CN104892804A - 14C-labeled polystyrene (PS) and synthesis method thereof - Google Patents
14C-labeled polystyrene (PS) and synthesis method thereof Download PDFInfo
- Publication number
- CN104892804A CN104892804A CN201510260827.0A CN201510260827A CN104892804A CN 104892804 A CN104892804 A CN 104892804A CN 201510260827 A CN201510260827 A CN 201510260827A CN 104892804 A CN104892804 A CN 104892804A
- Authority
- CN
- China
- Prior art keywords
- mark
- polystyrene
- ring
- vinylbenzene
- reaction
- 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.)
- Granted
Links
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 114
- 238000001308 synthesis method Methods 0.000 title abstract 4
- 229920002223 polystyrene Polymers 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 29
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 238000010790 dilution Methods 0.000 claims abstract description 5
- 239000012895 dilution Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 11
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- -1 phenyl aldehyde Chemical class 0.000 claims description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- QSDSNNSKORVORL-UHFFFAOYSA-N acetic acid;silver Chemical compound [Ag].CC(O)=O QSDSNNSKORVORL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000011097 chromatography purification Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 150000003053 piperidines Chemical class 0.000 claims description 3
- 238000012746 preparative thin layer chromatography Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000002285 radioactive effect Effects 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 13
- 229960001701 chloroform Drugs 0.000 description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 235000011181 potassium carbonates Nutrition 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000700 radioactive tracer Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 5
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000003550 marker Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 235000014443 Pyrus communis Nutrition 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 4
- 230000000155 isotopic effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 239000006166 lysate Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000010829 isocratic elution Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229930010796 primary metabolite Natural products 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012134 supernatant fraction Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 230000001228 trophic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses 14C-labeled polystyrene (PS) and its synthesis method and belongs to the field of radioactive isotope 14C-labeled compounds. According to the invention, 14C radioactive isotope label is introduced into the structure of polystyrene (PS). A 14C-labeled site is on a branched chain or a phenyl ring, and is respectively named [beta-14C]-PS and [U-ring-14C6]-PS. The general structural formula is as shown in the Figure 1, wherein * indicates the 14C-labeled site. The synthesis method comprises the following steps: adding the 14C-labeled styrene into non-labeled styrene for dilution, putting into a high-temperature and high-pressure reactor and reacting at 118-123 DEG C for 8-12 h; dissolving reaction products with chloroform, washing with methanol, depositing and purifying to obtain the 14C-labeled polystyrene. The synthesis method has the following advantages: reaction materials are easily available, unreacted raw materials can be recovered, and synthesis cost is low; reaction time is short and efficiency is high; and reaction conditions are mild, operation technique is safe, and the preparation technology is simple. Radioactive purity of the 14C-labelled polystyrene synthesized by the method reaches more than 99%.
Description
Technical field
The present invention relates to radio isotope
14the compou nd synthesis field of C mark, particularly
14c marks the synthetic method of polystyrene.The polystyrene that can be used for environmental science is degraded in the environment, conversion etc. returns the tracer study become.
Background technology
Polystyrene (Polystyrene, PS) is the polymkeric substance that styrene monomer is reacted by radical addition polymerization, is widely used in communication equipment, opticinstrument, transparent mould, packaging material for food and articles for daily use.Discarded polystyrene plastic fragment, may be eaten by mistake by biology, cause digestive tube to block, cause the minimizing of ingesting of self, also likely transfers to body-internal-circulation system and produces harm, also likely along food chain to higher trophic level transmission to organism.Therefore, research polystyrene plastic is in the surrounding medium such as soil, ocean, and environmental behaviour is in vivo significant.Biological corrosion, depolymerization, assimilation, mineralising four-stage are generally experienced in the biological degradation of macromolecular material.In the biological corrosion stage, polymkeric substance splits into little fragment, does not generally comprise the change of chemical structure; In the unzipping stage, generate oligomer, dimer or monomer; The assimilation stage, some molecular weight polymers bioavailable generation primary and secondary meta-bolites; In the mineralization stage, meta-bolites further complete oxidation in cell that assimilation produces, produces CO
2, N
2, H
2the materials such as O.
Measured the change of relative molecular mass size and relative molecular mass distribution by gel permeation chromatography (GPC), can judge whether to be degraded to oligomer.Whether have new functional group absorption peak occur, infer the structural changes of polymkeric substance if being detected by Fourier transform infrared chromatographic instrument (FTIR).Observe polymer surfaces structure by atom mechanics microscope (AFM), according to the 3-D view on surface, infer superficial degradation or the conversion of sample.And oligomer in liquid and monomer use high performance liquid chromatography (HPLC) and gas-chromatography (GC) to detect usually, after being further purified, Structural Identification can be carried out with mass spectrum (MS) or nucleus magnetic resonance (NMR).In the natural surroundings system of complexity, above-mentioned technique means is usually difficult to the interference getting rid of background, is extremely restricted.P-poly-phenyl ethene carries out
14c marks, and utilizes
14c isotopic tracer technique, can follow the trail of that polystyrene is degraded in the environment, transformed exactly, residual and enrichment etc. returns.Phenyl ring in p-poly-phenyl ethylene molecule and side chain mark respectively, will obtain the polystyrene of two kinds of marks, and the tracer study become returned by phenyl ring and the side chain that can be respectively used to be directed to polystyrene.
But, relevant
14it is very few that C marks polystyrene synthesis report.In the research of the people such as James E.Guillet, will
14c-marks styrene monomer and is dissolved in ketene, take benzoyl peroxide as catalyzer, and at 75 DEG C, reaction obtains side chain in 72 hours
14c marks polystyrene (J.E.Guillet; T.W.Regulski; T.B.McAneney, Biodegradability of Photodegraded Polymers II .Tracer Studies of Biooxidation of Ecolyte PS Polystyrene.Environ.Sci.Technol.1974,8,923-925.).Using ketene in the method, is poisonous gas under ketene room temperature, very unstable, can only preserve at low temperatures, 0 DEG C time, get final product polymerization reaction take place, generates dimer dicthenone.Ketene experiment is wayward, long reaction time.Because isotopic labeling material synthesis material is expensive, therefore require that experimental procedure is as far as possible few, treating processes is simple, and unreacted raw material reclaims as far as possible.In prior art
14c marks polystyrene preparation method and there is the higher problem of cost.
Summary of the invention
The technical problem that 1, will solve
In order to solve
14the problems such as C marks long reaction time in polystyrene synthesis, wayward, the polymerization degree is lower, reduce
14c marks polystyrene synthesis cost, the invention provides microsynthesis
14c marks the method for polystyrene, and the method adopts High Temperature High Pressure, overcomes the shortcoming that extent of polymerization under normal pressure is lower; Start mark raw material market is easy to get, and synthesis step is simple, and synthetic method has universality; Marker site is respectively on phenyl ring or side chain, and wherein there is not been reported for phenyl ring marker site, and market is also sold without corresponding product.Target compound radioactive purity reaches more than 99.9%, is follow-up employing
14the environment of C radio isotope tracer technique research polystyrene returns to become to providing condition.
2. technical scheme
Inventive principle: the object of the invention is to set up
14the synthetic method of polystyrene of C mark, isotopic labeling site on phenyl ring or side chain, respectively as shown in Fig. 1 Chinese style VII and formula IV.In synthesis
14before the polystyrene of C mark, first synthesize cold polystyrene with cold styrene monomer, to determine reaction conditions, and carry out structural characterization with the non-marked polystyrene to synthesis such as gel permeation chromatograph and nuclear magnetic resonance analyser, confirmation structure.
Object of the present invention is achieved through the following technical solutions.
A kind of synthesis
14the method of the polystyrene of C mark, concrete steps are as follows:
Will
14the vinylbenzene that C marks puts into high-temperature high-voltage reaction device after adding the dilution of non-marked vinylbenzene, and 118 ~ 123 DEG C are reacted 8 ~ 12 hours; Reaction product is through washing, and deposition and purification, obtains
14the polystyrene of C mark.Above-mentioned high-pressure scope is 0.1 ~ 0.2Mpa.
Synthesis
14in the method for the polystyrene of C mark, temperature of reaction is preferably 121 DEG C.
Further, synthesize
14washing concrete steps in the method for the polystyrene of C mark is: reaction product chloroform washs after dissolving in methyl alcohol.
Further, synthesize
14described in the method for the polystyrene of C mark
14the styrene monomer of C mark is side chain
14c mark [β-
14c]-vinylbenzene or phenyl ring
14[the U-ring-of C mark
14c6]-vinylbenzene.
Further, described side chain
14c mark [β-
14c]-vinylbenzene preparation comprise the steps:
S1. will
14the propanedioic acid of C mark
14cH
2(COOH)
2, phenyl aldehyde, piperidines, adds in reaction flask,
14cH
2(COOH)
2being 1:1.2 ~ 1.5 with the mol ratio of phenyl aldehyde, take pyridine as solvent, stirring reaction 9 ~ 14 hours at 100 ~ 110 DEG C; Reaction mixture adds hcl acidifying, extraction into ethyl acetate, and separating-purifying obtains side chain
14c mark [β-
14c]-styracin;
S2. side chain
14c mark [β-
14c]-styracin is dissolved in DMAc, and add catalyst acetic acid silver, Anhydrous potassium carbonate, ingredient proportion is, [β-
14c]-styracin: Silver monoacetate: Anhydrous potassium carbonate=1:0.2 ~ 0.5:0.3 ~ 0.8; Under nitrogen protection, back flow reaction 8 ~ 16 hours at 158 ~ 163 DEG C, extracts and obtains side chain
14c mark [β-
14c]-vinylbenzene.
Concrete, side chain
14c mark [β-
14c]-vinylbenzene preparation in, in step S1, separating-purifying step is specially: use Preparative TLC chromatographic purification, plate prepared by silica gel is 20cm × 20cm × 2mm, and developping agent is the mixed solution of normal hexane, ethyl acetate and formic acid, and proportions is 1:1 ~ 5:0.01; Normal hexane extraction is used in step S2. purifying.
Further, described phenyl ring
14[the U-ring-of C mark
14c6]-vinylbenzene preparation comprise the steps:
S3. phenyl ring
14[the U-ring-of C mark
14c6]-styracin is dissolved in DMAc, and add catalyst acetic acid silver, Anhydrous potassium carbonate, ingredient proportion is, [U-ring-
14c6]-styracin: Silver monoacetate: Anhydrous potassium carbonate=1:0.2 ~ 0.5:0.3 ~ 0.8; Under nitrogen protection, back flow reaction 8 ~ 16 hours at 158 ~ 163 DEG C; Extract, obtain phenyl ring
14[the U-ring-of C mark
14c6]-vinylbenzene.
Concrete, described phenyl ring
14[the U-ring-of C mark
14c6] use normal hexane extraction in step S3. purifying in the preparation of-vinylbenzene.
Above-mentioned synthetic method is prepared
14the polystyrene of C mark, for such as formula the side chain shown in IV
14c mark [β-
14c]-polystyrene, or for such as formula the phenyl ring shown in VII
14[the U-ring-of C mark
14c6]-polystyrene,
Above-mentioned
14the polystyrene number-average molecular weight Mn of C mark is 2 × 10
4~ 2 × 10
6.
Side chain
14c mark [β-
14c]-polystyrene ([β-
14c]-PS) preparation method of (IV), as shown in Figure 2 a, the steps include:
(1). will
14the propanedioic acid of C mark
14cH
2(COOH)
2(I), phenyl aldehyde, piperidines, adds in pear shape bottle, take pyridine as solvent, stirring reaction 9 ~ 14 hours at 105 DEG C.Reaction mixture adds hcl acidifying, extraction into ethyl acetate, uses Preparative TLC chromatographic purification; Plate prepared by silica gel is 20cm × 20cm × 2mm, and developping agent is the mixed solution of normal hexane, ethyl acetate and formic acid, obtains side chain
14c mark [β-
14c]-styracin (II).
(2). (II) is dissolved in DMAc (N,N-DIMETHYLACETAMIDE), adds catalyst acetic acid silver, Anhydrous potassium carbonate, and ingredient proportion is, [β-
14c]-styracin: Silver monoacetate: Anhydrous potassium carbonate=1:0.2:0.3.Under nitrogen protection, back flow reaction 8 ~ 16 hours at 160 DEG C.With normal hexane extraction, obtain side chain
14c mark [β-
14c]-vinylbenzene (III).
(3). after (III) being added the dilution of non-marked vinylbenzene, put into high-temperature high-voltage reaction device, 121 DEG C are reacted 8 ~ 12 hours; Reaction product chloroform washs after dissolving in methyl alcohol, and deposition and purification, obtains side chain
14c mark [β-
14c]-polystyrene ([β-
14c]-PS) (IV).
(4). product detects through the method for high performance liquid chromatography (HPLC) with radioactive detector (Ramona) coupling, and recording radioactive purity is 99.9%.GPC detects known, and number-average molecular weight Mn is 2 × 10
4~ 2 × 10
6.
Phenyl ring
14[the U-ring-of C mark
14c6]-polystyrene ([U-ring-
14c6]-PS) preparation method of (VII), as shown in Figure 2 b, the steps include:
(1). phenyl ring
14[the U-ring-of C mark
14c6]-styracin (V) (purchasing in Amersham International plc company of Britain) is dissolved in DMAc (N,N-DIMETHYLACETAMIDE), and add catalyst acetic acid silver, Anhydrous potassium carbonate, ingredient proportion is, [U-ring-
14c6]-styracin: Silver monoacetate: Anhydrous potassium carbonate=1:0.2:0.3.Under nitrogen protection, back flow reaction 8 ~ 16 hours at 160 DEG C.With normal hexane extraction, obtain phenyl ring
14c marks [U-ring-
14c6]-vinylbenzene (VI).
(2). after (VI) being added the dilution of non-marked vinylbenzene, put into high-temperature high-voltage reaction device, 121 DEG C are reacted 8 ~ 12 hours; Reaction product chloroform washs after dissolving in methyl alcohol, deposition and purification, obtains phenyl ring mark [U-ring-
14c6]-polystyrene ([U-ring-
14c6]-PS) (VII)
(3). product detects through the method for high performance liquid chromatography (HPLC) with radioactive detector (Ramona) coupling, and recording radioactive purity is 99.9%.GPC detects known, and number-average molecular weight Mn is 2 × 10
4~ 2 × 10
6.Remaining after reaction
14c-vinylbenzene carries out secondary response again.
The representational compound of the present invention comprises: side chain
14c mark [β-
14c]-polystyrene ([β-
14c]-PS) (IV) and phenyl ring
14[the U-ring-of C mark
14c6]-polystyrene ([U-ring-
14c6]-PS) (VII).
3, beneficial effect
Compared to prior art, the invention has the advantages that:
(1) utilize
14the polystyrene of C mark, binding radioactivity isotopic tracer technique, change polystyrene being detected that not only can be sensitiveer in complex system (as natural surroundings sample), the situation slowly of degrading, all right spike degraded product, for the research of degraded and conversion process and mechanism provides effective means;
(2) the present invention establish phenyl ring mark or side chain mark two kinds
14c marks the synthetic method of polystyrene; Reaction raw materials is easy to get, and synthesis cost is low, and unreacted raw material can be recycled, and loses little; Polystyrene synthesising reacting time is short, and efficiency is high; Reaction conditions is gentle, and operative technique safety, preparation technology is simple.Present method synthesis
14the polystyrene of C mark, radioactive purity reaches more than 99%; And phenyl ring marker site has no report, market is also sold without corresponding product.
Accompanying drawing explanation
Fig. 1 is
14(* is the polystyrene structural formula of C mark
14c marker site)
Fig. 2 is
14the synthetic schemes of the polystyrene of C mark; * be
14c marker site,
Wherein Fig. 2 a is side chain
14c mark [β-
14c]-polystyrene ([β-
14c]-PS) synthetic route of (IV); Fig. 2 b is phenyl ring
14[the U-ring-of C mark
14c6]-polystyrene ([U-ring-
14c6]-PS) synthetic route of (VII);
Fig. 3 be [β-
14c]-styracin radiated signal liquid chromatogram; Wherein, the display of 1# figure main peak be the ultraviolet response signal of styracin, the display of 2# figure main peak be [β-
14c] radiated signal of-styracin;
Fig. 4 be [β-
14c]-vinylbenzene radiated signal liquid chromatogram; Wherein, 1# figure main peak display be cinnamic ultraviolet response signal, 2# figure main peak display be [β-
14c]-vinylbenzene radiated signal;
Fig. 5 is [U-ring-
14c6]-vinylbenzene radiated signal liquid chromatogram; Wherein, what 1# figure main peak showed is cinnamic ultraviolet response signal, and that 2# figure main peak shows is [U-ring-
14c6]-cinnamic radiated signal;
Fig. 6 be [β-
14c]-PS gel permeation chromatography figure; Number-average molecular weight Mn is 2 × 10
5, polydispersity coefficient PD is 1.9;
Fig. 7 is [U-ring-
14c6]-PS gel permeation chromatography figure; Number-average molecular weight Mn is 5 × 10
4, polydispersity coefficient PD is 2.2;
Fig. 8 is non-marked polystyrene PS's
1h NMR schemes, and wherein scheming a is standard substance, and figure b is synthetic product;
Fig. 9 is non-marked polystyrene PS's
13c NMR schemes, and wherein scheming a is standard substance, and figure b is synthetic product.
Embodiment
Below in conjunction with Figure of description and specific embodiment, the present invention is described in detail.
Embodiment 1: side chain
14c mark [β-
14c]-polystyrene ([β-
14c]-PS) synthesis of (IV)
Composition graphs 1,2, side chain
14c mark [β-
14c]-polystyrene ([β-
14c]-PS) synthesis step of (IV) is:
(1) side chain is synthesized
14c mark styracin ([β-
14c]-styracin) (II):
Be 2.1 × 10 by specific activity
9bq mmol
-1's
14the propanedioic acid of C mark
14cH
2(COOH)
2(I) and appropriate cold propanedioic acid be dissolved in pyridine, join in 25mL pear shape bottle, obtaining specific activity is 4.2 × 10
7bq mmol
-1's
14c-propanedioic acid.Add phenyl aldehyde 0.1128g and piperidinyl-1 77.5 μ L successively,
14cH
2(COOH)
2(I) be 1:1.2 ~ 1.5 with the mol ratio of phenyl aldehyde, nitrogen protection, magnetic agitation, oil bath 105 DEG C, reacts 14 hours.After reaction terminates, be cooled to room temperature, add the hcl acidifying of 20mL 1M, make pH value of solution become acid.Extract 9 times by ethyl acetate, organic moiety merges.Anhydrous sodium sulfate drying, rotary evaporation is concentrated to only remaining trace solvent, prepares plate purify with TLC, and plate prepared by silica gel is 20cm × 20cm × 2mm, and developping agent is: normal hexane: ethyl acetate: formic acid=3:1:0.01 (v:v:v).By radioactive automatic developing, utilize Multi-functional scanning imaging system determination product position (R
fvalue is 0.67), scraped by the silica gel containing product region, ethyl acetate is extracted.Extracting solution anhydrous sodium sulfate drying, rotary evaporation is concentrated into dry.Radioactivity scintillation counter (LSC) measures, and obtains side chain
14c mark styracin ([β-
14c]-styracin) (II) about 1.2 × 10
7bq, specific activity is 4.2 × 10
7bq mmol
-1, detect through HPLC-Ramona, chemical purity 97%, radioactive purity >99.99%, productive rate 82.8%, [β-
14c]-styracin radiated signal liquid chromatogram is as shown in Figure 3.
(2) side chain is synthesized
14c mark vinylbenzene ([β-
14c]-vinylbenzene) (III):
By above-mentioned [β-
14c]-styracin (II) and appropriate non-marked styracin join in 25mL pear shape bottle, and be dissolved in 1mL DMAc (N,N-DIMETHYLACETAMIDE), obtaining specific activity is 4.2 × 10
6bq mmol
-1[β-
14c]-styracin.Add AgOAc 0.1011g and anhydrous K successively
2cO
30.1254g, [β-
14c]-styracin, Silver monoacetate and salt of wormwood three mol ratio be 1:0.2 ~ 0.5:0.3 ~ 0.8, nitrogen protection, magnetic agitation, oil bath 160 DEG C, reacts 8 hours.After reaction terminates, be cooled to room temperature, with normal hexane extraction 7 times, sodium hydrogen carbonate solution washes 3 times, each 2mL, and saturated sodium-chloride washes 3 times, each 2mL, and with anhydrous sodium sulfate drying, rotary evaporation concentrates.LSC measures, and obtains side chain
14c mark [β-
14c]-vinylbenzene (III) gross activity amount about 4.2 × 10
6bq, specific activity is 4.2 × 10
6bq mmol
-1.Detect through HPLC-Ramona, chemical purity 95%, radioactive purity >99.99%, productive rate 33.7%, [β-
14c]-vinylbenzene radiated signal liquid chromatogram, as shown in Figure 4.
(3) side chain is synthesized
14c mark [β-
14c]-polystyrene ([β-
14c]-PS) (IV)
Get above-mentioned [β-
14c]-vinylbenzene (III) 3.7 × 10
6bq and appropriate non-marked vinylbenzene, join in 10mL test tube, obtaining specific activity is 4.2 × 10
5bq mmol
-1[β-
14c]-vinylbenzene.Test tube is put into high-temperature high-voltage reaction device, react 8 hours at 121 DEG C.After reaction terminates, be cooled to room temperature.Get the methyl alcohol preserved in 4 DEG C of refrigerators, rinse its surface 3 times, use trichloromethane lysate, pour in the long-pending methyl alcohol of trichloromethane decaploid, product is separated out, filter and obtain sterling.Trichloromethane dissolves, and hydatogenesis film forming, LSC measures radioactivity, obtains side chain
14c mark [β-
14c]-polystyrene ([β-
14c]-PS) (IV), gross activity amount about 1.3 × 10
6bq, specific activity is 3200Bq mg
-1, productive rate 32.7%.
(4) product detects through the method for high performance liquid chromatography (HPLC) with radioactive detector (Ramona) coupling, and recording radioactive purity is 99.9%.GPC detects known, and number-average molecular weight Mn is 2 × 10
5, polydispersity coefficient PD is 1.9, [β-
14c] shown in-PS gel permeation chromatography figure Fig. 6.
Embodiment 2: phenyl ring
14[the U-ring-of C mark
14c6]-polystyrene ([U-ring-
14c6]-PS) synthesis of (VII)
Composition graphs 1,2, phenyl ring
14[the U-ring-of C mark
14c6]-polystyrene ([U-ring-
14c6]-PS)
(VII) synthesis step is:
(1) phenyl ring is synthesized
14the vinylbenzene ([U-ring-of C mark
14c6]-vinylbenzene) (VI)
Getting specific activity is 1.3 × 10
8bq mmol
-1phenyl ring
14styracin [the U-ring-of C mark
14c6]-styracin (V) and appropriate non-marked styracin, join in 25mL pear shape bottle, be dissolved in 1mL DMAc (N,N-DIMETHYLACETAMIDE), obtaining specific activity is: 1.3 × 10
7bq mmol
-1[U-ring-
14c6]-styracin.Add Silver monoacetate 0.0029g successively, Anhydrous potassium carbonate 0.0036g, [U-ring-
14c6]-styracin, Silver monoacetate and salt of wormwood three mol ratio be 1:0.2 ~ 0.5:0.3 ~ 0.8, nitrogen protection, magnetic agitation, oil bath 160 DEG C, reacts 8 hours.After reaction terminates, be cooled to room temperature, with normal hexane extraction 5 times, sodium hydrogen carbonate solution washes 3 times, each 2mL, and saturated sodium-chloride washes 3 times, each 2mL, anhydrous sodium sulfate drying, and rotary evaporation concentrates.LSC measures, and obtains phenyl ring
14[the U-ring-of C mark
14c6]-vinylbenzene (VI) gross activity amount about 1.0 × 10
6bq, specific activity is 1.3 × 10
7bq mmol
-1.Detect through HPLC-Ramona, chemical purity >99%, radioactive purity >99.99%, productive rate 9.5%, [U-ring-
14c6]-vinylbenzene radiated signal liquid chromatogram, as shown in Figure 5.
(2) phenyl ring is synthesized
14[the U-ring-of C mark
14c6]-polystyrene ([U-ring-
14c6]-PS) (VII)
Get above-mentioned phenyl ring mark [U-ring-
14c6]-vinylbenzene (VI) and appropriate non-marked vinylbenzene, join in 10mL test tube, obtaining specific activity is 1500Bq mmol
-1[U-ring-
14c6]-vinylbenzene.Test tube is put into high-temperature high-voltage reaction device, react 8 hours at 121 DEG C.After reaction terminates, shift out supernatant fraction, get the methyl alcohol preserved in 4 DEG C of refrigerators, rinse its surface 3 times, use trichloromethane lysate, pour in the long-pending methyl alcohol of trichloromethane decaploid, product is separated out, filter and obtain sterling.Trichloromethane dissolves, hydatogenesis film forming.LSC measures radioactivity, obtains phenyl ring
14[the U-ring-of C mark
14c6]-polystyrene ([U-ring-
14c6]-PS) (VII), radioactivity total amount 8.5 × 10
4bq, specific activity is 533Bq mmol
-1, productive rate is 6.5%.
(3) product detects through the method for high performance liquid chromatography (HPLC) with radioactive detector (Ramona) coupling, and recording radioactive purity is 99.9%.GPC detects known, and number-average molecular weight Mn is 5 × 10
4, polydispersity coefficient PD is 2.2, [U-ring-
14c6] shown in-PS gel permeation chromatography figure Fig. 7.Remaining after reaction
14c-vinylbenzene carries out secondary response again.
Synthesis [β-
14c]-PS and [U-ring-
14c6] before-PS, first synthesize corresponding non-marked PS, to determine reaction conditions; And carry out structural characterization, to confirm structure with the PS of nuclear magnetic resonance analyser to synthesis.Synthetic method is as follows:
Get vinylbenzene 800mg and 1mL normal hexane in test tube, in high-temperature high-voltage reaction device, react 8h at 121 DEG C.After reaction terminates, be cooled to room temperature, first with washed with methanol product to remove unreacted monomer, pour in the long-pending methyl alcohol of trichloromethane decaploid, product is separated out, filtration obtains sterling.Trichloromethane dissolves, hydatogenesis film forming.Obtain PS and put into loft drier dry 24 hours.The dried PS that takes a morsel is dissolved in tetrahydrofuran (THF), GPC determining molecular weight and molecular weight distribution, and result is: number-average molecular weight Mn is 1.8 × 10
5, molecular weight distribution PD is 2.1.
The structural characterization of non-marked PS:
Nuclear-magnetism condition: be interior mark with TMS, CDCl
3for solvent.Shown in Fig. 8 b is non-marked PS synthetics
1h-NMR, X-coordinate is chemical shift δ/ppm.Wherein 1.45 correspond to methylene radical (-CH
2-) on hydrogen, 1.86 correspond to the hydrogen on methyne (-CH-), and the corresponding δ of benzene ring hydrogen is respectively: 6.49,6.53,6.60,7.07,7.11, and solvent peak is 7.28.Shown in Fig. 9 b is non-marked PS synthetics
13c-NMR, X-coordinate is that the numbering of chemical shift δ/ppm, C is shown in Fig. 9 b upper right corner schematic diagram.The C ownership of each position is respectively: C1:40.38; C2:42.38,43.84,44.53,45.10,46.05; C3:145.11,145.33,145.65,145.86; C6:125.50,125.64; C4:127.69; C5:127.96; Solvent peak is 76.76 ~ 77.27.Except C1, the corresponding multiple signal of other carbon atoms, illustrate and there occurs splitting point of peak, these split the fine structure that swarming reflects polymer molecule inside.
Shown in Fig. 8 a and Fig. 9 a is non-marked PS standard substance
1h-NMR and
13c-NMR, contrast finds that the PS of synthesis is consistent with the spectrogram of standard substance PS, so can determine that synthesizing obtain certain is PS.
Accessory substance analytical procedure:
Attached 1) high performance liquid chromatography-radioactive detector: high performance liquid chromatograph is Agilent 1100 (Agilent Technologies), flow rate of mobile phase 1mL/min, and moving phase is methyl alcohol: water=85:15, isocratic elution, and the time is 7min.UV detector wavelength selective 2 45nm and 254nm.Radioactive detector is Ramona (Raytest, Straubenhardt, Germany), and scintillation solution is Gold Flow multipurpose (Meridian Biotechnologies Ltd., Epsom, UK), and flow velocity is 2.0mL/min.
Attached 2) gel permeation chromatography: gel permeation chromatograph is PL-GPC 120 (Polymer Labs, ENG), and moving phase is tetrahydrofuran (THF) (THF), and flow velocity is 1mL/min; Chromatographic column is PL gel-MIXED B 10 μm, 300 × 7.5mm and PL gel-MIXED C 5 μm, 300 × 7.5mm (Polymer Labs, ENG) series connection, and column temperature is 40 DEG C.
Claims (10)
1. a synthesis
14the method of the polystyrene of C mark, it is characterized in that, concrete steps are as follows:
Will
14the vinylbenzene that C marks puts into high-temperature high-voltage reaction device after adding the dilution of non-marked vinylbenzene, and 118 ~ 123 DEG C are reacted 8 ~ 12 hours; Reaction product is through washing, and deposition and purification, obtains
14the polystyrene of C mark.
2. synthesis according to claim 1
14the method of the polystyrene of C mark, it is characterized in that, described temperature of reaction is specially 121 DEG C.
3. synthesis according to claim 1
14the method of the polystyrene of C mark, it is characterized in that, described washing concrete steps are: reaction product chloroform washs after dissolving in methyl alcohol.
4. synthesis according to claim 1
14the method of the polystyrene of C mark, is characterized in that, described in
14the styrene monomer of C mark is side chain
14c mark [β-
14c]-vinylbenzene or phenyl ring
14[the U-ring-of C mark
14c6]-vinylbenzene.
5. synthesis according to claim 4
14the method of the polystyrene of C mark, is characterized in that, described side chain
14c mark [β-
14c]-vinylbenzene preparation comprise the steps:
S1. will
14the propanedioic acid of C mark
14cH
2(COOH)
2, phenyl aldehyde, piperidines, adds in reaction flask,
14cH
2(COOH)
2being 1:1.2 ~ 1.5 with the mol ratio of phenyl aldehyde, take pyridine as solvent, stirring reaction 9 ~ 14 hours at 100 ~ 110 DEG C; Reaction mixture adds hcl acidifying, extraction into ethyl acetate, and separating-purifying obtains side chain
14c mark [β-
14c]-styracin;
S2. side chain
14c mark [β-
14c]-styracin is dissolved in DMAc, and add catalyst acetic acid silver, Anhydrous potassium carbonate, ingredient proportion is, [β-
14c]-styracin: Silver monoacetate: Anhydrous potassium carbonate=1:0.2 ~ 0.5:0.3 ~ 0.8; Under nitrogen protection, back flow reaction 8 ~ 16 hours at 158 ~ 163 DEG C; Extract, obtain side chain
14c mark [β-
14c]-vinylbenzene.
6. synthesis according to claim 5
14the method of the polystyrene of C mark, it is characterized in that, in step S1., separating-purifying step is specially: use Preparative TLC chromatographic purification, and plate prepared by silica gel is 20cm × 20cm × 2mm, developping agent is the mixed solution of normal hexane, ethyl acetate and formic acid, and proportions is 1:1 ~ 5:0.01; Normal hexane extraction is used in step S2. purifying.
7. synthesis according to claim 4
14the method of the polystyrene of C mark, is characterized in that, described phenyl ring
14[the U-ring-of C mark
14c6]-vinylbenzene preparation comprise the steps:
S3. phenyl ring
14[the U-ring-of C mark
14c6]-styracin is dissolved in DMAc, and add catalyst acetic acid silver, Anhydrous potassium carbonate, ingredient proportion is, [U-ring-
14c6]-styracin: Silver monoacetate: Anhydrous potassium carbonate=1:0.2 ~ 0.5:0.3 ~ 0.8; Under nitrogen protection, back flow reaction 8 ~ 16 hours at 158 ~ 163 DEG C; Extract, obtain phenyl ring
14[the U-ring-of C mark
14c6]-vinylbenzene.
8. synthesis according to claim 7
14the method of the polystyrene of C mark, is characterized in that, use normal hexane extraction in step S3. purifying.
9. the method described in any one of claim 1-8 is prepared
14the polystyrene of C mark, is characterized in that, for such as formula the side chain shown in IV
14c mark [β-
14c]-polystyrene, or for such as formula the phenyl ring shown in VII
14[the U-ring-of C mark
14c6]-polystyrene,
10. according to claim 9
14the polystyrene of C mark, is characterized in that,
14the polystyrene number-average molecular weight Mn of C mark is 2 × 10
4~ 2 × 10
6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510260827.0A CN104892804B (en) | 2015-05-21 | 2015-05-21 | One kind synthesis14The method of the polystyrene (PS) of C flag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510260827.0A CN104892804B (en) | 2015-05-21 | 2015-05-21 | One kind synthesis14The method of the polystyrene (PS) of C flag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104892804A true CN104892804A (en) | 2015-09-09 |
| CN104892804B CN104892804B (en) | 2017-10-20 |
Family
ID=54025809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510260827.0A Active CN104892804B (en) | 2015-05-21 | 2015-05-21 | One kind synthesis14The method of the polystyrene (PS) of C flag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104892804B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112204093A (en) * | 2018-06-25 | 2021-01-08 | 国家航空航天技术研究所 | Isotopically labelled materials for degradation detection |
| CN113427660A (en) * | 2021-06-29 | 2021-09-24 | 南京大学 | Isotope element14Preparation method of C-labeled polystyrene micro-plastic |
| CN114805978A (en) * | 2022-03-11 | 2022-07-29 | 河海大学 | Stable isotope 13 Preparation method of C-marked polyethylene micro-plastic |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100552A (en) * | 1987-02-13 | 1988-08-24 | 军事医学科学院仪器中心 | Chemical tracer |
-
2015
- 2015-05-21 CN CN201510260827.0A patent/CN104892804B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100552A (en) * | 1987-02-13 | 1988-08-24 | 军事医学科学院仪器中心 | Chemical tracer |
Non-Patent Citations (3)
| Title |
|---|
| JAMES E. GUILLET,等: "Biodegradability of Photodegraded Polymers Ⅱ . Tracer Studies of Biooxidation of Ecolyte PS Polystyrene", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》 * |
| M.SIELICKI，等: "Microbial degradation of [14C]polystyrene and 1,3-diphenylbutane", 《CANADIAN JOURNAL OF MICROBIOLOGY》 * |
| 程兆瑞，等: "《塑料粘接技术手册》", 30 June 1962, 中国轻工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112204093A (en) * | 2018-06-25 | 2021-01-08 | 国家航空航天技术研究所 | Isotopically labelled materials for degradation detection |
| CN113427660A (en) * | 2021-06-29 | 2021-09-24 | 南京大学 | Isotope element14Preparation method of C-labeled polystyrene micro-plastic |
| CN113427660B (en) * | 2021-06-29 | 2022-10-18 | 南京大学 | Isotope element 14 Preparation method of C-labeled polystyrene micro-plastic |
| CN114805978A (en) * | 2022-03-11 | 2022-07-29 | 河海大学 | Stable isotope 13 Preparation method of C-marked polyethylene micro-plastic |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104892804B (en) | 2017-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Robbins et al. | Effects of Electronics, Aromaticity, and solvent polarity on the rate of azaquinone–methide-mediated depolymerization of aromatic carbamate oligomers | |
| CN108997520B (en) | Norbornene derivative homopolymer containing heterosaccharide unit and synthesis method thereof | |
| CN102898566B (en) | Preparation method of metal organic framework molecularly imprinted polymer used for enriching trace amounts of Metolcarb | |
| CN104892804A (en) | 14C-labeled polystyrene (PS) and synthesis method thereof | |
| Danjou et al. | Supramolecular assistance for the selective demethylation of calixarene-based receptors | |
| Zhao et al. | A reversible and visible colorimetric/fluorescent chemosensor for Al3+ and F− ions with a Large Stoke's shift | |
| CN109704926B (en) | Anticancer active molecular skeleton 1, 4-eneyne compound and preparation method and application thereof | |
| Polepally et al. | Michael acceptor approach to the design of new salvinorin A-based high affinity ligands for the kappa-opioid receptor | |
| Nagarajan et al. | Synthesis of expanded calix [n] pyrroles and their furan or thiophene analogues | |
| CN104768955B (en) | The improved method being acylated for maytansinol | |
| CN105837527B (en) | It is copolymerized 5 arene derivatives of column and its preparation and the application in detection iron ion | |
| Santoyo-González et al. | Regioselective monoalkylation of calixarenes. Synthesis of homodimer calixarenes | |
| Markad et al. | A primary amide-functionalized heterogeneous catalyst for the synthesis of coumarin-3-carboxylic acids via a tandem reaction | |
| CN113061088B (en) | Asymmetric column [5] arene and preparation method and application thereof | |
| Akkuş et al. | Synthesis of oligomeric calix [4] arene-crowns as novel ionophores for alkali and transition metals | |
| Manikowski et al. | An alternative route for fondaparinux sodium synthesis via selective hydrogenations and sulfation of appropriate pentasaccharides | |
| Zhuo et al. | An efficient and recyclable ionic liquid-supported proline catalyzed Knoevenagel condensation | |
| Schmuck et al. | Sequence‐Dependent Binding of Dipeptides by an Artificial Receptor in Water | |
| CN101558090B (en) | Methods for preparing polymers from phenolic materials and compositions relating thereto | |
| Turk et al. | 3-Akylpyridinium and 3-alkylpyridine compounds from marine sponges, their synthesis, biological activities and potential use | |
| US9073802B2 (en) | Method for producing 18F-labeled compound and high molecular compound to be used in the method | |
| Ma et al. | The novel macrocyclic compounds as chiral solvating agents for determination of enantiomeric excess of carboxylic acids | |
| CN101624408A (en) | Pendant naphthalene group-containing benzene ligand ferrocenium salt cationic photoinitiators and preparation method thereof | |
| Elçin et al. | A versatile approach toward chemosensor for Hg2+ based on para-substituted phenylazocalix [4] arene containing mono ethyl ester unit | |
| CN110407863A (en) | A method of passing through transfer boronation reaction synthesis ene boric acid ester type compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |