MXPA00010170A - Novel photoinitiators and applications therefor - Google Patents

Abstract

The present invention is directed to new, energy-efficient photoinitiators in the form of organic sulfur-containing compounds. The present invention is also directed to a method of generating reactive species which includes exposing one or more photoinitiators to radiation to form one or more reactive species. Also described are methods of polymerizing unsaturated monomers, methods of curing an unsaturated oligomer/monomer mixture, and methods of laminating using the photoinitiators of the present invention.

Description

NEW FOTOINICIATORS AND APPLICATIONS FOR THEMSELVES Technical Field The present invention relates to novel photomediators and methods for generating reactive spices using the photoinitiators. The present invention further relates to methods for polimeporating or photocuring the polymerizable unsaturated material using the above-mentioned photoinitiators.

BACKGROUND OF THE INVENTION Polymers have essentially served the needs in society. For many years, these needs were filled by natural polymers. More recently, synthetic polymers have played an increasingly larger role, particularly since the beginning of the 10th century. Particularly useful polymers are those prepared by the addition of a polymerization mechanism, for example, a free radical polymerization of more saturated monomers. , and includes, by way of example only, adhesive coatings. In fact, most commercially significant processes are based on the chemistry of free radical. That is, the chain polymerization is initiated by a reactive species which is frequently a free radical. The source of free radicals is called a initiator or a photoinitiator.

The improvements in the free radical chain polymerization have focused both on the polymer that is being produced and the photoinitiator. Whether a particular msatured monomer can be converted to a polymer requires the structural, thermodynamic and kinetic possibility. Even when all these three possibilities exist, the emetic facility is achieved in many cases only with a specific type of photoinitiator. In addition, the photomediators can have a significant effect on the reaction rate which, in turn, can determine the commercial success or failure of a particular polymerization process or product.

A free radical generation photomatter can generate free radicals in several different ways. For example, the homolytic disassociation of an initiator typically yields two free radicals per initiator molecule directly. A photomixer, for example, an initiator which absorbs light energy, can produce free radicals by any of two paths: (1) the photomizer suffers excitation by the absorption of energy with subsequent decomposition in one or more radicals; or (2) the photomizer undergoes excitation and the excited species interact with a second compound (by either the energy transfer or a redox reaction) to form the free radicals of the latter and / or the above compounds.

Even though any free radical chain polymerization process must avoid the presence of species which may prematurely terminate the polymerization reaction, the previous photomisers present special problems. For example, the absorption of light by means of the reaction medium can limit the amount of energy available for absorption by the photo-cycler. Also, the complex and frequently competitive emetics involved may have an adverse effect on the reaction rate. In addition, commercially available radiation sources, such as medium and high pressure xenon and mercury lamps, emit over a wide wavelength range, thereby producing individual mission bands of a relatively low intensity. Most photomultors only absorb over a small part of the ignition spectrum and, as a consequence, most of the radiation from the lamps remains unused. In addition, most known photomediators have only moderate "quantum performances" (usually less than 0.4) at these wavelengths, indicating that the conversion of light radiation to the Radical training can be more efficient.

Therefore, there are continuous opportunities for improvements in free radical polymerization photoinitiators. In addition, there is a need in the art for efficient and new energy photoimagers to be used in a variety of polymerization and light curing processes.

Synthesis of the Invention The present invention relates to some of the difficulties and problems discussed above by the discovery of energy efficient photomisers having the following general formula: wherein x is an integer from 1 to 4, and R, and R2 each - \ O N- independently represent H-; \ /; (R) 2N- wherein R is an alkyl group having from 1 to 6 carbon atoms; a chalcone; HS03-; and NaS03-. In a further embodiment, the present invention is directed to photoinitiators having the following formula: where x is an integer from 1 to 4.

The present invention is directed to the photoinitiators described above, to the compositions containing the same and to the methods for generating a reactive species which include providing one or more of the photos and irradiating said 1 or more photoinitiators. One of the main advantages of the photomisers of the present invention is that they can efficiently generate one or more species under extremely low energy lamps, such as excimer lamps, as compared to prior art photo-emitters.

The present invention is further directed to methods for using the above-described photo-etchants for polymerizing and / or photocuring a polymerizable material. The photomisers of the present invention result in fast curing times compared to the curing times of prior art photoinitiators, even with relatively low output lamps. The present invention includes a method for polimepting an unsaturated monomer by exposing the saturated monomer to the radiation in the presence of the specific photo-ionic composition of effective wavelength described above. When a more saturated oligomer / monomer mixture is used instead of the saturated monomer, curing is achieved.

The present invention further includes a film and a method for producing a film, by pulling a mixture of a water-soluble polymerizable material and one or more photomizers of the present invention, into a film and irradiating the film with a sufficient amount of radiation to polymerize the composition. The combination can be pulled on a film on a non-woven fabric or on a fiber, thereby providing a fiber or non-woven fabric coated with polymer, and a method for producing the same.

The present invention is also directed to an adhesive composition comprising a hydrated polymerizable material combined with one or more photoreagents of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the adhesive composition described above in which at least one layer is a nonwoven film or fabric. Therefore, the present invention provides a method for laminating a structure wherein a structure having at least two layers with the adhesive composition described above between the layers is irradiated to polymerize the adhesive composition.

These and other features and advantages of the present invention will become apparent upon review of the following detailed description of the embodiments described and the appended claims.

Detailed description of the invention The present invention is directed to energy-efficient reactive photomisers and methods for the use thereof. More particularly, the present invention is directed to new photomusers having the following general formula: wherein x is an integer from 1 to 4, and R, and R2 each O N- independently represent H-; \ /; (R) t - wherein R is an alkyl group having from 1 to 6 carbon atoms; a chalcone; H? 03-; and NaS03-. In a further embodiment of the present invention, the photoinitiator comprises bis-phthaloylglycine sulfide compounds having the following formula: where x is an integer from 1 to 4.

The present invention also includes a method for polymerizing an unsaturated polymerizable material by exposing the unsaturated material to the radiation in the presence of one or more of the photomediators described above. Furthermore, the present invention is directed to a film and a method for producing a film, by pulling a mixture of unsaturated polymerizable material and one or more of the photomediators described above, into a film and irradiating the film with a sufficient amount of radiation to polymerize the combination The present invention is further directed to an adhesive composition comprising a mixed microsaturated polymerizable material and one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the adhesive composition. described above. The present invention further provides a method for laminating a structure wherein a structure has at least two layers with the adhesive composition described above between the layers is irradiated to polimepzar the adhesive composition.

After the following definitions, the photoinitiators of the present invention will be described in detail followed by a detailed description of the method of the reactive generating species, and the various representative applications of the method.

Definitions As used herein, the term "reactive species" is used herein to mean any chemically reactive species including, but not limited to, free radicals, cations, anions, nitrenes and carbenes. Below are illustrated examples of several such species. Examples of the carbenes include, for example, methylene or carbene, dichlorocarbene, diphenylcarbene, alkylcarbonylcohenes, siloxycarbenes, and dicarbenes. Examples of the nitrenes also include, by way of example, nitrene, alkyl n-rings and aplo nitrenes. The cations (sometimes referred to as carbonations or carbonium ions) include, by way of illustration, the primary, secondary, and tertiary alkylcarbons such as methyl cation, cation lime, propyl cation, t-butyl cation, t-pentyl cation, t-hexyl cation; allylic cations; benzylic cations; aplo cations such as diphenyl cation; cyclopropylmethyl cations; methoxymethyl cation; triapl sulfonium cations and acyl cations. The cations also include those formed from various metal salts such as the salts of tetra-n-butylamine tretrahaloaurate (III); Sodium tetrachloroaurate (III); vanadium tetrachloride; and triflates of silver, copper (I) and (II), and thallium (I). Examples of anions (sometimes referred to as carbanions) include, by way of example, alkyl anions, such as the lime anion, the n-propyl anion, the isobutyl anion, and the neopentyl anion; cycloalkyl anions, such as the cyclopropyl anion, the cyclobutyl anion and the cyclopentyl anion; the allylic anions; benzylic anions; the aryl cations; and alkyl anions containing sulfur or phosphorus. Finally, examples of the organometallic photoinners include titanocenes, fluorinated diapltiranocenes, arene and iron complexes, decacarbonyl manganese and tpcarbonyl manganese methyl c clopentadienyl. Organometallic photoinitiators generally produce free radicals or cations.

As used herein, the term "quantum yield" is used here to indicate the efficiency of a photochemical process. More particularly, quantum performance is a measure of the probability that a particular molecule It will absorb a quantity of light during its interaction with a photon. The term expresses the number of photochemical events per absorbed photon. Therefore, quantum yields can vary from zero (no absorption) to 1.

As used herein, the term "polymerization" is used herein to mean the combination, for example, the covalent attachment, of large numbers of smaller molecules, such as monomers, to form very large molecules, for example macromolecules or polymers. . The monomers can be combined to form only linear macromolecules or these can be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.

As used herein, the term "curing" means the polymerization of functional monomers and oligomers, or even polymers, in a crosslinked polymer network. Thus, curing is the polymerization of the saturated oligomers or monomers in the presence of cross-linking agents.

As used herein, the terms "unsaturated monomer," "functional oligomer," and "cross-linking agent" are used herein with their usual meanings and are well understood by those having ordinary skill in the art. art. The singular form of each is intended to include both the singular and the plural, for example, one or more of each respective material. As used herein, the term "unsaturated polymerizable material" is intended to include any unsaturated material capable of undergoing polymerization. The term encompasses unsaturated monomers, oligomers and cross-linking agents. Again, the singular form of the term is intended to include both the singular and the plural.

As used herein, the term "fiber" is used herein to denote a thread type structure. The fibers used in the present invention can be any fibers known in the art. As used herein, the term "non-woven fabric" is used herein to denote a fabric type material comprising one or more interconnected or overlapping fibers in a non-woven manner. It should be understood that any nonwoven fibers known in the art can be used in the present invention.

Photoinitiators of the Present Invention The present invention is directed to the new photomitators having the following general formula: ;: »- -ai: where x is an integer from 1 to 4, and R, and R2 each O N- independently represent H-; \ /; (R) 2N- wherein R is an alkyl group having from 1 to 6 carbon atoms; a chalcone; HS03-; and NaS03-. In a further embodiment of the present invention, the photoinitiator comprises bis-m-morpholinobenzoyl trisulfide compounds having the following formula: or bis-p-morphorobenzoyl trisulfide having the following formula: (- Hs- In another embodiment of the present invention the photocatalyst comprises a bis-dialkylamide obenzoyl trisulfide having the following formula: wherein R is an alkyl group having from 1 to 6 carbon atoms. Desirably, the photoinitiator comprises bis-m-di-ethylaminobenzoyl trisulfide having the following formula. or bis-p-dimethylaminobenzoyl trisulfide having the following formula: In still another embodiment of the present invention the photoinitiator comprises a water-soluble photoimagent having the following structure: In another embodiment of the present invention, the photoimator comprises the bis-phthaloylglycine trisulfide having the following formula: A method for producing the photoinitiators of the present invention is discussed below. However, it should be noted that the photoinitiators of the present invention can be prepared by any reaction mechanism known to those of ordinary skill in the art. In an embodiment of the present invention, the special reagents used to prepare the photomizers of the present invention are produced by reacting sulfur with a desired amount of lithium triethylborohydride to produce the lithium sulfide compounds. The reaction described above is shown by the following mechanisms: 2Li (CHj) 3BH + yS? Li2Sy Various lithium sulfide compounds can be produced by the reaction described above including, but not limited to L? 2S, L? 2S2, and L? 2S3. Preferably y is an integer from 1 to 4. The reaction described above results in a variety of lithium sulfide compounds wherein y ranges from 1 to 3. However, these compounds can be separated using separation known to those with an ordinary skill in art if desired.

The lithium sulfide compounds can be further reacted with substituted benzoyl chloride, a phthaloylglycine chloride or other carbonyl chloride compounds to produce one or more photoinitiators of the present invention. In one embodiment of the present invention, a morpholmobenzoyl chloride is reacted with one or more lithium sulfide compounds to produce one or more morpholmobenzoyl sulfide compounds. In a further embodiment of the present invention the phthaloylglycine chloride is reacted with one or more lithium sulfide compounds to produce one or more phthaloylglycine sulfide compounds.

The resulting photographers are stable at room temperature (from about 15 degrees centigrade to 25 degrees centigrade) and normal room humidity (from about 30% to 60%). However, with exposure to radiation, photoinitiators efficiently produce one or more free radicals. The photographers of the present invention have a high absorption intensity. For example, photographers of the present invention may have a molar extinction coefficient greater than about 2,000 liters per mole per centimeter (1 mol'cm 1) at maximum absorption. As another example, the photoinitiators of the present invention can have a molar extinction coefficient (absorption) greater than about 5,000 1 mol'cm1. As another example, the photoinitiators of the present invention may have a molar extinction coefficient (absorbency) of greater than about 10,000 1 mol'cm1. As a further example, the photoinitiators of the present invention will have a molar extinction coefficient greater than about 20,000 1 mol'cm1.

Method for Generating Reactive Species and Applications for the Same The present invention is also directed to a method for generating a reactive species. The method of generating a reactive species involves generating a reactive species by exposing one or more of the photoinitiators described above to radiation. The exposure of photoinitiators to a radiation source triggers a photochemical process. As I said above, the term "quantum yield" is used here to indicate the efficiency of a photochemical process. More particularly, the quantum yield is a measure of the probability that a particular molecule (photoinitiator) will absorb a quantity of light during its interaction with a photon. The term expresses the number of photochemical events per absorbed photon. Therefore, the quantum yield can vary from zero (no absorption) to 1.

The photomisers of the present invention absorb photons having a specific wavelength and transfer the absorbed energy to one or more excitable parts of the molecule. The excitable part of the molecule absorbs enough energy to cause a breakdown of binding which generates one or more reactive species. The efficiency with which a reactive species is generated with the photographers of the present invention is significantly greater than that experienced with prior art photoinitiators as indicated by the faster curing times. For example, the photoinitiators of the present invention will desirably have a quantum yield greater than about 0.5. More desirably, the quantum yield of the photographers of the present invention will be greater than about 0.6. Even more desirably, the quantum yield of the photographers of the present invention will be greater than about 0.7. Even more desirably, the quantum yield of the photographers of the present invention will be greater than about 0.8, with the most desirable quantum yield being greater than about 0.9.

The exposure of the photomisers of the present invention to radiation results in the generation of one or more reactive species. Therefore, photographers can be employed in any situation where reactive species are required, such as for the polymerization of a unsaturated monomer and curing of an unsaturated monomer / oligomer mixture. The saturated monomers and oligomers may be any of those known to one having ordinary skill in the art. In addition, the polymerization and curing medium may also contain other materials as desired, such as pigments, extenders, amine glycerides, and such other additives as are well known to those of ordinary skill in the art.

By way of illustration only, examples of the unsaturated oligomers and monomers include ethylene, propylene, vinyl chloride, isobutylene, styrene, isoprene, acplonitplo, acrylic acid, methacrylic acid, ethyl acrylate, methyl metaplate, vinyl acrylate, metacreature of aillo , tripropylene glycol diacrylate, tpmethylol propane ethoxylate actable, epoxy actable, such as the reaction product of an epoxide bisphenol A with acrylic acid; polyester acrylates such as the reaction product of acrylic acid with a polyester based on hexanediol / adipic acid, urethane acutates, such as the reaction product of hydroxypropyl acrylate with d-phenomethane-4,4'd? soc? anato, and polybutadiene diaccolate oligomer.

The types of reactions in which several reactive species enter include, but are not limited to, addition reactions, including the reactions of polymerization; the reactions of abstraction; the rearrangement reactions; elimination reactions, including decarboxylation reactions; the oxidation-reduction reactions (redox); substitution reactions; and the conjugation / deconjugation reactions.

Therefore, the present invention also comprises a method for polymerizing a saturated monomer by exposing the msatured monomer to radiation in the presence of the effective photomizers of the present invention described above. When a more saturated oligomer / monomer mixture is employed instead of a saturated monomer, curing is achieved. It should be understood that the polymerizable material combined with the photoinitiators of the present invention will be mixed by means known in the art, and that the mixture will be irradiated with a sufficient amount of radiation to polymerize the material. The amount of radiation sufficient to polimepzar the material. it is easily determined by one of ordinary skill in the art, and will depend on the identity and number of photoinitiators, the identity and amount of the polymerizable material, the intensity and the wavelength of the radiation, and the duration of exposure to radiation.

It is believed that exposure to radiation results in the generation of free radicals from photoinitiators in the present invention by one or more of the following: splitting of a sulfide-sulfide bond resulting in two free radicals ending in sulfide; and the splitting of a bond of sulfur and carbon resulting in a free radical ending in carbon and a free radical ending in sulfur.

Polymer Films, Coated Fibers and Fabrics, and Adhesive Compositions The present invention further includes a film and a method for producing a film, by pulling a combination of the polymerized hydrated material and one or more photoreagents of the present invention, into a film and irradiating the film with a sufficient amount of radiation to polymerize the composition. When the more saturated polymerizable material is a mixture of saturated oligomer / monomer, curing is achieved. Any film thickness can be produced, as by the thickness of the mixture formed, provided that the mixture sufficiently polimepce with radiation exposure. The combination can be pulled on a film on a non-woven fabric or on a fiber, thereby providing a fiber or non-woven fabric coated with polymer, and a method for producing the same. Any method known in the art of pulling the mixture into a film can be used in the present invention. The amount of radiation sufficient to polimepzar the material is determinable easily by one with ordinary skill in the art and will depend on the identity and quantity of the photoinitiator, the identity and the amount of the polishable material, the thickness of the mixture, the intensity and the wavelength of the radiation, and the duration of exposure to radiation.

The present invention also includes an adhesive composition comprising a saturated polymerizable material combined with one or more photoreagents of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the adhesive composition described above. In one embodiment of the present invention, a laminate is produced wherein at least one layer is a nonwoven film or fabric. of polyolefin or cellulosic. Therefore, the present invention provides a method for laminating a structure wherein a structure has at least two layers with the adhesive composition described above between the layers being irradiated to polymerize the adhesive composition. When the polymerizable material saturated in the adhesive is an oligomer / monomer mixture, the adhesive is irradiated to cure the composition.

It should be understood that any layers can be used in the laminates of the present invention, provided that at least one of the layers allows penetration enough radiation through the layer to allow the combination to polymerize sufficiently. Therefore, any polyolefin or cellulosic nonwoven fabric or fabric known in the art can be used as one of the layers as long as they allow radiation to pass therethrough. Again, the amount of radiation sufficient to polymerize the combination is easily determined by one of ordinary skill in the art, and will depend on the identity and amount of the photoinitiator, the amount and identity of the polymerizable material, and the thickness of the the combination of the identity and the thickness of the layer, the intensity and the wavelength of the irradiation and the duration of the radiation exposure.

The radiation to which the photomizers of the present invention can be exposed will generally have a wavelength of from about 4 to about 1,000 nanometers. Therefore, the radiation can be ultraviolet radiation, including near the ultraviolet and beyond or the ultraviolet radiation of vacuum; visible radiation; and almost infrared radiation. Desirably, the radiation will have a wavelength of from about 100 to about 900 nanometers. More desirably, the radiation will have a wavelength of from about 100 to 700 nanometers. Desirably, the radiation will be ultraviolet radiation having a wavelength of from about a to about 400 nanometers More desirably the radiation will have a wavelength of from about 100 to about 390 nanometers, and even more desirably will have a wavelength of from 200 to about 380 nanometers. For example, the radiation will have a wavelength of from about 222 to about 370 nanometers. The radiation will desirably be inconsistent, ultraviolet radiation pulsed from a dielectric barrier discharge excimer lamp or radiation from a mercury lamp.

Excimers are molecular complexes of unstable excited state which occur only under extreme conditions, such as those that exist temporarily in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. The excimer complexes disassociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation. The dielectric barrier excimer generally emits in the range of from about 125 nm to about 500 nm depending on the excimer gas mixture.

The dielectric barrier discharge excimer lamps (also referred to hereinafter as "excimer lamp") are described, for example by U.

Kogelschatz, "Silent Discharges for the Generation of Ultraviolet Vacuum and Ultraviolet Radiation". Chemical and Pure Application, 62, No. 9, pages 1667-1674 (1990); and E. Eliasson and U. Kogelschatz, "Radiation of Ultraviolet Excimer from Dielometric Barrier Downloads". Physical Application, B. 4.6, pages 299-303 (1988). The excimer lamps were developed by ABB Infocam Limited, of Lenzburg, Switzerland, and at the present time are available from Heraeus Noblelight GmbH, Kleinostheim, Germany.

The excimer lamp emits pulsed and incoherent ultraviolet radiation. Such radiation has a relatively narrow bandwidth, for example, the average width is of the order of about 5 to 100 nanometers. Desirably, the radiation will have an average width of the order of about 5 to 50 nanometers, and more desirably will have an average width of the order of 5 to 25 nanometers. More desirably, the average width will be of the order of about 5 to 15 nanometers.

The ultraviolet radiation emitted from the excimer lamp can be emitted in a plurality of wavelengths, wherein one or more of the wavelengths within the band are emitted at a maximum intensity. Therefore, a scheme of the wavelengths in the band against the intensity for each wavelength in the band produces a bell curve. The "average width" of the range of ultraviolet radiation emitted by an excimer lamp is defined as the width of the bell curve at 50% of the maximum height of the bell curve.

The radiation emitted by an excimer lamp is incoherent and pulsed, the frequency of the pulsations will depend on the frequency of the alternating current power supply which is typically in the range of from about 20 to about 300 kilohertz. An excimer lamp is typically identified or mentioned by the wavelength at which the maximum intensity of the radiation occurs, whose convexion is followed through this description and the claims. Therefore, in comparison with most other commercially useful sources of ultraviolet radiation that typically emit over the entire ultraviolet spectrum and even within the visible region, the excimer lamp radiation is essentially monochromatic.

The source of the radiation used with the photoinitiators of the present invention can be any radiation source known to those of ordinary skill in the art. In one embodiment of the present invention, a mercury lamp with a D-focus, which produces the radiation having an emission peak of 350 nm, is used to produce free radicals from the photomediators. described above. This source of radiation is particularly useful when marrying one or more photographers of the present invention having a maximum absorption of 350 nanometers, which corresponds to the maximum emission of the mercury lamp.

As a result of the photoreagents of the absorbing radiation of the present invention in the range of about 250 to about 350 nanometers, the photoinitiators of the present invention will generate one or more species reactive with exposure to sunlight. Therefore, these photoinitiators of the present invention provide a method for the generation of reactive species and do not require the presence of a special light source.

The photoinitiators of the present invention allow the production of adhesive and coating compositions that consumers can apply to a desired object and polymerize or cure with exposure to sunlight. These photomediators also allow numerous industrial applications where saturated polymerizable materials can be polymerized merely upon exposure to sunlight. Therefore, depending on how the photo-izer is designed, the photomizer of the present invention can eliminate the cost of buying and maintaining light sources in numerous industries where such light sources are necessary without the photomisers of the present invention.

The effective tuning of the photomixers of the present invention for a specific wavelength band allows the photographers of said present invention to more efficiently use the target radiation in the emission spectrum of the radiation source corresponding to the band. of "refined" wavelength, even though the intensity of such radiation may be much lower than, for example, radiation from a narrow band emitter, such as an excimer lamp. For example, it may be desirable to use an excimer lamp, or other source of radiation emission, which emits the radiation having a wavelength of about 222 nm with the phthaloylglycol-containing photo-chemicals of the present invention. Similarly, it may be desirable to use a mercury lamp that emits radiation having a wavelength of about 350 nm with the substituted benzoyl-containing photomisers of the present invention. However, the effectiveness of the photoinitiators of the present invention will not necessarily depend on the availability or use of a narrow wavelength band radiation source.

Therefore, an additional advantage of the photoinitiators of the present invention is that they have fast curing times compared to the curing times of the prior art. Another advantage of the present invention is that the photographers of the present invention are Photographers are highly sensitive and are beneficially used in situations that have lower light levels.

The present invention is further described by the following examples. Such examples, however, should not be construed as limiting in any way either the spirit or the scope of the present invention. In the examples, all parts are by weight, unless stated otherwise.

EXAMPLE 1 Preparation of 3-morpholinobenzoic acid This example describes a method for synthesizing the following compound, 3-β-morpholinobenzoic, which is used in the reaction mechanism to prepare the bis-m-morfolmobenzoyl trisulfide: The reaction proceeded as shown below: 4. 3 grams of KOH were dissolved in 200 milliliters of ethanol and 100 milliliters of water. Then 5.0 g of morpholmobenzoic acid 3-ester were added and the mixture was stirred while heating to reflux for about 2 hours. The mixture was neutralized with diluted HCL and subsequently filtered to give a white solid. The white solid was dried by a Dean & Stark using toluene to remove water. The reaction yielded 4.4 grams of white powder, 3-obenzoic morphol acid.

EXAMPLE 2 Preparation of 3-orfolinobenzoylchloride This example describes a method for synthesizing the following compound, 3-morpholinobenzoyl chloride, which is used as a reagent to form the bis-m-t-sulphide morpholmobenzoyl: The reaction proceeded as shown below: The aforementioned reagents, including 25 grams of 3-alpha-morpholinobenzoic acid and 15.2 grams of oxalyl chloride were mixed in dioxane at 0 degrees centigrade under argon gas. The reaction proceeded for about 2 hours, one hour at 0 degrees centigrade and one hour at room temperature. The solvent was then removed under reduced pressure to give 22.1 grams of 3-chloro morphine obenzoyl which was used without further purification.

EXAMPLE 3 Preparation of bis-m-trisulfide morpholinobenzoyl This example describes a method for synthesizing the following compound, bis-m-trisulfide morpholinobenzoyl: The reaction proceeded as follows: S + üBjBh In the first step of the aforementioned reaction, 0.1 grams of sulfur was added to a 100 milliliter three neck bottle with a magnetic stir bar and drained with argon. 20 milliliters of 1M lithium triethylborohydride were added slowly to the bottle. The reagents were mixed at room temperature in tetrahydrofuran (THF) for about 30 minutes resulting in a pale yellow solution. To this solution were added 50 milliliters of tetrahydrofuran followed by 4.4 degrees of 3-chloro-morphorobenzoyl chloride. The solution turned yellow / ro or deep and was allowed to stir at room temperature for about one hour. After about one hour the mixture became a thick paste with a yellow color.

The reaction product was filtered to give a yellow solid which was washed with water, benzene, and subsequently dried under vacuum. The reaction yielded 3.4 grams of bis-m-trisulfide morpholmobenzoyl.

The reaction HPLC showed a complete reaction after about 30 minutes giving two products with retention times of about 10 and about 15 minutes respectively in a ratio of about 25:75. The peak of 75% was the bis-m-trisulfide morpholmobenzoyl solid while the peak at 25% was in the filtrate.

EXAMPLE 4 Photocuration of bis-m-trisulfide morpholinobenzoyl in Red Flexo Resin A 2% w / w mixture of bis-m-t-sulphide morpholmobenzoyl powder was added to a sample of 1 g of red flexo ink (Gama Charts). The solubility was poor at room temperature; however, the solubility improved upon heating the mixture on a hot plate. A drop of the mixture was placed on a metal plate and pulled down with a zero bar. The thin film was exposed to a short flash of a lamp from a D (Fusion Systems) bulb. The thin film was cured instantly.

Another sample of thin film was cured using a medium pressure mercury lamp. The mercury lamp had a good emission at a wavelength of 350 nm. Exposure of less than one second resulted in a complete cure of the thin film.

EXAMPLE 5 Preparation of morpholinobenzoyl p-ester The formation of the morpholinobenzoyl p-ester was carried out by means of the following reaction: The aforementioned reagents including 100 g of ethyl 4-aminobenzoic acid ester and 114 grams of oxalyl chloride were placed in a three liter round bottom bottle with a condenser and a mechanical stirrer. The reaction mixture was stirred at reflux for 15 hours. The hot solution was filtered to remove the solvent and give a white solid. The white solid was crystallized from benzene to give 100 grams of a white crystalline solid of morpholmobenzoyl p-ester.

EXAMPLE 6 Hydrolysis of morpholinobenzoyl p-ester Hydrolysis of the morpholinobenzoyl p-ester proceeded as shown in the following reaction: . 2 grams of KOH were dissolved in 200 milliliters of ethanol and 100 milliliters of water. To the mixture were added 80 grams of morpholinobenzoyl p-ester. The mixture was stirred at room temperature overnight. The mixture was neutralized with diluted HCL and subsequently filtered to give a white solid. The white solid was dried by means of a Dean & Stark using toluene to remove water. The reaction gave 65 grams of 4-morpholinobenzoic acid.

EXAMPLE 7 Preparation of 4-morpholinobenzoyl chloride The preparation of 4-morpholinobenzoyl chloride was carried out using the following reaction: A solution with 60g of 4-acid was formed morpholinobenzoic in toluene at 0 degrees centigrade. To the solution was added 28.5 g of oxalyl chloride in 50 milliliters of THF over a period of about 10 minutes. The reaction mixture was stirred at 0 degrees centigrade for about one hour followed by stirring at room temperature for about 2 hours. The solution was filtered and the solvent was removed under reduced pressure to give a white solid. The reaction gave 58.2 g of 4-morpholmobenzoyl chloride, which was used in subsequent reactions without further purification.

EXAMPLE 8 Preparation of the bis-p-trisulfide morphobenzoyl The preparation of bis-p-trisulfide morphobenzoyl proceeded as shown in the following reaction: In a 250 milliliter round bottom flask equipped with a condenser and a magnetic stir bar, and drained with argon, 1 gram of sulfur was added. 20 milliliters of lithium triethylborohydride were added to the sulfur by using a syringe over a period of about 3 minutes. The mixture was stirred at room temperature for 30 minutes. minutes, after which, the mixture stopped the bubbling (evolution H2). The color of the solution turned from red to pale yellow. To the mixture were added 4.4 grams of 4-chlorobenzoyl chloride over a period of about 5 minutes. The reaction mixture was stirred for about 1 hour. The reaction mixture was filtered to remove a yellow filtrate which was subsequently washed with toluene and dried under vacuum. The solid yellow was recrystallized from acetonitrile to give 2.1 g of bis-p-trisulfide morpholmobenzoyl.

EXAMPLE 9 Photocuration of bis-p-trisulfide morpholinobenzoyl in Red Flexo Resin A mixture of 2% by weight / weight of bis-p-trisulfide morpholinobenzoyl and 1.0 g of red flexo resin (Gama Charts) was mixed for about 5 minutes while stirring at a temperature at about 30 to 40 degrees centigrade . A drop of the mixture was placed on a metal plate and pulled down with a bar of 0. The resulting film was exposed to radiation from a medium pressure mercury lamp for approximately 0.1 seconds to completely cure the film.

EXAMPLE 10 Preparation of bis-p-dimethylaminobenzoyl chloride The preparation of the bis-chloride dimethylaminobenzoyl proceeded as shown in the following reaction: To a solution of 60 grams of p-dimethylaminobenzoic acid in toluene at 0 degrees centigrade, 46.1 grams of oxalyl chloride and 50 milliliters of THF were slowly added over a period of about 10 minutes. The mixture was stirred at 0 degrees centigrade for about one hour followed by stirring at room temperature for about 2 hours. The mixture was filtered to remove the solvent and give 62 grams of a solid bis-p-dimethylaminobenzoyl chloride. The solid was used in the following examples without further purification.

EXAMPLE 11 Preparation of bis-p-trisulfide dimethylaminobenzoyl The preparation of bis-p-dimethylaminobenzoyl trisulfide proceeded as shown in the following reaction: + LiEtjBH THF LHSI + Mci "l - @ - a In a 250 milliliter round bottom flask equipped with a condenser and a magnetic stir bar, and drained with argon gas, 1 gram of sulfide was added. To the sulfide, 20 milliliters of a 1M solution of lithium tpethylborohydride was added over a period of about 3 minutes by means of a syringe. The mixture was stirred at room temperature for about 30 minutes, to the mixture were added 3.7 grams of p-dimethylaminobenzoyl chloride over a period of about 5 minutes. The mixture was stirred for about 1 hour and subsequently filtered to remove a yellow solid. The yellow solid was washed with toluene and subsequently dried to give 2 1 grams of bis-p-t-sulphide dimethylaminobenzoyl. The HPLC of the reaction showed a product having a retention time of about 15 minutes at a maximum wavelength of 360 nm.

EXAMPLE 12 Photocuring of bis-p-trisulfide dimethylaminobenzoyl in Red Flexo Resin A mixture of 2% by weight / weight of p-trisulfide dimethylamine obenzoyl and 1.0 g of red flexo resin (gamma graphs) was mixed for about 5 minutes with stirring at a temperature at about 30 to 40 degrees centigrade. A drop of the mixture was placed on a metal plate and pulled down with a bar of 0. The resulting film was exposed to radiation from a medium pressure mercury lamp for approximately 0.1 seconds to completely cure the film.

Even though the description has been carried out in detail with respect to specific incorporations of the same, it will be appreciated that those skilled in the art, to achieve an understanding of the above, can easily conceive alterations, variations and equivalents to these modalities. , the scope of the present invention should be established as that of the appended claims and of any equivalents thereof.

Claims (18)

1. R E I V I N D I C A C I O N E S A photomizer that has the following formula: ]:)? ^^ where x is an integer from 1 to 4, and Rt and R2 each ~ independently represent H-; \ /; (R) ^ - wherein R is an alkyl group having from 1 to 6 carbon atoms; a chalcone; HS03-; or NaS03-.
2. 2. A photoinitiator that has the following formula: where x is an integer from 1 to 4.
3. 3. A method for generating a reactive species, which comprises irradiating the photo-reactor as claimed in clause 1 with radiation.
4. 4. A method for generating a reactive species, which comprises irradiating the photo-reactor as claimed in clause 2 with radiation.
5. 5. A method for polimepting an unsaturated polymerizable material comprising irradiating a combination of a polymerizable material and the photoinitiator as claimed in clause 1.
6. 6. A method for polymerizing a more saturated polymerizable material comprising irradiating a combination of a saturated polymerizable material and the photoinitiator as claimed in the clause.
7. 7. A polymer film produced by the process of: providing a mixture of a more saturated polymerizable material and the photomizer as claimed in clause 1 which has been pulled into a film; Y irradiate the film with a sufficient amount of radiation to polymerize the mixture.
8. 8. A polymer film produced by the process of: providing a combination of a polymerizable macrosaturated material and the photoimager as claimed in clause 2 which has been pulled into a film; Y irradiate the film with a sufficient amount of radiation to polymerize the mixture.
9. 9. A method for coating a non-woven fabric comprising: providing a non-woven fabric coated with a combination of a saturated polymerizable material and the photo-maker as claimed in clause 1; Y irradiate the coating of the tissue with a sufficient amount of radiation to polymerize the mixture.
10. 10. A method for coating a non-woven fabric comprising: providing a non-woven fabric coated with a combination of a polymerizable material and the photo-initiator as claimed in clause 2; Y irradiate the coating on the fabric with a sufficient amount of radiation to polimepzar the mixture.
11. 11. A method for coating a fiber comprising: providing a fiber coated with a combination of the unsaturated polymerizable material and the photoinitiator as claimed in clause 1; Y irradiate the coating on the fiber with a sufficient amount of radiation to polymerize the mixture.
12. 12. A method for coating a fiber comprising: providing a fiber coated with a combination of an unsaturated polymerizable material and the photo-sater as claimed in clause 2; Y irradiate the coating on the fiber with a sufficient amount of radiation to polimepzar the mixture.
13. 13. The photocator as claimed in clause 1 characterized in that the photoinitiator has the following formula:
14. 14. The photoinitiator as claimed in clause 1 characterized in that the photoinitiator has the following formula:
15. 15. The photoimager as claimed in clause 1 characterized in that the photoinitiator has the following formula: wherein R is an alkyl group having from 1 to 6 carbon atoms.
16. 16. The photoinitiator as claimed in clause 15 characterized in that the photocator has the following formula: kcH
17. 17. The photoinitiator as claimed in clause 1 characterized in that the photoinitiator has the following formula: wherein R is an alkyl group having from 1 to 6 carbon atoms.
18. 18. The photoinitiator as claimed in clause 2 characterized in that the photoinitiator has the following formula: SUMMARIZES The present invention is directed to new energy efficient photoinitiators in the form of organic sulfur containing compounds. The present invention is also directed to a method for generating reactive species which include exposing one or more photomitators to the radiation to form one or more reactive species. Also disclosed are methods for polymerizing saturated monomers, methods for curing a saturated monomer / oligomer mixture, and methods for laminating using the photomizers of the present invention.