Photoactive bulk polymerized polycyclic olefin composition as an optical material having a long-term stable shelf life

Abstract

Embodiments according to the present application comprise a composition comprising a latent organoruthenium compound, a photosensitizer, and one or more monomers that undergo ring-opening metathesis polymerization (ROMP) when the composition is exposed to suitable actinic radiation to form a substantially transparent film or three-dimensional object. Surprisingly, the composition is very stable under ambient conditions at temperatures up to 80 °C for weeks and only undergoes bulk polymerization when exposed to suitable actinic radiation under an inert atmosphere, such as a nitrogen blanket. Thus, the compositions of the present application can be used in a variety of optoelectronic applications including 3D printing materials, coatings, encapsulants, fillers, leveling agents, and the like.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefits of U.S. Provisional Application No. 63 / 144,604, filed February 2, 2021, and U.S. Provisional Application No. 63 / 247,597, filed September 23, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] According to embodiments of the present invention, a one-component bulk polymerizable polycyclic olefin monomer composition comprising a latent organorruthenium compound and exhibiting long-term stability is provided, which undergoes rapid bulk polymerization via ring-opening shift polymerization under suitable photolysis conditions. Specifically, the composition of the present invention exhibits long-term storage stability for months at temperatures ranging from ambient to 80°C, particularly when stored in an inert atmosphere and in the dark, and undergoes rapid bulk polymerization only upon exposure to suitable photochemical radiation to form a transparent optical layer suitable for various optoelectronic applications, including 3D printing materials, encapsulation materials, coatings, and fillers. More specifically, the present invention relates to a one-component stable composition comprising norbornene (NB)-based olefin monomers, which possesses high optical transparency and exhibits desired properties in the manufacture of devices such as optical sensors, light-emitting diodes (LEDs), organic light-emitting diodes (OLEDs), and 3D printing materials. Background Technology

[0004] Organic light-emitting diodes (OLEDs) are becoming increasingly important in a variety of applications, including flat-panel TVs and other flexible displays. However, existing OLEDs, especially bottom-emitting OLEDs, suffer from the drawback that only about half of the generated photons are incident on the glass substrate, with 25% being released into the atmosphere. The remaining half of the photons are guided and dissipated within the OLED stack. This photon loss is primarily due to the mismatch in refractive index (n) between the organic layer (n = 1.7–1.9) and the glass substrate (n = 1.5). By aligning the refractive index (n = 1.8) of the substrate with that of the organic layer and increasing the distance from the emission region to the cathode, plasma loss can be suppressed, increasing the amount of light incident on the substrate to 80–90%. See, for example, G. Gaertner et al., Proc. Of SPIE, Vol. 6999, 69992T pp 1-12 (2008).

[0005] Furthermore, OLEDs also face other challenges. Because they are formed from organic materials, they are typically sensitive to moisture, oxygen, temperature, and other harsh conditions. Therefore, it is necessary to protect OLEDs from these harsh atmospheric conditions. For example, refer to US Patent No. US2012 / 0009393A1.

[0006] Furthermore, these OLED devices are typically encapsulated by optically transparent insulating materials with low dielectric constant (Dk) and low loss (also known as dielectric loss factor (Df)). Generally, in most such devices, a suitable insulating material must have a dielectric constant of less than 3 and a loss of less than 0.001 at high frequencies (e.g., above 50 GHz). Moreover, due to the advantages of organic dielectric materials, such as their ease of fabrication, there is increasing interest in developing organic dielectric materials.

[0007] To address some of the problems faced in this field, U.S. Patent No. 8,263,235 discloses the use of a light-emitting layer formed from at least one organic light-emitting material and an aliphatic compound without aromatic rings, wherein the refractive index of the emitted light is in the range of 1.4 to 1.6. Typically, the aliphatic compounds described in the aforementioned patent are known to be various polyalkyl ethers, etc., which are unstable at high temperatures; for example, see Rodriguez et al., I&EC Product Research and Development, Vol. 1, No. 3, 206-210 (1962).

[0008] U.S. Patent No. 9,944,818 discloses a two-component bulk polymerizable composition that can be tuned to a desired refractive index and is suitable as a filler and protective coating material, thus showing potential use in the fabrication of various OLED devices. While this method offers certain advantages, it still suffers from the drawbacks of a two-component system, and the organic polymer may not be able to provide the high refractive index required for OLED applications on its own. Furthermore, the bulk polymerizable composition needs to be stabilized for days to months at temperatures ranging from room temperature to up to 80°C to allow it to be preserved under various processing conditions, such as VAT 3D printing, where the liquid composition is preserved in a 3D printer under OLED manufacturing conditions, but polymerizes immediately under suitable photolysis conditions and / or high temperatures. Moreover, it has been observed that, especially under 3D printing conditions, compositions preserved in VAT may polymerize prematurely due to factors such as exposure to light.

[0009] Therefore, a filler material is still needed that complements the refractive index of OLEDs while exhibiting the desired properties such as high transparency, low dielectric constant, and good thermal properties. Furthermore, an organic filler material is needed that readily forms a permanent protective coating and can be used as a single-component composition dispensed into OLED layers or VAT 3D printing operations. Summary of the Invention

[0010] Therefore, the object of the present invention is to provide a composition that overcomes the difficulties faced in the art. More specifically, the object of the present invention is to provide a one-component composition that undergoes bulk polymerization under 3D printing manufacturing conditions and / or OLED device manufacturing conditions. Another object of the present invention is to provide a stable and one-component bulk polymerizable composition that exhibits no viscosity change under normal or abnormal storage conditions (including temperatures up to 80°C), and undergoes bulk polymerization only under the process conditions for ultimately manufacturing 3D objects or OLED devices using radiation or the like.

[0011] The following describes in detail other objects and further scope of the present invention.

[0012] Invention Effects

[0013] Surprisingly, it has now been discovered that by combining a series of novel organorruthenium compounds described in this specification with one or more olefin monomers and a suitable photoactivator, it is possible to manufacture 3D objects or OLED devices with a transparent optical layer possessing properties that have not been achieved until now: for example, a refractive index in the range of 1.4 to 1.8 or higher; high colorless optical transparency; a dielectric constant of less than 1.5; a filler layer thickness typically in the range of 10 to 20 μm, but adjustable to thinner or thicker thicknesses depending on the application; suitability for OLED stacks, especially for cathode layers (extremely thin layers located on top of OLED stacks); suitability for polymerization of formulations on OLED stacks, including rapid polymerization times and the ability to undergo photolysis; and strong adhesion to OLED stacks and glass covers. Especially when used in 3D printed devices, the polymerization rate per layer can be less than 5 seconds. It should also be noted that the compositions of the present invention are expected to exhibit excellent uniform leveling properties in OLED layers where low viscosity is typically required. Furthermore, due to their rigid polycyclic olefin structure, the compositions of the present invention are also expected to exhibit low shrinkage. Furthermore, because the components of this invention undergo rapid bulk polymerization upon application, no short-lived small molecules that could potentially damage OLED stacks are left behind. Typically, no other small molecule additives are required, thus providing an additional advantage. More importantly, the compositions of this invention are stable under atmospheric conditions (including for hours to days at temperatures up to 80°C), and are particularly stable when kept under inert conditions (i.e., no change in viscosity), undergoing bulk polymerization only under UV exposure. Crucially, the compositions of this invention exhibit excellent shelf-life stability, thus maintaining their initial viscosity for several days (at least 5 to 10 days).

[0014] Advantageously, the compositions of the present invention are also suitable for "one-drop fill" (commonly referred to as "ODF"). In a typical ODF process (typically used in the manufacture of top-emitting OLED devices), a special optical fluid is applied to enhance the light transmittance between the device and the top cover glass, and the fluid is distributed using the ODF method. This method may be misleading due to the term ODF, but typically involves distributing a few drops or strands of material within a seal line. After the fluid is applied, it diffuses along with the stack of top glass in a manner similar to die-attach epoxy. This process is typically performed under vacuum to prevent air trapping. The present invention provides a low-viscosity material that can be easily and uniformly coated onto a substrate through rapid flow over a short period. More advantageously, the present invention overcomes the shortcomings of the prior art, namely, that using a one-component composition is more convenient than using a two-component system, especially in the ODF method. Furthermore, when the compositions of the present invention are used according to the process conditions described in this specification, a more transparent 3D object with good mechanical and thermal properties is provided. Detailed Implementation

[0015] The terms used in this specification have the following meanings:

[0016] Unless otherwise specified, the articles “a / an” and “the” used in this specification include multiple objects.

[0017] Unless otherwise specified, all numbers, values ​​and / or expressions relating to the amounts of ingredients, reaction conditions, etc., used in this specification and the claims herein are subject to various measurement uncertainties encountered in obtaining said values, and therefore should be understood to be modified by the term "about" in all cases.

[0018] The numerical ranges disclosed in this specification are continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when a range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Moreover, when multiple ranges are provided to describe a characteristic or feature, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed in this specification should be understood to include any range and all subranges that it possesses. For example, the specified range from "1 to 10" should be considered to include any range between the minimum value 1 and the maximum value 10, as well as all subranges. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, etc.

[0019] As used in this specification, "hydrocarbyl" refers to a group containing carbon and hydrogen atoms, with non-limiting examples including alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, and alkenyl groups. The term "halohydrocarbyl" refers to a hydrocarbon group in which at least one hydrogen atom is halogenated. The term "perhalocarbyl" refers to a hydrocarbon group in which all hydrogen atoms are halogenated.

[0020] As used in this specification, the term "alkyl" refers to a substituent in a saturated straight-chain or branched hydrocarbon having a specified number of carbon atoms. Specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. For example, the derived terms "alkoxy," "thioalkyl," "alkoxyalkyl," "hydroxyalkyl," "alkylcarbonyl," "alkoxycarbonylalkyl," "alkoxycarbonyl," "diphenylalkyl," "phenylalkyl," "phenylcarboxyalkyl," and "phenoxyalkyl" shall also be interpreted accordingly.

[0021] The term "cycloalkyl" as used in this specification includes all known cyclic groups. Representative examples of "cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. For example, the derived terms "cycloalkoxy," "cycloalkylalkyl," "cycloalkylaryl," and "cycloalkylcarbonyl" should also be interpreted accordingly.

[0022] The term "perhaloalkyl" as used in this specification refers to the aforementioned alkyl groups in which all hydrogen atoms are replaced by halogen atoms selected from fluorine, chlorine, bromine, or iodine. Exemplary examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, and straight-chain or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecylfluoropentyl, undecylchloropentyl, tridecafluorohexyl, and tridecachlorohexyl. The derived term "perhaloalkoxy" should also be interpreted accordingly. Certain alkyl groups described in this specification, such as "alkyl" that can be partially fluorinated (i.e., only a portion of the hydrogen atoms in the alkyl group are replaced by fluorine atoms), should also be interpreted accordingly.

[0023] The term "acyl group" as used in this specification shall have the same meaning as "alkanoyl group" and can also be represented structurally as "R-CO-", where R is an "alkyl group" having a specified number of carbon atoms. Furthermore, the meaning of "alkyl carbonyl group" shall be the same as that of "acyl group" as described in this specification. Specifically, "(C1-C4)acyl group" includes methyl acyl, acetyl / ethanoyl, propionyl, n-butyryl, etc. For example, the derived terms "acyloxy group" and "acyloxyalkyl group" shall also be interpreted accordingly.

[0024] As used in this specification, the term "aryl" refers to a substituted or unsubstituted phenyl or naphthyl group. Specific examples of substituted phenyl or substituted naphthyl groups include o-tolyl, p-tolyl, m-tolyl, 1,2-xylyl, 1,3-xylyl, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. "Substituted phenyl" or "substituted naphthyl" also includes any possible substituents further defined in this specification or known in the art.

[0025] The term "arylalkyl" as used in this specification refers to an aryl group further linked to an alkyl group. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, etc.

[0026] As used in this specification, the term "alkenyl" refers to a non-cyclic, straight-chain or branched hydrocarbon chain having a specified number of carbon atoms and at least one carbon-carbon double bond, including vinyl and straight-chain or branched propenyl, butenyl, pentenyl, and hexenyl. For example, the derived terms "aryl alkenyl" and 5- or 6-membered "heteroaryl alkenyl" should also be interpreted accordingly. Exemplary examples of such derived terms include furan-2-vinyl, phenyl vinyl, 4-methoxyphenyl vinyl, etc.

[0027] The term "heteroaryl" as used in this specification includes all known aromatic groups containing heteroatoms. Representative 5-membered heteroaryl groups include furanyl, thiophene or phenylthio, pyrroleyl, isopyrroleyl, pyrazolyl, imidazoyl, oxazolyl, thiazoyl, isothiazolyl, etc. Representative 6-membered heteroaryl groups include pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc. Representative examples of bicyclic heteroaryl groups include benzofuranyl, benzophenylthio, indolyl, quinolinyl, isoquinolinyl, cenolinyl, benzimidazolyl, inzolyl, pyridinylfuranyl, pyridinylthiophene, etc.

[0028] "Halogen" or "halogenated" refers to chlorine, fluorine, bromine, and iodine.

[0029] In a broad sense, the term "substituted" is considered to encompass all permissible substituents in an organic compound. In some specific embodiments disclosed in this specification, the term "substituted" means substituted with one or more substituents independently selected from the group consisting of (C1-C6)alkyl, (C2-C6)alkenyl, (C1-C6)perfluoroalkyl, phenyl, hydroxyl, -CO2H, ester, amide, (C1-C6)alkoxy, (C1-C6)thioalkyl, and (C1-C6)perfluoroalkoxy. However, any other suitable substituents known to those skilled in the art may also be applied to these embodiments.

[0030] It should be noted that any atom that does not satisfy the valence in the text, schemes, embodiments and tables of this specification is assumed to have an appropriate number of hydrogen atoms to satisfy the valence.

[0031] The term "latent organotransition metal catalyst" refers to an organotransition metal compound that exhibits little or no catalytic activity at specific (typically atmospheric) temperatures, and whose activity is induced under thermal or light conditions, or both. Typically, the catalytic activity of the catalyst can remain latent for extended periods (5 days or more), especially when stored at room temperature or in the dark. Higher temperatures and / or light may promote catalytic activity.

[0032] The terms "photochemical radiation" or "photochemical conditions" refer to placing the composition of the present invention under suitable "electromagnetic radiation" that can be emitted by lasers, digital processing (DLP) projectors, lamps, light-emitting diodes (LEDs), mercury arc lamps, optical fibers, or liquid crystal displays (LCDs).

[0033] In this specification, the terms "dielectric" and "insulating" should be understood to be used interchangeably. Therefore, references to insulating materials or insulating layers include dielectric materials or dielectric layers, and vice versa. Furthermore, the term "organic electronic device" as used in this specification should be understood to include the term "organic semiconductor device" and specific implementations using such devices, such as in the electronics, automotive, or other industries.

[0034] The dielectric constant (Dk) of the materials used in this specification is the ratio of the charge stored in the insulating material between two metal plates to the charge that could be stored if the insulating material were replaced by a vacuum or air. It is also called electric permittivity (or simply permittivity). Sometimes it is also referred to as relative permittivity because it is a relative measurement based on the permittivity of free space.

[0035] As used in this specification, "low loss" refers to the loss factor (Df), which measures the rate of energy loss in an oscillating mode (mechanical, electrical, or electromechanical) of a dissipative system. It is the reciprocal of the quality factor and represents the "quality" or persistence of the oscillation.

[0036] The term “derivative” refers to the polymerization of repeating units, for example, from polycyclic norbornene monomers according to general formula (I) or (III) or (VIII), wherein the resulting polymer is a ring-opening shift polymer (ROMP), for example, the 2,3 double bond of the norbornene monomer undergoes ring-opening polymerization as follows.

[0037]

[0038] Therefore, according to an embodiment of the present invention, a one-component composition is provided, comprising:

[0039] a) One or more monomers of general formula (I):

[0040]

[0041] in:

[0042] m is an integer of 0, 1, or 2;

[0043] R1, R2, R3, and R4 may be the same or different, and each is independently selected from hydrogen, halogen, methyl, ethyl, straight-chain or branched (C3-C4) 16 )alkyl, perfluorinated (C1-C 12 )alkyl, hydroxyl (C1-C 16 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 Bicycloalkyl, (C7-C 14 Tricycloalkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C6)alkyl, perfluorinated (C6-C6)alkyl 10 aryl, perfluorinated (C6-C) 10 The group consisting of aryl (C1-C6)alkyl, tri(C1-C6)alkoxysilyl and groups of general formula (A):

[0044] -Z-Aryl(A)

[0045] in:

[0046] Z is a bond or a group selected from the following group:

[0047] (CR5R6) a O(CR5R6) a (CR5R6) a O, (CR5R6) a -O-(CR5R6) b (CR5R6) a -O-(SiR5R6) b (CR5R6) a -(CO)O-(CR5R6) b (CR5R6) a -O(CO)-(CR5R6) b (CR5R6) a -(CO)-(CR5R6) b , where a and b can be the same or different integers, and each is independently 1 to 12;

[0048] R5 and R6 may be the same or different, and each is independently selected from the group consisting of hydrogen, methyl, ethyl, straight-chain or branched (C3-C6) alkyl, hydroxy, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, straight-chain or branched hydroxy (C3-C6) alkyl, phenyl and phenoxy.

[0049] The aryl group is phenyl or phenyl substituted with one or more groups selected from the group consisting of: methyl, ethyl, straight-chain or branched (C3-C6) alkyl, hydroxy, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, straight-chain or branched hydroxy (C3-C6) alkyl, phenyl, and phenoxy; or

[0050] One of R1 or R2 and one of R3 or R4 together with the carbon atom they are attached to form a double bond between the two carbon atoms;

[0051] b) Organorruthenium compounds of general formula (II):

[0052]

[0053] in:

[0054] c and d are integers from 0 to 5;

[0055] Z represents oxygen or sulfur;

[0056] R7 is selected from hydrogen, (C1-C) 20 )alkyl, (C2-C 20 )alkenyl, (C2-C 20 ) ynyl group and (C6-C 10 The group consisting of aryl groups; and

[0057] R8, R9, R 10 and R 11 They may be the same or different, and each is independently chosen from hydrogen, halogens, (C1-C) 16 )alkyl, (C1-C 16 )alkoxy, (C1-C 16 Perfluoroalkyl, (C3-C7)cycloalkyl, (C2-C 16 )alkenyl, (C6-C 14 )Aryl, (C6-C 14 Perfluoroaryl, (C3-C 12 Heterocyclic groups, -OR 16 -NO2, -COOH, -COOR 16 -CONR 16 R 17 -SO2NR16 R 17 -SO2R 16 -CHO and -COR 16 The group consisting of R 16 and R 17 They may be the same or different, and each is independently selected from (C1-C6)alkyl, (C1-C6)perfluoroalkyl, (C6-C6)alkyl, and (C6-C6)alkyl groups. 14 )Aryl and (C6-C 14 The group consisting of perfluoroaryl groups; or of which,

[0058] R8, R9, R 10 and R 11 Two or more carbon atoms in the ring together form substituted or unsubstituted fused (C4-C8) carbon rings or substituted or unsubstituted fused aromatic rings;

[0059] Each R 12 R 13 and R 14 They can be the same or different, and each can be independently chosen from hydrogen, halogens, (C1-C) 16 )alkyl, (C1-C 16 )alkoxy, (C1-C 16 Perfluoroalkyl, (C3-C7)cycloalkyl, (C2-C 16 )alkenyl, (C6-C 14 )Aryl, (C6-C 14 Perfluoroaryl, (C3-C 12 Heterocyclic groups, -OR 16 -NO2, -COOH, -COOR 16 -CONR 16 R 17 -SO2NR 16 R 17 -SO2R 16 -CHO and -COR 16 The group consisting of R 16 and R 17 They may be the same or different, and each is independently selected from (C1-C6)alkyl, (C1-C6)perfluoroalkyl, (C6-C6)alkyl, and (C6-C6)alkyl groups. 14 )Aryl, (C6-C 14 The group consisting of perfluoroaryl groups;

[0060] R 15 Choose freely (C1-C) 16 )alkyl, (C1-C 16 Perfluoroalkyl, (C3-C 16 )cycloalkyl, (C6-C 14 )Aryl, (C6-C14 Perfluoroaryl and (C3-C) 12 Groups composed of heterocyclic groups;

[0061] Ar1 and Ar2 may be the same or different, and each is independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl groups, wherein each substituent is independently selected from the group consisting of methyl, ethyl, and straight-chain or branched (C3-C6) alkyl groups; and

[0062] c) Photoactive compounds.

[0063] As described above, the compositions of the present invention are in the form of a transparent liquid at room temperature and remain a transparent solution for about 3 to 6 months at a temperature of about 25°C to about 80°C. It has now been found that the viscosity of the compositions generally remains substantially unchanged during the 3 to 6 months. In some embodiments, the viscosity changes by about 10 to 20% after storage for about 3 to 6 months. As further described in detail below, the stability of the compositions is also increased by storing them in an inert atmosphere and in the dark.

[0064] The aryl groups used in this specification may further include the following:

[0065] The following general formulas contain substituted or unsubstituted biphenyls:

[0066]

[0067] The following general formulas contain substituted or unsubstituted naphthyl groups:

[0068]

[0069] The following general formulas of substituted or unsubstituted terphenyls:

[0070]

[0071] Substituted or unsubstituted anthracene groups of the following general formulas:

[0072]

[0073] Substituted or unsubstituted fluorene groups of the following general formulas:

[0074]

[0075] Among them, R in each formula x Independently selected from methyl, ethyl, straight-chain or branched (C3-C4) 12 )alkyl or (C6-C 10 Aryl.

[0076] As described above, the monomer of general formula (I) has a refractive index of at least 1.5. The composition is a transparent liquid at room temperature. Surprisingly, as described above, the compositions of the present invention are stable in a temperature range from room temperature to 80°C, thus providing excellent shelf-life stability. "Stable" as used in this specification means that the compositions of the present invention remain transparent and do not increase in viscosity when stored in a temperature range from room temperature to 80°C, especially in a dark environment such as an amber or brown container without any light. Therefore, in some embodiments, the viscosity of the compositions of the present invention does not change when stored at temperatures below 80°C for more than 30 days. Therefore, in some embodiments, the viscosity of the compositions of the present invention increases by less than 5% when stored at temperatures below 80°C for more than 40 days. In other embodiments, the viscosity change of the compositions of the present invention is less than 10% when stored at temperatures below 80°C for 60 to 90 days. In still other embodiments, the viscosity change of the compositions of the present invention is less than 20% when stored at temperatures below 80°C for at least 120 to 180 days. In other embodiments, the viscosity of the compositions of the present invention changes by less than 2% when stored, for example, at an ambient temperature of about 20°C to 25°C for an extended period (120 to 300 days or longer). That is, the viscosity of the composition remains substantially unchanged when stored at ambient temperature, but as confirmed by UV-DSC measurements, the composition undergoes rapid bulk polymerization when exposed to suitable photochemical radiation, indicating that the heat of polymerization remains unchanged even when the composition is stored for the aforementioned extended period.

[0077] The monomers used in this invention are described in the literature or can be prepared by any method known to those skilled in the art.

[0078] Furthermore, the monomers described in this specification are readily subjected to bulk polymerization, i.e., bulk polymerization in their undoped form without the use of any solvent, under ring-opening shift bulk polymerization (ROMP) conditions using certain transition metal catalysts (e.g., organorruthenium and organosmium compounds). For example, see RH Grubbs et al., Handbook of Metathesis, Ed.: Wiley-VCH, Weinheim, Germany, 2003; RH Grubbs et al., Acc. Chem. Res. 2001, 34, 18-29; RH Grubbs et al., Angew. Chem. Int. Ed., 2006, 45, 3760-3765. Also, see U.S. Patent No. 6,838,489, the relevant portions of which are incorporated herein by reference. The term "bulk polymerization" as used herein should have the meaning generally accepted in the art. That is, polymerization reactions are typically carried out under conditions where no solvent is present. However, in some cases, a small amount of solvent may be present in the reaction medium. For example, small amounts of such solvents can be used to dissolve latent catalysts and / or activators or to transport them into the reaction medium. Furthermore, some solvents can be used to reduce the viscosity of the monomers. The amount of solvent that can be used in the reaction medium, relative to the total weight of the solvents employed, can range from 0 to 5% by weight. Any suitable solvent that dissolves the catalyst, activator, and / or monomers can be used in this invention. Examples of such solvents include alkanes, cycloalkanes, toluene, THF, dichloromethane, dichloroethane, etc.

[0079] Advantageously, it has been found that one or more monomers can be used to dissolve both latent catalysts and activators, thus avoiding the need for solvents. Furthermore, one monomer can be used as a solvent for other monomers, thus eliminating the need for additional solvents. For example, if the first monomer of general formula (I) is solid at room temperature, then the second monomer of general formula (I), which is liquid at room temperature, can be used as a solvent for the solid first monomer of general formula (I), and vice versa. Therefore, in such cases, one or more monomers can be used in the compositions of the present invention.

[0080] Therefore, it has been surprisingly found that monomers of formula (I) can be used as materials with low or high refractive indices, imparting low or high refractive indices to polymer films obtained by bulk polymerization under different temperatures and / or conditions than those for application on the desired substrate. Generally, monomers of formula (I) suitable for use in this invention are characterized by exhibiting a refractive index of at least 1.5. In some embodiments, the refractive index of monomers of formula (I) is higher than 1.5. In other embodiments, the refractive index of monomers of formula (I) is in the range of about 1.5 to 1.6. In still other embodiments, the refractive index of monomers of formula (I) is higher than 1.55, 1.6, or 1.65. In still other embodiments, the refractive index is even higher than 1.7.

[0081] Typically, the compositions of the present invention exhibit low viscosity, which can be below 100 cP or lower. In some embodiments, the viscosity of the compositions of the present invention is below 80 cP. In other embodiments, the viscosity of the compositions of the present invention is in the range of about 10 to 100 cP. In still other embodiments, the viscosity of the compositions of the present invention is below 70 cP, below 60 cP, below 40 cP, or below 20 cP. In yet other embodiments, the viscosity can even be below 10 cP and can vary in the range of 4 cP to 9 cP.

[0082] When the compositions of the present invention contain two or more monomers, they can be present in any desired amount to bring about the expected benefits (including improvement in refractive index or viscosity, or both). Therefore, the molar ratio of the first monomer of formula (I) to the second monomer of formula (II) can be 1:99 to 99:1. In some embodiments, the molar ratio of the first monomer of formula (I) to the second monomer of formula (I) is in the range of 5:95 to 95:5; in other embodiments, this molar ratio is 10:90 to 90:10; 20:80 to 80:20; 30:70 to 70:30; 60:40 to 40:60; 50:50, etc. Similarly, when using two or more different monomers of formula (I), any proportion of such monomers that bring about the desired results can be used.

[0083] Typically, the compositions according to the invention comprise one or more monomers of the above general formula (I) and more monomers of general formula (I) that are different from each other as needed. As described below, compositions of various embodiments can be selected to impart the properties required for the intended use of that embodiment, thereby enabling the embodiment to be adapted for various specific uses.

[0084] For example, as described above, by appropriately combining different monomers of general formula (I), the composition can be tailored to have the desired refractive index, viscosity, and light transmission properties. Furthermore, as further explained in this specification, it may be necessary to include other polymeric materials or monomeric materials such as inorganic nanoparticles, which are suitable for providing the desired optical properties depending on the end use. Therefore, the compositions of the present invention can also include other high-refractive-index polymeric materials and / or nanoparticles that provide such anticipated benefits. Examples of such polymers include, but are not limited to, poly(α-methylstyrene), poly(vinyl-toluene), copolymers of α-methylstyrene and vinyl-toluene, etc. Examples of nanoparticles will be described in further detail below.

[0085] Advantageously, it has also been found that the compositions of the present invention can also contain other monomers. In some embodiments, the compositions according to the present invention may further comprise one or more monomers selected from general formula (III).

[0086] The monomer of general formula (III) is

[0087]

[0088] in:

[0089] Where o is an integer from 0 to 2;

[0090] D is SiR 21 R 22 R 23 Or selected from the following groups:

[0091] (CH2) c -O-SiR 21 R 22 R 23 (E);

[0092] (CH2) c -SiR 21 R 22 R 23 (F); and

[0093] (SiR 21 R 22 ) c -O-SiR 21 R 22 R 23 (G);

[0094] Where c is an integer from 1 to 10, and one or more CH2 can be (C1-C 10 )alkyl, (C1-C 10 Perfluoroalkyl or (C6-C) 14 aryl substitution;

[0095] R 18 R 19 and R 20 They may be the same or different, and each is independently selected from hydrogen, halogens, and hydrocarbon groups, wherein the hydrocarbon group is selected from methyl, ethyl, straight-chain or branched (C3-C4) groups. 12 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 Bicycloalkyl, (C7-C 14 Tricycloalkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C3)alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkoxy, (C6-C 12 )bicycloalkoxy, (C7-C 14 Tricycloalkoxy, (C6-C 10 ) aryloxy (C1-C3) alkyl or (C6-C 10 ) aryloxy group; and

[0096] R 21 R 22 and R 23 Each is independently methyl, ethyl, straight-chain or branched (C3-C9) alkyl, substituted or unsubstituted (C6-C9) 14 ) aryl, methoxy, ethoxy, straight-chain or branched (C3-C9) alkoxy, or substituted or unsubstituted (C6-C9) alkoxy 14 )aryloxy group.

[0097] It has now been found that monomers of general formula (III) offer further advantages in this aspect of the invention. Specifically, monomers of general formula (III) impart high or low refractive indices and low or high dielectric constants to the composition, depending on the properties of the monomer, and can therefore be adjusted to meet specific needs. Furthermore, monomers of general formula (III) typically enhance adhesive properties, and thus can be used as "adhesive modifiers." Finally, monomers of general formula (III) can exhibit advantages such as low viscosity and good solubility in latent catalysts and / or activators.

[0098] In some embodiments, the composition of the present invention comprises a first monomer and a second monomer of different types of general formula (I), one of which has a refractive index of at least 1.5 and a viscosity of less than 100 cP, and the first monomer is completely miscible with the second monomer to form a transparent solution. However, as described above, any one or more monomers of general formula (III) can be used in this embodiment of the present invention.

[0099] In some embodiments, the compositions of the present invention may also comprise one or more monomers of general formula (VIII):

[0100]

[0101] in:

[0102] p is an integer from 0 to 2;

[0103] R 24 and R 25 They may be the same or different, and each is independently selected from the group consisting of hydrogen, methyl, ethyl, straight-chain or branched (C3-C6) alkyl, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, acetoxy, (C2-C6) acyl, phenyl, and phenoxy; or

[0104] R 24 With R 25 Together with the carbon atoms they are attached to, they form (C5-C7) carbon rings that can contain more than one double bond;

[0105] R 26 Hydrogen, halogen, methyl, ethyl, straight-chain or branched (C3-C) 16 )alkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C6) alkyl, hydroxyl, methoxy, ethoxy, straight-chain or branched (C3-C6) 16 )alkoxy, (C6-C 10 ) aryloxy group, (C6-C 10 aryl (C1-C6)alkoxy, -O(CO)R 27 OR-O(CO)OR 27 , where R 27 Methyl, ethyl, straight-chain or branched (C3-C) 16 )alkyl, (C6-C 10 ) aryl or (C6-C 10 )Aryl (C1-C6)alkyl.

[0106] Therefore, any monomer within the range of monomers of general formula (I) or general formula (III) can be used in the compositions of the present invention. Representative examples of monomers of general formula (I) or general formula (III) include, but are not limited to, the following:

[0107]

[0108] 5-(4-Phenylacetyl)bicyclo[2.2.1]hept-2-ene;

[0109]

[0110] 5-(3-Phenylacetyl)bicyclo[2.2.1]hept-2-ene;

[0111]

[0112] 5-Phenylacetylbicyclo[2.2.1]hept-2-ene (PENB);

[0113]

[0114] 3-(bicyclo[2.2.1]hept-5-en-2-yl)-7-oxabicyclo[4.1.0]heptane (CHEpNB);

[0115]

[0116] 5-(benzyloxy)bicyclo[2.2.1]hept-2-ene;

[0117]

[0118] 5-(2-([1,1'-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene;

[0119]

[0120] 5-(2-([1,1'-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtO-2-PhPh);

[0121]

[0122] 5-Butylbicyclo[2.2.1]hept-2-ene (BuNB);

[0123]

[0124] 5-Hexylbicyclo[2.2.1]hept-2-ene (HexylNB);

[0125]

[0126] 5-Octylbicyclo[2.2.1]hept-2-ene (OctNB);

[0127]

[0128] 5-Decylbicyclo[2.2.1]hept-2-ene (DecNB);

[0129]

[0130] 5-Ethylenebicyclo[2.2.1]hept-2-ene;

[0131]

[0132] 2-Ethylene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene;

[0133]

[0134] 5-Norbornel-methyleugenol acetate (EuAcNB);

[0135]

[0136] 5-Norborneol-enylmethyleugenol (EuOHNB);

[0137]

[0138] (Bicyclo[2.2.1]hepten-5-en-2-ylmethoxy)(methyl)diphenylsilane (NBCH2OSiMePh2);

[0139]

[0140] (Bicyclo[2.2.1]hepten-5-en-2-ylmethoxy)(ethyl)diphenylsilane;

[0141]

[0142] (Bicyclo[2.2.1]hepten-5-en-2-ylmethoxy)(ethyl)(methyl)(phenyl)silane;

[0143]

[0144] (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethyl(phenyl)silane;

[0145]

[0146] Bicyclo[2.2.1]hept-5-en-2-yltrimethoxysilane (TMSNB);

[0147]

[0148] Bicyclo[2.2.1]hepten-5-en-2-yltriethoxysilane (NBSi(OC2H5)3);

[0149]

[0150] Bicyclo[2.2.1]hept-5-en-2-yl(tert-butoxy)dimethoxysilane;

[0151]

[0152] (2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)trimethoxysilane;

[0153]

[0154] NB(MeOH)2;

[0155]

[0156] PhAcNB;

[0157]

[0158] Tetracyclic dodecene (TD);

[0159]

[0160] 5-(phenoxymethyl)bicyclo[2.2.1]hept-2-ene (NBMeOPh);

[0161]

[0162] 5-(([1,1'-biphenyl]-2-yloxy)methyl)bicyclo[2.2.1]hept-2-ene (NBMeOPhPh);

[0163]

[0164] 2-Phenylacetyl-Tetracyclododecene (PhTD);

[0165]

[0166] 2-Benzyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene;

[0167]

[0168] 2-Phenylacetyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD);

[0169]

[0170] 2-Butyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (ButylTD);

[0171]

[0172] 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD);

[0173]

[0174] 2-Octyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (OctylTD);

[0175]

[0176] 2-Ceyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (DecylTD);

[0177]

[0178] 2-Cyclohexyl-tetracyclododecene (CyclohexylTD);

[0179]

[0180] 2-Cyclohexylepoxy-tetracyclododecene (CHEpTD);

[0181]

[0182] 2-Cyclohexylmethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene;

[0183]

[0184] 2-Cyclohexylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene;

[0185]

[0186] (1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridgednaphthalene-2-yl)methyl acetate (TDMeOAc); and

[0187]

[0188] Tetracyclic dodecadiene (TDD).

[0189] Representative examples of monomers of general formula (VIII) include, but are not limited to, the following:

[0190]

[0191] Dicyclopentadiene (DCPD);

[0192]

[0193] 4,4a,4b,5,8,8a,9,9a-octahydro-1H-1,4:5,8-dimethylfluorene (one of the cyclopentadiene trimers,

[0194] TCPD2);

[0195]

[0196] 1-Methoxy-dicyclopentadiene;

[0197]

[0198] 1-(n-Butoxy)-Dicyclopentadiene;

[0199]

[0200] 1-(n-octyloxy)-biscyclopentadiene;

[0201]

[0202] 3a,4,7,7a-tetrahydro-1H-4,7-methyl-indene-1-yl acetate;

[0203]

[0204] 3a,4,7,7a-tetrahydro-1H-4,7-methyl-indene-1-ylbenzoate;

[0205]

[0206] 3a,4,7,7a-tetrahydro-1H-4,7-methyl-indene-1-yl-2-phenylacetic acid ester;

[0207]

[0208] 3a,4,7,7a-tetrahydro-1H-4,7-methyl-inden-1-yl-3-phenylpropionate;

[0209]

[0210] 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethylbridged cyclopenta[b]naphthalene (one of the cyclopentadiene trimers, TCPD1, also known as CPD3);

[0211]

[0212] 4,4a,9,9a-tetrahydro-1H-1,4-methyl-bridged fluorene, also known as norbornene-indene (NB-Indene); and

[0213]

[0214] 4b,5a,6,9,9a,10,10a,11-octahydro-5H-5,10:6,9-dimethylbridged benzo[b]fluorene, also known as tetracyclic dodecene-indene (TD-Indene).

[0215] As described above, the compositions of the present invention comprise at least one organorruthenium compound of general formula (II), which, when exposed to suitable photochemical radiation, undergoes the bulk polymerization described herein under ROMP conditions. Typically, such organorruthenium compounds of general formula (II) are "latent" and are active only under certain conditions. Furthermore, "latency" as used herein refers to the prolonged inactivity of the organorruthenium catalyst in the compositions of the present invention when stored under ambient conditions up to 80°C. Therefore, in some embodiments, the latency of the organorruthenium catalyst is maintained for more than 30 days when stored at temperatures below 80°C. In other embodiments, the latency of the organorruthenium catalyst is maintained for 40 to 90 days when stored at temperatures below 50°C.

[0216] Generally, any latent organorruthenium compound of general formula (II) capable of inducing ring-opening shift polymerization of monomers of general formula (I), (III), or (VIII) can be used in the compositions of the present invention. Interestingly, organorruthenium compounds of general formula (II) have been found to be very stable in the temperature range from about 25°C (i.e., ambient conditions) to about 80°C, and can be stored alone or in the presence of one or more monomers of general formula (I), (III), or (VIII) for several days, or even for 3 to 6 months or longer. That is, organorruthenium compounds of general formula (II) act as latent catalysts, remaining stable at or near room temperature up to 80°C but readily activated only when needed by various conditions, including but not limited to thermal, acidic, photochemical, and chemical activation. Chemical activation may include the use of thermal or photochemical acid generators.

[0217] Several known latent catalysts in the literature are not stable under the conditions defined in this specification, and most do not exhibit the stability described in this specification for their shelf life. For example, see Grubbs et al., Organometallics, 2011, 30(24): 6713-6717; Sutar et al., Angew. Chem. Int. Ed. 2016, 55, 764-767; Leitgeh et al., Monatsh Chem (2014) 145: 1513-1517; van Hensbergen et al., J. Mater. Chem. C. 2015, 3, 693-702; Grubbs et al., J. Am. Chem. Soc., 2009, 131, 203802039; Zak et al., Eur. J. Inorg. Chem., 2014, 1131-1136; Gawin et al., ACS Catal. 2017, 7, 5443-5449. Other examples of such catalysts can be found in U.S. Patent No. 9,328,132, the relevant portions of which are incorporated herein by reference. Therefore, compositions comprising organorruthenium compounds of general formula (II), as described herein, offer advantages in a variety of applications that have not been realized until now.

[0218] Therefore, in some embodiments, the compositions of the present invention comprise an organorruthenium compound of general formula (II), wherein:

[0219] Z stands for oxygen;

[0220] R7 is hydrogen;

[0221] R8, R9, R 10 and R 11 They may be the same or different, and each is independently selected from the group consisting of hydrogen, methyl, ethyl and NO2;

[0222] Each R 12 R 13 and R 14 They may be the same or different, and each is independently selected from the group consisting of hydrogen, methyl, ethyl and NO2;

[0223] R 15 Select from the group consisting of methyl, ethyl, and cyclohexyl groups;

[0224] Ar1 and Ar2 may be the same or different, and each is independently selected from the group consisting of phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di(isopropyl)phenyl and 2,4,6-trimethylphenyl.

[0225] Therefore, some exemplary latent catalysts within the scope of organorruthenium compounds of general formula (II) can be selected without restriction from the group consisting of:

[0226]

[0227] [1,3-Bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II)(Ru-1);

[0228]

[0229] [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II)(Ru-2);

[0230]

[0231] [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II)(Ru-3);

[0232] and

[0233]

[0234] [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II)(Ru-4).

[0235] Interestingly, it has been found that organorruthenium compounds of general formula (II) can be activated by some known photoactive compounds under suitable photolysis conditions, thus promoting the bulk polymerization of one or more monomers of general formula (I), (III), or (VIII) contained in the compositions of the present invention under the ROMP conditions described herein. Therefore, some known photoactive compounds have been found suitable for this purpose, such as substituted xanthonesone derivatives represented by structural formula (VI):

[0236]

[0237] in:

[0238] Y is a halogen; and

[0239] R 30 and R 31 They may be the same or different, and each is independently selected from hydrogen, methyl, ethyl, straight-chain or branched (C3-C) 12 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 Bicycloalkyl, (C7-C 14 Tricycloalkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C3)alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkoxy, (C6-C 12 )bicycloalkoxy, (C7-C 14 Tricycloalkoxy, (C6-C 10 ) aryloxy (C1-C3) alkyl and (C6-C 10 A group composed of aryl groups.

[0240] In some embodiments, compounds of general formula (VI) have the following characteristics:

[0241] Y is either chlorine or bromine; and

[0242] R 30 and R 31 They may be the same or different, and each is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, cyclohexyl, methoxy, ethoxy, n-propoxy, and phenoxy.

[0243] Representative examples of compounds of general formula (VI) may include, but are not limited to, the following:

[0244]

[0245] 1-Chloro-4-methoxy-9H-thioxanthro-9-one;

[0246]

[0247] 1-Chloro-4-ethoxy-9H-thioxanthone;

[0248]

[0249] 1-Chloro-4-propoxy-9H-thioxanth-9-one (commercially available by Lambson under the product name CPTX);

[0250]

[0251] 1-Chloro-2-propoxy-9H-thioxanth-9-one;

[0252]

[0253] 1-Chloro-2-ethoxy-9H-thioxanthone;

[0254]

[0255] 1-Chloro-2-methoxy-9H-thioxanth-9-one;

[0256]

[0257] 1-Chloro-4-methyl-9H-thioxanth-9-one;

[0258]

[0259] 1-Chloro-4-ethyl-9H-thioxanth-9-one;

[0260]

[0261] 1-Bromo-4-propoxy-9H-thioxanthone; and

[0262]

[0263] 1-Chloro-4-phenoxy-9H-thioxanth-9-one.

[0264] Furthermore, it has been found that the compositions of the present invention can contain more than one organic base, such as pyridine and quinoline derivatives. Therefore, in some embodiments, the compositions of the present invention contain more than one compound of general formula (IV) or more than one compound of general formula (V), which can provide additional shelf-life stability.

[0265]

[0266] in:

[0267] e is an integer from 0 to 4;

[0268] Each R 28 Independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; and

[0269] Each R 29 Independently selected from methyl, ethyl, straight-chain or branched (C3-C6) alkyl, (C6-C6) alkyl groups. 10 ) aryl, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, (C6-C 10 The group consisting of aryl groups and halogens.

[0270] Any compound within the range of compounds of general formula (IV) or (V) may be used in the compositions of the present invention. In some embodiments, the compositions of the present invention comprise a compound of general formula (IV) or a compound of general formula (V), wherein:

[0271] e is an integer from 0 to 2;

[0272] Each R 28 Independently selected from the group consisting of methyl, ethyl, isopropyl, and tert-butyl; and

[0273] Each R 29 It is independently selected from the group consisting of methyl, ethyl, isopropyl, tert-butyl, phenyl, methoxy, ethoxy, phenoxy, fluorine, and chlorine.

[0274] Non-limiting examples of compounds of general formula (IV) or general formula (V) are selected from the group consisting of:

[0275] N,N-Dimethylpyridine-4-amine (DMAP);

[0276] N,N-Diethylpyridine-4-amine;

[0277] N,N-Diisopropylpyridine-4-amine;

[0278] N,N-di-tert-butylpyridine-4-amine;

[0279] N,N-Dimethyl-2-methylpyridine-4-amine;

[0280] N,N-di-tert-butyl-2-methylpyridine-4-amine;

[0281] 2-Methoxy-N,N-dimethylpyridine-4-amine;

[0282] 2-Fluoro-N,N-Dimethylpyridin-4-amine;

[0283] N,N-Dimethylquinoline-4-amine;

[0284] N,N-2-Trimethylquinoline-4-amine;

[0285] 2-Methoxy-N,N-dimethylquinoline-4-amine; and

[0286] 2-Chloro-N,N-Dimethylquinoline-4-amine.

[0287] The compositions of the present invention may further comprise certain additives that provide additional stability depending on the intended use or application. Advantageously, it has been found that use in combination with certain ultraviolet (UV) light blockers surprisingly imparts further stability to the compositions of the present invention, especially in UV-exposed environments, such as in the VAT of 3D printers. Furthermore, it has been surprisingly noted that the use of more than one of these UV blockers does not reduce the bulk polymerization activity of the compositions of the present invention upon exposure to suitable photochemical radiation, thus providing a synergistic and beneficial effect.

[0288] Therefore, in some embodiments, the compositions of the present invention may comprise compounds of general formula (VII):

[0289]

[0290] in:

[0291] n is an integer from 0 to 4;

[0292] Each R 32 Independently selected from hydrogen, methyl, ethyl, straight-chain or branched (C3-C) 12 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 Bicycloalkyl, (C7-C 14 Tricycloalkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C3)alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkoxy, (C6-C 12 )bicycloalkoxy, (C7-C 14 Tricycloalkoxy, (C6-C 10 ) aryloxy (C1-C3) alkyl and (C6-C 10 A group composed of aryl groups.

[0293] By including compounds of formula (VII), the stability of the composition and the optical properties of 3D objects made from the composition are significantly improved. Compounds of formula (VII) are considered to act as UV blockers, thereby imparting superior stability to the composition during peripheral contact with any UV light during UV exposure, the composition being removed from VAT to form the desired 3D object. Therefore, any compound capable of acting similarly to compounds of formula (VII) can be used in the compositions of the present invention, such as any other known UV blockers. Any amount of compounds of formula (VII) that provide the desired benefits can be used in the compositions of the present invention. Typically, such an amount can vary in the range of about 1:200 molar ratio of compounds of formula (VII):compound of formula (II). In other embodiments, such an amount can be about 1:100 molar ratio of compounds of formula (VII):compound of formula (II); or 1:50 molar ratio of compounds of formula (VII):compound of formula (II), etc.

[0294] Representative examples of compounds of general formula (VII) may include, but are not limited to, the following:

[0295]

[0296] 2,5-Bis(5-(tert-butyl)benzo[d]oxazol-2-yl)thiophene (BTBBT), manufactured by Mayzo Corporation.

[0297] Benetex OB Plus is available in the market;

[0298]

[0299] 5-(tert-butyl)-2-(5-(5-isopropylbenzo[d]oxazol-2-yl)thiophen-2-yl)benzo[d]oxazol;

[0300]

[0301] 2,5-Bis(5-isopropylbenzo[d]oxazol-2-yl)thiophene;

[0302]

[0303] 5-Ethyl-2-(5-(5-isopropylbenzo[d]oxazol-2-yl)thiophen-2-yl)benzo[d]oxazol;

[0304]

[0305] 2,5-Bis(5-ethylbenzo[d]oxazol-2-yl)thiophene;

[0306]

[0307] 5-Ethyl-2-(5-(5-methylbenzo[d]oxazol-2-yl)thiophen-2-yl)benzo[d]oxazol; and

[0308]

[0309] 2-(5-(benzo[d]oxazol-2-yl)thiophen-2-yl)-5-(tert-butyl)benzo[d]oxazol.

[0310] Various other UV light blocking compounds and / or UV light absorbers that can be used in the compositions of the present invention include the following:

[0311] and

[0312]

[0313] Wherein, n and R 32 As defined in this specification.

[0314] Representative compounds within the scope of compounds of general formulas (VIIa) and (VIIb) are listed below:

[0315]

[0316] 1,2-Bis(4-(benzo[d]oxazol-2-yl)phenyl)ethylene, commercially available by Mayzo as Benextex OB-1; and

[0317]

[0318] Sodium 2,2'-([1,1'-biphenyl]-4,4'-dimethylbis(ethylene-2,1-dimethyl))diphenylsulfonate is commercially available from Mayzo under the name Benextex OB-M1.

[0319] Surprisingly, it was further discovered that by adding additives capable of removing any halide radicals generated during exposure, additional benefits could be provided when forming transparent objects using the compositions of the present invention. Furthermore, such additives can also act as chain terminators to prevent dark reactions. Dark reactions, as described in this specification, refer to polymer chain growth in unexposed areas. Any additives that contribute to the removal of such halide radicals and chain termination can be used in the present invention. It has now been found that the use of certain acrylates can provide the advantageous benefits described in this specification. Suitable exemplary acrylates include, but are not limited to, alkyl acrylates, aryl acrylates, alkyl methacrylates, aryl methacrylates, etc. Non-limiting examples of such specific acrylics include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, phenyl methacrylate, etc.

[0320] Any amount of acrylate monomer that brings the intended benefits can be used in the compositions of the present invention. Generally, as those skilled in the art will understand, such an amount depends on the various other additives used in the compositions of the present invention. In some embodiments, one or more acrylate monomers are used in sufficient amounts, which may be about 1 to 50 moles relative to a total of 5,000 to 10,000 moles of monomers of general formula (I) or with monomers of general formula (III) and / or (VIII). In some embodiments, the amount of acrylate monomer used may be about 5 to 20 moles relative to a total of 10,000 moles of monomers of general formulas (I), (III), and (VIII) (if used).

[0321] Surprisingly, as mentioned above, it has now been found that when the composition is exposed to suitable photochemical radiation (typically wavelengths of about 240 nm to 410 nm), the use of a suitable combination of a compound of formula (II) with one or more compounds of formula (IV), or a compound of formula (V), or a compound of formula (VI) can initiate bulk polymerization of the monomers, and the composition undergoes ring-opening shift bulk polymerization (ROMP) to form a transparent film or transparent object.

[0322] Any amount of organorruthenium compound of general formula (II) capable of producing the desired results can be used in the compositions of the present invention. Typically, the total molar ratio of monomers of general formulas (I), (III), and (VIII) to compound of general formula (II) is in the range of 10,000:1 to 5,000:1 or lower. In other embodiments, such molar ratio of monomer to compound of general formula (II) is 15,000:1, 20,000:1, or higher.

[0323] If desired, any amount of a compound of formula (IV), formula (V), or formula (VI) that produces the desired results in the compositions of the present invention can be used. Typically, the molar ratio of a compound of formula (II) to a compound of formula (IV), (V), or (VI) is in the range of 1:50 or higher. In other embodiments, the molar ratio of a compound of formula (II) to a compound of formula (IV), (V), or (VI) is 1:10, 1:15, 1:20, 1:25, 1:30, 1:40, etc.

[0324] In some embodiments, the compositions of the present invention undergo bulk polymerization upon exposure to suitable UV radiation to form a substantially transparent film. The film formed by the bulk polymerization of monomers is substantially transparent to visible light; that is, most visible light passes through the film. In some embodiments, such films formed from the compositions of the present invention exhibit visible light transmittance of 90% or more. In other embodiments, such films formed from the compositions of the present invention exhibit visible light transmittance of 95% or more.

[0325] In another embodiment, when exposed to suitable UV radiation at a temperature of 80°C to 100°C, the composition of the present invention undergoes bulk polymerization to form a substantially transparent film or transparent object.

[0326] In some embodiments, the compound of formula (VI) can be activated at certain wavelengths of electromagnetic radiation (typically in the range of about 240 nm to 400 nm). Therefore, any compound active under such electromagnetic radiation can be used in the compositions of the present invention, which are stable in 3D fabrication methods. In some embodiments, the radiation wavelength for activating the compound of formula (VI) is 260 nm. In other embodiments, the radiation wavelength for activating the compound of formula (VI) is 310 nm. In still other embodiments, the radiation wavelength for activating the compound of formula (VI) is 395 nm.

[0327] However, any other known photoactive compounds capable of activating latent organorruthenium compounds of general formula (II) can also be used in the compositions of the present invention. All such compounds are part of the present invention.

[0328] Advantageously, it has now been further discovered that by using appropriate amounts of monomeric or polymeric crosslinking agents, the mechanical properties of three-dimensional objects formed from the compositions of the present invention can be significantly enhanced. Representative examples of such suitable monomeric crosslinking agents are selected from the group consisting of:

[0329] i) Compounds of general formula (IXa):

[0330]

[0331] ii) Compounds of general formula (IXb):

[0332]

[0333] iii) Compounds of general formula (IXc):

[0334]

[0335] in:

[0336] m is an integer of 0, 1, or 2;

[0337] b is an integer from 1 to 10;

[0338] K is selected from the group consisting of CH2, CH2-CH2, O and S;

[0339] X is the key or can be selected from O, S, NR. a SR b R c SiR b R c O(SiR b R c O) n SiR b R c SiR b R c (C6-C 10 )ArylSiR b R c Part of the group consisting of -C(O)-, -C(O)O-, -OC(O)-, -OC(O)-O-, -SC(O)-, -C(O)-S-, -CH=CH- and -C≡C-;

[0340] R a R b and R c Each is independently selected from hydrogen, methyl, ethyl, or straight-chain or branched (C3-C) 12 alkyl, (C3-C8)cycloalkyl, (C5-C 12 Bicycloalkyl, (C5-C 12Bicycloalkenyl and (C5-C) 12 The group consisting of bicyclic alkenyl (C1-C3)alkyl Si(CH3)2, and O, NR a S atoms do not directly bond with each other; and

[0341] n is an integer from 0 to 10.

[0342] Advantageously, it has been found that by using one or more compounds of general formula (IXa), (IXb), or (IXc) in combination, the properties of the composition can be adjusted to meet the intended purpose. For example, suitable combinations of one or more compounds of general formula (IXa), (IXb), or (IXc) with the compositions of the present invention can currently improve the mechanical properties, etc., of objects formed from the compositions of the present invention. More specifically, it has been found that the combined use of certain siloxane compounds within the range of compounds of general formula (IXa) or (IXb) can improve the impact strength of objects formed therefrom. Any amount of one or more compounds of general formula (IXa), (IXb), or (IXc) that brings the desired advantages can be used. Generally, the amount of one or more compounds of general formula (IXa), (IXb), or (IXc) can be in the range of 0 to 20 mol% of the total molar amount of monomers of general formula (I), monomers of general formula (III), or (VIII) (if used, including one or more compounds of general formula (IXa), (IXb), or (IXc)). In some embodiments, the above amount can be in the range of 1 to 15 mol%, in other embodiments, the above amount can be in the range of 0.5 to 10 mol%, and in still other embodiments, the above amount can be in the range of 0.5 to 5 mol%.

[0343] Therefore, in some embodiments, the polymer formed from the composition of the present invention has an impact strength of at least 40 J / m. In other embodiments, the polymer formed from the composition of the present invention has an impact strength of at least 60 J / m. In still other embodiments, the polymer formed from the composition of the present invention has an impact strength of at least 80 J / m, more than 100 J / m, more than 140 J / m, or greater than 160 J / m, for example, greater than 170 J / m, greater than 180 J / m, greater than 200, 220, or 240 J / m, or even greater than 500, 550, 600, 700, or 800 J / m, as described in this specification, depending on the type of monomer used. In some embodiments, the polymer formed from the composition of the present invention comprising one or more monomers of general formula (I) can itself exhibit unusual impact strength, ranging from 50 to 800 J / m.

[0344] In some embodiments, compounds of formula (IXa), (IXb), or (IXc) have m = 0 and K = CH2, respectively. In some embodiments, compounds of formula (IXa), (IXb), or (IXc) have m = 1 and K = CH2, respectively. In still other embodiments, compounds of formula (IXa), (IXb), or (IXc) have m = 2 and K = CH2, respectively.

[0345] Representative examples of compounds within the range of general formula (IXa) or (IXb) include, but are not limited to, the following:

[0346]

[0347] 1,3-Bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane

[0348] (BisENBTMDS);

[0349]

[0350] 1,1,3,3-Tetramethyl-1,3-bis(2-(1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridgednaphthyl-2-yl)ethyl)disiloxane;

[0351]

[0352] 1,5-Bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane

[0353] (BisENBHMTS);

[0354]

[0355] 1,1,3,3,5,5-Hexamethyl-1,5-bis(2-(1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridgednaphthyl-2-yl)ethyl)trisiloxane;

[0356]

[0357] 1,4-Bis((2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)dimethylsilyl)benzene;

[0358]

[0359] 3,3'-Oxybis(1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-3-cyclohexyl-1,1,5,5-tetramethyltrisiloxane)(TeTENBOMSS);

[0360]

[0361] (bicycloheptenyl)ethyl-terminated polydimethylsiloxane, wherein n is 2 to 4; and

[0362]

[0363] 3,7,14-Tris(((2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)dimethylsilyl)oxy)-1,3,5,7,9,11,14-heptaisobutyl-2,4,6,8,10,12,13,15,16-nonaoxa-1,3,5,7,9,11,14-heptasiltricyclo[7.3.3.15,11]hexadecane (trisnorbornenylisobutyl POSS).

[0364] Furthermore, various other oligomeric or polymeric polysiloxanes having polyfunctional cyclic olefin side chain groups are suitable as crosslinking molecules in the compositions of the present invention (which may or may not be within the scope of compounds of general formula (IXa)). Examples of this include oligosiloxanes of the following general formula:

[0365]

[0366] Where b is an integer from 1 to 9;

[0367] n is an integer from 1 to 10; and

[0368] R b and R c Each is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and phenyl.

[0369] Various other non-limiting examples of compounds of general formula (IXa), (IXb) or (IXc) may be selected from the group consisting of:

[0370]

[0371] 1,4-Di(bicyclo[2.2.1]hept-5-en-2-yl)butane;

[0372]

[0373] 5,5'-(oxybis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0374]

[0375] 5,5'-(oxybis(ethane-2,1-diyl))bis(bicyclo[2.2.1]hept-2-ene);

[0376]

[0377] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methane;

[0378]

[0379] 5,5'-((propane-2,2-diylbis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0380]

[0381] 5,5'-((propane-1,1-diylbis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0382]

[0383] 5,5'-(((1-phenylethane-1,1-diyl)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]

[0384] (hept-2-ene);

[0385]

[0386] 1,2-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethane;

[0387]

[0388] 1,3-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)propane;

[0389]

[0390] 1,4-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)butane;

[0391]

[0392] 1,6-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)hexane;

[0393]

[0394] 1,8-bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)octane;

[0395]

[0396] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethylsilane;

[0397]

[0398] Where n is 2 to 4;

[0399]

[0400] Where R and R' are independently selected from (C1-C1) 12 Alkyl), (C6-C 10 (aryl) and (C6-C) 10 Aryl)

[0401] (C1-C 12 alkyl);

[0402]

[0403] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)(phenyl)silane;

[0404]

[0405] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)diphenylsilane;

[0406]

[0407] 1,4-Di(bicyclo[2.2.1]hept-5-en-2-yl)benzene;

[0408]

[0409] 1,3-Bis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)benzene;

[0410]

[0411] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethyl) carbonate;

[0412]

[0413] Bicyclic [2.2.1]hept-5-en-2-ylmethylbicyclic [2.2.1]hept-5-en-2-carboxylic acid ester;

[0414]

[0415] Where b is an integer from 1 to 6;

[0416]

[0417] Bis(bicyclo[2.2.1]hept-5-en-2-ylmethyl) p-phthalate;

[0418]

[0419] Bicyclic [2.2.2]oct-5-en-2-ylmethylbicyclic [2.2.2]oct-5-en-2-carboxylic acid ester;

[0420]

[0421] 5,5'-((((propane-2,2-dimethylbis(4,1-phenylene))bis(oxy))bis(2,3,5,6-tetrafluoro-4,1-phenylene))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0422]

[0423] 5,5'-(((((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(oxy))bis(2,3,5,6-tetrafluoro-4,1-phenylene))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene)

[0424]

[0425] 1,4,4a,4b,5,8,8a,8b-octahydro-1,4:5,8-dimethylbridged biphenyl;

[0426]

[0427] 4,4a,4b,5,8,8a,9,9a-octahydro-1H-1,4:5,8-dimethylfluorene;

[0428]

[0429] 1,4,4a,5,8,8a,9,9a,10,10a-decahydro-1,4:5,8-dimethylbridged anthracene;

[0430]

[0431] 1,4,4a,5,6,6a,7,10,10a,11,12,12a-dodecylhydro-1,4:7,10-dimethylbridged dibenzo[a,e][8]annulene;

[0432] and

[0433]

[0434] 1,4,4a,5,5a,5b,6,6a,7,10,10a,11,11a,11b,12,12a-hexadecylhydro-1,4:5,12:6,11:7,10-tetramethylbridged dibenzo[b,h]biphenylene.

[0435] Various other non-limiting examples within the scope of compounds of general formulas (IXa), (IXb) and (IXc) are listed below:

[0436]

[0437] 1,3-Di(bicyclo[2.2.1]hept-5-en-2-yl)propane;

[0438]

[0439] 5,5'-(2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)propane-1,3-diyl)bis(bicyclo[2.2.1]hept-2-ene);

[0440]

[0441] Bis(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane;

[0442]

[0443] Tris(4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl)methane;

[0444]

[0445] 5,5'-(((2-((bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl)-2-methylpropane-1,3-diyl)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0446]

[0447] 5,5'-(((bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(oxy))bis(methylene))bis(bicyclo[2.2.1]hept-2-ene);

[0448]

[0449] Tris(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)silane; and

[0450]

[0451] Bicyclo[2.2.1]hept-5-en-2-ylbis(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)silane.

[0452] If various other known monomeric or polymeric crosslinking agents are used in the compositions of the present invention, they can advantageously bond with one or more monomers of general formula (I) or one or more monomers of general formula (III) or (VIII) (if used) upon exposure to suitable radiation. Typically, bonding with one or more monomers of general formula (I) or one or more monomers of general formula (III) or (VIII) (if used) is a crosslinking reaction initiated by light radiation generated during light irradiation at a suitable temperature. Furthermore, such crosslinking can be further improved, for example, by curing for a suitable time at a suitable temperature (typically above 150°C) after light irradiation. However, it should be noted that, as demonstrated above and by the numerical values ​​of the following examples, the three-dimensional objects obtained by curing the compositions of the present invention exhibit surprisingly high impact strength.

[0453] Representative examples of such polymer crosslinkers include, but are not limited to, homopolymers containing pendent epoxides of monomer side chains, such as CHEpNB (resulting in pCH-O-NB) or CHEpTD (resulting in pCH-O-TD). Various other polymer crosslinkers containing norbornene-type groups formed by ring-opening of bicyclic epoxy groups or oxybutyl groups and polyether bonds can also be used.

[0454]

[0455] In some embodiments of the invention, the compositions of the invention may further comprise other photosensitizer compounds capable of activating organorruthenium compounds of general formula (II) to promote the bulk polymerization of monomers of general formula (I) and monomers of general formula (III) or (VIII) (if present). For this purpose, any suitable sensitizer compound can be used in the compositions of the invention. These suitable sensitizer compounds include photosensitizers, such as anthracene, phenanthrene, etc. Benzo[a]pyrene, fluoranthene, rubrene, pyrene, xanthone, indigoferazone, and mixtures thereof. In some embodiments, suitable sensitizer components include mixtures thereof. Typically, the photosensitizer absorbs energy from a radiation source and transfers that energy to the desired substrate / reactant used in the compositions of the present invention.

[0456] The compositions according to the invention may further contain any additives for improving the properties of the composition and articles made therefrom. Examples of such additives may include antioxidants and synergists. Any antioxidant that provides the intended benefits can be used in the compositions of the invention. Non-limiting examples of such antioxidants include pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (IRGANOX). TM 1010 (from BASF), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (IRGANOX) TM 1076 (from BASF) and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (IRGANOX) TM 1035 (from BASF). Non-limiting examples of such synergists include some co-antioxidants that provide additional benefits such as preventing degradation of the compositions of the present invention by preventing auto-oxidation and extending the performance of the primary antioxidant. Examples of such synergists include tris(2,4-di-tert-butylphenyl) phosphite, marketed by BASF as IRGAFOS 168.

[0457] The compositions of the present invention may also contain viscosity modifiers to control the viscosity of the composition. Typically, such viscosity modifiers used are those suitable for the compositions of the present invention and for certain applications. Examples of such viscosity modifiers include, but are not limited to, acrylates, methacrylates, and styrene polymers. Such viscosity modifiers can be used in any suitable amount to provide the intended benefit.

[0458] Therefore, in some embodiments, the composition of the present invention may further comprise one or more additives selected from the group consisting of organic bases, UV blockers, viscosity modifiers, halide scavengers, antioxidants, synergists, and mixtures thereof as described herein.

[0459] In another embodiment of the invention, the composition comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0460] In another embodiment of the invention, the composition comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthion-9-one (CPTX), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0461] In another embodiment of the invention, the composition comprises 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), tris(2,4-di-tert-butylphenyl) phosphite (IRGAFOS168), and 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (IRGANOX). TM A mixture of 1076) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0462] In another embodiment of the invention, the composition comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthion-9-one (CPTX), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-2).

[0463] In some other embodiments of the invention, the composition of the invention comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 5-phenylethylbicyclo[2.2.1]hept-2-ene (PENB), 1-chloro-4-propoxy-9H-thioxanthione-9-one (CPTX), N,N-dimethylpyridin-4-amine (DMAP), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-2).

[0464] In another embodiment of the invention, the composition comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthion-9-one (CPTX), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-3).

[0465] In some other embodiments of the invention, the composition comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthione (CPTX), N,N-dimethylpyridin-4-amine (DMAP), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-3).

[0466] In some other embodiments of the invention, the composition comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthione (CPTX), N,N-dimethylpyridin-4-amine (DMAP), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-4).

[0467] In another embodiment of the invention, the composition of the invention comprises a mixture of 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), 1-chloro-4-propoxy-9H-thioxanthione (CPTX), N,N-dimethylpyridin-4-amine (DMAP), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-4).

[0468] In another embodiment of the present invention, the composition of the present invention comprises 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox1076), and tris(2,4-di-tert-butylphenyl) phosphite (Irgafos). A mixture of 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0469] In another embodiment of the invention, the composition of the invention comprises a mixture of 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0470] In another embodiment of the invention, the composition comprises 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), 4b,5a,6,9,9a,10,10a,11-octahydro-5H-5,10:6,9-dimethylbridged benzo[b]fluorene (TD-Indene), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), and 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox). A mixture of 1076), tris(2,4-di-tert-butylphenyl) phosphite (Irgafos168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0471] In another embodiment of the present invention, the composition comprises 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 4b,5a,6,9,9a,10,10a,11-octahydro-5H-5,10:6,9-dimethylbridged benzo[b]fluorene (TD-Indene), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), and 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox). A mixture of 1076), tris(2,4-di-tert-butylphenyl) phosphite (Irgafos168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0472] In another embodiment of the invention, the composition of the invention comprises a mixture of 4b,5a,6,9,9a,10,10a,11-octahydro-5H-5,10:6,9-dimethylbridged benzo[b]fluorene (TD-Indene), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0473] In another embodiment of the invention, the composition comprises a mixture of 4,4a,9,9a-tetrahydro-1H-1,4-methylfluorene (NB-Indene), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0474] In another embodiment of the invention, the composition of the invention comprises a mixture of 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethylbridged cyclopenta[b]naphthalene (CPD3), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0475] In another embodiment of the present invention, the composition of the present invention comprises 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), 1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane (BisENBHMTS), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox1076), and tris(2,4-di-tert-butylphenyl) phosphite (Irgafos). A mixture of 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0476] In another embodiment of the present invention, the composition of the present invention comprises 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane (BisENBHMTS), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), and tris(2,4-di-tert-butylphenyl)phosphite (Irgafos). A mixture of 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0477] In another embodiment of the present invention, the composition of the present invention comprises 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (BisENBTMDS), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), and tris(2,4-di-tert-butylphenyl) phosphite (Irgafos). A mixture of 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0478] In another embodiment of the invention, the composition comprises a mixture of 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), a polyether homopolymer of CHEpTD (pCHO-TD), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0479] In another embodiment of the invention, the composition comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), a polyether homopolymer of CHEpTD (pCHO-TD), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0480] In another embodiment of the invention, the composition comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), a polyether homopolymer of CHEpNB (pCHO-NB), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0481] In another aspect of the invention, a kit is provided for forming a substantially transparent film. The kit contains the composition of the invention. Therefore, in some embodiments, a kit is provided containing one or more monomers of general formula (I), an organorruthenium compound of general formula (II), and a compound of general formula (VI), and, if desired, one or more monomers of general formula (III) or one or more monomers of general formula (VIII) and various other additives described herein.

[0482] Therefore, in some embodiments of the present invention, the kit according to the present invention comprises one or more monomers of general formula (I), an organorruthenium compound of general formula (II), a compound of general formula (IV), a compound of general formula (VI), and a compound of general formula (VII).

[0483] In some other embodiments, the kit according to the invention comprises one or more monomers of general formula (I), an organorruthenium compound of general formula (II), a compound of general formula (IV), a compound of general formula (VI), a compound of general formula (VII), and one or more additives described in this specification.

[0484] In some embodiments, the kit comprises two or more monomers of general formula (I) that are different from each other as described above. In other embodiments, the kit of the present invention comprises at least two monomers, wherein the first monomer is used to promote the dissolution of the second monomer as described above and / or organorruthenium compounds and additives of general formula (II) or (III). In this embodiment, any monomer of general formula (I) described herein can be used. The molar ratio of the first monomer to the second monomer of general formula (I) contained in these components is not fixed and can be in the range of 1:99 to 99:1, 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 60:40 to 40:60, or 50:50, etc. In other embodiments, the kit may comprise a composition containing two or more monomers of general formula (I) that are different from each other. In addition, as described above, the first monomer of general formula (I) can be completely dissolved in the second monomer of general formula (I) to form a transparent solution at room temperature. In some embodiments, the monomer mixture can become a transparent solution at a slightly higher temperature, such as 30°C, 40°C, or 50°C.

[0485] In another aspect of this embodiment of the invention, the composition of the invention undergoes bulk polymerization when exposed to suitable radiation for a sufficiently long period of time to form a polymer film or solid object. That is, the composition of the invention is poured onto the surface or substrate to be encapsulated and exposed to suitable radiation to allow the monomers to polymerize and form a solid transparent polymer (which may be in the form of a transparent film or solid object). Typically, as described above, such polymerization can be carried out under photochemical radiation with wavelengths in the range of about 240 nm to 410 nm. It is also possible to expose the composition to suitable radiation while simultaneously heating to initiate bulk polymerization. By implementing the invention, polymer films that are substantially transparent or solid objects can be obtained on such substrates, depending on the manufacturing method employed. As used herein, "substantially transparent film" means that the film formed from the composition of the invention is optically transparent under visible light. Therefore, in some embodiments of the invention, such films have at least 90% visible light transmittance, and in other embodiments, films formed from the composition of the invention exhibit at least 95% visible light transmittance.

[0486] In some embodiments, the kit described herein comprises a composition comprising a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0487] In another embodiment of the invention, the kit described herein comprises the composition of the invention, which comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthion-9-one (CPTX), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0488] In another embodiment of the invention, the kit described in this specification comprises the composition of the invention, which includes 5-phenylethylbicyclo[2.2.1]hept-2-ene (PENB), 1-chloro-4-propoxy-9H-thioxanth-9-one (CPTX), tris(2,4-di-tert-butylphenyl) phosphite (IRGAFOS168), and 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (IRGANOX). TM A mixture of 1076) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0489] In another embodiment of the invention, the kit described in this specification comprises the composition of the invention, which includes 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthyl (HexylTD), 1-chloro-4-propoxy-9H-thioxanthion-9-one (CPTX), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT), tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS168), and 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (IRGANOX). TM A mixture of 1076) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0490] In some other embodiments of the invention, the kit described herein comprises the composition of the invention, which comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 5-phenylethylbicyclo[2.2.1]hept-2-ene (PENB), 1-chloro-4-propoxy-9H-thioxanthione (CPTX), N,N-dimethylpyridin-4-amine (DMAP), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-2).

[0491] In some other embodiments of the invention, the kit described herein comprises the composition of the invention, which comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthione (CPTX), N,N-dimethylpyridin-4-amine (DMAP), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-3).

[0492] In some other embodiments of the invention, the kit described herein comprises the composition of the invention, which comprises a mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 1-chloro-4-propoxy-9H-thioxanthione (CPTX), N,N-dimethylpyridin-4-amine (DMAP), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-4).

[0493] In another embodiment of the invention, the kit described in this specification comprises the composition of the invention, which comprises a mixture of 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), 1-chloro-4-propoxy-9H-thioxanthione (CPTX), N,N-dimethylpyridin-4-amine (DMAP), (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BTBBT) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-4).

[0494] In another embodiment of the invention, the kit described in this specification comprises the composition of the invention, which includes 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), a polyether homopolymer of CHEpTD (pCHO-TD), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), and tris(2,4-di-tert-butylphenyl) phosphite (Irgafos). A mixture of 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0495] In another embodiment of the present invention, the kit described herein comprises a mixture of 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0496] In another embodiment of the present invention, the kit described in this specification comprises 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (PETD), 4b,5a,6,9,9a,10,10a,11-octahydro-5H-5,10:6,9-dimethylbridged benzo[b]fluorene (TD-Indene), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), and tris(2,4-di-tert-butylphenyl) phosphite (Irgafos). A mixture of 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0497] In another embodiment of the present invention, the kit described in this specification comprises 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene (HexylTD), 4b,5a,6,9,9a,10,10a,11-octahydro-5H-5,10:6,9-dimethylbridged benzo[b]fluorene (TD-Indene), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), and tris(2,4-di-tert-butylphenyl) phosphite (Irgafos). A mixture of 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II))(Ru-1).

[0498] In another embodiment of the present invention, the kit described herein comprises a mixture of 4b,5a,6,9,9a,10,10a,11-octahydro-5H-5,10:6,9-dimethylbridged benzo[b]fluorene (TD-Indene), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168), and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0499] In another embodiment of the present invention, the kit described herein comprises a mixture of 4,4a,9,9a-tetrahydro-1H-1,4-methylfluorene (NB-Indene), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0500] In another embodiment of the present invention, the kit described herein comprises a mixture of 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethylbridged cyclopenta[b]naphthalene (CPD3), 1-chloro-4-propoxy-9H-thioxanthone-9-one (CPTX), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid (Irganox 1076), tris(2,4-di-tert-butylphenyl)phosphite (Irgafos 168) and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II) (Ru-1).

[0501] In another aspect of the invention, a method for forming a substantially transparent film (for manufacturing various optoelectronic devices) is further provided, the method comprising the following steps:

[0502] The step of forming a homogeneous and transparent composition comprising one or more monomers of general formula (I), an organorruthenium compound of general formula (II), a compound of general formula (VI), and, if necessary, one or more monomers of general formula (III) or (IX) and one or more additives described in this specification.

[0503] The steps of coating the composition onto a suitable substrate or pouring the composition onto a suitable substrate to form a film; and

[0504] The step of exposing the membrane to suitable radiation or heating it to a suitable temperature to initiate the polymerization of monomers.

[0505] The step of coating a desired substrate with the composition of the present invention to form a film can be carried out by any coating step described in this specification and / or known to those skilled in the art, such as spin coating. Other suitable coating methods include, but are not limited to, spraying, blade coating, meniscus coating, inkjet coating, and slot coating. The mixture can also be poured onto a substrate to form a film. Suitable substrates include any suitable substrate that can be used in electrical, electronic, or optoelectronic devices, such as semiconductor substrates, ceramic substrates, and glass substrates.

[0506] Next, the coated substrate is exposed to suitable photochemical radiation, specifically radiation within the wavelength range of 240 nm to 410 nm as described in this specification, to promote bulk polymerization. In some embodiments, the substrate is exposed to radiation and baked at a temperature of approximately 60°C to approximately 90°C for 2 to 10 minutes. In other embodiments, the substrate is exposed to radiation and baked at a temperature of approximately 60°C to approximately 90°C for 5 to 20 minutes.

[0507] The optical properties of the thus formed film are then evaluated using any method known to those skilled in the art. For example, the refractive index of the film in the visible spectrum can be determined by ellipsometry. The optical properties of the film can be determined by visual observation. The quantitative transparency % can be measured by visible spectroscopy. Generally, the film formed according to the present invention exhibits excellent optical transparency properties and, as described in this specification, can be adjusted to the desired refractive index.

[0508] Therefore, in some embodiments of the present invention, an optically transparent film obtained by bulk polymerization of the composition described in this specification is also provided. In another embodiment, an optoelectronic device comprising the transparent film of the present invention described in this specification is provided.

[0509] As described above, the compositions of the present invention can be used in any known three-dimensional (3D) printing technology and other printing technologies. Some 3D printing processes known in the art include continuous liquid interface production (CLIP), layer-by-layer (LBL), inkjet printing, and front-end polymerization methods such as front-end open-loop shifting (FROMP) technology, see Robertson et al., Nature, Vol. 557, 223-227 (2018).

[0510] In the CLIP process, a continuous series of UV images (generated by a digital light processing (DLP) imaging unit or a laser used to generate the part) are projected through an oxygen-permeable, UV-transmittable window located beneath a liquid resin bath containing the composition of the present invention, thereby continuously forming a 3D object. An oxygen-free zone established on this window maintains the liquid interface below the advancing part. Above this oxygen-free zone, the cured part is continuously extracted from the resin bath. The suction force generated by this extraction simultaneously replenishes the resin bath. In this way, parts of various sizes, ranging from resolutions below 100 μm to several centimeters, can be manufactured.

[0511] In 3D inkjet printing technology, the compositions of the present invention can be used as photopolymerizable ink compositions to form lines and vias on substrates, particularly silicon wafers. Therefore, the compositions of the present invention can be used to manufacture a variety of parts for electronic and optoelectronic applications. Non-limiting examples of such applications include the fabrication of OLED devices on various substrates, which can be produced in high yields in substantially clean environments. The compositions of the present invention can be used as organic encapsulation layers and / or filler materials in these OLED devices.

[0512] Therefore, in some other aspects of the present invention, a method for forming a three-dimensional object is further provided, the method comprising:

[0513] The step of placing a homogeneous, transparent composition in a suitable container covered with an inert atmosphere, the composition comprising one or more monomers of general formula (I), at least one organorruthenium compound of general formula (II), a compound of general formula (VI), and, if necessary, one or more monomers of general formula (III) and / or one or more monomers of general formula (VIII) and one or more additives described in this specification.

[0514] While removing the composition from the container, expose it to suitable UV radiation; and

[0515] The steps to create a three-dimensional object.

[0516] It has been discovered that by placing a composition in a suitable container covered by an inert atmosphere, it is possible to form 3D objects without any voids and exhibiting excellent optical, thermal, and mechanical properties. Such a covered inert atmosphere can be achieved by using any inert gas that produces this effect. Non-limiting examples of such inert gases include nitrogen, helium, argon, etc. In some embodiments, the inert atmosphere used is achieved by purging with dry nitrogen.

[0517] Therefore, the 3D objects formed according to the method of the present invention exhibit excellent optical, thermal, and mechanical properties. Generally, the properties of these objects can be adjusted to suit the intended end use. For example, the thermal properties of the 3D objects can be adjusted to be stable at temperatures up to 180°C or higher, depending on the type of monomer of general formula (I) used in forming such 3D objects (if used, it can be used in combination with monomers of general formula (III) or (VIII)). Similarly, the mechanical properties can also be adjusted to the desired mechanical properties by selecting suitable monomers. Generally, by appropriately adjusting the selection of monomers, parts with extremely high impact resistance can be manufactured. Most importantly, the compositions of the present invention are stable under 3D printing conditions, withstanding temperatures up to 80°C for several days in the range of 5 to 10 days without any degradation and / or premature polymerization, thus providing benefits such as long-term stability over a long shelf life. In some embodiments, the compositions of the present invention are stable at 80°C for at least 6 days. In other embodiments, the compositions of the present invention are stable at 50°C for at least 10 days. In still other embodiments, the compositions of the present invention are stable at 80°C for at least 8 days.

[0518] Therefore, in some embodiments of the present invention, a three-dimensional object comprising the composition of the present invention is also provided, which exhibits excellent optical, thermal and mechanical properties.

[0519] The compositions of this invention can also be used as protective layers in various electronic or optoelectronic devices, especially organic electronic devices sensitive to environmental conditions, particularly oxygen and moisture. As such protective layers, the compositions of this invention provide much-needed protection against environmental conditions. Typically, in applications such as organic light-emitting diode (OLED) devices, OLEDs or multilayer OLED stacks are encapsulated using the compositions of this invention after being formed on a suitable substrate.

[0520] The encapsulation of OLED stacks can be performed by any known method, including dip coating, spray coating, and spin coating, but is not limited to these. Then, the coated OLED stack is placed under suitable photochemical radiation to form a transparent polymer layer on the OLED stack via ROMP. Next, a conductive layer is deposited on the polymer layer. Typically, such a conductive layer is an inorganic material such as silicon nitride. This conductive layer can be deposited by any known method, such as chemical vapor deposition (CVD). The polymer layer formed by the composition of the present invention is stable in the CVD process and retains its properties, especially transparency and other properties described in this specification. Finally, the OLED device can be protected as needed by forming another polymer layer (as described above, by coating the composition of the present invention and placing it under suitable photochemical radiation).

[0521] The following examples illustrate in detail the preparation and use of certain compounds / monomers, polymers, and compositions of the present invention. The specific preparation methods are within the scope of the general description above and are used for illustrative purposes. These examples are for illustrative purposes only and are not intended to limit the scope of the invention. The monomer-to-catalyst ratio used in the examples and throughout the specification is a molar ratio.

[0522] Example

[0523] The following abbreviations used in this specification are used to describe some of the compounds, instruments and / or methods employed in specific embodiments of the present invention:

[0524] HexylTD: 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; PETD: 2-phenylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; CPD3: 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethylbridged cyclopentane[b]naphthalene; NB-Indene: 4,4a,9,9a-tetrahydro-1H-1,4-methylbridged fluorene; TD-In dene: 4b,5a,6,9,9a,10,10a,11-octahydro-5H-5,10:6,9-dimethylbridged benzo[b]fluorene; BisENBTMDS: 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane; BisENBHMTS: 1,5-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3,5,5-hexamethyltrisiloxane; pCH-O -NB: Polyether homopolymer of CHEpNB; pCH-O-TD: Polyether homopolymer of CHEpTD; Ru-1: [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); Ru-2: [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[ Isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); Ru-3: [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); CPTX: 1-chloro-4-propoxy-9H-thioxanth-9-one; Irganox 1076: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid; Irgafos 168: tris(2,4-di-tert-butylphenyl)phosphite; phr: parts per hundred monomers; TGA: thermogravimetric analysis.

[0525] The various monomers used in this specification are commercially available or can be readily prepared according to the steps described in co-pending U.S. Patent Application No. 9,944,818.

[0526] The following examples demonstrate that the compositions of the present invention are very stable for several days at room temperature or 60°C, and as described below, can be readily bulk polymerized by exposure to UV light to form the desired object.

[0527] Examples 1-2

[0528] Storage stability at 60°C

[0529] CPTX (0.1 phr) was dissolved in HexylTD (10,000 mol parts) in two separate amber glass vials by sonication at 30°C for 20 minutes, thus forming a clear solution. The solution was rinsed with nitrogen for 8 hours. Ru-1 catalyst (0.5 mol parts in Example 1 and 0.25 mol parts in Example 2) was added to the rinsing solution in a glove box and sonicated for 30 minutes to completely dissolve the catalyst. The compositions of Examples 1 and 2 were stored at 60°C for 14 days. UV DSC (400 nm, 250 mW / cm²) was used to analyze the results. 2 The heat of reaction was monitored over 14 days. The viscosity remained constant during this period. The results are shown in Table 1.

[0530] Table 1

[0531]

[0532] As can be seen from the data in Table 1, the compositions of Examples 1 and 2 remained stable after being stored at 60°C for 14 days, and maintained the same activity after being stored at 60°C for 14 days, as confirmed by the fact that the heat of reaction of the fresh sample at 0 days was the same as that of the sample after 14 days of storage.

[0533] Examples 3-4

[0534] Shelf life stability in the presence of antioxidants

[0535] In two separate amber glass vials, CPTX (0.1 phr in Example 3, 0.4 phr in Example 4), Irganox 1076 (1 phr), and Irgafos 168 (0.25 phr) were dissolved in HexylTD (10,000 moles) to form clear solutions by sonication at 30°C for 20 minutes. The solutions were then rinsed with nitrogen for 8 hours. Ru-1 catalyst (1 mole) was added separately to each rinse solution in a glove box, and sonication was performed for 30 minutes to completely dissolve the catalyst. The compositions were stored at 60°C for 32 days. UV DSC (400 nm, 250 mW / cm²) was used to analyze the solutions. 2 The heat of reaction was monitored over 32 days, and remained substantially constant during this period, indicating that the composition retained its activity, as shown in Table 2. The viscosity of the sample also remained constant during this period.

[0536] Table 2

[0537]

[0538] Example 5

[0539] Storage stability at 23°C

[0540] CPTX (0.1 phr) was dissolved in HexylTD (10,000 moles) in a brown glass bottle by sonication at 30°C for 20 minutes, thus forming a clear solution. The solution was rinsed with nitrogen for 8 hours. Ru-1 catalyst (1 mole) was added to the rinsing solution in a glove box, and sonication was performed for 30 minutes to completely dissolve the catalyst. The composition was stored at 23°C for 270 days. The composition was analyzed using UV DSC (at 400 nm, 250 mW / cm²). 2 The heat of reaction was monitored over 270 days, during which it remained substantially constant, as shown in Table 3. The viscosity of the composition also remained substantially constant during this period.

[0541] Table 3

[0542]

[0543] Examples 6 and 7

[0544] In Examples 6 and 7, as shown in Table 4, different organorruthenium compounds of general formula (II) were used as latent catalysts; otherwise, the steps of Example 5 were substantially repeated. The compositions formed in Examples 6 and 7 were stored at 23°C for 30 days. UV DSC (at 400 nm, 250 mW / cm²) was used to measure the results. 2 The heat of reaction was monitored over 30 days. As shown in Table 4, the viscosity and reactivity remained essentially constant throughout the period.

[0545] Table 4

[0546]

[0547] Example 8

[0548] Shelf life stability at 70°C in the presence of UV blockers

[0549] In a brown glass bottle, CPTX (0.2 phr) and a UV blocker (BTBBT, 0.5 phr) were dissolved in HexylTD (10,000 moles) by sonication at 30°C for 20 minutes, thus forming a clear solution. The solution was rinsed with nitrogen for 8 hours. Ru-1 catalyst (1 mole) was added to the rinsing solution in a glove box, and sonication was performed for 30 minutes to completely dissolve the catalyst. The composition was stored at 70°C for 21 days. UV DSC (at 400 nm, 950 mW / cm²) was used to analyze the solution. 2 The heat of reaction was monitored over 21 days. During this period, the viscosity of the composition remained essentially constant. The results are shown in Table 5.

[0550] Table 5

[0551]

[0552] Examples 9-19

[0553] Bulk polymerization of PETD and HexylTD with monomer crosslinking agents

[0554] In separate brown glass vials, CPTX (0.1 phr), Irganox 1076 (1 phr), and Irgafos 168 (0.25 phr) were dissolved in the monomer mixture (10,000 moles) shown in Table 6 by ultrasonic treatment at 30°C for 20 minutes, thereby forming clear solutions in Examples 9–16 and 19. The monomers used in Examples 17 and 18, CPD3 and TD-Indene, were solids at room temperature; therefore, sample preparation and curing were performed at 70°C in these two examples. The compositions of Examples 17 and 18 were purged with nitrogen for 8 hours. Ru-1 catalyst (1 mole) was added to each purging composition in a glove box, and ultrasonic treatment was performed for 30 minutes to completely dissolve the catalyst. Bulk polymerization was carried out under UV light (LED, 1 W / cm²). 2 The assay was performed at 8 seconds, 395 nm. Table 6 shows the monomers used in Examples 9-14, the molar ratios used, and the measured properties of the obtained polymers.

[0555] Table 6

[0556]

[0557] Examples 20-21

[0558] Bulk polymerization of PETD and HexylTD with polymer crosslinking agents

[0559] In a brown glass bottle, CPTX (0.1 phr), Irganox 1076 (1 phr), Irgafos 168 (0.25 phr), and pCH-O-TD (a polyether homopolymer of CHEpTD, 10 phr) were dissolved in monomers (10,000 moles) by ultrasonic treatment at 30°C for 60 minutes, thus forming a clear solution. The solution was rinsed with nitrogen for 8 hours. Ru-1 catalyst (1 mole) was added to the rinsing solution in a glove box, and ultrasonic treatment was performed for 30 minutes to completely dissolve the catalyst. Bulk polymerization was carried out under UV light (LED, 1 W / cm²). 2 The assay was performed at 8 seconds (395 nm). Table 7 shows the monomers used and the properties of the obtained polymers. The data in Table 7 show that using polymer crosslinking agents such as pCHO-TD increases the modulus of the resulting polymer by 15–20%.

[0560] Table 7

[0561]

[0562] Example 22

[0563] In Example 22, pCH-O-NB was used as the polymer crosslinking agent, and the steps of Example 20 were otherwise substantially repeated. As shown in Table 8, the ETB of the obtained polymer increased slightly, but the modulus decreased by about 10%.

[0564] Table 8

[0565]

[0566] Comparative Example 1

[0567] In Comparative Example 1, an organorruthenium compound Ru-y known in the art was used as a catalyst (e.g., refer to U.S. Patent Application No. 2020-0002466A1), and the steps of Example 5 were otherwise substantially repeated. The viscosity remained substantially unchanged, but the reactivity began to decrease after storage at 23°C for 21 days.

[0568]

[0569] 1,3-Bis(2,4,6-trimethylphenylimidazolidine-2-ylylene)-(2-oxobenzyme)-2-(((2,6-

[0570] Diisopropylphenyl-imino)methyl)phenoxy)ruthenium (Ru-y);

[0571] While the invention has been described through some embodiments, it should not be construed as limiting it, but rather understood that the invention encompasses the general scope described above. Various modifications may be made without departing from the spirit and scope of the invention.

Claims

1. A composition comprising: a) One or more monomers of general formula (I): （I） in: m is an integer of 0, 1, or 2; R1, R2, R3, and R4 may be the same or different, and each is independently selected from hydrogen, halogen, methyl, ethyl, straight-chain or branched (C3-C4). 16 )alkyl, perfluorinated (C1-C 12 )alkyl, hydroxyl (C1-C 16 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 Bicycloalkyl, (C7-C 14 Tricycloalkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C6) alkyl, perfluorinated (C6-C6) 10 aryl, perfluorinated (C6-C) 10 The group consisting of aryl (C1-C6)alkyl, tri(C1-C6)alkoxysilyl and groups of general formula (A): -Z-Aryl (A) in: Z is a bond or a group selected from the following group: (CR5R6) a O (CR5R6) a (CR5R6) a O, (CR5R6) a -O- (CR5R6) b (CR5R6) a -O-(SiR5R6) b (CR5R6) a -(CO)O-(CR5R6) b (CR5R6) a -O(CO)-(CR5R6) b (CR5R6) a -(CO)-(CR5R6) b , where a and b can be the same or different integers, and each is independently 1 to 12; R5 and R6 may be the same or different, and each is independently selected from the group consisting of hydrogen, methyl, ethyl, straight-chain or branched (C3-C6) alkyl, hydroxyl, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, straight-chain or branched hydroxy (C3-C6) alkyl, phenyl, and phenoxy; and The aryl group is phenyl or phenyl substituted with one or more groups selected from the group consisting of: methyl, ethyl, straight-chain or branched (C3-C6) alkyl, hydroxy, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, straight-chain or branched hydroxy (C3-C6) alkyl, phenyl, and phenoxy; or One of R1 or R2 and one of R3 or R4 together with the carbon atom they are attached to form a double bond between the two carbon atoms; b) Organorruthenium compounds of general formula (II): (II) in: c and d are integers from 0 to 5; Z represents oxygen or sulfur; R7 is selected from free hydrogen, (C1-C) 20 )alkyl, (C2-C 20 )alkenyl, (C2-C 20 ) ynyl group and (C6-C 10 The group consisting of aryl groups; and R8, R9, R 10 and R 11 They may be the same or different, and each is independently chosen from hydrogen, halogens, (C1-C) 16 )alkyl, (C1-C 16 )alkoxy, (C1-C 16 Perfluoroalkyl, (C3-C7)cycloalkyl, (C2-C7)cycloalkyl 16 )alkenyl, (C6-C 14 )Aryl, (C6-C 14 Perfluoroaryl, (C3-C 12 Heterocyclic groups, -OR 16 -NO2, -COOH, -COOR 16 -CONR 16 R 17 -SO2NR 16 R 17 -SO2R 16 -CHO and -COR 16 The group consisting of R 16 and R 17 They may be the same or different, and each is independently selected from (C1-C6) alkyl, (C1-C6) perfluoroalkyl, (C6-C6) alkyl, and perfluoroalkyl groups. 14 ) aryl and (C6-C 14 The group consisting of perfluoroaryl groups; or of which, R8, R9, R 10 and R 11 Two or more carbon atoms in the ring together form substituted or unsubstituted fused (C4-C8) carbon rings or substituted or unsubstituted fused aromatic rings; Each R 12 R 13 and R 14 They can be the same or different, and each can be independently chosen from hydrogen, halogens, (C1-C) 16 )alkyl, (C1-C 16 )alkoxy, (C1-C 16 Perfluoroalkyl, (C3-C7)cycloalkyl, (C2-C7)cycloalkyl 16 )alkenyl, (C6-C 14 )Aryl, (C6-C 14 Perfluoroaryl, (C3-C 12 Heterocyclic groups, -OR 16 -NO2, -COOH, -COOR 16 -CONR 16 R 17 -SO2NR 16 R 17 -SO2R 16 -CHO and -COR 16 The group consisting of R 16 and R 17 They may be the same or different, and each is independently selected from (C1-C6) alkyl, (C1-C6) perfluoroalkyl, (C6-C6) alkyl, and perfluoroalkyl groups. 14 )Aryl, (C6-C 14 The group consisting of perfluoroaryl groups; R 15 Choose freely (C1-C) 16 )alkyl, (C1-C 16 Perfluoroalkyl, (C3-C 16 )cycloalkyl, (C6-C 14 )Aryl, (C6-C 14 Perfluoroaryl and (C3-C) 12 The group consisting of heterocyclic groups; and Ar1 and Ar2 may be the same or different, and each is independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl groups, wherein each of the substituents is independently selected from the group consisting of methyl, ethyl, and straight-chain or branched (C3-C6) alkyl groups; and c) Photoactive compounds.

2. The composition according to claim 1, further comprising one or more monomers of general formula (VIII): (VIII) in: p is an integer from 0 to 2; R 24 and R 25 They may be the same or different, and each is independently selected from the group consisting of hydrogen, methyl, ethyl, straight-chain or branched (C3-C6) alkyl, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, acetoxy, (C2-C6) acyl, phenyl, and phenoxy; or R 24 With R 25 Together with the carbon atoms they are attached to, they form (C5-C7) carbon rings that can contain more than one double bond; and R 26 Hydrogen, halogen, methyl, ethyl, straight-chain or branched (C3-C) 16 )alkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C6) alkyl, hydroxyl, methoxy, ethoxy, straight-chain or branched (C3-C6) 16 )alkoxy, (C6-C 10 ) aryloxy group, (C6-C 10 aryl (C1-C6)alkoxy, -O(CO)R 27 OR -O(CO)OR 27 , where R 27 Methyl, ethyl, straight-chain or branched (C3-C) 16 )alkyl, (C6-C 10 ) aryl or (C6-C 10 )Aryl (C1-C6)alkyl.

3. The composition according to claim 1, wherein, The monomers of the general formula (I) are selected from the group consisting of: 5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene; 5-(3-Phenylacetyl)bicyclo[2.2.1]hept-2-ene; 5-Phenylacetylbicyclo[2.2.1]hept-2-ene; 5-(benzyloxy)bicyclo[2.2.1]hept-2-ene; 5-(2-([1,1'-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; 5-(2-([1,1'-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene; 5-Butylbicyclo[2.2.1]hept-2-ene; 5-Hexylbicyclo[2.2.1]hept-2-ene; 5-Octylbicyclo[2.2.1]hept-2-ene; 5-Decylbicyclo[2.2.1]hept-2-ene; 5-Ethylenebicyclo[2.2.1]hept-2-ene; 2-Ethylene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 5-Norbornenylmethyleugenol acetate; 5-Norbornel-methyleugenol; NB(MeOH)2; PhAcNB; Tetracyclododecene; 2-Phenylacetyl-Tetracyclododecene; 2-Benzyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Phenylacetyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Butyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Octyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Ceyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Cyclohexyl-tetracyclododecene; 2-Cyclohexylmethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Cyclohexylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; (1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridgednaphthalene-2-yl)methyl acetate; and Tetracyclic dodecadiene.

4. The composition according to claim 1, wherein, The organorruthenium compounds of general formula (II) are selected from the group consisting of: [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinediyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzyl-κC]ruthenium(II); [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzyl-κC]ruthenium(II); and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II).

5. The composition according to claim 2, wherein, The monomers of the general formula (VIII) are selected from the group consisting of: Dicyclopentadiene; 4,4a,4b,5,8,8a,9,9a-octahydro-1H-1,4:5,8-dimethylfluorene; 1-Methoxy-dicyclopentadiene; 1-(n-Butoxy)-Dicyclopentadiene; 1-(n-Octyloxy)-Dicyclopentadiene; 3a,4,7,7a-tetrahydro-1H-4,7-methyl-indene-1-yl acetate; 3a,4,7,7a-tetrahydro-1H-4,7-methyl-indene-1-ylbenzoate; 3a,4,7,7a-tetrahydro-1H-4,7-methyl-indene-1-yl-2-phenylacetic acid ester; 3a,4,7,7a-tetrahydro-1H-4,7-methyl-inden-1-yl-3-phenylpropionate; 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethylbridged cyclopentane[b]naphthalene; 4,4a,9,9a-tetrahydro-1H-1,4-methylfluorone; and 4b,5a,6,9,9a,10,10a,11-octahydro-5H-5,10:6,9-dimethylbridged benzo[b]fluorene.

6. The composition according to claim 1, wherein, The photoactive compound is a compound of general formula (VI): (WE) in: Y is a halogen; and R 30 and R 31 They may be the same or different, and each is independently selected from hydrogen, methyl, ethyl, straight-chain or branched (C3-C4). 12 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 Bicycloalkyl, (C7-C 14 Tricycloalkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C3)alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkoxy, (C6-C 12 ) Bicycloalkoxy, (C7-C 14 Tricycloalkoxy, (C6-C 10 ) aryloxy (C1-C3) alkyl and (C6-C 10 A group composed of aryl groups.

7. The composition according to claim 6, wherein, Y is either chlorine or bromine; and R 30 and R 31 They may be the same or different, and each is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, cyclohexyl, methoxy, ethoxy, n-propoxy, and phenoxy.

8. The composition according to claim 6, wherein, The compounds of general formula (VI) are selected from the group consisting of: 1-Chloro-4-methoxy-9H-thioxanthro-9-one; 1-Chloro-4-ethoxy-9H-thioxanthone; 1-Chloro-4-propoxy-9H-thioxanth-9-one; 1-Chloro-2-propoxy-9H-thioxanth-9-one; 1-Chloro-2-ethoxy-9H-thioxanthone; 1-Chloro-2-methoxy-9H-thioxanth-9-one; 1-Chloro-4-methyl-9H-thioxanth-9-one; 1-Chloro-4-ethyl-9H-thioxanth-9-one; 1-Bromo-4-propoxy-9H-thioxanthone; and 1-Chloro-4-phenoxy-9H-thioxanth-9-one.

9. The composition according to claim 1, further comprising one or more additives selected from the group consisting of organic bases, UV blockers, viscosity modifiers, halide scavengers, antioxidants, synergists, and mixtures thereof.

10. The composition according to claim 1, wherein the composition is selected from the group consisting of: A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthrol-9-one and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthion-9-one, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthrol-9-one, tris(2,4-di-tert-butylphenyl) phosphite, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthone, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene, tris(2,4-di-tert-butylphenyl) phosphite, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinediyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 5-phenylethylbicyclo[2.2.1]hept-2-ene, 1-chloro-4-propoxy-9H-thioxanthone, N,N-dimethylpyridin-4-amine, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthione, N,N-dimethylpyridine-4-amine, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthione, N,N-dimethylpyridine-4-amine, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthone, N,N-dimethylpyridin-4-amine, a mixture of (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); and A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthione, N,N-dimethylpyridine-4-amine, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II).

11. A kit for forming a substantially transparent film, comprising: a) One or more monomers of general formula (I): （I） in: m is an integer of 0, 1, or 2; R1, R2, R3, and R4 may be the same or different, and each is independently chosen from hydrogen, halogen, methyl, ethyl, straight-chain or branched (C3-C4). 16 )alkyl, perfluorinated (C1-C 12 )alkyl, hydroxyl (C1-C 16 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 Bicycloalkyl, (C7-C 14 Tricycloalkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C6) alkyl, perfluorinated (C6-C6) 10 aryl, perfluorinated (C6-C) 10 The group consisting of aryl (C1-C3)alkyl, tri(C1-C6)alkoxysilyl and groups of general formula (A): -Z-Aryl (A) in: Z is a bond or a group selected from the following group: (CR5R6) a O (CR5R6) a (CR5R6) a O, (CR5R6) a -O- (CR5R6) b (CR5R6) a -O-(SiR5R6) b (CR5R6) a -(CO)O-(CR5R6) b (CR5R6) a -O(CO)-(CR5R6) b (CR5R6) a -(CO)-(CR5R6) b , where a and b can be the same or different integers, and each is independently 1 to 12; R5 and R6 may be the same or different, and each is independently selected from the group consisting of hydrogen, methyl, ethyl, straight-chain or branched (C3-C6) alkyl, hydroxyl, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, straight-chain or branched hydroxy (C3-C6) alkyl, phenyl, and phenoxy; and The aryl group is phenyl or phenyl substituted with one or more groups selected from the group consisting of: methyl, ethyl, straight-chain or branched (C3-C6) alkyl, hydroxy, methoxy, ethoxy, straight-chain or branched (C3-C6) alkoxy, acetoxy, (C2-C6) acyl, hydroxymethyl, hydroxyethyl, straight-chain or branched hydroxy (C3-C6) alkyl, phenyl, and phenoxy; or One of R1 or R2 and one of R3 or R4 together with the carbon atom they are attached to form a double bond between the two carbon atoms; b) Organorruthenium compounds of general formula (II): (II) in: c and d are integers from 0 to 5; Z represents oxygen or sulfur; R7 is selected from free hydrogen, (C1-C) 20 )alkyl, (C2-C 20 )alkenyl, (C2-C 20 ) ynyl group and (C6-C 10 The group consisting of aryl groups; and R8, R9, R 10 and R 11 They may be the same or different, and each is independently chosen from hydrogen, halogens, (C1-C) 16 )alkyl, (C1-C 16 )alkoxy, (C1-C 16 Perfluoroalkyl, (C3-C7)cycloalkyl, (C2-C7)cycloalkyl 16 )alkenyl, (C6-C 14 )Aryl, (C6-C 14 Perfluoroaryl, (C3-C 12 Heterocyclic groups, -OR 16 -NO2, -COOH, -COOR 16 -CONR 16 R 17 -SO2NR 16 R 17 -SO2R 16 -CHO and -COR 16 The group consisting of R 16 and R 17 They may be the same or different, and each is independently selected from (C1-C6) alkyl, (C1-C6) perfluoroalkyl, (C6-C6) alkyl, and perfluoroalkyl groups. 14 ) aryl and (C6-C 14 The group consisting of perfluoroaryl groups; or of which, R8, R9, R 10 and R 11 Two or more carbon atoms in the ring together form substituted or unsubstituted fused (C4-C8) carbon rings or substituted or unsubstituted fused aromatic rings; Each R 12 R 13 and R 14 They can be the same or different, and each can be independently chosen from hydrogen, halogens, (C1-C) 16 )alkyl, (C1-C 16 )alkoxy, (C1-C 16 Perfluoroalkyl, (C3-C7)cycloalkyl, (C2-C7)cycloalkyl 16 )alkenyl, (C6-C 14 )Aryl, (C6-C 14 Perfluoroaryl, (C3-C 12 Heterocyclic groups, -OR 16 -NO2, -COOH, -COOR 16 -CONR 16 R 17 -SO2NR 16 R 17 -SO2R 16 -CHO and -COR 16 The group consisting of R 16 and R 17 They may be the same or different, and each is independently selected from (C1-C6) alkyl, (C1-C6) perfluoroalkyl, (C6-C6) alkyl, and perfluoroalkyl groups. 14 )Aryl, (C6-C 14 The group consisting of perfluoroaryl groups; R 15 Choose freely (C1-C) 16 )alkyl, (C1-C 16 Perfluoroalkyl, (C3-C 16 )cycloalkyl, (C6-C 14 )Aryl, (C6-C 14 Perfluoroaryl and (C3-C) 12 The group consisting of heterocyclic groups; and Ar1 and Ar2 may be the same or different, and each is independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl groups, wherein each of the substituents is independently selected from the group consisting of methyl, ethyl, and straight-chain or branched (C3-C6) alkyl groups; and c) Photoactive compounds.

12. The set according to claim 11, wherein, The monomers of the general formula (I) are selected from the group consisting of: 5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene; 5-Phenylacetylbicyclo[2.2.1]hept-2-ene; 5-Octylbicyclo[2.2.1]hept-2-ene; 5-Decylbicyclo[2.2.1]hept-2-ene; 2-Phenylacetyl-Tetracyclododecene; 2-Phenylacetyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Ceyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene; 2-Cyclohexyl-tetracyclododecene; and 2-Cyclohexylethyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene.

13. The set according to claim 11, wherein, The organorruthenium compounds of general formula (II) are selected from the group consisting of: [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinediyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzyl-κC]ruthenium(II); [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzyl-κC]ruthenium(II); and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II).

14. The set according to claim 11, wherein, The photoactive compound is a compound of general formula (VI): (WE) in: Y is a halogen; and R 30 and R 31 They may be the same or different, and each is independently selected from hydrogen, methyl, ethyl, straight-chain or branched (C3-C4). 12 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 Bicycloalkyl, (C7-C 14 Tricycloalkyl, (C6-C 10 )Aryl, (C6-C 10 aryl (C1-C3)alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkoxy, (C6-C 12 ) Bicycloalkoxy, (C7-C 14 Tricycloalkoxy, (C6-C 10 ) aryloxy (C1-C3) alkyl and (C6-C 10 A group composed of aryl groups.

15. The set according to claim 11, wherein, The photoactive compound is selected from the group consisting of: 1-Chloro-4-methoxy-9H-thioxanthro-9-one; 1-Chloro-4-ethoxy-9H-thioxanthone; 1-Chloro-4-propoxy-9H-thioxanth-9-one; 1-Chloro-2-propoxy-9H-thioxanth-9-one; 1-Chloro-2-ethoxy-9H-thioxanthone; 1-Chloro-2-methoxy-9H-thioxanth-9-one; 1-Chloro-4-methyl-9H-thioxanth-9-one; 1-Chloro-4-ethyl-9H-thioxanth-9-one; 1-Bromo-4-propoxy-9H-thioxanthone; and 1-Chloro-4-phenoxy-9H-thioxanth-9-one.

16. The kit according to claim 11, further comprising one or more additives selected from the group consisting of organic bases, UV blockers, viscosity modifiers, halide scavengers, antioxidants, synergists, and mixtures thereof.

17. The kit of claim 11, comprising a mixture selected from the group consisting of: A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthrol-9-one and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthion-9-one, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthrol-9-one, tris(2,4-di-tert-butylphenyl) phosphite, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthone, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene, tris(2,4-di-tert-butylphenyl) phosphite, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-octadecyl phenylpropionic acid and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinediyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 5-phenylethylbicyclo[2.2.1]hept-2-ene, 1-chloro-4-propoxy-9H-thioxanthone, N,N-dimethylpyridin-4-amine, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthione, N,N-dimethylpyridine-4-amine, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[cyclohexylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthione, N,N-dimethylpyridine-4-amine, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); 2-Hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthone, N,N-dimethylpyridin-4-amine, a mixture of (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[methylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II); and A mixture of 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 1-chloro-4-propoxy-9H-thioxanthione, N,N-dimethylpyridine-4-amine, (2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]{2-[(E)-({2-[isopropylthio-κS]phenyl}imino-κN)methyl]phenoxy-κO}[2-(oxy-κO)benzylidene-κC]ruthenium(II).

18. A membrane comprising the composition of claim 1.

19. A membrane formed from the sleeve as described in claim 11.

20. A method for forming a 3D printed object, comprising the following steps: Place the composition of claim 1 into a container covered by an inert atmosphere; While removing the composition from the container, expose it to suitable UV radiation; and To form a three-dimensional object.

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