Photoinitiator

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Large format sheets with a thin photopolymer coating cured with a UV lamp. Sheets-emerge-from-the-UV-curing-lamps.jpg
Large format sheets with a thin photopolymer coating cured with a UV lamp.

In chemistry, a photoinitiator is a molecule that creates reactive species (free radicals, cations or anions) when exposed to radiation (UV or visible). Synthetic photoinitiators are key components in photopolymers (for example, photo-curable coatings, adhesives and dental restoratives).

Contents

Some small molecules in the atmosphere can also act as photoinitiators by decomposing to give free radicals (in photochemical smog). For instance, nitrogen dioxide (NO2) is produced in large quantities by gasoline-burning internal combustion engines. NO2 in the troposphere gives smog its brown coloration and catalyzes production of toxic ground-level ozone (O3). Molecular oxygen (O2) also serves as a photoinitiator in the stratosphere, breaking down into atomic oxygen and combining with O2 in order to form the ozone in the ozone layer.

Reactions

Photoinitators can create reactive species by different pathways including photodissociation and electron transfer. As an example of dissociation, hydrogen peroxide can undergo homolytic cleavage, with the O−O bond cleaving to form two hydroxyl radicals.

H2O2 → 2 ·OH

Certain azo compounds (such as azobisisobutyronitrile), can also photolytically cleave, forming two alkyl radicals and nitrogen gas:

RCH2−N=N−H2CR → 2 RCH2 + N2

These free radicals can now promote other reactions.

Atmospheric photoinitiators

Peroxides

Hydrogen peroxide, the simplest peroxide Hydrogen-peroxide-3D-vdW.png
Hydrogen peroxide, the simplest peroxide

Since molecular oxygen can abstract H atoms from certain radicals, the HOO· radical is easily created. This particular radical can further abstract H atoms, creating H2O2, or hydrogen peroxide; peroxides can further cleave photolytically into two hydroxyl radicals. More commonly, HOO can react with free oxygen atoms to yield a hydroxyl radical (·OH) and oxygen gas. In both cases, the ·OH radicals formed can serve to oxidize organic compounds in the atmosphere. [1]

H2O2 → 2 ·OH
HOO· + O → O2 + ·OH
·OH + CH4·CH3 + H2O

Nitrogen dioxide

Nitrogen dioxide, a large contributor to the production of smog Nitrogen-dioxide-3D-vdW.png
Nitrogen dioxide, a large contributor to the production of smog

Nitrogen dioxide can also be photolytically cleaved by photons of wavelength less than 400 nm [2] producing atomic oxygen and nitric oxide.

NO2 → NO + O

Atomic oxygen is a highly reactive species, and can abstract a H atom from anything, including water.

O + H2O → 2 ·OH

Nitrogen dioxide can be regenerated through a reaction between certain peroxy-containing radicals and NO.

ROO· + NO → NO2 + RO·

Molecular oxygen

In the stratosphere, molecular oxygen (O2) is an important photoinitiator that begins the ozone-production process in the ozone layer. Oxygen can be photolyzed into atomic oxygen by light with wavelength less than 240 nm. [3]

O2 → 2O

Atomic oxygen can then combine with more molecular oxygen to form ozone.

O + O2 → O3

However, ozone can also be photolyzed back into O and O2.

O3 → O + O2

Furthermore, atomic oxygen and ozone can combine into O2.

O + O3 → 2 O2

This set of reactions govern the production of ozone and can be combined to calculate its equilibrium concentration.

Commercial photoinitiators and uses

AIBN

Azobisisobutyronitrile, a commonly used industrial photoinitiator, and its breakdown into two radicals and nitrogen gas Formation of Radicals from AIBN.png
Azobisisobutyronitrile, a commonly used industrial photoinitiator, and its breakdown into two radicals and nitrogen gas

Azobisisobutyronitrile is a white powder often used as a photoinitiator for vinyl-based polymers such as polyvinyl chloride, also known as PVC. Because this particular photoinitiator produces nitrogen gas (N2) upon decomposition, it is often used as a blowing agent to change the shape and/or texture of plastics.

Benzoyl peroxide

Benzoyl peroxide, a common photoinitiator used in plastics production and in acne medication Benzoyl-peroxide.svg
Benzoyl peroxide, a common photoinitiator used in plastics production and in acne medication

Benzoyl peroxide, much like azobisisobutyronitrile, is a white powder used as a photoinitiator in various commercial and industrial processes, including plastics production. Unlike AIBN, however, benzoyl peroxide produces oxygen gas upon decomposing, giving this compound a host of medical uses as well. [4]

Upon contact with the skin, benzoyl peroxide breaks down, producing oxygen gas, among other things. The oxygen gas is absorbed into the pores of the skin, where it kills off the acne-causing bacterium Cutibacterium acnes .

In addition, the free radicals produced can break down dead skin cells. Clearing out these dead cells prevents pore blockage and, by extension, acne breakouts. [5]

2,2-Dimethoxy-2-phenylacetophenone

example of acrylate polymerization via radical photoinitiation. This type of hydrogel is sometimes used for biosensors as the conditions used are relatively mind to protein allowing them to be entrapped in the hydrogel, whilst retaining functionality and are porous enough to allow the diffusion of small molecules. Photoinititaed polymerization.svg
example of acrylate polymerization via radical photoinitiation. This type of hydrogel is sometimes used for biosensors as the conditions used are relatively mind to protein allowing them to be entrapped in the hydrogel, whilst retaining functionality and are porous enough to allow the diffusion of small molecules.

Camphorquinone

Camphorquinone (CQ) is a photosensitiser used with an amine system, that generates primary radicals with light irradiation. These free electron then attack the double bonds of resin monomers resulting in polymerization. The physical properties of the cured resins are affected by the generation of primary radicals during the initial stage of polymerization.

Irgacure 819

Mechanism of Irgacure 819 to form 4 radicals. Irgacure 819 forming radicals.png
Mechanism of Irgacure 819 to form 4 radicals.


Irgacure 819 (BAPO Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide) is a Norrish type photoinitiator used in polymerization processes like two-photon Polymerization. [7] When exposed to light it forms four radicals (2, 3, 5) per decomposed molecule (1), making it highly efficient in initiating polymerization. The second set of radicals forms through abstraction or chain transfer, further driving the reaction. [8]


See also

Related Research Articles

<span class="mw-page-title-main">Hydrogen peroxide</span> Chemical compound

Hydrogen peroxide is a chemical compound with the formula H2O2. In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution in water for consumer use and in higher concentrations for industrial use. Concentrated hydrogen peroxide, or "high-test peroxide", decomposes explosively when heated and has been used as both a monopropellant and an oxidizer in rocketry.

<span class="mw-page-title-main">Ozone</span> Allotrope of oxygen (O₃) present in Earths atmosphere

Ozone is an inorganic molecule with the chemical formula O
3
. It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope O
2
, breaking down in the lower atmosphere to O
2
(dioxygen). Ozone is formed from dioxygen by the action of ultraviolet (UV) light and electrical discharges within the Earth's atmosphere. It is present in very low concentrations throughout the atmosphere, with its highest concentration high in the ozone layer of the stratosphere, which absorbs most of the Sun's ultraviolet (UV) radiation.

<span class="mw-page-title-main">Oxidizing agent</span> Chemical compound used to oxidize another substance in a chemical reaction

An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.

<span class="mw-page-title-main">Nitric oxide</span> Colorless gas with the formula NO

Nitric oxide is a colorless gas with the formula NO. It is one of the principal oxides of nitrogen. Nitric oxide is a free radical: it has an unpaired electron, which is sometimes denoted by a dot in its chemical formula. Nitric oxide is also a heteronuclear diatomic molecule, a class of molecules whose study spawned early modern theories of chemical bonding.

<span class="mw-page-title-main">Nitrogen dioxide</span> Chemical compound with formula NO₂

Nitrogen dioxide is a chemical compound with the formula NO2. One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, NO2 is an intermediate in the synthesis of nitric acid, millions of tons of which are produced each year, primarily for the production of fertilizers.

<span class="mw-page-title-main">Chemiluminescence</span> Emission of light as a result of a chemical reaction

Chemiluminescence is the emission of light (luminescence) as the result of a chemical reaction, i.e. a chemical reaction results in a flash or glow of light. A standard example of chemiluminescence in the laboratory setting is the luminol test. Here, blood is indicated by luminescence upon contact with iron in hemoglobin. When chemiluminescence takes place in living organisms, the phenomenon is called bioluminescence. A light stick emits light by chemiluminescence.

<span class="mw-page-title-main">Dinitrogen pentoxide</span> Chemical compound

Dinitrogen pentoxide is the chemical compound with the formula N2O5. It is one of the binary nitrogen oxides, a family of compounds that only contain nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.

<span class="mw-page-title-main">Ozone–oxygen cycle</span> Biogeochemical cycle

The ozone–oxygen cycle is the process by which ozone is continually regenerated in Earth's stratosphere, converting ultraviolet radiation (UV) into heat. In 1930 Sydney Chapman resolved the chemistry involved. The process is commonly called the Chapman cycle by atmospheric scientists.

<span class="mw-page-title-main">Benzoyl peroxide</span> Chemical compound with uses in industry and acne treatment

Benzoyl peroxide is a chemical compound (specifically, an organic peroxide) with structural formula (C6H5−C(=O)O−)2, often abbreviated as (BzO)2. In terms of its structure, the molecule can be described as two benzoyl (C6H5−C(=O)−, Bz) groups connected by a peroxide (−O−O−). It is a white granular solid with a faint odour of benzaldehyde, poorly soluble in water but soluble in acetone, ethanol, and many other organic solvents. Benzoyl peroxide is an oxidizer, which is principally used in the production of polymers.

In chemistry, radical initiators are substances that can produce radical species under mild conditions and promote radical reactions. These substances generally possess weak bonds—bonds that have small bond dissociation energies. Radical initiators are utilized in industrial processes such as polymer synthesis. Typical examples are molecules with a nitrogen-halogen bond, azo compounds, and organic and inorganic peroxides.

<span class="mw-page-title-main">Chemical decomposition</span> Breakdown of a chemical species into two or more parts; reverse process of a synthesis reaction

Chemical decomposition, or chemical breakdown, is the process or effect of simplifying a single chemical entity into two or more fragments. Chemical decomposition is usually regarded and defined as the exact opposite of chemical synthesis. In short, the chemical reaction in which two or more products are formed from a single reactant is called a decomposition reaction.

<span class="mw-page-title-main">Oxygen fluoride</span> Any binary compound of oxygen and fluorine

Oxygen fluorides are compounds of elements oxygen and fluorine with the general formula OnF2, where n = 1 to 6. Many different oxygen fluorides are known:

<span class="mw-page-title-main">Azobisisobutyronitrile</span> Chemical compound

Azobisisobutyronitrile (abbreviated AIBN) is an organic compound with the formula [(CH3)2C(CN)]2N2. This white powder is soluble in alcohols and common organic solvents but is insoluble in water. It is often used as a foamer in plastics and rubber and as a radical initiator.

<span class="mw-page-title-main">Organic peroxides</span> Organic compounds of the form R–O–O–R’

In organic chemistry, organic peroxides are organic compounds containing the peroxide functional group. If the R′ is hydrogen, the compounds are called hydroperoxides, which are discussed in that article. The O−O bond of peroxides easily breaks, producing free radicals of the form RO. Thus, organic peroxides are useful as initiators for some types of polymerization, such as the acrylic, unsaturated polyester, and vinyl ester resins used in glass-reinforced plastics. MEKP and benzoyl peroxide are commonly used for this purpose. However, the same property also means that organic peroxides can explosively combust. Organic peroxides, like their inorganic counterparts, are often powerful bleaching agents.

<span class="mw-page-title-main">Ozonide</span> Polyatomic ion (O3, charge –1), or cyclic compounds made from ozone and alkenes

Ozonide is the polyatomic anion O−3. Cyclic organic compounds formed by the addition of ozone to an alkene are also called ozonides.

Autoxidation refers to oxidations brought about by reactions with oxygen at normal temperatures, without the intervention of flame or electric spark. The term is usually used to describe the gradual degradation of organic compounds in air at ambient temperatures. Many common phenomena can be attributed to autoxidation, such as food going rancid, the 'drying' of varnishes and paints, and the perishing of rubber. It is also an important concept in both industrial chemistry and biology. Autoxidation is therefore a fairly broad term and can encompass examples of photooxygenation and catalytic oxidation.

<span class="mw-page-title-main">Manganese heptoxide</span> Chemical compound

Manganese(VII) oxide (manganese heptoxide) is an inorganic compound with the formula Mn2O7. Manganese heptoxide is a volatile liquid with an oily consistency. It is a highly reactive and powerful oxidizer that reacts explosively with nearly any organic compound. It was first described in 1860. It is the acid anhydride of permanganic acid.

Advanced oxidation processes (AOPs), in a broad sense, are a set of chemical treatment procedures designed to remove organic (and sometimes inorganic) materials in water and wastewater by oxidation through reactions with hydroxyl radicals (·OH). In real-world applications of wastewater treatment, however, this term usually refers more specifically to a subset of such chemical processes that employ ozone (O3), hydrogen peroxide (H2O2) and UV light or a combination of the few processes.

There are several known allotropes of oxygen. The most familiar is molecular oxygen, present at significant levels in Earth's atmosphere and also known as dioxygen or triplet oxygen. Another is the highly reactive ozone. Others are:

<span class="mw-page-title-main">Caesium superoxide</span> Chemical compound

Caesium superoxide is a chemical compound with the chemical formula CsO2. It consists of caesium cations Cs+ and superoxide anions O−2. It is an orange solid.

References

  1. vanLoon, pp. 52–53
  2. vanLoon, pp. 74–79
  3. vanLoon, pp. 48–49
  4. "Benzoyl Peroxide", chemicalland21.com, accessed October 29, 2009
  5. "Benzoyl Peroxide" Archived 2010-05-26 at the Wayback Machine , http://www.about.com, accessed October 29, 2009
  6. Liao KC, Hogen-Esch T, Richmond FJ, Marcu L, Clifton W, Loeb GE (2008). "Percutaneous fiber-optic sensor for chronic glucose monitoring in vivo" (PDF). Biosens Bioelectron. 23 (10): 1458–65. doi:10.1016/j.bios.2008.01.012. PMID   18304798. Archived from the original (PDF) on 2012-04-26.
  7. Ge, Dandan; Aubard, Jean; Bodinier, Erell; Jradi, Safi; Lau-Truong, Stéphanie; Felidj, Nordin; Bachelot, Renaud; Baudrion, Anne-Laure (2023). "Two-photon photopolymerization directly initiated by spiropyran photochromic molecules". Light: Advanced Manufacturing. 4 (1): 1. doi:10.37188/lam.2023.004. ISSN   2831-4093.
  8. Neumann, Miguel G.; Schmitt, Carla C.; Ferreira, Giovana C.; Corrêa, Ivo C. (2006-06-01). "The initiating radical yields and the efficiency of polymerization for various dental photoinitiators excited by different light curing units". Dental Materials. 22 (6): 576–584. doi:10.1016/j.dental.2005.06.006. ISSN   0109-5641.

Bibliography