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词条 Allyl glycidyl ether
释义

  1. Preparation

  2. Uses

  3. Reactions

      Polymerization    Hydrosilylation  

  4. References

{{Chembox
| ImageFile = Allyl glycidyl ether.svg
| ImageSize =
| ImageAlt = Skeletal structure of allyl glycidyl ether
| IUPACName = 2-(prop-2-enoxymethyl)oxirane
| OtherNames = AGE; 1-Allyloxy-2,3-epoxypropane; Glycidyl allyl ether; [(2-Propenyloxy)methyl] oxirane[1]
|Section1={{Chembox Identifiers
| CASNo = 106-92-3
| PubChem = 7838
| EINECS = 203-442-4
| ChemSpiderID = 13836520
| SMILES = C=CCOCC1CO1
| InChI = 1/C6H10O2/c1-2-3-7-4-6-5-8-6/h2,6H,1,3-5H2
| InChIKey = LSWYGACWGAICNM-UHFFFAOYAR
| StdInChI = 1S/C6H10O2/c1-2-3-7-4-6-5-8-6/h2,6H,1,3-5H2
| StdInChIKey = LSWYGACWGAICNM-UHFFFAOYSA-N
|Section2={{Chembox Properties
| C=6 | H=10 | O=2
| Appearance = Colorless liquid[1]
| Odor = pleasant[1]
| Density = 0.97 g/mL (20 °C)[1]
| MeltingPtF = -148
| MeltingPt_notes = [1]
| BoilingPtF = 309
| BoilingPt_notes = [1]
| Solubility = 14% (20°C)[1]
| Solubility1 = miscible (acetone, toluene, octane)[8]
| Solvent1 = organic solvents
| VaporPressure = 2 mmHg (20 °C)[1]
| RefractIndex = 1.4348 (20 °C)[8][2]
|Section3={{Chembox Hazards
| MainHazards = poisonous, mild irritant[3]
| HPhrases = H226, H351, H341, H332, H302, H335, H315, H318, H317, H412
| GHSSignalWord = DANGER
| FlashPtF = 135
| FlashPt_notes = [1]
| AutoignitionPt =
| IDLH = 50 ppm[1]
| REL = TWA 5 ppm (22 mg/m3) ST 10 ppm (44 mg/m3) [skin][1]
| PEL = 10 ppm (45 mg/m3)[1]
| LC50 = 270 ppm (mouse, 4 hr)
670 ppm (rat, 8 hr)[4]
}}

Allyl glycidyl ether is an organic compound used in adhesives and sealants and as a monomer for polymerization reactions. It is formally the condensation product of allyl alcohol and glycidol via an ether linkage. Because it contains both an alkene and an epoxide group, either group can be reacted selectively to yield a product where the other functional group remains intact for future reactions.

Preparation

An industrial preparation of this compound is the reaction between allyl alcohol and epichlorohydrin. Hydrogen chloride, the byproduct of their condensation, is removed by subsequent treatment with a base.[5]

The chemical can also be synthesized by epoxidation of one of the two alkene units of diallyl ether either using peracetic acid[19] or using a peroxide oxygen-atom donor such as TBHP[6] or H2O2[7] in the presence of various titanium catalysts.

Successive oxidation of the second alkene would produce diglycidyl ether.

Allyl glycidyl ether is chiral, having two enantiomeric forms. Whereas simple epoxidation of an allyl group would yield a racemic mixture, microbial oxidation mediated by a monooxygenase enzyme gives an enantioselective result.[8]

Alternately, nucleophilic cyclization of either chirality of the secondary alcohol onto a primary tosylate gives the chiral epoxide product.[9]

Uses

Allyl glycidyl ether is used in adhesives and sealants[3] and as a monomer for various types of polymer preparations.

Reactions

Polymerization

As a bifunctional compound, the alkene group or the epoxide group can be reacted selectively to yield a product where the other functional group remains intact for future reactions. For example, either one of them could be used for linear polymerization, and then the other used for cross-linking.[10]

Radical polymerization of the propylene portion in the presence of methyl acrylate yields a block copolymer with a high epoxide content.[11] Similarly, it is can be used in the production of polyvinylcaprolactam as a chain transfer agent.[12]Nucleophilic polymerization of the epoxide groups gives a material that has the same backbone as polyethylene glycol, with allyl-ether side chains. The additional Lewis basic ether sites alter ion transport in the polymer and also affect the transient inter-chain crosslinking and glass transition temperature in the presence of metal ions. These properties suggest that the material may have applications as an alternative electrolyte for lithium-ion batteries. The alkenes can be elaborated into short polyethylene-glycol oligomers to further increase the ion-binding ability and enhance the resulting material properties.[13]

Block copolymers with ethylene oxide form micelles, which could be useful for encapsulating other molecules as part of a drug delivery system. The alkenes of these macromolecular structures can also be cross-linked via radical polymerization.[14]

Lewis-acid-catalyzed co-polymerication with carbon dioxide likewise gives a polycarbonate material with allyl side chains that can be further elaborated.[15]

Hydrosilylation

Rather than polymerization, the alkene group can undergo a hydrosilylation reaction with siloxanes in the presence of chloroplatinic acid as catalyst.[16] Like the polymerization reactions, this reaction also leaves the epoxide intact. By this reaction, allyl glycidyl ether finds use as an intermediate in the production of silane coatings for electrical applications.[17]

References

1. ^1 2 3 4 5 6 7 8 9 10 11 {{PGCH|0019}}
2. ^Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982., p. 2199
3. ^1 2 3 {{PubChem|7838}}
4. ^{{IDLH|106923|Allyl glycidyl ether}}
5. ^{{cite book |editor1-last= Clayton |editor1-first= G. D. |editor2-first= F. E. |editor2-last= Clayton |title= Patty's Industrial Hygiene and Toxicology |volume= Volume 2A, 2B, 2C: Toxicology |edition= 3rd |location= New York |publisher= John Wiley Sons |year= 1981–1982 |page= 2197 }}
6. ^{{cite journal |title= Synthesis of allyl-glycidyl ether by the epoxidation of diallyl ether with t-butyl hydroperoxide over the Ti-MWW catalyst |first1= Agnieszka |last1= Wróblewska |first2= Marika |last2= Walasek |first3= Beata |last3= Michalkiewicz |journal= Current Chemistry Letters |volume= 6 |issue= 1 |year= 2017 |pages= 7–14 |doi= 10.5267/j.ccl.2016.11.002 }}
7. ^{{cite journal |journal= Reaction Kinetics, Mechanisms and Catalysis |date= August 2016 |volume= 118 |issue= 2 |pages= 719–931 |title= The epoxidation of diallyl ether to allyl-glycidyl ether over the TS-1 catalyst |first1= Agnieszka |last1= Wróblewska |first2= E. |last2= Drewnowska |first3= A. |last3= Gawarecka |doi= 10.1007/s11144-016-1028-3 }}
8. ^{{cite journal |title= Pseudomonas oleovorans monooxygenase-catalyzed asymmetric epoxidation of allyl alcohol derivatives and hydroxylation of a hypersensitive radical probe with the radical ring-opening rate exceeding the oxygen-rebound rate |first1= Hong |last1= Fu |first2= Martin |last2= Newcomb |first3= Chi Huey |last3= Wong |journal= J. Am. Chem. Soc. |year= 1991 |volume= 113 |issue= 15 |pages= 5878–5880 |doi= 10.1021/ja00015a061 }}
9. ^{{cite journal |title= Enzymes in organic synthesis: synthesis of highly enantiomerically pure 1,2-epoxy aldehydes, epoxy alcohols, thiirane, aziridine, and glyceraldehyde 3-phosphate |first1= Richard L. |last1= Pederson |first2= Kevin K. C. |last2= Liu |first3= James F. |last3= Rutan |first4= Lihren |last4= Chen |first5= Chi Huey |last5= Wong |journal= J. Org. Chem. |year= 1990 |volume= 55 |issue= 16 |pages= 4897–4901 |doi= 10.1021/jo00303a026 }}
10. ^1 {{cite journal |title= Synthesis of Some Epoxy Vinyl Monomers by Epoxidation with Peracetic Acid |first1= Frederick C., Jr. |last1= Frostick |first2= Benjamin |last2= Phillips |first3= Paul S. |last3= Starcher |journal= J. Am. Chem. Soc. |year= 1959 |volume= 81 |issue= 13 |pages= 3350–3356 |doi= 10.1021/ja01522a048 }}
11. ^{{cite journal |title= Living free-radical copolymerization of allyl glycidyl ether with methyl acrylate |journal= Frontiers of Chemistry in China |first1= Yu |last1= Qingbo |first2= Zhang |last2= Mingxu |first3= Li |last3= Xianhua |first4= Bai |last4= Ruke |date= October 2007|volume= 2 |issue= 4 |pages= 414–418 |doi= 10.1007/s11458-007-0078-5 }}
12. ^{{cite journal |title = Control of the molecular weight of polyvinylcaprolactam |last = Kudyshkin |first = Mukhitdinova |journal = Russian Journal of Applied Chemistry |year = 1999 |volume = 72 |issue = 10 |pages = 1846–1848}}
13. ^{{cite journal|last1=Barteau|first1=Katherine P.|last2=Wolffs|first2=Martin|last3=Lynd|first3=Nathaniel A.|last4=Fredrickson|first4=Glenn H.|last5=Kramer|first5=Edward J.|last6=Hawker|first6=Craig J.|year=2013|title=Allyl Glycidyl Ether-Based Polymer Electrolytes for Room Temperature Lithium Batteries|journal=Macromolecules|volume=46|issue=22|pages=8988–8994|doi=10.1021/ma401267w|bibcode=2013MaMol..46.8988B}}
14. ^{{cite journal|last1=Hrubý|first1=M.|last2=Koňák|first2=Č.|last3=Ulbrich|first3=K.|year=2004|title=Poly(allyl glycidyl ether)‐block‐poly(ethylene oxide): A novel promising polymeric intermediate for the preparation of micellar drug delivery systems|journal=Journal of Applied Polymer Science|volume=95|issue=2|pages=201–211|doi=10.1002/app.21121}}
15. ^{{cite journal |journal= Macromolecular Rapid Communications |volume= 21 |issue= 11 |pages= 754–757 |title= Synthesis of functional polycarbonates by copolymerization of carbon dioxide with allyl glycidyl ether |first1= Jan |last1= Łukaszczyk |first2= Katarzyna |last2= Jaszcz |first3= Witold |last3= Kuran |first4= Tomasz |last4= Listos |year= 2000 |doi= 10.1002/1521-3927(20000701)21:11<754::AID-MARC754>3.0.CO;2-O }}
16. ^{{cite web |url= https://www.sigmaaldrich.com/catalog/product/ALDRICH/A32608 |title= Allyl glycidyl ether |publisher= Sigma-Aldrich |accessdate= December 24, 2018 }}
17. ^{{cite book |title= Handbook of Fillers, Extenders, and Diluents |editor1-first= Michael |editor1-last= Ash |editor2-first= Irene |editor2-last= Ash |publisher= Synapse Info Resources |year= 2007 |isbn= 9781890595968 |page= 224 |url= https://books.google.com/books?id=C4Cr8dHupVsC&pg=PA224 }}

3 : Ethers|Allyl compounds|Epoxides
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