CN104788602A - Phenylboronic acid-modified covalent affinity hypercrosslinked resin, and preparation method and application thereof - Google Patents
Phenylboronic acid-modified covalent affinity hypercrosslinked resin, and preparation method and application thereof Download PDFInfo
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- 0 CCC(C(C)C)[C@@](CCC1C=CC(B(O)O)=CC1)C(C=C(C)C*(C(CC)I)=CC(C)=CC)=CCC(C)C Chemical compound CCC(C(C)C)[C@@](CCC1C=CC(B(O)O)=CC1)C(C=C(C)C*(C(CC)I)=CC(C)=CC)=CCC(C)C 0.000 description 1
- BLDHSSRMVCSAHZ-AMGKYWFPSA-N CCCCC1(CC)C=CC(B(O)O)=C[C@@H]1C Chemical compound CCCCC1(CC)C=CC(B(O)O)=C[C@@H]1C BLDHSSRMVCSAHZ-AMGKYWFPSA-N 0.000 description 1
- GFQBTBNCPSKZHE-ULUSZKPHSA-N C[C@@H]1C=CC=CC1[BH2-]O Chemical compound C[C@@H]1C=CC=CC1[BH2-]O GFQBTBNCPSKZHE-ULUSZKPHSA-N 0.000 description 1
- YPNIUIRSYZWQBO-UHFFFAOYSA-N Cc1ccc(BO)cc1 Chemical compound Cc1ccc(BO)cc1 YPNIUIRSYZWQBO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a phenylboronic acid-modified covalent affinity hypercrosslinked resin and a preparation method thereof. The performance of the phenylboronic acid-modified covalent affinity hypercrosslinked resin used as a solid phase extraction filler is evaluated. The preparation method comprises the following steps: carrying out a non-aqueous precipitation polymerization reaction on vinylbenzyl chloride, divinyl benzene and 4-vinylphenylboronic acid as reaction raw materials with azodiisobutyronitrile as an initiator and iron trichloride as a catalyst to synthesize phenylboronic acid-containing resin white balls, and carrying out a Friedel-Crafts crosslinking reaction to synthesize the covalent affinity hypercrosslinked resin. The covalent affinity hypercrosslinked resin is a new generation porous polymer resin, has an ultrahigh specific surface area (800m<2>/g) and particle size of 3-5[mu]m, has covalent affinity action force and non-polar action force compounding functions, and can be used in the separation enrichment of cis-diol compounds in complex samples as a solid phase extraction filler.
Description
[technical field]
The present invention relates to resin technology field, specifically, is affine hypercrosslinked polymeric resin of covalency of a kind of phenylo boric acid modification and preparation method thereof and application.
[background technology]
In Sample Pretreatment Technique, solid phase extraction techniques simply, efficiently, easily realizes automatization because of it and the advantage such as organic solvent consumption is low, instead of traditional liquid-liquid extraction method gradually, becomes the main flow pre-treating process that complex system is analyzed.The clastotype of Solid-Phase Extraction depends primarily on the wire feeding in stationary phase.In the polymer packing of general type, owing to adopting macroporous resin material more, therefore its specific surface area less (< 500m2/g), loading capacity is not high; And because its characterization of adsorption is by the restriction of monomer used, inadequate to the selectivity with specific groups compound, its selectivity must be improved by the method for chemically modified.Therefore, development has high-specific surface area polymeric material---the modification type hypercrosslinked polymeric resin filler of strong adsorptive power and selective enrichment effect, will become an important directions of complex sample Solid-Phase Extraction analysis field.
In complex sample is analyzed, for the polarity strengthening compound containing Cis-hydroxyl groups structure, as saccharide compound, lack effective as selective enrichment material, but in the body of this type of material, synthesis and metabolism often play important role in life system all the time.Therefore, develop that to have the covalency affine hypercrosslinked polymeric resin material of specificity selective power to carbohydrate significant.This filler modifies phenylo boric acid group on hypercrosslinked polymeric resin material, utilizes boron hydroxyl can be interacted by covalency avidity with containing syn diol structure under specific pH environment, thus improves its selectivity.Literature search shows, affine hypercrosslinked polymeric resin of novel covalency that this phenylo boric acid is modified and preparation method thereof does not appear in the newspapers.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, the covalency providing a kind of phenylo boric acid to modify is affine hypercrosslinked polymeric resin and preparation method thereof and application.
The object of the invention is to be achieved through the following technical solutions:
The affine hypercrosslinked polymeric resin of covalency that phenylo boric acid is modified, its skeleton is made up of Vinylstyrene, 4-1-chloro-4-methyl-benzene and 4-vinylphenylboronic acid, and its chemical structure of general formula is as follows:
A preparation method for the affine hypercrosslinked polymeric resin of covalency that phenylo boric acid is modified, its concrete steps are:
A () utilizes 1-chloro-4-methyl-benzene, Vinylstyrene, 4-vinylphenylboronic acid to be reaction monomers, be initiator with Diisopropyl azodicarboxylate, acetonitrile is reaction solvent, by oxygen that is ultrasonic and that lead to continuously in nitrogen removing reaction system, non-water precipitation polyreaction is adopted to synthesize the 1-chloro-4-methyl-benzene-Vinylstyrene-vinylphenylboronic acid multipolymer of low crosslinking degree, select methyl alcohol, toluene and acetone to remove the linear structure produced in reaction raw materials residual in reaction system and building-up process, then obtain the low cross-linking resin particle of white through vacuum-drying;
The charging capacity of described reaction monomers is that reaction system comprises 2% of all material total mass marks of solvent.
The massfraction of described 4-vinylphenylboronic acid in three kinds of reaction monomers is the massfraction of 5 ~ 20%, 4-1-chloro-4-methyl-benzene in three kinds of reaction monomers is 65 ~ 40%, and the massfraction of Vinylstyrene in three kinds of reaction monomers is 20 ~ 50%;
The charging capacity of initiator Diisopropyl azodicarboxylate accounts for 2% of the molar fraction of all double bonds in three kinds of reaction monomers;
The amount of reaction solvent acetonitrile is 400ml, and in resin washing process, the usage quantity of methyl alcohol, toluene, acetone is 60ml.
In step (a), in order to solve the bad problem of 4-vinylphenylboronic acid solvability in reaction system, adopt the solubility promoter of dehydrated alcohol as 4-vinylphenylboronic acid of 15 ~ 50ml; In order to solve the low problem of iron trichloride solubleness in ethylene dichloride in step (b), adopting 15 ~ 40ml Nitromethane 99Min. to dissolve iron trichloride, then dropping in reaction system.
Normally carry out to make reaction and obtain the comparatively suitable low cross-linking polymkeric substance of particle diameter, temperature of reaction system controls at 50 ~ 80 DEG C, and the reaction times is 46 hours.Control temperature is exactly to control suitable speed of reaction, controls this temperature range and can control resin particle diameter within the scope wanted, as solid phase extraction filler.Because temperature is low, the resin particle diameter obtained is larger; And temperature is high, the resin particle diameter obtained is less.
1-chloro-4-methyl-benzene-Vinylstyrene-vinylphenylboronic acid the multipolymer of b low crosslinking degree that above-mentioned steps (a) obtains by (), swell in dichloroethane solvent, by the oxygen in ultrasonic and continuous logical nitrogen removing system, adding iron trichloride is catalyzer, step reaction to 80 DEG C, react after 18 hours, obtain the 1-chloro-4-methyl-benzene-Vinylstyrene-vinylphenylboronic acid polymkeric substance of high-crosslinking-degree;
The volume of described ethylene dichloride reaction solvent is 40ml;
The amount of substance of described ferric chloride catalyst is 1: 1 with the ratio of the amount of chlorine elemental substance in the affine low cross-linking resin of covalency.
C () reaction terminates after, centrifugal removing reaction mother liquor, repeatedly washs with the hydrochloric acid of methyl alcohol and 2mol/L successively by the solid obtained, the iron trichloride that ethylene dichloride in removing resin and reaction system remain, by the resin after washing, take acetone as solvent, apparatus,Soxhlet's refluxes 12 hours;
The object of described methanol wash is to remove 1,2-residual ethylene dichloride, and the hydrochloric acid of 2mol/L is in order to wash away iron trichloride residual in resin, and washings potassium thiocyanate detects, till redfree.
D () reaction terminates after, reaction system is cooled to room temperature, and the acetone in centrifugal removing reaction system, uses methyl alcohol and washed with diethylether repeatedly successively, the centrifugal highly cross-linked resin obtaining washes clean, and vacuum-drying obtains the affine hypercrosslinked polymeric resin of covalency.
The affine hypercrosslinked polymeric resin of covalency that obtained phenylo boric acid is modified contains abundant micropore distribution, and specific surface area reaches 800m
2/ g.
The application of the affine hypercrosslinked polymeric resin of covalency in solid phase extraction filler that a kind of phenylo boric acid is modified.
Compared with prior art, positively effect of the present invention is:
(1) the invention provides affine hypercrosslinked polymeric resin of a kind of phenylo boric acid modification type covalency and preparation method thereof, the parent of resin is the polymkeric substance of Vinylstyrene and styrene compound, resin has superhigh specific surface area and pore volume, better absorption property can be provided, resin is monodispersed bead, is desirable solid phase extraction filler.
(2) in resins synthesis step, add 4-vinylphenylboronic acid, make this resin have good covalency affinity interaction, cis-diol compound in complex system can be adsorbed.This resin changes the complete hydrophobic framework of pure divinylbenzene resins, makes it in use can avoid reactivation process.
(3) this resin preparation process is simple, the resin of preparation has good kinetics of adsorption performance, is convenient to be separated, in practical application, by selecting suitable drip washing and elution step, removing is disturbed matrix and is adsorbed the saccharide compound containing syn diol structure better fast.
[accompanying drawing explanation]
Fig. 1 is the scanning electron microscope (SEM) photograph that the present invention synthesizes the affine hypercrosslinked polymeric resin of covalency that phenylo boric acid is modified;
Fig. 2 is the covalency affine low cross-linking resin infrared spectrogram that the present invention synthesizes phenylo boric acid modification;
Fig. 3 is the infrared spectrogram that the present invention synthesizes the affine hypercrosslinked polymeric resin of covalency that phenylo boric acid is modified;
Fig. 4 is synthetic resins of the present invention to the high-efficient liquid phase chromatogram of each step effluent liquid of Solid-Phase Extraction of pyrocatechol and Resorcinol.
[embodiment]
Affine hypercrosslinked polymeric resin of covalency below providing a kind of phenylo boric acid of the present invention to modify and preparation method thereof and the embodiment applied.
Embodiment 1
The preparation of the affine hypercrosslinked polymeric resin of covalency that phenylo boric acid is modified, comprises the steps:
A (), in the 500ml there-necked flask that reflux condensing tube, thermometer and nitrogen protection device are housed, adds 400ml acetonitrile, system ice bath is cooled to 0 DEG C;
B () is in ice-water bath system, add Diisopropyl azodicarboxylate 0.25g successively, Vinylstyrene 2.98ml, 4-1-chloro-4-methyl-benzene 3.81ml and 4-vinylphenylboronic acid 1.2g, wherein 4-vinylphenylboronic acid needs to join reaction system with after 40ml anhydrous alcohol solution, system temperature maintains 0 DEG C, and logical nitrogen 2 hours, to eliminate the oxygen in system;
C then reaction is transferred in oil bath by (), regulate magnetic stirring apparatus to suitable rotating speed, system is slowly risen to 70 DEG C (temperature rise rates by 4min/ DEG C) by room temperature, maintains this temperature and continues reaction 46 hours;
D () reaction terminates after, reaction system is cooled to room temperature, the reaction solution nylon filter membrane filtration of 0.2 μm, 60ml methyl alcohol, 60ml toluene, each supersound washing of 60ml acetone twice used successively by filter cake, filter cake 40 DEG C of vacuum-dryings, to constant weight, obtain the matrix polymer particulate of white.
E () is in the 250ml there-necked flask that reflux condensing tube, thermometer and nitrogen protection device are housed, add white matrix polymer particulate and 40ml 1 that 1.5g above-mentioned steps (d) obtains successively, 2-ethylene dichloride, system fully swelling 1.5 hours under nitrogen atmosphere, makes the affine low cross-linking resin swelling of covalency become ball;
F () takes FERRIC CHLORIDE ANHYDROUS 0.9g, add 40ml Nitromethane 99Min., makes iron trichloride dissolve completely;
In (g) to (e) gained mixing solutions, drip the nitromethane solution containing iron trichloride of step (f) gained, regulate magnetic stirring apparatus to suitable rotating speed, be rapidly heated after dripping off to 80 DEG C, and continue reaction 18 hours at such a temperature;
H () reaction terminates after, reaction system is cooled to room temperature, and reaction solution filtration under diminished pressure, discards filtrate, and filter cake washs repeatedly colourless to filtrate with methyl alcohol, 2mol/L hydrochloric acid soln successively, obtains yellow-brown solid;
I (), by above-mentioned yellow-brown solid, is that solvent apparatus,Soxhlet's extracts 12 hours continuously with acetone;
J () has extracted after, gained solid uses methyl alcohol, washed with diethylether repeatedly more successively, filters, and filter cake vacuum-drying 40 DEG C time, to constant weight, obtains the affine hypercrosslinked polymeric resin particulate of covalency that faint yellow phenylo boric acid is modified.
The affine hypercrosslinked polymeric resin of covalency that k phenylo boric acid that () obtains is modified, surface sweeping Electronic Speculum figure as shown in Figure 1.The synthesized affine hypercrosslinked polymeric resin particle diameter of covalency is mainly distributed as 3-5 μm, BET specific surface area 800m
2/ g.Low cross-linking resin infrared spectra as shown in Figure 2 with the infrared spectra of highly cross-linked resin as shown in Figure 3, the infrared spectra display of resin, resin is at 1507cm
-1and 1341cm
-1place has a sharp-pointed absorption peak respectively, is B-O stretching vibration, at 1441cm
-1there is the absorption peak of a medium tenacity at place, is the stretching vibration of Ph-B key, illustrates that 4-vinylphenylboronic acid has successfully passed non-water precipitation polyreaction and has been modified on resin.The contrast of the two infrared spectrogram is visible, and covalency is affine low cross-linking resin is at 673cm
-1there is an obvious C-Cl absorption peak at place, and the affine hypercrosslinked polymeric resin of covalency nearly disappears at the absorption peak at this place.In addition the affine low cross-linking resin of covalency is at 1262cm
-1having the absorption peak that sharp-pointed, is CH
2the in-plane bending vibration of c h bond on the phenyl ring of-Cl strengthening, and the affine hypercrosslinked polymeric resin of covalency absorption peak herein obviously reduces or disappears, and illustrates that C-Cl key obviously reduces in reaction process.Organic element analysis result shows, and in resin Archon, the content of chlorine element is 7.92%, and after fourier crosslinking reaction, the content of chlorine element is less than 0.5%, illustrates that benzyl chloride constituent content greatly reduces, and superhigh cross-linking reaction is carried out smoothly.
Embodiment 2
The affine hypercrosslinked polymeric resin of covalency of this example is used as solid phase extraction filler, is separated pyrocatechol (c/s-diol type) and Resorcinol (non-c/s-diol type) isomer, the steps include:
A the preparation of () solvent: accurately take Sodium phosphate dibasic 0.1750g, constant volume obtains pH=8.5 phosphoric acid buffer A to 500ml.Accurately pipette 0.5ml trifluoroacetic acid and 15ml acetonitrile, being settled to 50ml with ultrapure water must containing the acetonitrile of 1% trifluoroacetic acid: water=30: 70 solution B.Accurately pipette 10ml acetonitrile, be settled to 100ml with ultrapure water and obtain acetonitrile: water=10: the acetonitrile solution C of 90.
B () prepares liquid to be measured: accurately take pyrocatechol, each 0.2000g of Resorcinol, be settled to 50ml respectively with the solution that step (a) is prepared.
The filling of (c) solid-phase extraction column: accurately take the covalency affine hypercrosslinked polymeric resin resin 60mg that phenylo boric acid is modified, disperse with 30ml anhydrous methanol, adopting wet method dress post resin to be loaded volume is in the Solid-Phase Extraction void column pipe of 3ml, the height obtaining filler is 3mm, internal diameter is 9mm, the sieve plate compacting of resin two ends.
(d) Solid-Phase Extraction activation step: used by the solid-phase extraction column filled 5ml methyl alcohol, 3ml step (a) gained solution B, 3ml step (a) gained solution A to activate successively, flow velocity is 0.5ml/min.
(e) Solid-Phase Extraction loading step: accurately pipette pyrocatechol, each 1ml of Resorcinol liquid to be measured in the solid-phase extraction column activated, flow velocity 0.3ml/min, collects effluent liquid to be measured.
F () Solid-Phase Extraction rinsing step: accurately pipetting 3.0ml step (a) gained solution C is leacheate, flow rate control, at 0.5ml/min, collects Solid-Phase Extraction effluent liquid to be measured.
G () SPE elution step: accurately pipetting 3ml step (a) gained solution B is elutriant, flow velocity 0.5ml/min, collects Solid-Phase Extraction effluent liquid to be measured.
Adopt high performance liquid chromatography to measure the sample that each step obtains, the chromatographic peak peak area of comparative sample and standard specimen, obtain pyrocatechol and the Resorcinol rate of recovery in each step, experimental result is as shown in table 1:
Table 1 pyrocatechol and the Resorcinol rate of recovery in Solid-Phase Extraction respectively walks
| Sample recovery rate (%) | Pyrocatechol | Resorcinol |
| Sample solution | 0 | 0 |
| Rinsing step | 0 | 98.36 |
| Elution step | 97.03 | 0 |
Pyrocatechol, Resorcinol are after Solid-Phase Extraction, and the liquid chromatogram of each step effluent liquid as shown in Figure 3.Experimental result shows, in the basic conditions, has good reservation in the affine hypercrosslinked polymeric resin of covalency that pyrocatechol and Resorcinol are modified at phenylo boric acid; When the acetonitrile solution by certain drip washing intensity, Resorcinol drip washing can be got off, but under the condition of equality strength, due to its syn diol structure, there is covalency affinity interaction power with the boron hydroxyl in resin, be thus retained in pyrocatechol; Containing in 1% trifluoroacetic acid-acetonitrile solution, the covalency affinity interaction power between pyrocatechol and boron hydroxyl is destroyed, thus pyrocatechol is eluted.The above results illustrates the affine hypercrosslinked polymeric resin of covalency that the phenylo boric acid synthesized by the present invention is modified, there are the nonpolar and affine two class reactive forces of covalency simultaneously, and have the affine adsorption of strong covalency to c/s-diol compounds, can realize effectively being separated and enrichment this compounds.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (8)
1. the affine hypercrosslinked polymeric resin of covalency of phenylo boric acid modification, it is characterized in that, its skeleton is made up of Vinylstyrene, 4-1-chloro-4-methyl-benzene and 4-vinylphenylboronic acid, and its chemical structure of general formula is as follows:
2. a preparation method for the affine hypercrosslinked polymeric resin of covalency of phenylo boric acid modification, it is characterized in that, its concrete steps are:
A () utilizes 1-chloro-4-methyl-benzene, Vinylstyrene, 4-vinylphenylboronic acid to be reaction monomers, be initiator with Diisopropyl azodicarboxylate, acetonitrile is reaction solvent, by oxygen that is ultrasonic and that lead to continuously in nitrogen removing reaction system, non-water precipitation polyreaction is adopted to synthesize the 1-chloro-4-methyl-benzene-Vinylstyrene-vinylphenylboronic acid multipolymer of low crosslinking degree, select methyl alcohol, toluene and acetone to remove the linear structure produced in reaction raw materials residual in reaction system and building-up process, then obtain the low cross-linking resin particle of white through vacuum-drying;
1-chloro-4-methyl-benzene-Vinylstyrene-vinylphenylboronic acid the multipolymer of b low crosslinking degree that above-mentioned steps (a) obtains by (), swell in dichloroethane solvent, by the oxygen in ultrasonic and continuous logical nitrogen removing system, adding iron trichloride is catalyzer, step reaction to 80 DEG C, react after 18 hours, obtain the 1-chloro-4-methyl-benzene-Vinylstyrene-vinylphenylboronic acid polymkeric substance of high-crosslinking-degree;
C () reaction terminates after, centrifugal removing reaction mother liquor, repeatedly washs with the hydrochloric acid of methyl alcohol and 2mol/L successively by the solid obtained, the iron trichloride that ethylene dichloride in removing resin and reaction system remain, by the resin after washing, take acetone as solvent, surname extraction refluxes 12 hours;
D () reaction terminates after, reaction system is cooled to room temperature, and the acetone in centrifugal removing reaction system, uses methyl alcohol and washed with diethylether repeatedly successively, the centrifugal highly cross-linked resin obtaining washes clean, and vacuum-drying obtains the affine hypercrosslinked polymeric resin of covalency.
3. the preparation method of the affine hypercrosslinked polymeric resin of covalency of a kind of phenylo boric acid modification as claimed in claim 2, it is characterized in that, in described step (a), the charging capacity of described reaction monomers is that reaction system comprises 2% of all material total mass marks of solvent.
4. the preparation method of the affine hypercrosslinked polymeric resin of covalency of a kind of phenylo boric acid modification as claimed in claim 2, it is characterized in that, in described step (a), the massfraction of described 4-vinylphenylboronic acid in three kinds of reaction monomers is 5 ~ 20%, the massfraction of 4-1-chloro-4-methyl-benzene in three kinds of reaction monomers is 65 ~ 40%, and the massfraction of Vinylstyrene in three kinds of reaction monomers is 20 ~ 50%.
5. the preparation method of the affine hypercrosslinked polymeric resin of covalency of a kind of phenylo boric acid modification as claimed in claim 2, it is characterized in that, in described step (a), temperature of reaction system controls at 50 ~ 80 DEG C, and the reaction times is 46 hours.
6. the preparation method of the affine hypercrosslinked polymeric resin of covalency of a kind of phenylo boric acid modification as claimed in claim 2, it is characterized in that, in described step (b), the amount of substance of described ferric chloride catalyst is 1: 1 with the ratio of the amount of chlorine elemental substance in the affine low cross-linking resin of covalency.
7. the preparation method of the affine hypercrosslinked polymeric resin of covalency of a kind of phenylo boric acid modification as claimed in claim 2, it is characterized in that, in described step (d), the affine hypercrosslinked polymeric resin of covalency that obtained phenylo boric acid is modified contains abundant micropore distribution, and specific surface area reaches 800m
2/ g.
8. the application of the affine hypercrosslinked polymeric resin of covalency in solid phase extraction filler of a phenylo boric acid modification.
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| CN105344333A (en) * | 2015-11-06 | 2016-02-24 | 辽宁大学 | Styrene-(4-vinylphenylboronic acid)copolymer microsphere, preparation method and application thereof |
| CN110845645A (en) * | 2019-11-26 | 2020-02-28 | 中国科学院青岛生物能源与过程研究所 | Functionalized post-crosslinked resin and preparation method and application thereof |
| CN112724455A (en) * | 2020-12-10 | 2021-04-30 | 中国科学院青岛生物能源与过程研究所 | Preparation method of efficient high-selectivity polyol adsorption material |
| CN112724321A (en) * | 2020-12-29 | 2021-04-30 | 中国科学院兰州化学物理研究所 | Boric acid functionalized monodisperse porous microsphere and preparation method and application thereof |
| CN114874397A (en) * | 2022-05-12 | 2022-08-09 | 安徽大学 | Method for toughening polylactic acid based on reversible covalent crosslinking |
| CN114875553A (en) * | 2022-07-11 | 2022-08-09 | 比音勒芬服饰股份有限公司 | Polyester composite material garment with sweat-discharging and air-permeable functions |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105344333A (en) * | 2015-11-06 | 2016-02-24 | 辽宁大学 | Styrene-(4-vinylphenylboronic acid)copolymer microsphere, preparation method and application thereof |
| CN110845645A (en) * | 2019-11-26 | 2020-02-28 | 中国科学院青岛生物能源与过程研究所 | Functionalized post-crosslinked resin and preparation method and application thereof |
| CN110845645B (en) * | 2019-11-26 | 2022-04-22 | 中国科学院青岛生物能源与过程研究所 | Functionalized post-crosslinked resin and preparation method and application thereof |
| CN112724455A (en) * | 2020-12-10 | 2021-04-30 | 中国科学院青岛生物能源与过程研究所 | Preparation method of efficient high-selectivity polyol adsorption material |
| CN112724455B (en) * | 2020-12-10 | 2022-12-23 | 中国科学院青岛生物能源与过程研究所 | Preparation method of efficient high-selectivity polyol adsorption material |
| CN112724321A (en) * | 2020-12-29 | 2021-04-30 | 中国科学院兰州化学物理研究所 | Boric acid functionalized monodisperse porous microsphere and preparation method and application thereof |
| CN114874397A (en) * | 2022-05-12 | 2022-08-09 | 安徽大学 | Method for toughening polylactic acid based on reversible covalent crosslinking |
| CN114875553A (en) * | 2022-07-11 | 2022-08-09 | 比音勒芬服饰股份有限公司 | Polyester composite material garment with sweat-discharging and air-permeable functions |
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