CN103497341B - A kind of separation material preparation method based on removable linking agent - Google Patents
A kind of separation material preparation method based on removable linking agent Download PDFInfo
- Publication number
- CN103497341B CN103497341B CN201310467289.3A CN201310467289A CN103497341B CN 103497341 B CN103497341 B CN 103497341B CN 201310467289 A CN201310467289 A CN 201310467289A CN 103497341 B CN103497341 B CN 103497341B
- Authority
- CN
- China
- Prior art keywords
- linking agent
- rotaxane
- removable
- preparation
- ethyl cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a kind of separation material preparation method based on linking agent.The removable linking agent that the present invention relates to take cyclodextrin derivative as matrix, utilize cyclodextrin derivative mobility, give linking agent removable performance, large preparation is: mixed by the tolysulfonyl polyethylene glycol of tosylation and cyclodextrin molecular by two ends of polyoxyethylene glycol, obtains the inclusion operation of accurate poly-rotaxane; Described standard is gathered the end capping of rotaxane and phenol derivatives, obtain the termination procedure of two end-capped; And poly-rotaxane and glycidyl allyl ether are reacted in solvent dimethyl sulfoxide (DMSO), prepare the operation of novel crosslinker.Then adopt solvent casting method to obtain ethyl cellulose and be separated material, the ethyl cellulose formed based on removable linking agent finally by preparation after removable linking agent process is separated material.This separation material all has good solvent resistance in all kinds of SOLVENTS, and Stability Analysis of Structures.
Description
Technical field
The present invention relates to the separation of organic mixture system, particularly relevant to oil fuel system.Oil fuel is by paraffinic hydrocarbons, naphthenic hydrocarbon, alkene, aromatic hydrocarbon and a small amount of complex mixture formed containing heteroatomic compounds such as S, N, O.The present invention intends improving by crosslinked the solvent resistance, intensity and the toughness that are separated material, simultaneously significant to the exploitation of complicated ORGANIC SOLVENT MIXTURES separation material.
Background technology
Along with the development of the isolation technique such as infiltration evaporation, having higher requirement to separation material, in order to overcome the shortcomings such as the ubiquitous intensity of polymerizable material is lower, solvent resistance is poor, take crosslinking technological as the polymerizable material modification technology development of representative.Linking agent can make high molecular polymer change tridimensional network into from linear structure efficiently rapidly, to reduce the swelling of polymkeric substance, improves the solvent resistance of polymerizable material.Its intensity is improved simultaneously, can meet the demand of the isolation technique such as infiltration evaporation.
After conventional cross-linking agent process, be separated material, although its intensity is improved, along with improving constantly of crosslinking degree, there is the defect that toughness significantly declines in the separation material after crosslinked.The present invention is matrix with cyclodextrin derivative, utilizes its removable performance, gives linking agent removable performance, increases crosslinking reaction site, and the toughness of crosslinked rear material, intensity and solvent resistance are improved.Cyclodextrin derivative is that a class contains multiple ring molecule, and the inner-lock-type Subjective and Objective supramolecular system formed by the group end capping of large volume.Its maximum feature is that cyclodextrin molecular can move freely in polymer molecular chain, and containing multiple active group, is conducive to the carrying out of chemical reaction, thus provides raw material for the preparation of Novel moveable linking agent.
Summary of the invention
The object of the invention is to the separation material after solving conventional cross-linking agent process and there is the relative poor problem of solvent resistance, intensity and toughness, the invention provides a kind of separation material preparation method based on removable linking agent, its solvent resistance, intensity and toughness are all significantly improved.
The present invention is achieved through the following technical solutions goal of the invention: the preparation of removable linking agent, adopts solvent casting method to prepare ethyl cellulose and is separated material, and the ethyl cellulose prepared after crosslinked based on removable linking agent is separated material.Specifically comprise the following steps:
One, the preparation of removable linking agent:
1. the preparation of cyclodextrin derivative:
(1) preparation of tolysulfonyl polyethylene glycol: polyoxyethylene glycol and Tosyl chloride react in triethylamine solution, prepare white product through a series of processes such as extracting, stir, filter and be concentrated, final productive rate is more than 90%;
(2) preparation of inclusion complex: cyclodextrin and tolysulfonyl polyethylene glycol mix in water, obtain product through ultrasonic, stirring, centrifugation and vacuum-drying, ultimate yield is more than 92%;
(3) synthesis of cyclodextrin derivative: MX and inclusion complex and hydrogenation are received and reacted in organic solvent, must precipitate after vacuum-drying after repeatedly purifying, filtering, final productive rate is about 39%.
2. based on the removable linking agent preparation of cyclodextrin derivative:
The reaction in solvent dimethyl sulfoxide (DMSO) (DMSO) of cyclodextrin derivative and glycidyl allyl ether (AGE), obtains white product, is the removable linking agent of preparation after the process such as potassium hydroxide, acetone, vacuum-drying.
Prepared by the separation material two, based on removable linking agent:
With polymkeric substance ethyl cellulose for substrate material, ethanol and toluene are solvent, benzophenone is as initiator, adopt homemade removable linking agent, obtain ethyl cellulose by solvent casting method and be separated material, cause crosslinking reaction through uv irradiating, final preparation is separated material based on the ethyl cellulose of removable linking agent.
Wherein: the polyoxyethylene glycol (PEG) used in (1), its molecular weight does not limit, as long as high molecular is greater than 1500g/mol;
(2) cyclodextrin used in can use various types of cyclodextrin.Such as, alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin etc., preferred alpha-cylodextrin;
(3) organic solvent used in refers to the solvent that inclusion complex can be dissolved, and comprises the organic solvents such as DMF, N,N-dimethylacetamide and dimethyl sulfoxide (DMSO);
Compared with prior art, the present invention has following beneficial effect:
First the present invention is that matrix prepares removable linking agent with cyclodextrin derivative, give its removable performance, then adopt solvent casting method to obtain ethyl cellulose and be separated material, the ethyl cellulose prepared based on removable linking agent finally by removable linking agent process is separated material, system thinking normal heptane, toluene and thiophene equal solvent are separated the swelling behavior in material at this, result shows, this separation material all has good solvent resistance in all kinds of SOLVENTS.Carried out mechanical analysis test to this separation material, result shows that this separation material has higher intensity and toughness simultaneously, and Stability Analysis of Structures.Simultaneously the method has the advantages such as raw material commercialization, easy to operate, environmental protection.
Accompanying drawing explanation
Fig. 1 is the ethyl cellulose separation material preparation technology flow process based on removable linking agent.
Fig. 2 is that the ethyl cellulose of different crosslinking time (crosslinking degree) is separated the swelling curve of material in thiophene/n-heptane system.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Below by way of specific embodiment, the present invention will be described in more detail.Embodiment is only illustrate one of the present invention, and is not construed as limiting the invention.Embodiment is practical application example, is easy to grasp and verifies for those skilled in the art.If make certain to change on basis of the present invention, so its essence does not exceed scope of the present invention.
Embodiment 1:
Get PEG-4000 (20g, 5mmol) be dissolved in dichloromethane solution (100ml), add triethylamine (28m1) solution of Tosyl chloride (3.81g, 20mmol), abundant mixing, room temperature reaction 12h, extracts with the dilute hydrochloric acid of 150ml1mol/L, in organic phase, adds excessive sodium carbonate solution, abundant stirring, till bubble-free produces, filter, use Rotary Evaporators concentrated filtrate.(temperature about 40 degree), remove methylene dichloride, the filtrate after concentrated is instilled excessive ether, obtains white precipitate, suction filtration, then suction filtration thing is dissolved in the methylene dichloride of 10ml, elimination insolubles, solution is instilled in excessive ether, obtain white precipitate, suction filtration, vacuum-drying 24h, obtains white product.Final productive rate is more than 90%.
Embodiment 2:
Get cyclodextrin (25.6g; 26.4mmol) be dissolved in 200ml water; form solution; get the tolysulfonyl polyethylene glycol (5.98g of above-mentioned preparation; 1.386mmol) be dissolved in 136ml distilled water; the aqueous solution of tolysulfonyl polyethylene glycol is joined in the aqueous solution of cyclodextrin; supersound process 30min; room temperature for overnight; by the inclusion complex centrifugation formed; then put into vacuum drying oven dry at 70 DEG C, obtain inclusion complex, the mol ratio of cyclodextrin and tolysulfonyl polyethylene glycol is 19:1.Ultimate yield is more than 92%.
Embodiment 3:
Getting MX (10.32g, 84mmol) is dissolved in 144mlDMF, then it is slowly added drop-wise to hydrogenation and receives in the round-bottomed flask of (4.0g).Solution becomes brown, and this process nitrogen is as protection gas.Getting inclusion complex (13.94g) is dissolved in the DMF of 56ml, then adds above-mentioned brown solution, stirs 12h.Reaction solution is divided in two beakers, add the anhydrous methanol of about 200ml respectively, filter to obtain precipitation.By methanol wash precipitation, at twice, each 20ml, is dissolved in the precipitation obtained in the DMSO of 40ml, and then adds the anhydrous methanol of 240ml, and obtain precipitation, filtration is precipitated, and washs with anhydrous methanol, at twice, and each 20ml.Then be dissolved in DMSO by precipitation, add water, form precipitation, filter and to obtain precipitation, finally will to be deposited in vacuum drying oven dried in vacuo overnight at 110 DEG C, final productive rate is about 39%.
Embodiment 4:
Add the cyclodextrin derivative of metering, AGE and 20mlDMSO, be heated with stirring to 80 DEG C, add appropriate KOH, reaction 8h, is cooled to room temperature, fully washs with acetone, then dry 24h in 25 DEG C of thermostatic drying chambers, obtains white solid, is required removable linking agent.
Embodiment 5:
Get 3.6g ethyl cellulose, 0.77g benzophenone and metering self-made movable linking agent, add 18.2ml toluene and 9.1ml ethanol, obtain ethyl cellulose by solvent casting method and be separated material, crosslinking reaction is caused finally by uv irradiating, the obtained separation material based on removable linking agent, technical process as shown in Figure 1.
Embodiment 6:
Take respectively 5 parts of quality be 0.1g be cross-linked after ethyl cellulose be separated material, be placed in toluene/n-heptane mixed system (volume ratio is 1:9) and carry out equilibrium swelling experiments, swelling time 0,0.2,0.4,1.0 and 2.0h, calculate the separation material swelling ratio under different swelling time.
Embodiment 7:
Take respectively 5 parts of quality be 0.1g be cross-linked after ethyl cellulose be separated material, be placed in thiophene/normal heptane mixed system (volume ratio is 1:9) and carry out equilibrium swelling experiments, swelling time 0,0.2,0.4,1.0 and 2.0h, calculate the separation material swelling ratio under different swelling time, swelling curve as shown in Figure 2.
Embodiment 8:
Get respectively and be separated material based on conventional cross-linking agent with the ethyl cellulose of removable linking agent and carry out mechanical stretch experiment, in test specimen loading procedure, observe the relation of load and deformation, thus determine the relevant mechanical property of material.The indexs such as the Young's modulus of material under unidirectional action of pulling stress (toughness) and yield strength, tensile strength, unit elongation, sectional shrinkage can be measured by tension test.
Claims (1)
1., based on a separation material preparation method for removable linking agent, it is characterized in that, it comprises the following steps:
Solvent casting operation: with polymkeric substance ethyl cellulose for matrix, toluene and ethanol are solvent, utilize solvent casting method to prepare ethyl cellulose and are separated material; Cross-linking process step: adopt homemade removable linking agent, benzophenone as initiator, ultraviolet lighting causes crosslinking reaction, and the ethyl cellulose that preparation is formed based on removable linking agent is separated material;
Described removable linking agent preparation method, it comprises:
Tosylation operation: two ends of polyoxyethylene glycol and Tosyl chloride are reacted under the condition of methylene dichloride and pyridine, generates tolysulfonyl polyethylene glycol;
Inclusion operation: tolysulfonyl polyethylene glycol by tosylation of two ends of polyoxyethylene glycol and cyclodextrin molecular are mixed, the tolysulfonyl polyethylene glycol of chain forms accurate poly-rotaxane through the cavity of multiple cyclodextrin molecular;
And termination procedure: make to have the END CAPPED GROUP of the group that can react with p-toluenesulfonyl and described standard and gather rotaxane and react, obtain at two ends by the poly-rotaxane of end-blocking, with 3, the standard of 5-xylenol and described inclusion operation gained is gathered rotaxane generation substitution reaction and is obtained described poly-rotaxane, and, this substitution reaction carries out in the mixed system of DMF and sodium hydride;
Olefination operation: poly-rotaxane and glycidyl allyl ether are reacted in solvent dimethyl sulfoxide (DMSO), prepares the removable linking agent based on cyclodextrin derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310467289.3A CN103497341B (en) | 2013-10-08 | 2013-10-08 | A kind of separation material preparation method based on removable linking agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310467289.3A CN103497341B (en) | 2013-10-08 | 2013-10-08 | A kind of separation material preparation method based on removable linking agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103497341A CN103497341A (en) | 2014-01-08 |
| CN103497341B true CN103497341B (en) | 2016-03-30 |
Family
ID=49862610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310467289.3A Expired - Fee Related CN103497341B (en) | 2013-10-08 | 2013-10-08 | A kind of separation material preparation method based on removable linking agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103497341B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483506A (en) * | 2013-10-08 | 2014-01-01 | 天津工业大学 | Preparation method of novel crosslinking agent based on cyclodextrin derivative |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102492A (en) * | 2013-03-07 | 2013-05-15 | 天津工业大学 | Cyclodextrin-based polyrotaxane production method |
| CN103483506A (en) * | 2013-10-08 | 2014-01-01 | 天津工业大学 | Preparation method of novel crosslinking agent based on cyclodextrin derivative |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2829864C (en) * | 2011-03-14 | 2018-07-10 | Advanced Softmaterials Inc. | Hydrophilic modified polyrotaxane composition |
-
2013
- 2013-10-08 CN CN201310467289.3A patent/CN103497341B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102492A (en) * | 2013-03-07 | 2013-05-15 | 天津工业大学 | Cyclodextrin-based polyrotaxane production method |
| CN103483506A (en) * | 2013-10-08 | 2014-01-01 | 天津工业大学 | Preparation method of novel crosslinking agent based on cyclodextrin derivative |
Non-Patent Citations (3)
| Title |
|---|
| Pervaporation properties of EC membrane crosslinked by hyperbranched-polyester acrylate;Yunjun Luo et al;《journal of membrane Science》;20070721;第303卷(第1-2期);第183-193页 * |
| β-环糊精交联聚合物的制备及性能研究;王宝琦等;《广州化工》;20110915;第39卷(第17期);第37-39页 * |
| β-环糊精侧基聚硅氧烷的合成与表征;冯武;《日用化学工业》;20080814;第38卷(第4期);第214-218页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103497341A (en) | 2014-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112592376B (en) | Method for preparing mannose-containing derivative for post-polymerization modification by using double-click chemistry combination | |
| CN109054042A (en) | The supermolecule polymer of Subjective and Objective assembling based on twin columns [5] aromatic hydrocarbons and its preparation and application | |
| CN103102492B (en) | A kind of poly-rotaxane manufacture method based on cyclodextrin | |
| CN108840994B (en) | Synthesis method of random copolymer containing α -D-mannose and β -D-glucose | |
| CN104845612B (en) | Polystyrene mercury ion fluorescence recognition materials and preparation method thereof | |
| CN103254421B (en) | High pressure synthesis method for aromatic polysulfone resin | |
| CN103483506A (en) | Preparation method of novel crosslinking agent based on cyclodextrin derivative | |
| JP5775072B2 (en) | Compositions and methods for cyclofructans as separating agents | |
| Liu et al. | Separation of short-chain glucan oligomers from molten salt hydrate and hydrolysis to glucose | |
| Chen et al. | Synthesis of chitosan 6-OH immobilized cyclodextrin derivates via click chemistry | |
| CN103497341B (en) | A kind of separation material preparation method based on removable linking agent | |
| Sun et al. | Reduction of lignin heterogeneity using aqueous two-phase system: A facile and universal “one-step-three-fractions” approach | |
| CN108929433B (en) | Preparation method of star polymer with cyclodextrin at tail end | |
| CN104031179B (en) | A kind of 6 monosubstituted-beta-schardinger dextrin-function monomers and preparation method thereof | |
| CN101712734B (en) | High molecular metal complex containing cluster compounds and preparation method thereof | |
| Yu et al. | Photo-responsive gels based on cyclic/linear polymers: efficient synthesis and properties | |
| CN103483590B (en) | The method of bottle brush shaped polymer is prepared in Subjective and Objective self assembly | |
| CN101016246A (en) | 2-Vinyl-terephthalic acid bis-(4-butoxy-phenyl) ester, its polymer, preparing method and application | |
| CN115028760B (en) | Degradable polystyrene synthesis method based on nitrobenzyl disulfide and pyridinium ester block macromolecular chain transfer agent | |
| CN101863986B (en) | Microcrystalline cellulose derivative and preparation method and application thereof | |
| CN107474162B (en) | A kind of universal gel-like polyrotaxane crosslinking agent and preparation method thereof | |
| Deng et al. | Synthesis and application of chitosan thiourea derivatives as chiral stationary phases in HPLC | |
| CN114808176A (en) | Light-operated elastic fiber and preparation method thereof | |
| CN110437466B (en) | Host-guest complexed supramolecular polymer reticular gel and application thereof | |
| CN112940162A (en) | Synthetic method of highly-ordered dendritic heterogeneous sugar-containing polymer containing multiple glycosyl groups |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160330 Termination date: 20201008 |