, shows higher catalytic activity in esterification and acylation reaction.Chlorosulfonic acid can be regarded as
SO3The complex compound of HCl, it is soluble in the sulfur trioxide of chloroform, carbon tetrachloride, the organic solvent of nitrobenzene and liquid, adopts
The advantages of making sulfonating agent with chlorosulfonic acid is that respond is strong, and the HCl of generation is easy to be discharged, and is conducive to reaction and carries out completely；It removes
Outside exclusive use chlorosulfonic acid, solvent can be also added.
In organic synthesis commonly use some strong acid as catalyst, be applied to esterification, hydrolysis, ester exchange reaction,
Hydration reaction etc..Replace above-mentioned acid with acidic resins, be equally catalyzed above-mentioned reaction also can, and advantage is more.As resin is repeatable
It is easy to control etc. using, environmental protection, catalysis reaction.Such as in tert amyl methyl ether(TAME)（TAME）, tertiary amyl ethyl ether（ETBE）, cyclopenta
Methyl ether（CPME）In preparation with loxoprofen acid, so that it may make catalyst with highly acidic resin.Such as：By isobutene and methanol, second
Alcohol reaction generates a kind of ether organic solvent.For another example, esterification during preparing anti-inflammation and analgesic drugs loxoprofen acid, water
Solution reaction commonly uses the concentrated sulfuric acid or p-methyl benzenesulfonic acid as catalyst.Since the oxidisability of the concentrated sulfuric acid easily causes raw material 2- (4- bromines
Aminomethyl phenyl) propionic acid oxidation, addition p-methyl benzenesulfonic acid is also easy to produce intractable work as esterification catalyst in traditional industry
The problem of industry waste water.In these organic esterified, ester hydrolysis reactions, the concentrated sulfuric acid is replaced using highly acidic resin or to toluene sulphur
Acid, can effectively be catalyzed the progress of reaction, and it is dense to reduce raw material or product caused by traditional sulphuric acid catalysis process
Sulfuric acid oxidation and introduce impurity, etching apparatus and generate more industrial wastewater the problems such as.
To solve the negative effect brought using the concentrated sulfuric acid or oleum in existing highly acidic resin preparation process and showing
There is highly acidic resin poor etc. the limitation of existing thermal stability in use, expand highly acidic resin uses model
It encloses, further meets in organic synthesis catalyst in harsh conditions（The conditions such as high temperature, high pressure, strong corrosive solvent）It uses
Requirement, present invention applicant uses p-nitrophenyl ethylene for main raw material monomer, using divinylbenzene as crosslinking agent, by not
Disconnected exploration, is repeatedly practised, and is surprisingly found very much：By our synthetic process, it is right p-nitrophenyl ethylene-has been obtained
The polymer of divinylbenzene, the sulfonation using chlorosulfonic acid and a series of last handling process, are honored to obtain very much
A kind of novel highly acidic resin, is analyzed by thermal performance test, shows that the highly acidic resin has high thermal stability,
Hot property is significantly better than existing resin, and it is catalyzed iso-amylene and methanol reaction synthesis TAME, iso-amylene and second at high temperature
Alcohol reaction synthesis ETBE, cyclopentene react synthesis of precursor loxoprofen acid of synthesis CPME and loxoprofen sodium etc. with methanol instead
Should have good catalytic performance and high temperature resistance, can recycle, be that a kind of green with good performance is high
Imitate environment-friendly type catalysis material.
Invention content
It is an object of the invention to overcome prior art defect, using p-nitrophenyl ethylene as principal monomer, with divinylbenzene
For crosslinking agent, it is blended with dispersant, initiator, pore-foaming agent and microspheroidal solid is made, the washing removal pore-foaming agent in petroleum ether, most
Macropore strong acid resin is made by the sulfonation of chlorosulfonic acid, for improving the defect of existing acidic resins high temperature easy in inactivation.
Simultaneously because the continuous research and probe and experiment test of the present inventor, have been surprisingly found that, the macropore strong acid resin is as catalysis
When agent, there is the catalytic activity of superelevation to many synthetic reactions！Such as：The macropore strong acid resin prepared using the present invention is to urge
Agent is catalyzed iso-amylene and methanol reaction synthesis TAME, iso-amylene and ethanol synthesis synthesis ETBE, ring penta using supercritical technology
Alkene reacts synthesis CPME with methanol, and for reactions such as the synthesis of precursor loxoprofen acid of promise rope ibuprofen sodium, all has pole
High catalytic activity is easily recycled after and uses again.It can multiple Reusability.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of macropore strong acid resin, it is characterized in that：It is using p-nitrophenyl ethylene as main monomer, is crosslinking with divinylbenzene
Agent is blended with dispersant, initiator, pore-foaming agent and microballoon is made, the washing removal pore-foaming agent in petroleum ether, then in sulfonating agent
The macropore strong acid resin is finally made under effect.
A kind of preparation method of macropore strong acid resin, it is characterised in that it includes the following steps：
Step 1：Weigh a certain amount of p-nitrophenyl ethylene, divinylbenzene, pore-foaming agent and initiator.Mix p-nitrophenyl second
Alkene and divinylbenzene are washed 2 times with 5%NaOH solution；It is washed with water 2 times, to slough polymerization inhibitor therein；It is 10- in absolute pressure
Vacuum distillation obtains the mixture of purified p-nitrophenyl ethylene and divinylbenzene at 100Pa and 45 DEG C, to p-nitrophenyl second
Alkene, divinylbenzene mixture in pore-foaming agent and initiator is added, after to be triggered dose of dissolving, pour into equipped with 0.2%~1.5% dispersion
In the three-necked flask of agent solution；
Step 2：Control rotating speed is warming up to 65 DEG C under the conditions of 1000r/min~4000r/min, keeps the temperature 1h~3h；It is warming up to again
75 DEG C, keep the temperature 4h~8h；Then 90 DEG C are warming up to, 0.5h~2h is kept the temperature.Cooling, filtering, washing, drying, then washed with petroleum ether
It washs to obtain p-nitrophenyl ethylene-divinylbenzene microspheres solid；
Step 3：By p-nitrophenyl ethylene-divinylbenzene Archon prepared by step 2 in CCl4Middle swelling 1h~4h, is being stirred
Under the conditions of be added with p-nitrophenyl ethylene-divinylbenzene microspheres mass ratio be 1 ﹕ 0.5~2 chlorosulfonic acid, react 3h, then successively
With ethyl alcohol and it is washed to neutrality, is filtered, is dried in vacuo to get macropore afterwards for 24 hours with 15-25 DEG C of deionized water immersion at room temperature
Highly acidic resin.
Preferably the mass ratio of p-nitrophenyl ethylene, divinylbenzene, pore-foaming agent and initiator is 1 ﹕, 0.05~0.3 ﹕ 0.05
~1.5 ﹕ 0.005~0.03.
Preferred dispersant is arbitrary in polyvinyl alcohol, methylcellulose, lauryl sodium sulfate and active calcium phosphate
One or more kinds of mixing.
Preferred initiator is azodiisobutyronitrile AIBN, azobisisoheptonitrile ABVN, azo-bis-iso-dimethyl, mistake
It is one or more kinds of mixed in Benzoyl Oxide BPO, benzoyl peroxide tert-butyl ester BPB and pentaerythritol tetrachloroacetate
Close object.
Preferred pore-foaming agent is the mixing of any one or two kinds in toluene and paraffin oil.
Due to the adoption of the above technical scheme, the present invention has the positive effect that compared with prior art：
The present invention increases the key between phenyl ring and sulfonic group by introducing electron-withdrawing group nitro on polystyrene resin
Can, sulfonic group is more firm on phenyl ring, to make thermal stability enhance.Existing polystyrene resin use temperature upper limit is
It 140 DEG C, decomposes at 140 DEG C ~ 150 DEG C, macropore strong acid resin temperature in use prepared by the present invention is up to 260 DEG C, 300
DEG C just there is notable inactivation.
Using the macropore strong acid resin as catalyst, efficiently it is catalyzed iso-amylene and is reacted with methanol and synthesize TAME, different
Amylene synthesizes ETBE with ethanol synthesis, cyclopentene reacts the precursor loxoprofen acid for synthesizing CPME and loxoprofen sodium with methanol
The reactions such as synthesis, are easily recycled after and use again.Can multiple Reusability under high temperature environment, expanded the large porous strong acid
Application range of the property resin in field of catalytic reactions.
In addition, replacing the concentrated sulfuric acid or oleum to realize to the sulfonated of polyethylene-based ion exchange resin, also using chlorosulfonic acid
It has the advantages that：Chlorosulfonic acid can be regarded as SO3The complex compound of HCl, it is soluble in chloroform, carbon tetrachloride, nitrobenzene
The advantages of waiting organic solvents and the sulfur trioxide of liquid, making sulfonating agent using chlorosulfonic acid is that respond is strong, the HCl of generation
It is easy to be discharged, is conducive to reaction and carries out completely.The present invention is increased by introducing electron-withdrawing group nitro on polystyrene resin
The bond energy between phenyl ring and sulfonic group is added, sulfonic group is more firm on phenyl ring, to make thermal stability enhance.This enhancing
Thermal stability can make such resin that can repeatedly be used repeatedly as catalyst in organic pyroreaction, and it is big to have expanded this
Application range of the hole highly acidic resin in field of catalytic reactions.
Description of the drawings
Fig. 1 is a kind of TG figures of macropore strong acid resin prepared by the present invention.
Fig. 2 is a kind of DSC figures of macropore strong acid resin prepared by the present invention.
Fig. 3 is the synthetic route chart of loxoprofen acid.
Specific implementation mode
For a better understanding of the present invention, with reference to embodiment, present disclosure is preferably illustrated, but the present invention
Content is not limited solely to the following examples, is also not construed as limitation of the present invention.
Following example 1 ~ 5 are respectively the preparating example of 1 ~ A5 of macropore strong acid Resin A.
Embodiment 1
A kind of preparation method of macropore strong acid resin, is as follows：
Step 1：Weigh p-nitrophenyl ethylene, divinylbenzene, toluene and the azo two that mass ratio is 1 ﹕, 0.05 ﹕, 0.05 ﹕ 0.005
Different heptonitrile, wherein the quality for the p-nitrophenyl ethylene chosen is 7.458g.P-nitrophenyl ethylene and divinylbenzene are mixed, with 5%
（Mass fraction, similarly hereinafter）NaOH solution is washed 2 times, is washed with water 2 times, to slough hydroquinone type polymerization inhibitor therein, in 10Pa
（Absolute pressure, similarly hereinafter）And vacuum distillation obtains the mixture of purified p-nitrophenyl ethylene and divinylbenzene at 45 DEG C.?
P-nitrophenyl ethylene, divinylbenzene mixture in toluene is added, azobisisoheptonitrile is uniformly mixed, and is subsequently poured into dress
There is 30ml0.2%（Mass fraction, similarly hereinafter）In the three-necked flask of methocel solution；
Step 2：Control rotating speed is warming up to 65 DEG C under the conditions of 1000r/min, keeps the temperature 1h；It is warming up to 75 DEG C again, keeps the temperature 4h；So
After be warming up to 90 DEG C, keep the temperature 0.5h.Cooling, filtering, washing, drying, then with drying after about 30mL petroleum ethers, be crosslinked
Poly- p-nitrophenyl ethylene microballoon；
Step 3：By the poly- p-nitrophenyl ethylene microballoon of crosslinking prepared by step 2 in CCl4Middle swelling 1h, under agitation
It is added and then uses second successively with the chlorosulfonic acid that the mass ratio of p-nitrophenyl ethylene-divinylbenzene microspheres is 1 ﹕ 0.5, reaction 3 hours
Alcohol and water is washed till neutrality, is filtered after impregnating 24 hours at room temperature with deionized water, vacuum drying, you can obtain macropore strong acid
Resin A 1.
Embodiment 2
A kind of preparation method of macropore strong acid resin, is as follows：
Step 1：Weigh p-nitrophenyl ethylene, divinylbenzene, paraffin oil and the peroxidating two that mass ratio is 1 ﹕, 0.3 ﹕, 1.5 ﹕ 0.03
Benzoyl, wherein the quality for the p-nitrophenyl ethylene chosen is 7.458g.It is washed 2 times, is washed with water 2 times with 5%NaOH aqueous solutions,
To slough hydroquinone type polymerization inhibitor therein, at 10Pa and 45 DEG C vacuum distillation obtain purified p-nitrophenyl ethylene and
The mixture of divinylbenzene.P-nitrophenyl ethylene, divinylbenzene mixture in be added paraffin oil oil, dibenzoyl peroxide
（BPO）Afterwards, it pours into the three-necked flask equipped with 30ml1.5% methocel solutions；
Step 2：Control rotating speed is warming up to 65 DEG C under the conditions of 4000r/min, keeps the temperature 3h；It is warming up to 75 DEG C again, keeps the temperature 8h；So
After be warming up to 90 DEG C, keep the temperature 2h.Cooling, filtering, washing, drying, then with after the drying of about 30mL petroleum ethers, obtain Cross-linked
Poly- p-nitrophenyl ethylene microballoon；
Step 3：By the crosslinked poly- p-nitrophenyl ethylene microballoon prepared by step 2 in CCl4Middle swelling 4h is added and to nitre
Base styrene-divinylbenzene microspheres quality reacts 3 hours, than the chlorosulfonic acid for 1 ﹕ 2 then successively with ethyl alcohol and in being washed to
Property, it is impregnated with deionized water and is filtered afterwards for 24 hours at room temperature, is dried in vacuo, you can obtain macropore strong acid Resin A 2.
Embodiment 3
A kind of preparation method of macropore strong acid resin, is as follows：
Step 1：Weigh p-nitrophenyl ethylene, divinylbenzene, paraffin oil and the azo that mass ratio is 1 ﹕, 0.16 ﹕, 0.75 ﹕ 0.015
Two isobutyl dimethyl phthalates, wherein the quality for the p-nitrophenyl ethylene chosen is 7.458g.Mix p-nitrophenyl ethylene and divinyl
Benzene is washed 2 times with 5%NaOH solution, is washed with water 2 times, to slough hydroquinone type polymerization inhibitor therein, at 10Pa and 45 DEG C
Vacuum distillation obtains the mixture of purified p-nitrophenyl ethylene and divinylbenzene.In p-nitrophenyl ethylene, divinylbenzene
It is added paraffin oil in mixture, after azo-bis-iso-dimethyl, pours into three mouthfuls of burnings equipped with 30ml0.85% poly-vinyl alcohol solutions
In bottle；
Step 2：Control rotating speed is warming up to 65 DEG C under the conditions of 2500r/min, keeps the temperature 2h；It is warming up to 75 DEG C again, keeps the temperature 6h；So
After be warming up to 90 DEG C, keep the temperature 1.25h.Cooling, filtering, washing, drying, then with after the drying of about 30mL petroleum ethers, handed over
Join poly- p-nitrophenyl ethylene microballoon；
Step 3：By the crosslinked poly- p-nitrophenyl ethylene microballoon prepared by step 2 in CCl4Middle swelling 2.5h, in stirring bar
The chlorosulfonic acid that p-nitrophenyl ethylene-divinylbenzene microspheres mass ratio is 1 ﹕ 1.25 is added under part, reacts 3 hours, then uses successively
Ethyl alcohol and it is washed to neutrality, is impregnated with deionized water and filtered afterwards for 24 hours at room temperature, is dried in vacuo, you can obtain macropore strong acid
Resin A 3.
Embodiment 4
A kind of preparation method of macropore strong acid resin, is as follows：
Step 1：Weigh p-nitrophenyl ethylene, divinylbenzene, toluene and the benzoyl peroxide that mass ratio is 1 ﹕, 0.3 ﹕, 0.65 ﹕ 0.025
The formyl tert-butyl ester, wherein the quality for the p-nitrophenyl ethylene chosen is 7.458g.P-nitrophenyl ethylene and divinylbenzene are mixed, is used
5%NaOH solution is washed 2 times, is washed with water 2 times, to slough hydroquinone type polymerization inhibitor therein, is depressurized and is steamed at 10Pa and 45 DEG C
Evaporate the mixture of p-nitrophenyl ethylene and divinylbenzene after being purified.In p-nitrophenyl ethylene, the mixture of divinylbenzene
Middle addition toluene after the benzoyl peroxide tert-butyl ester, pours into the three-necked flask equipped with 30ml0.6% poly-vinyl alcohol solutions.
Step 2：Control rotating speed is warming up to 65 DEG C under the conditions of 2000r/min, keeps the temperature 1.5h；It is warming up to 75 DEG C again, heat preservation
5h；Then 90 DEG C are warming up to, 1h is kept the temperature.Cooling, filtering, washing, drying, then with after the drying of about 30mL petroleum ethers, obtain
It is crosslinked poly- p-nitrophenyl ethylene microballoon；
Step 3：By the poly- p-nitrophenyl ethylene microballoon of crosslinking prepared by step 2 in CCl4Middle swelling 2h, under agitation
The chlorosulfonic acid that p-nitrophenyl ethylene-divinylbenzene microspheres mass ratio is 1 ﹕ 1 is added, reacts 3 hours, then uses second alcohol and water successively
It is washed till neutrality, is impregnated with deionized water and is filtered afterwards for 24 hours at room temperature, is dried in vacuo, you can obtain macropore strong acid Resin A 4.
Embodiment 5
A kind of preparation method of macropore strong acid resin, is as follows：
Step 1：Weigh p-nitrophenyl ethylene, two isobutyl of divinylbenzene, toluene and azo that mass ratio is 1 ﹕, 0.3 ﹕, 1.5 ﹕ 0.03
Nitrile, wherein the quality for the p-nitrophenyl ethylene chosen is 7.458g.P-nitrophenyl ethylene and divinylbenzene are mixed, it is molten with 5%NaOH
Liquid is washed 2 times, is washed with water 2 times, to slough hydroquinone type polymerization inhibitor therein, is evaporated under reduced pressure and is obtained only at 10Pa and 45 DEG C
The mixture of p-nitrophenyl ethylene and divinylbenzene after change.P-nitrophenyl ethylene, divinylbenzene mixture in first is added
Benzene after azodiisobutyronitrile, pours into the three-necked flask equipped with 30ml0.6% poly-vinyl alcohol solutions.
Step 2：Control rotating speed is warming up to 65 DEG C under the conditions of 2000r/min, keeps the temperature 3h；It is warming up to 75 DEG C again, heat preservation
8h；Then 90 DEG C are warming up to, 2h is kept the temperature.Cooling, filtering, washing, drying, then with after the drying of about 30mL petroleum ethers, obtain
It is crosslinked poly- p-nitrophenyl ethylene microballoon；
Step 3：By the poly- p-nitrophenyl ethylene microballoon of crosslinking prepared by step 2 in CCl4Middle swelling 2h, under agitation
It is added and then uses second successively with the chlorosulfonic acid that the mass ratio of p-nitrophenyl ethylene-divinylbenzene microspheres is 1 ﹕ 1.5, reaction 3 hours
Alcohol and water is washed till neutrality, is impregnated with deionized water and is filtered afterwards for 24 hours at room temperature, vacuum drying, you can obtain macropore strong acid tree
Fat A5.
Following example 6 ~ 9 are respectively application examples of the 1 ~ A5 of macropore strong acid Resin A as catalyst.
Embodiment 6
The macropore strong acid resin catalysis synthesizing methyl tert-amyl ether (TAME) is specific as follows：
3.4 grams of macropore strong acid Resin A 1 is weighed to be added in the stainless steel autoclave of 500mL, by 40ml methanol and
210ml iso-amylene is quickly adding into reaction kettle successively；Adjusting reacting kettle inner pressure be 8Mpa, by reaction system be rapidly heated to
250 DEG C, 4 h of isothermal reaction obtains TAME.The type for changing macropore strong acid resin, obtains that the results are shown in Table 1.
Influence of the different macropore strong acid resin of table 1. to TAME synthetic reactions
| Resin sample | Resin catalyst/g | Iso-amylene conversion ratio/% | TAME molar yields/% | Selectivity/% |
| A1 | 3.4 | 98.93 | 97.77 | 98.83 |
| A2 | 3.4 | 98.00 | 95.81 | 97.77 |
| A3 | 3.4 | 98.25 | 95.49 | 97.19 |
| A4 | 3.4 | 98.47 | 95.66 | 97.15 |
| A5 | 3.4 | 98.98 | 97.18 | 98.18 |
Patent CN103787842B uses heteropoly acid/aluminum-base composite metal oxide for catalysis using iso-amylene and methanol as raw material
Agent, reaction temperature are 60 DEG C~120 DEG C, and pressure is 0.05Mpa~3.0Mpa, and run time is 50~1000 hours, iso-amylene
Conversion ratio be 97.6%~98.6%.Macropore strong acid resin prepared by the present invention has high temperature resistant, high pressure, corrosion-resistant molten
The critical conditions such as agent, using supercritical reaction technology, make methanol in iso-amylene reacts preparation TAME with methanol under high temperature and pressure
It is reacted in the supercritical state, increases the contact area of methanol and iso-amylene and catalyst so that be catalyzed the efficiency of reaction
The time that reaction is also reduced while greatly promoting, be conducive to industrialized production.
Embodiment 7
The macropore strong acid resin catalysis synthesis tertiary amyl ethyl ether (ETBE) is specific as follows：
It weighs 4.7 grams of macropore strong acid Resin A 1 to be added in 500mL stainless steel autoclaves, by 58ml ethyl alcohol and 210ml
Iso-amylene is quickly adding into reaction kettle successively；Adjusting reacting kettle inner pressure is 8Mpa, and reaction system is rapidly heated to 260
DEG C, isothermal reaction 5h obtains ETBE.Change macropore strong acid resin types and obtains that the results are shown in Table 2.
Influence of the different macropore strong acid resins of table 2. to the synthetic reaction of ETBE
| Resin sample | Resin catalyst/g | Iso-amylene conversion ratio/% | TAME molar yields/% | Selectivity/% |
| A1 | 4.7 | 97.55 | 96.36 | 98.78 |
| A2 | 4.7 | 97.78 | 96.69 | 98.89 |
| A3 | 4.7 | 98.11 | 96.33 | 98.19 |
| A4 | 4.7 | 97.32 | 95.84 | 98.48 |
| A5 | 4.7 | 97.99 | 96.99 | 98.98 |
CN103787841B using iso-amylene and ethyl alcohol as raw material, use the aluminum-base composite metal oxide of Tricesium dodecatungstophosphate acid salt for
Catalyst, reaction temperature are 100 DEG C~180 DEG C, and pressure is 2.0Mpa~6.0Mpa, and run time is 50~1000 hours, different
The conversion ratio of amylene is 88.4%~79.5%.Macropore strong acid resin prepared by the present invention has high temperature resistant, high pressure, is able to bear strong corrosion
Property the critical conditions such as solvent, using supercritical reaction technology, make under high temperature and pressure in iso-amylene and ethanol synthesis prepare ETBE
Ethyl alcohol is reacted in the supercritical state, increases the contact area of ethyl alcohol and iso-amylene and catalyst so that be catalyzed reaction
The time that reaction is also reduced while efficiency greatly promotes, be conducive to industrialized production.
Embodiment 8
The macropore strong acid resin catalysis synthesizes CPME, specific as follows：
It weighs 4.2 grams of macropore strong acid Resin A 1 to be added in 500mL stainless steel autoclaves, by 40ml methanol and 88ml rings
Amylene is quickly adding into reaction kettle successively；Adjusting reacting kettle inner pressure is 8Mpa, and reaction system is rapidly heated to 250 DEG C,
Isothermal reaction 5h obtains CPME.Change macropore strong acid resin types and obtains that the results are shown in Table 3.
Influence of the 3. macropore strong acid resin of table to CPME synthetic reactions
| Resin sample | Resin catalyst/g | Cyclopentene conversion ratio/% | CPME molar yields/% | Selectivity/% |
| A1 | 4.2 | 97.55 | 93.46 | 95.81 |
| A2 | 4.2 | 98.12 | 92.35 | 94.12 |
| A3 | 4.2 | 98.36 | 93.33 | 94.89 |
| A4 | 4.2 | 97.88 | 93.10 | 95.12 |
| A5 | 4.2 | 98.44 | 94.06 | 95.55 |
Cyclopentene is reacted with methanol can obtain a kind of environmentally friendly solvent C PME, it is that a kind of novel hydrophobic ethers is molten
Agent is more easy to be separated from water back with tetrahydrofuran, methyltetrahydrofuran, methyl tertiary butyl ether(MTBE) He compared with the ether solvents such as dioxane
It receives, reduces sewage discharge.As reaction dissolvent, it is anti-to can be used for coupling reaction, grignard reaction, coupling aminating reaction, n-BuLi
It answers, metal reduction reaction, lewis acid react and the reactions such as Friedel-Grafts.Simultaneously extraction, crystallization, surface treatment and
Also available to cyclopentyl methyl ether in polymerization process.The only a small amount of report of the study on the synthesis of cyclopentyl methyl ether at present.
CN103787841B uses general highly acidic resin object for catalyst, reaction temperature 20 using cyclopentene and methanol as raw material
DEG C~80 DEG C, pressure is 0.3Mpa~1.0Mpa, and run time is 300 hours, the conversion ratio of cyclopentene is only 14.5%~
14.7%.Macropore strong acid resin prepared by the present invention has the critical conditions such as high temperature resistant, high pressure resistant, corrosion-resistant solvent,
Cyclopentene and methanol reaction are prepared in CPME, and using supercritical reaction technology, ethyl alcohol is made under high temperature and pressure in the supercritical state
It is reacted, increases the contact area of methanol and cyclopentene and catalyst so that while being catalyzed the efficiency of reaction and greatly promote
The time for also reducing reaction, be conducive to industrialized production.
Experimental example 9
The macropore strong acid resin catalysis synthesis loxoprofen acid, synthetic route is as shown in figure 3, specific as follows：
25ml methanol, 6.14g2- (4- 2-bromomethylphenyls) propionic acid and 2.5g highly acidic resin A1 are taken, three-necked flask is added sequentially to
In, setting temperature is 60 DEG C, is stirred to react 8h.Filtering is concentrated under reduced pressure filter vacuum and removes methanol.Then be added 10ml water,
15ml toluene extracts reaction solution；Appropriate anhydrous sodium sulfate is added into organic phase, removes remaining moisture in organic phase.
It filters again, revolving removes toluene, obtains colourless oil liquid, as 2- (4- 2-bromomethylphenyls) methyl propionate.
The toluene and 1.40g potassium carbonate for taking 1.5ml2- oxo cyclopentanecarboxylic acids ethyl ester, 10ml, are added sequentially to three-necked flask
In.90 DEG C of reflux are warming up to, the 5ml toluene solutions of 2.57g2- (4- 2-bromomethylphenyls) methyl propionate are slowly added dropwise, are continued 90
Back flow reaction 12h under the conditions of DEG C.Filtering, the distilled water for being added 10ml in filtrate washed, liquid separation, and organic layer uses anhydrous sulphur
Sour sodium drying, is filtered again, after revolving removes toluene, obtains yellow oily liquid, as 2- [4- (1- carbethoxyl group -2- oxygen
Generation -1- cyclopentyl-methyls) phenyl] methyl propionate.
Take 3.32g2- [4- (1- carbethoxyl group -2- oxo -1- cyclopentyl-methyls) phenyl] methyl propionate, 5ml acetic acid and
0.33g highly acidic resins A1 is added sequentially in single-necked flask, is warming up to 90 DEG C of back flow reaction 10h.Resin, filtrate is recovered by filtration
It is extracted with toluene, saturated nacl aqueous solution washing is added 0.05g activated carbon decolorizings, is concentrated under reduced pressure and removes toluene, obtain Huang
Color oily thick liquid, as loxoprofen acid.
It compares conventional method and adds the concentrated sulfuric acid as esterification catalyst, it is easy to avoid raw material 2- (4- 2-bromomethylphenyls) propionic acid
It is aoxidized by the concentrated sulfuric acid, product colour yellowing, it must be through repeatedly handle could problem up to standard.It is used to methylbenzene sulphur with conventional method
Acid is compared as ester hydrolysis catalyst, solves the problems, such as that p-methyl benzenesulfonic acid is also easy to produce intractable industrial wastewater.
Present embodiment has the positive effect that compared with prior art：
The present invention increases the key between phenyl ring and sulfonic group by introducing electron-withdrawing group nitro on polystyrene resin
Can, sulfonic group is more firm on phenyl ring, to make thermal stability enhance.Existing polystyrene resin use temperature upper limit is
140 DEG C, in 140 DEG C of complete deactivations；Macropore strong acid resin prepared by the present invention can be normal at a high temperature of 260 DEG C or so
Using without will produce sulfonic abjection, increasing the application range of macropore strong acid resin in the industrial production.
Fig. 1 is a kind of TG figures of macropore strong acid Resin A 1 prepared by the present invention.From figure it will be seen that in temperature
Occur a rapid drawdown when being 100 DEG C, shows that forming in resin is sloughed with water at this time；Occur one again at 300 DEG C drastically to decline,
Show that the sulfonic group in resin at this time is sloughed；The decline for occurring a curve again at 400 DEG C, shows styrene-diethyl at this time
The copolymer of alkenyl benzene starts to decompose；After 400 DEG C even 500 DEG C, slope of a curve becomes flat, and illustrates in resin at this time
Effective group has been sloughed, and weight is held essentially constant.These illustrate that macropore strong acid resin has good thermal stability,
There is great advantage in the catalyzed side reaction face of high temperature.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications can be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and changes of the present invention
Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to exist comprising these modification and variations
It is interior.
Claims (7)
1. a kind of macropore strong acid resin, it is characterised in that it is main single that the macropore strong acid resin, which is with p-nitrophenyl ethylene,
Using divinylbenzene as crosslinking agent, with dispersant, initiator, pore-foaming agent blending reaction, microspheroidal solid is made, in petroleum ether in body
Middle washing removes pore-foaming agent, is most made afterwards through the sulfonation of chlorosulfonic acid.
2. a kind of preparation method of macropore strong acid resin, it is characterised in that the preparation method of the macropore strong acid resin includes
Following steps：
Step 1：Weigh a certain amount of p-nitrophenyl ethylene, divinylbenzene, pore-foaming agent and initiator.Mix p-nitrophenyl ethylene
With divinylbenzene, first washed 2 times with 5.0 %NaOH solution of mass fraction；It is washed with water 2 times, to slough polymerization inhibitor therein, exhausted
It is that vacuum distillation obtains the mixture of purified p-nitrophenyl ethylene and divinylbenzene at 10-100Pa and 45 DEG C to pressure；To
P-nitrophenyl ethylene, divinylbenzene mixture in pore-foaming agent and initiator is added, it is 0.2% to be subsequently poured into equipped with mass fraction
In the three-necked flask of~1.5% aqueous dispersant；
Step 2：It controls rotating speed and reaction system is warming up to 65 DEG C under the conditions of 1000r/min~4000r/min, heat preservation 1h~
3h；It is warming up to 75 DEG C again, keeps the temperature 4h~8h；Then 90 DEG C are warming up to, 0.5h~2h is kept the temperature；Cooling, filtering, washing, drying, then
With drying after petroleum ether, p-nitrophenyl ethylene-divinylbenzene polymer microsphere solid is obtained；
Step 3：By the polymer microballoon solid of p-nitrophenyl ethylene-divinylbenzene prepared by step 2 in CCl4Middle swelling 1h
~4h, be added under good stirring condition with the mass ratio of the polymer microballoon of p-nitrophenyl ethylene-divinylbenzene be 1 ﹕ 0.5~
2 chlorosulfonic acid reacts 1h ~ 2h at a reflux temperature, then successively with ethyl alcohol and neutrality is washed to, at room temperature with 15-25 DEG C
Deionized water impregnate for 24 hours after, filtering, be dried in vacuo to get macropore strong acid resin.
3. the preparation method of the macropore strong acid resin according to claim 1 and 2, it is characterised in that p-nitrophenyl ethylene,
The mass ratio of divinylbenzene, pore-foaming agent and initiator is 1 ﹕, 0.05~0.3 ﹕, 0.05~1.5 ﹕ 0.005~0.03.
4. the preparation method of the macropore strong acid resin according to claim 1 and 2, it is characterised in that the dispersant is
Polyvinyl alcohol, methylcellulose, lauryl sodium sulfate（SDS）With one or more kinds of mixing in active calcium phosphate
Object.
5. the preparation method of the macropore strong acid resin according to claim 1 and 2, it is characterised in that the initiator is
Azodiisobutyronitrile AIBN, azobisisoheptonitrile ABVN, azo-bis-iso-dimethyl, benzoyl peroxide BPO, benzoyl peroxide
One or more kinds of mixtures in formyl tert-butyl ester BPB and pentaerythritol tetrachloroacetate.
6. the preparation method of the macropore strong acid resin according to claim 1 and 2, it is characterised in that the pore-foaming agent is
The mixing of any one or two kinds in the paraffin oil that toluene and condensation point are -20 DEG C~10 DEG C.
7. the macropore strong acid resin described in claim 1 and 2, it is characterised in that the macropore strong acid resin can be efficient
It is catalyzed iso-amylene and methanol reacts synthesizing methyl tert-amyl ether（TAME）, efficient catalytic iso-amylene and ethanol synthesis synthesize ethyl uncle
Amyl ether（ETBE）, efficient catalytic cyclopentene reacted with methanol synthesis cyclopentyl methyl ether（CPME）.And to loxoprofen sodium before
The reactions such as the synthesis of body-loxoprofen acid have high catalytic activity.
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