Diallyl carbonate

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Diallyl carbonate
Allyl carbonate.png
Names
IUPAC name
Bis(prop-2-enyl) carbonate
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 239-106-9
PubChem CID
UNII
  • InChI=1S/C7H10O3/c1-3-5-9-7(8)10-6-4-2/h3-4H,1-2,5-6H2
    Key: JKJWYKGYGWOAHT-UHFFFAOYSA-N
  • C=CCOC(=O)OCC=C
Properties
C7H10O3
Molar mass 142.154 g·mol−1
Density 0.991 g/mL
Melting point −70 °C (−94 °F; 203 K)
Boiling point 95–97 °C (203–207 °F; 368–370 K) 60 mmHg
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Diallyl carbonate (DAC) is a colorless liquid with a pungent odor. Its structure contains allyl groups and a functional carbonate group. [1] The presence of double bonds in the allyl groups makes it reactive in various chemical processes. This compound plays a key role in the production of polymers, including polycarbonates and polyurethanes. Diallyl carbonate is soluble in ethanol, methanol, toluene, and chloroform. Diallyl carbonate reacts with amines, alcohols, and thiols.

Contents

DAC is also used as an acrylate agent. Allyl carbonates are widely used in Tsuji-Trost allylation, promoting the formation of carbanions, boronates, phosphides, amides, and alkoxides. They act as in situ nucleophiles,[ citation needed ] increasing the reaction rate compared to allyl acetate. These compounds are of great interest for the design of intramolecular decarboxylate asymmetric compounds.

History

The Tsuji-Trost reaction was first introduced in 1962. This method played an important role in the synthesis of diallyl carbonate. The first mention of its commercial production dates back to 1982, when Tokuyama Corporation synthesized it for the first time using the sodium carbonate method. [2] [ failed verification ] This milestone marked the beginning of the sale of diallyl carbonate as a raw material for the production of plastic lenses.[ citation needed ]

Synthesis

Diallyl carbonate can be synthesized by consecutive nucleophilic acyl substitution reactions using two equivalents of allyl alcohol and any of several electrophilic carbonyl donors. The monoallyl intermediate can be isolated and then separately converted to the diallyl product, or the whole process can be run in a single reactor.

From phosgene

Phosgene is a highly reactive electrophile. It reacts easily with allyl alcohol. A base is often used to neutralize the hydrogen chloride byproduct. The intermediate allyl chloroformate need not be isolated. Alternately, allyl chloroformate can be used as a starting-point if it is already available.

Allyl carbonate from phosgene.png

From urea

Urea is a stable reagent that reacts in two stages. In the first stage, this reaction proceeds rapidly and yields acetaldehyde [ failed verification ] as an intermediate. To enable the second substitution requires a catalyst, such as LaCl3. [3]

Diallylcarbonateurea.png

From other carbonates

Catechol carbonate is a versatile intermediate for ester-exchange reactions. It is available from a variety of reactions, including ester-exchange of dimethyl carbonate with catechol. Catechol carbonate reacts with allyl alcohol in reactive distillation system with sodium methoxide or other base catalyst. [4]

Diallylcarbonatecc.png

Polymers

Poly(2,2'-(oxybis(ethylene sulfonyl)) diallyl carbonate-co-allyl diglycol carbonate)

This polymer comprises 2,2'-(oxybis(ethylene sulfonyl)) diallyl carbonate (OESDAC) and its copolymers with allyl diglycol carbonate (ADC), wherein the resulting polymer can be further converted into a film. OESDAC is synthesized in two steps. First, a condensation of 2,2'-bis(2-hydroxyethylsulfanyl)diethyl ether with 3,9-dithia-6-oxa-undecane-1,11-diol-bis(allyl carbonate) is carried out in the presence of alkali at low temperatures. Second, the oxidation of 3,9-dithia-6-oxa-undecane-1,11-diol bis(allyl carbonate) with hydrogen peroxide in acidic medium is carried out. The synthesis of ADC involves the condensation of diethylene glycol with allyl chloroformate in the presence of pyridine at low temperatures.

The copolymerization of OESDAC and ADC is performed in the presence of the initiator IPP and the plasticizer DOP. The resulting polymer films can be used as nuclear trace detectors to record and study traces of energetic particles such as alpha particles and fission fragments. [5]

Poly(1-benzoate-2,3-diallylcarbonate glycerol)

The polymer poly(1-benzoate-2,3-diallylcarbonate glycerol) is currently obtained from the monomer BDACG, which undergoes gamma irradiation in a vacuum at various doses and temperatures using a 60°C gamma irradiation source. This process results in the formation of branched polymers (PBDACG) with different gel contents.

Additionally, BDACG is currently subjected to UV irradiation in the presence of the photoinitiator Darocur 1173, leading to the formation of a polymer with high gel content and a network structure.

Applications currently include the use of gamma-polymerized BDACG for producing transparent thermoplastic polycarbonates in optical applications and as materials with internal crosslinking. Photopolymerized BDACG is currently suitable for polymers with high gel content, making them applicable in optical purposes and as nuclear track detectors in technical areas. [6]

Polycarbonate

The monomer (1,1'-biphenyl)-4,4'-diallylcarbonate is synthesized by reacting 4,4'-biphenyl, pyridine, and allyl chlorocarbonate at 5°C. Simultaneously, the monomer hexa(4-allylcarbonatephenoxy)cyclotriphosphazene is prepared by the reaction of Allyl(4-hydroxyphenyl) carbonate with hexachlorocyclotriphosphazene.

Following the acquisition of the two monomers, a polymerization process is conducted by reacting them together, utilizing benzoyl peroxide as the initiator. Two distinct polycarbonates are produced: the first after three hours of polymerization and the second after 34 hours. The primary distinction lies in their thermal stability, with the first polycarbonate remaining stable up to 250 °C, while the second begins decomposition at 240 °C. At 800 °C, the first polycarbonate loses 90% of its mass, whereas the second polycarbonate only loses 28%. Additionally, the second polycarbonate exhibits a higher limiting oxygen index (LOI) of 46.3%. In comparison to the classic polycarbonate, the second polycarbonate demonstrates superior LOI but has lower thermal stability, remaining stable only up to 150 °C. [7]

Non-isocyanate polyurethane

Diallyl carbonate is currently employed in the synthesis of the polymer through a thiol-ene reaction with dithiols. This component undergoes synthesis from hydroxamic acid and diallyl alcohol, with TBD catalyst facilitating the process. The outcome is a carbonaceous polymer characterized by high viscosity and transparency. The polymer exhibits thermal properties such as a glass transition occurring at temperatures between -12 and -15 °C. The introduction of bulk groups leads to a reduction in crystallization.

The synthesis of non-isocyanate polyurethanes currently entails the reaction of hydroxamic acid with two equivalents of diallyl alcohol, employing catalytic amounts of TBD as a base in diallyl carbonate. The reaction mixture is presently heated at 110 °C overnight, following a methodology described for catalytic Lossen rearrangements. This process results in the formation of both carbamate and urea. Subsequently, a reaction occurs between cyclooctane-1,4-diol and either carbamate or urea. The compounds obtained are then polymerized via a highly efficient thiol–ene reaction, leading to the production of non-isocyanate polyurethanes with Mn values up to 26 kg/mol, containing thioether linkages.

Similarly, the primary by-product of the Lossen rearrangement, symmetric urea, can currently undergo polymerization using the same method. Importantly, from an ecological perspective, the monomeric mixture can be directly utilized without the need for separation. [8]

Related Research Articles

<span class="mw-page-title-main">Polymerization</span> Chemical reaction to form polymer chains

In polymer chemistry, polymerization, or polymerisation, is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many forms of polymerization and different systems exist to categorize them.

<span class="mw-page-title-main">Polyurethane</span> Polymer composed of a chain of organic units joined by carbamate (urethane) links

Polyurethane refers to a class of polymers composed of organic units joined by carbamate (urethane) links. In contrast to other common polymers such as polyethylene and polystyrene, polyurethane is produced from a wide range of starting materials. This chemical variety produces polyurethanes with different chemical structures leading to many different applications. These include rigid and flexible foams, and coatings, adhesives, electrical potting compounds, and fibers such as spandex and polyurethane laminate (PUL). Foams are the largest application accounting for 67% of all polyurethane produced in 2016.

<span class="mw-page-title-main">Petrochemical</span> Chemical product derived from petroleum

Petrochemicals are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as maize, palm fruit or sugar cane.

<span class="mw-page-title-main">Thermosetting polymer</span> Polymer obtained by irreversibly hardening (curing) a resin

In materials science, a thermosetting polymer, often called a thermoset, is a polymer that is obtained by irreversibly hardening ("curing") a soft solid or viscous liquid prepolymer (resin). Curing is induced by heat or suitable radiation and may be promoted by high pressure or mixing with a catalyst. Heat is not necessarily applied externally, and is often generated by the reaction of the resin with a curing agent. Curing results in chemical reactions that create extensive cross-linking between polymer chains to produce an infusible and insoluble polymer network.

A diol is a chemical compound containing two hydroxyl groups. An aliphatic diol may also be called a glycol. This pairing of functional groups is pervasive, and many subcategories have been identified. They are used as protecting groups of carbonyl groups, making them essential in synthesis of organic chemistry.

<span class="mw-page-title-main">Carbamate</span> Chemical group (>N–C(=O)–O–)

In organic chemistry, a carbamate is a category of organic compounds with the general formula R2NC(O)OR and structure >N−C(=O)−O−, which are formally derived from carbamic acid. The term includes organic compounds, formally obtained by replacing one or more of the hydrogen atoms by other organic functional groups; as well as salts with the carbamate anion H2NCOO.

<span class="mw-page-title-main">Polyurea</span> Class of elastomers

Polyurea is a type of elastomer that is derived from the reaction product of an isocyanate component and an amine component. The isocyanate can be aromatic or aliphatic in nature. It can be monomer, polymer, or any variant reaction of isocyanates, quasi-prepolymer or a prepolymer. The prepolymer, or quasi-prepolymer, can be made of an amine-terminated polymer resin, or a hydroxyl-terminated polymer resin.

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<span class="mw-page-title-main">Carbonate ester</span> Chemical group (R–O–C(=O)–O–R)

In organic chemistry, a carbonate ester is an ester of carbonic acid. This functional group consists of a carbonyl group flanked by two alkoxy groups. The general structure of these carbonates is R−O−C(=O)−O−R' and they are related to esters, ethers and also to the inorganic carbonates.

<span class="mw-page-title-main">Polyester</span> Category of polymers, in which the monomers are joined together by ester links

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In polymer chemistry, the term prepolymer or pre-polymer, refers to a monomer or system of monomers that have been reacted to an intermediate-molecular mass state. This material is capable of further polymerization by reactive groups to a fully cured, high-molecular-mass state. As such, mixtures of reactive polymers with un-reacted monomers may also be referred to as pre-polymers. The term "pre-polymer" and "polymer precursor" may be interchanged.

Moisture-cure polyurethanes -- or polyurethane prepolymer -- are isocyanate-terminated prepolymers that are formulated to cure with ambient water. Cured PURs are segmented copolymer polyurethane-ureas exhibiting microphase-separated morphologies. One phase is derived from a typically flexible polyol that is generally referred to as the “soft phase”. Likewise the corresponding “hard phase” is born from the di- or polyisocyanates that through water reaction produce a highly crosslinked material with softening temperature well above room temperature.

<span class="mw-page-title-main">Off-stoichiometry thiol-ene polymer</span>

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<span class="mw-page-title-main">Allyl glycidyl ether</span> Chemical compound

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.

3,9-Diethylidene-2,4,8,10-tetraoxaspiro[5.5]undecane (DETOSU) is a bicyclic ketene acetal derived from the isomeric allyl acetal 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane (DVTOSU). As a bifunctional monomer, DETOSU is an important building block for polyorthoesters formed by the addition of diols to the activated double bond of the diketene acetal.

Vinylene carbonate (VC) or 1,3-dioxol-2-one, is the simplest unsaturated cyclic carbonic acid ester. Vinylene carbonate can also be thought of as the cyclic carbonate of the hypothetical (Z)-ethene-1,2-diol. The activated double bond in this five-membered oxygen-containing heterocycle makes the molecule a reactive monomer for homopolymerization and copolymerization and a dienophile in Diels-Alder reactions. Below room temperature vinylene carbonate is a colorless stable solid.

Polyurethane dispersion, or PUD, is understood to be a polyurethane polymer resin dispersed in water, rather than a solvent, although some cosolvent maybe used. Its manufacture involves the synthesis of polyurethanes having carboxylic acid functionality or nonionic hydrophiles like PEG incorporated into, or pendant from, the polymer backbone. Two component polyurethane dispersions are also available.

3,9-Divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane (DVTOSU) is a bicyclic organic molecule having a central quaternary carbon atom with which two alicyclic rings are linked, each comprising five atoms. DVTOSU is a diallyl acetal and the precursor for the isomeric ketene acetal monomer 3,9-diethylidene-2,4,8,10-tetraoxaspiro[5.5]undecane (DETOSU) which is a building block for polyorthoesters.

<span class="mw-page-title-main">Glycerol-1,2-carbonate</span> Organic chemical compound

Glycerol-1,2-carbonate is formally the cyclic ester of carbonic acid with glycerol and has aroused great interest as a possible product from the "waste materials" carbon dioxide CO2 and glycerol (especially from biodiesel production) with a wide range of applications.

References

  1. "Buy Diallyl carbonate | 15022-08-9". Smolecule. Retrieved 2023-11-26.
  2. "Tokuyama". www.tokuyama.co.jp. Retrieved 2023-11-26.
  3. Wang, Dengfeng; Zhang, Xuelan; Luo, Hainan; Wei, Shuwei; Zhao, Xueying (2019-04-15). "Direct Synthesis of Diallyl Carbonate Via Urea Transesterification with Allyl Alcohol Over Metal Chlorides". Catalysis Letters. 149 (4): 1067–1074. doi:10.1007/s10562-019-02693-y. ISSN   1011-372X. S2CID   104332089.
  4. Tabanelli, T.; Monti, E.; Cavani, F.; Selva, M. (2017-03-20). "The design of efficient carbonate interchange reactions with catechol carbonate". Green Chemistry. 19 (6): 1519–1528. doi:10.1039/C6GC03466G. hdl: 10278/3686257 . ISSN   1463-9270.
  5. Shetgaonkar, Abhijit D.; Mandrekar, Vinod K.; Nadkarni, Vishnu S.; Naik, Diptesh G. (2023-11-01). "Novel poly (disulfonyl diallyl carbonate) polymers for swift solid state nuclear track detection applications". Radiation Measurements. 168: 107002. Bibcode:2023RadM..168j7002S. doi:10.1016/j.radmeas.2023.107002. ISSN   1350-4487. S2CID   261590040.
  6. López, Delia; Plata, Pedro; Burillo, Guillermina; Medina, Carlos (August 1997). "Synthesis and radiation polymerization of 1-benzoate-2,3-diallylcarbonate glycerol". Radiation Physics and Chemistry. 50 (2): 171–173. Bibcode:1997RaPC...50..171L. doi:10.1016/s0969-806x(96)00187-9. ISSN   0969-806X.
  7. Herrera-González, A M; García-Serrano, J; Pelaez-Cid, A A; Montalvo-Sierra, I (2013-06-07). "Efficient method for polymerization of diallycarbonate and hexa(allylcarbonate) monomers and their thermal properties". IOP Conference Series: Materials Science and Engineering. 45 (1): 012008. Bibcode:2013MS&E...45a2008H. doi: 10.1088/1757-899x/45/1/012008 . ISSN   1757-8981.
  8. Filippi, Luca; Meier, Michael A. R. (February 2021). "Fully Renewable Non-Isocyanate Polyurethanes via the Lossen Rearrangement". Macromolecular Rapid Communications. 42 (3). doi: 10.1002/marc.202000440 . ISSN   1022-1336.