Composition based on allyl monomers and on peroxide, for the manufacture of organic glasses

Abstract

The present invention relates to the use of one or more peresters of formula (I) for the polymerisation of at least one allyl monomer and / or of at least one allyl copolymer. The invention also relates to a polymerisable composition comprising at least one allyl monomer and / or at least one allyl copolymer, and at least said perester. The invention also relates to the use of the polymerisable composition as defined above for the manufacture of an organic glass, preferably an ophthalmic lens. The present invention also relates to an organic glass obtained from the polymerisation of the polymerisable composition as defined above.

Description

[0001] DESCRIPTION

[0002] TITLE: Composition based on allylic monomers and peroxide for the manufacture of organic glasses

[0003] The present invention relates to the use of one or more peresters, as defined below, for the polymerization of at least one allylic monomer and / or at least one allylic copolymer.

[0004] The invention also relates to a polymerizable composition comprising at least one allylic monomer and / or at least one allylic copolymer, and at least said perester.

[0005] The invention also relates to the use of the polymerizable composition, as defined above, for the manufacture of an organic glass, preferably an ophthalmic lens.

[0006] The present invention also relates to an organic glass obtained from the polymerization of the polymerizable composition as defined above.

[0007] Organic glasses, such as windows for optical instruments or detectors or even ophthalmic lenses, can be prepared from the radical polymerization of one or more allylic monomers and / or allylic copolymers in the presence of one or more polymerization initiators, in particular organic peroxides.

[0008] Such radical polymerization can in particular be carried out by casting a polymerizable composition based on allylic monomers and / or allylic copolymers and organic peroxides, into a mold, in particular a mineral glass mold, having a geometric shape adapted to the desired application.

[0009] The mold is generally an assembly that may consist of two glass parts, particularly mineral glass, which are spaced apart from each other by a recess and held together by the presence of a watertight seal, made of elastomer and / or thermoplastic material, positioned at the periphery. The polymerizable composition is thus poured into the cavity formed between the two glass parts of the mold to undergo a suitable thermal cycle during which the temperature can be increased more or less gradually, possibly respecting one or more temperature stages.

[0010] During such a thermal cycle, the composition polymerizes and hardens in the mold to lead, after demolding, to an organic glass that can subsequently undergo different types of treatment depending on the desired applications. The mold is usually reused in many thermal cycles. Organic peroxides, regularly used as polymerization initiators, are generally very unstable species when heated. Indeed, in the event of an uncontrolled rise in temperature, certain organic peroxides can undergo self-accelerated exothermic decomposition with a risk of catching fire and / or decomposing violently. Such behavior is therefore difficult to reconcile with the rules in force regarding the transport and storage of hazardous materials in places intended for the production of organic glasses.

[0011] It is therefore particularly advantageous to formulate such organic peroxides in liquid form in solvents, also called phlegmatizers, i.e. in a diluted state, to reduce their thermal instability and ensure that they can be stored and transported in safer conditions.

[0012] For this purpose, the use of diisopropyl peroxydicarbonate, generally called IPP, solubilized in an allylic monomer such as diethylene glycol bis (allyl carbonate), at a content of 27% by weight relative to the total weight of the composition, for the radical polymerization of allylic monomer(s) and / or allylic copolymer(s), makes it possible to produce organic glasses having good optical properties, in particular in terms of transparency and low coloration, aesthetic and mechanical properties. In other words, the organic glasses obtained with such an organic peroxide composition have the advantage of being transparent, colorless and of having good mechanical properties, for example in terms of hardness and wear. By way of illustration, such a composition may be marketed under the trade name Luperox ® IPP27 by the company Arkema or under the trade name Perkadox® IPP-NS27 by the company Nouryon.

[0013] However, such a composition based on diisopropyl peroxydicarbonate presents too high risks of uncontrolled decomposition during storage and transport in the event of an uncontrolled rise in temperature.

[0014] In fact, diisopropyl peroxydicarbonate is a so-called cold peroxide, that is to say that it has, alone or in a mixture, with other peroxides and / or reactive or non-reactive phlegmatizers, a maximum transport temperature, also called control temperature, set at - 20°C in accordance with the recommendations for the transport of dangerous goods UN, 19 eme 2015 edition, in section 2.5.3.2.4 relating to organic peroxides. More generally, for the purposes of the present invention, cold peroxide means any peroxide-based composition having a maximum transport temperature of 20°C.

[0015] Thus, despite the dilution of diisopropyl peroxydicarbonate in the allylic monomer, it is necessary to constantly maintain very low temperatures, particularly temperatures below 20°C, during storage and circulation, particularly during maritime transport, of products such as Luperox ® IPP27 or Perkadox® IPP-NS27, in order to minimize the risks of decomposition, which greatly complicates their use.

[0016] In addition, it is necessary to control the temperature during the transport and storage of these products in order to reduce the risks of the start of polymerization of the allylic monomer which has the function of phlegmatizing the organic peroxide.

[0017] Furthermore, diisopropyl peroxydicarbonate also has the disadvantage of being too reactive to be stored and transported at concentrations higher than 30% by weight in the allylic monomer.

[0018] In order to overcome these numerous difficulties, it has been considered to replace diisopropyl peroxydicarbonate with organic peroxides, such as aromatic peroxides of the diacyl type or peresters, which can be stored and transported at room temperature.

[0019] However, such organic peroxides have the drawback of causing high polymerization temperatures, which can be higher than 120°C or even higher than 125°C, instead of being around 80°C with diisopropyl peroxydicarbonate. Such polymerization temperatures thus tend to damage more or less quickly the surface geometry of the glass molds as well as the elastomeric and / or thermoplastic seals, preventing, on the one hand, their reuse in numerous subsequent thermal cycles and, on the other hand, causing mechanical and optical defects in the organic glasses formed.

[0020] In particular, a significant increase in the breakage rate during demolding of organic glasses formed with such organic peroxides is observed.

[0021] Furthermore, such high polymerization temperatures increase the risk of yellowing of organic lenses. Indeed, this type of organic peroxide, particularly benzoyl peroxide, can cause significant yellowing of organic lenses, which requires the use of coloring agents capable of compensating, if possible, for this yellowing. Their presence is, however, not always effective most of the time or acceptable when wearing corrective glasses.

[0022] Finally, thermal cycles, during which polymerization temperatures are at least 40°C higher than the polymerization temperature generally applied with diisopropyl peroxydicarbonate, generate significant excess energy consumption resulting in associated additional costs in the annual production of organic glasses.

[0023] In other words, the low reactivity of these organic peroxides, which can be stored and transported at room temperature, proves to be incompatible with the molding materials, thus leading to deterioration of the molds used and of the elastomeric and / or thermoplastic seals, promotes the formation of mechanical and optical defects in the organic glasses obtained, in particular by accentuating their yellowing, and increases production costs.

[0024] As a result, such peroxides, although allowing work in safer conditions, most often lead to organic glasses with significantly lower mechanical and optical properties than those of organic glasses obtained with cold peroxides.

[0025] In view of the above, one of the objectives of the present invention is to overcome the previously mentioned drawbacks, that is to say to substitute the organic peroxides, commonly used during the polymerization of allylic monomers and / or allylic copolymers, by other polymerization initiators which can be stored and transported, alone or in mixtures, at room temperature, to obtain organic glasses having good optical, aesthetic and mechanical properties, and this without degrading the industrial equipment used during their manufacture.

[0026] In other words, there is a real need to implement other polymerization initiators that can be stored and transported, alone or in a mixture, at room temperature, i.e. under safe conditions, while allowing the manufacture of organic glasses with good properties in terms of transparency, color, in particular yellowing, hardness and wear.

[0027] In particular, one of the aims of the present invention is to improve the safety conditions for obtaining organic glasses without distorting their optical, aesthetic and mechanical properties and without degrading the glass molds, in particular their geometric parameters, for example their surface geometries, and the elastomeric and / or thermoplastic seals necessary for their manufacture.

[0028] The present invention therefore relates in particular to the use of one or more peresters corresponding to the following formula (I):

[0029] [Chem 1]

[0030] Formula (I) in which:

[0031] • Ri represents a linear or branched, non-aromatic, C1-C10 alkyl group, preferably Ri represents a linear, C1-C3, more preferably C1-C2 alkyl group, even more preferably is a CH3 group

[0032] • R2 and R3 represent a hydrogen atom,

[0033] • R4 represents a hydrogen atom or a linear or branched C1-C16 alkyl group, preferably R4 represents an alkyl group, linear C1-C11, more preferably C3-C11, even more preferably C5-C10, even more preferably C1-C6, and even more preferably C5; for the polymerization of one or more allylic monomers and / or allylic copolymers.

[0034] The perester(s) according to the invention is / are thus one or more non-aromatic tert-alkyl peroxyester(s).

[0035] The peresters according to the invention have the advantage of being able to be stored and transported, alone or in mixtures, with other peroxides and / or reactive or non-reactive phlegmatizers, at room temperature, that is to say in better safety conditions.

[0036] By "ambient temperature" is meant a temperature ranging from 21°C to 30°C. Thus, the peresters according to the invention have the advantage of having, alone or in mixtures, with other peroxides and / or reactive or non-reactive phlegmatizers, a maximum transport temperature, also called control temperature, strictly higher than 20°C in accordance with the recommendations for the transport of dangerous goods UN, 19 eme 2015 edition, in section 2.5.3.2.4 relating to organic peroxides.

[0037] The safety conditions for transport and storage are therefore improved compared to the use of cold peroxides, as defined above, in particular with respect to organic peroxides belonging to the family of dialkyl peroxydicarbonates, in particular diisopropyl peroxydicarbonate solubilized in diethylene glycol bis (allyl carbonate), and marketed under the name Luperox ® IPP27 or the name Perkadox ® IPP-NS27.

[0038] The peroxyesters, in accordance with the invention, are in fact more easily handled, which has the advantage of significantly reducing the costs associated with their transport and storage, and can be distributed more widely throughout the world, including in the least accessible places, under safe conditions.

[0039] Peresters also have the advantage of being able to be used alone, i.e. in an undiluted state, which makes it possible to avoid, on the one hand, the use of a non-polymerizable solvent, such as oils, imposed for safety reasons and likely to have a negative impact on the optical and mechanical qualities of the organic glasses obtained and, on the other hand, the use of a polymerizable solvent, such as an allylic monomer, likely to increase the risks during transport or storage of the start of polymerization not regulated in temperature.

[0040] More generally, the peresters according to the invention make it possible to avoid the need to install any type of storage dedicated to the polymerizable or non-polymerizable solvent on peroxide production sites (or a device intended to store a solvent), which leads to significant space savings and a reduction in maintenance costs.

[0041] In other words, the peroxides according to the invention make it possible to overcome all types of problems linked to the use of polymerizable or non-polymerizable solvents.

[0042] More particularly, the peresters according to the invention make it possible to dispense with the usual phlegmatizers of peroxides such as hydrocarbons, for example isododecane, mineral oils, esters such as liquid phthalates, ethylbenzene, allylic monomers. Thus the peresters can be packaged in a greater variety of containers or devices than conventional peroxides which are thermally unstable and liable to decompose during an uncontrolled increase in temperature.

[0043] Furthermore, the peresters according to the invention have sufficient reactivity to induce polymerization temperatures significantly lower than those of organic peroxides, storable and transportable at room temperature, previously used, without harming the industrial equipment used during molding and without degrading the optical, aesthetic and mechanical properties of organic glasses.

[0044] “Polymerization temperature” means the maximum temperature reached during the polymerization thermal cycle.

[0045] In particular, the peresters according to the invention do not degrade the geometric constants of the glass molds, for example their surface geometries, as well as the quality of the elastomeric and / or thermoplastic seals, which makes it possible to ensure the reuse of the glass molds for the following thermal cycles.

[0046] In other words, the peresters according to the invention have the advantage of being compatible with glass molding technology and elastomeric and / or thermoplastic seals.

[0047] The use of peresters according to the invention also makes it possible to improve the industrial-scale development of organic glasses, in particular to minimize the breakage rate of organic glasses after demolding, and to reduce any excess energy consumption linked to their production.

[0048] The organic glasses thus obtained are notably transparent, weakly colored or even colorless, and have good mechanical properties, particularly in terms of hardness and wear.

[0049] Finally, the peresters according to the invention are notably derived from bio-sourced raw materials, which makes their production more environmentally friendly and more sustainable.

[0050] The invention also relates to a polymerizable composition comprising one or more peresters corresponding to formula (I), previously described, and one or more allylic monomers and / or allylic copolymers.

[0051] The composition according to the invention makes it possible, after polymerization, to produce organic glasses having good optical, aesthetic and mechanical properties. The composition according to the invention is therefore polymerizable or capable of polymerizing.

[0052] The invention also relates to the use of the composition as defined above for the manufacture of an organic glass.

[0053] Another object according to the present invention relates to an organic glass obtained by polymerization of the composition as defined previously.

[0054] Organic glass has good aesthetic, optical and mechanical properties.

[0055] In particular, organic glass has improved hardness compared to organic glasses obtained with other organic peroxides that can be stored and transported at room temperature.

[0056] Other characteristics and advantages of the invention will appear more clearly on reading the description and examples which follow.

[0057] In the following, and at least one other indication, the limits of a domain of values ​​are included in this document.

[0058] The expression "at least one" is equivalent to the expression "one or more".

[0059] For the purposes of the present invention, the terms “peresters” and “peroxyesters” are used interchangeably.

[0060] Use

[0061] As indicated above, the invention relates to the use of one or more peresters corresponding to the formula (I) previously described for the polymerization of one or more allylic monomers and / or allylic copolymers.

[0062] For the purposes of the present invention, the term “non-aromatic” means that Ri does not comprise an aromatic cycle.

[0063] In other words, Ri represents a C 1 -C 10 aliphatic alkyl group.

[0064] Preferably, in formula (I), Ri represents a linear or branched, non-aromatic alkyl group, C1-C6, even more preferably C1-C5, better still C1-C4, even more preferably C1-C3. Advantageously, in formula (I), Ri represents a linear alkyl group, C1-C3, more preferably C1-C2, even more preferably is a CH3 group.

[0065] Advantageously, in formula (I), R4 represents a hydrogen atom or a linear C1-C16 alkyl group.

[0066] Preferably, in formula (I), R4 represents a linear or branched alkyl group, C1-C11, more preferably C3-C11, even more preferably C5-C10, even more preferably C1-C10, and even more preferably C5.

[0067] Preferably, in formula (I), R4 represents an alkyl group, linear in C1-C11, more preferably in C3-C11, even more preferably in C5-C10, even more preferably in CS-CÔ, and even more preferably in C5.

[0068] Advantageously, in formula (I):

[0069] Ri represents a linear alkyl group, C1-C3, more preferably C1-C2, still preferably is a CH3 group,

[0070] R2 and R3 represent a hydrogen atom and

[0071] R4 represents a linear or branched alkyl group, C1-C11, more preferably C3-C11, even more preferably C5-C10, preferably R4 represents a linear alkyl group, C1-C11, more preferably C3-C11, even more preferably C5-C10, even more preferably C5-C10, and even more preferably C5.

[0072] The perester(s) according to the invention is or are preferably chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-hexylperoxy-n-heptanoates, tert-heptylperoxy-n-heptanoates, tert-octylperoxy-n-heptanoates, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, tert-hexylperoxy-n-octanoates, tert-heptylperoxy-n-octanoates, tert-octylperoxy-n-octanoates, tert-butyl-3,5,5-trimethylhexaneperoxoate, tert-amyl-3,5,5-trimethylhexaneperoxoate, tert-hexyl-3,5,5-trimethylhexaneperoxoates, tert-heptyl-3,5,5-trimethylhexaneperoxoates, tert-octyl-3,5,5-trimethylhexaneperoxoates and mixtures thereof.Preferably, the perester(s) according to the invention is or are chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, tert-butyl-3,5,5-trimethylhexaneperoxoate, tert-amyl-3,5,5-trimethylhexaneperoxoate, and mixtures thereof.

[0073] Advantageously, the perester(s) is or are chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, and mixtures thereof, more preferably, the perester(s) according to the invention is or are chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, and mixtures thereof, more preferably is a tert-butylperoxy-n-heptanoate.

[0074] The peresters according to the invention are or are in particular obtained from the reaction between tert-alkyl hydroperoxides and acid halides, in particular acid chlorides, in particular in the presence of one or more alkaline agents.

[0075] Preferably, the peresters according to the invention are or are in particular obtained from the reaction between tert-butyl or tert-amyl hydroperoxides and acid halides, preferably acid chlorides, in particular n-heptanoyl or n-octanoyl chlorides.

[0076] Preferably, the perester(s) according to the invention has (or have) a half-life temperature of 10 hours, denoted HLT 100, greater than or equal to 75°C.

[0077] The "10-hour half-life temperature" is the temperature at which half of the peroxide has decomposed within 10 hours. In other words, it is the temperature at which a loss of half of the active oxygen content of the peroxide occurs after 10 hours.

[0078] The 10-hour half-life temperature, denoted HLT 100, of the peroxyesters according to the invention is preferably measured in an isododecane solution.

[0079] Preferably, the peresters according to the invention have a half-life temperature of 10 hours, denoted HLT 100, less than or equal to 110°C.

[0080] Preferably, the peresters according to the invention have a 10-hour half-life temperature of between 70°C and 110°C, more preferably of between 75°C and 105°C. Preferably, the peresters according to the invention have a 10-hour half-life temperature (HLT 10h) ranging from 95°C to 105°C.

[0081] The peresters according to the invention may further have a self-accelerating decomposition temperature (SADT) greater than or equal to 50°C, preferably greater than or equal to 60°C.

[0082] The term "self-accelerating decomposition temperature" (SADT) is used to describe the lowest temperature at which an uncontrolled reaction occurs, i.e., self-accelerating decomposition in its packaging. Preferably, this self-accelerating decomposition is measured in a 25kg HDPE packaging. In other words, the self-accelerating decomposition temperature represents the temperature at which the chemical process leading to uncontrolled decomposition, possibly accompanied by self-combustion and explosion phenomena, begins. The self-accelerating decomposition temperature is, for example, measured according to UN standard H.3 of the United Nations Manual of Tests and Criteria, T revised edition of 2019.

[0083] Advantageously, the peresters according to the invention have a 10-hour half-life temperature (HLT 100) greater than or equal to 75°C and a self-accelerating decomposition temperature (SADT) greater than or equal to 50°C, preferably greater than or equal to 60°C.

[0084] Preferably, the peresters according to the invention correspond to formula (I) in which R4 represents a linear C1-C7 alkyl group, in particular C5 or C6, and have a half-life temperature at 10 hours (HLT 10h) ranging from 95°C to 105°C.

[0085] Advantageously, the perester(s) according to the invention is or are derived from bio-sourced raw materials.

[0086] By "bio-sourced", it is meant for the purposes of the present invention that the perester(s) is or are derived from compounds of plant and / or animal origin, preferably plant.

[0087] The perester(s) according to the invention may comprise a content of biosourced carbon, i.e. of plant and / or animal origin, in particular of plant origin, of at least 20% by weight, preferably at least 50% by weight, more preferably 100% by weight, relative to the total weight of carbons present in the perester compound.

[0088] Advantageously, the perester(s) according to the invention may comprise a carbon content from renewable raw materials greater than or equal to 50% by weight, preferably ranging from 55 to 70% by weight, more preferably ranging from 60 to 65% by weight, relative to the total weight of carbons present in the perester compound.

[0089] The content of 14 C is substantially constant from the extraction of the renewable raw materials, until the manufacture of the copolymer according to the invention and even until the end of life of the object manufactured from said copolymer.

[0090] Therefore, the presence of 14 C in a material, whatever the quantity, gives an indication of the origin of the molecules constituting it, namely that they come from renewable raw materials and not from fossil materials.

[0091] The quantity of 14 C in a material can be determined by one of the methods described in ASTM D6866-06 (Standard Test Methods for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis).

[0092] This standard includes three methods for measuring organic carbon from renewable raw materials, known in English as "biobased carbon". The proportions indicated for the perester of the invention are preferably measured according to the mass spectrometry method or the liquid scintillation spectrometry method described in this standard, and most preferably by mass spectrometry.

[0093] These measurement methods assess the ratio of isotopes 14 C / 12 C in the sample and compare it to a ratio of isotopes 14 C / 12 C in a material of biological origin giving the 100% standard, in order to measure the percentage of organic carbon in the sample.

[0094] Preferably, the perester(s) according to the invention is or are liquid at room temperature, i.e. at a temperature ranging from 21°C to 30°C.

[0095] The allylic monomer(s) may be chosen from the group consisting of bis(allyl carbonate) monomers.

[0096] Advantageously, the allylic monomer(s) is(are) chosen from the group consisting of the bis(allyl carbonate) monomers of the following formula (II): [Chem 2]

[0097] Formula (II) in which:

[0098] • R a and R c , identical or different, represent an allyl group of the following formula:

[0099] [Chem 3]

[0100] Formula in which Ra is chosen from:

[0101] - a hydrogen atom,

[0102] - a halogen atom, preferably a fluorine or chlorine atom,

[0103] - a linear or branched C1-C4 alkyl group,

[0104] • Rb is selected from alkylene groups, alkylene ether groups, aromatic alkylene ether groups, alkylene polyether groups, alkylene carbonate groups and mixtures thereof.

[0105] Preferably, in formula (II), R a and R c are identical.

[0106] Preferably, R a and R c are identical and represent an allyl group in which Ra represents a hydrogen atom, a chlorine atom, a fluorine atom, a methyl or ethyl group.

[0107] More preferably still, R a and R c are identical and represent an allyl group in which Ra represents a hydrogen atom.

[0108] Preferably, Rb represents an alkylene group, an alkylene ether group or an aromatic alkylene ether group.

[0109] “Alkylene group” means an alkyl group with unsaturation.

[0110] More preferably, Rb represents an alkylene group or an alkylene ether group.

[0111] Even more preferably, Rb represents an alkylene ether group, in particular the group of the following formula: [Chem 4] -CH2CH2-O-CH2'CH2-

[0112] In formula (II), Rb is preferably aliphatic, i.e. it does not represent an aromatic alkylene ether group. In other words, the allylic monomer(s) is(are) preferably chosen from bis(allyl carbonate) monomers of formula (II).

[0113] The allylic monomer(s) is or are preferably selected from the group consisting of ethylene glycol bis allyl carbonate, diethylene glycol bis 2-methyl carbonate, diethylene glycol bis (allyl carbonate) or ADC, ethylene glycol bis (2-chloro allyl carbonate), triethylene glycol bis (allyl carbonate), 1,3-propane bis (allyl carbonate), propylene glycol bis (2-ethyl allyl carbonate), 1,3-butene bis (allyl carbonate), 1,4-butene bis (2-bromo allyl carbonate), dipropylene glycol bis (allyl carbonate), trimethylene glycol bis (2-ethyl allyl carbonate), pentamethylene glycol bis (allyl carbonate), isopropylene bis phenol-A bis (allyl carbonate) and mixtures thereof.

[0114] Preferably, the allylic monomer is diethylene glycol bis(allyl carbonate), also called ADC.

[0115] Other allylic monomers may be used alone or in combination with the bis(allyl carbonate) monomers mentioned above, such as, for example, bis(allyl mono-carbonate) monomers.

[0116] The allylic copolymer(s) can be obtained from the polymerization of the bis(allyl carbonate) monomers mentioned above.

[0117] The allylic copolymer(s) is(are) preferably chosen from polyol poly(allyl carbonates).

[0118] The poly(allyl carbonate) polyol(s) is(are) obtained from the polymerization of a polyol and a bis(allyl)carbonate monomer.

[0119] Among the polyols used in the preparation of poly(allyl carbonates) of polyols, mention may in particular be made of polyols chosen from 1,6-hexanediol, 1,4-dimethanol cyclohexane, polylactone diols, polyethoxylated glycerol diols, alpha, alpha-xylenediol, 1,4-bis(hydroxyethyl)toluene, 2,2-(bis(4-hydroxyethyl)phenyl)propane, pentaerythritol, trimethylol propane, dipentaerythritol, ditrimethylol propane, tris(hydroxyethyl)isocyanurate. The allylic copolymer(s) chosen from poly(allyl carbonates) of polyols may be used in combination with the aforementioned allylic monomers, in particular the bis(allyl carbonate) monomers of formula (II).

[0120] The allylic copolymer(s) may also be obtained from the polymerization of a bis(allyl)carbonate monomer and a polyether diol.

[0121] The polyether diol is preferably chosen from homopolymers, copolymers or block polymers of polyether diols such as those described in patent application US 6506864.

[0122] Preferably, the invention relates to the use of at least one peroxyester of formula (I) for the radical polymerization of one or more allylic monomers and / or allylic copolymers, preferably one or more allylic monomers, in particular those chosen from the group consisting of bis(allyl carbonate) monomers of formula (II).

[0123] More preferably, the invention relates to the use of at least one peroxyester chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, tert-butyl-3,5,5-trimethylhexaneperoxoate and mixtures thereof, for the polymerization of diethylene glycol bis(allyl carbonate) (ADC).

[0124] Composition

[0125] As indicated previously, the composition according to the invention is a polymerizable composition comprising one or more peresters corresponding to formula (I) as described previously, and one or more allylic monomers and / or allylic copolymers, as defined previously.

[0126] Preferably, the composition comprises at least one allylic monomer selected from the group consisting of bis(allyl carbonate) monomers.

[0127] Advantageously, the composition comprises: at least one perester of formula (I), in which: o Ri represents a linear or branched alkyl group, C1-C3, more preferably C1-C2, even more preferably is a CH3 group, o R2 and R3 represent a hydrogen atom and o R4 represents a linear or branched alkyl group, C1-C11, more preferably C3-C11, even more preferably C5-C10, preferably R4 represents a linear alkyl group, C1-C11, more preferably C3-C11, even more preferably C5-C10, even more preferably C5-C6, and even more preferably C5 and at least one allylic monomer chosen from the group consisting of bis(allyl carbonate) monomers.

[0128] Preferably, the composition comprises at least one allylic monomer chosen from the group consisting of bis(allyl carbonate) monomers of formula (II), as described above.

[0129] More preferably, the composition comprises at least one allylic monomer chosen from the group consisting of bis(allyl carbonate) monomers of formula (II), in which R a and R c are identical and represent an ally group in which Ra represents a hydrogen atom, and Rb represents an alkylene group or an alkylene ether group.

[0130] Preferably, the composition according to the invention comprises:

[0131] - at least one perester selected from the group consisting of tert-butylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-hexylperoxy-n-heptanoates, tert-heptylperoxy-n-heptanoates, tert-octylperoxy-n-heptanoates, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, tert-hexylperoxy-n-octanoates, tert-heptylperoxy-n-octanoates, tert-octylperoxy-n-octanoates, tert-butyl-3,5,5-trimethylhexaneperoxoate, tert-amyl-3,5,5-trimethylhexaneperoxoate, tert-hexyl-3,5,5-trimethylhexaneperoxoates, tert-heptyl-3,5,5-trimethylhexaneperoxoates, tert-octyl-3,5,5-trimethylhexaneperoxoates and mixtures thereof, preferably at least one perester chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, and mixtures thereof, more preferably tert-butylperoxy-n-heptanoate,

[0132] - at least one allylic monomer, preferably chosen from the group consisting of bis(allyl carbonate) monomers, more preferably chosen from the group consisting of aliphatic bis(allyl carbonate) monomers of formula (II) as defined above.

[0133] Advantageously, the composition according to the invention comprises:

[0134] - at least one perester chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, tert-butyl-3,5,5-trimethylhexaneperoxoate, tert-amyl-3,5,5-trimethylhexaneperoxoate, and mixtures thereof, preferably at least one perester chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, and mixtures thereof, more preferably is tert-butylperoxy-n-heptanoate and

[0135] - diethylene glycol bis(allyl carbonate) (ADC).

[0136] The peresters may be present in the composition according to the invention in a content ranging from 0.1 to 20% by weight, preferably in a content ranging from 1 to 16% by weight, preferably in a content ranging from 2 to 15% by weight, relative to the total weight of the allylic monomer(s) and / or allylic copolymer(s) present in the composition.

[0137] Preferably, the active oxygen content relative to the total weight of the composition is between 0.1 and 0.5% by weight, preferably in a content between 0.15 and 0.4% by weight, more preferably between 0.2 and 0.35%. The term "active oxygen content" (also called "active O", "AO") means the percentage by weight of oxygen radicals (one oxygen atom per perester function) relative to the total weight of the composition. In other words, the active oxygen content expressed in % can be calculated as: 16 / molar mass of the organic peroxide x the mass concentration of the organic peroxide in the composition.

[0138] The composition according to the invention may further comprise at least one polymerization initiator different from the peroxyesters according to the invention.

[0139] In this case, the polymerization initiator may be an additional organic peroxide different from the peresters according to the present invention or a non-peroxide compound, preferably an additional organic peroxide different from the peresters according to the present invention.

[0140] Preferably, the composition according to the invention comprises at least one perester, as defined above, at least one additional organic peroxide, different from the perester(s) according to the invention, and one or more allylic monomers and / or allylic copolymers.

[0141] The composition according to the invention may also comprise one or more photoinitiators such as those chosen from acetophenonone and benzophenone derivatives.

[0142] The composition according to the invention may also comprise one or more additional monomers other than the allylic monomers. The additional monomer(s) is or are chosen from acrylic monomers or methacrylic monomers such as those chosen from methyl acrylate, methyl methacrylate, phenyl methacrylate, vinyl acetate, isoallyl isophthalate, diallyl terephthalate and diallyl adipate.

[0143] The composition according to the invention may also comprise at least one pigment and / or at least one organic colorant, i.e. at least one coloring agent.

[0144] In this case, the composition may also comprise at least one dispersing agent having the function of dispersing the pigment(s) within said composition.

[0145] According to a preferred embodiment, the composition comprises: diethylene glycol bis(allyl carbonate), at least one perester selected from the group consisting of tert-butylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, tert-butyl-3,5,5-trimethylhexaneperoxoate, tert-amyl-3,5,5-trimethylhexaneperoxoate, and mixtures thereof, preferably at least one perester selected from the group consisting of tert-butylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, and mixtures thereof, more preferably tert-butylperoxy-n-heptanoate, and at least one perester selected from the group consisting of tert-butylperoxy-n-heptanoate, tert-butyl ... at least one pigment and / or organic colorant and optionally at least one dispersing agent.

[0146] Preferably, the coloring agent is a pigment.

[0147] The pigment that may be present in the composition may be organic or inorganic.

[0148] Among the inorganic pigments, we can notably cite mineral pigments which can be optionally surface treated.

[0149] The mineral pigment(s) are preferably chosen from titanium oxides, in particular titanium dioxide, iron oxides such as red iron oxide, yellow iron oxide, and zirconium oxides.

[0150] The organic pigments may be selected from phthalocyanine blue, phthalocyanine green, chromophthal violet, and chromophthal green oxide. Examples of pigments include phthalocyanine pigments, particularly copper phthalocyanine pigments, including blue copper phthalocyanine pigment, and iron oxides.

[0151] Advantageously, the polymerizable composition is free of pigments.

[0152] The composition according to the invention may also comprise one or more release agents, such as the agent sold under the trade name Zelec® UN, available from the Stepan Company.

[0153] The composition according to the invention is in particular liquid in a temperature range which can go from 10°C to 30°C, preferably still from 15°C to 25°C.

[0154] The composition according to the invention as defined above is a polymerizable composition, that is to say that it is capable of polymerizing under the action of heat.

[0155] The invention also relates to the use of the polymerizable composition, as defined above, for the manufacture of an organic glass, preferably an ophthalmic lens.

[0156] Organic glass

[0157] Preferably, the polymerizable composition according to the invention leads after polymerization to an organic glass.

[0158] Thus, the present invention also relates to an organic glass obtained from the polymerization of a composition as defined previously.

[0159] More specifically, the invention also relates to an organic glass obtained from the radical polymerization of a composition as defined above.

[0160] Organic glass is preferably selected from the group consisting of instrument windows, optical detectors and ophthalmic lenses.

[0161] Preferably, the organic glass is chosen from the group consisting of ophthalmic lenses.

[0162] For the purposes of the present invention, the term ophthalmic means a lens capable of being mounted as spectacles and whose function is to protect the eyes against the sun, in particular ultraviolet rays (solar lens), or to correct vision. In the latter case, the ophthalmic lens is preferably afocal, unifocal, bifocal, trifocal or progressive. Thus the ophthalmic lens may be of the multifocal or progressive or degressive multifocal type, that is to say multifocal lenses with variable power.

[0163] The resulting ophthalmic lens can be coated or surface treated.

[0164] Advantageously, the invention relates to an ophthalmic lens obtained from the polymerization of a composition as defined above.

[0165] According to one embodiment, the ophthalmic lens is obtained from the polymerization of a composition comprising at least one perester according to the invention chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, tert-butyl-3,5,5-trimethylhexaneperoxoate, tert-amyl-3,5,5-trimethylhexaneperoxoate and mixtures thereof, and at least one allylic monomer chosen from the group consisting of bis(allyl carbonate) monomers of formula (II) as described above, in particular diethylene glycol bis(allyl carbonate).

[0166] Product from the polymerizable composition

[0167] Another subject of the present invention relates to the product resulting from the polymerization of one or more allylic monomers and / or one or more allylic copolymers in the presence of one or more peresters according to the invention, as defined previously.

[0168] Thus the product is a polymer composition (or polymer product) resulting from the radical polymerization of one or more allylic monomers and / or one or more allylic copolymers in the presence of one or more peresters according to the invention, as defined previously.

[0169] The polymer composition is therefore obtained by polymerization of the polymerizable composition as defined above, and more precisely of the different constituents of the polymerizable composition.

[0170] In other words, the polymer composition corresponds to a resin that can serve as a basic material for manufacturing any type of object used for its good mechanical, aesthetic and optical properties, particularly for its optical qualities.

[0171] Preferably, the polymer product or the polymer composition can be shaped so as to obtain an organic glass or any other object used for its good mechanical and optical properties, in particular for its transparency and its low coloration or even its colorlessness. The polymer composition is in particular in solid form in a temperature range between 10°C and 30°C, preferably still between 15°C and 25°C.

[0172] Polymerization process

[0173] Likewise, the invention also relates to a process for polymerizing the polymerizable composition, as defined above, comprising at least one step of polymerizing a polymerizable composition as defined above, preferably at one or more temperatures less than or equal to 110°C.

[0174] The invention also relates to a process for preparing the polymer composition, as defined above, comprising at least one step of polymerization of a polymerizable composition as defined above, preferably at one or more temperatures less than or equal to 110°C.

[0175] Process for the preparation of organic glass

[0176] The process for preparing an organic glass comprises at least one step of polymerization of a composition, as defined previously, preferably at one or more temperatures less than or equal to 110°C, in a device comprising at least one mold.

[0177] According to one embodiment, the method for preparing organic glass comprises at least the following steps:

[0178] - a step of introducing a polymerizable composition, as defined previously, into a device comprising at least one mold,

[0179] - a step of polymerization of said composition, preferably at one or more temperatures less than or equal to 110°C; preferably, the polymerization step is a succession of steps at different temperatures making it possible to control shrinkage and polymerization,

[0180] - a stage of recovery of organic glass.

[0181] According to this embodiment, the introduction step is a step of casting or injecting the polymerizable composition according to the invention into a device comprising at least one mold. The device may comprise at least one mold having a complex geometry, for example a bi-planar mold, a mold comprising a concave part and a convex part or even a concave-shaped mold.

[0182] Preferably, the device comprises at least one mold comprising at least one concave portion and at least one convex portion.

[0183] More generally, the device comprises at least one mold whose geometric shape presents the final geometry of the desired organic glass.

[0184] The device may also comprise at least one mold having one face having a geometry corresponding to the final geometry of the desired organic glass and another face which is not adjusted according to the final geometry of the organic glass but which makes it possible to prepare a second face of the organic glass which can then be processed.

[0185] Preferably, the introduction step consists of casting the polymerizable composition between two molds having the required surface geometries, for example a mold having a concave shape and a mold having a convex shape.

[0186] The polymerization step is notably a radical polymerization.

[0187] The polymerization step may be carried out by carrying out thermal cycles in a temperature range of less than or equal to 110°C for a time sufficient to carry out the polymerization, in particular times which may range from 10 hours to 30 hours, preferably a time of 30 hours.

[0188] Thus the temperature can be increased gradually during the polymerization stage.

[0189] The polymerization step leads to the desired organic glass.

[0190] The process for preparing the organic glass may comprise, after the polymerization step, a step of annealing the organic glass intended to eliminate any residual stresses in the glass. The annealing step may take place at temperatures ranging from 60 to 130°C, preferably 70 to 100°C, and for a duration ranging from 1 hour to 20 hours.

[0191] The step of recovering organic glass can be a step of opening the mold and collecting the organic glass.

[0192] Thus, the method for preparing organic glass preferably comprises a step of casting or injecting the composition according to the invention into a device comprising at least one mold having at least one concave part and at least one convex part, a step consisting of closing the mold, a step of polymerizing the composition as defined previously, and a step consisting of opening the mold and collecting the organic glass.

[0193] The method according to the invention makes it possible in particular to prepare an ophthalmic lens as described previously.

[0194] The organic glass obtained following this preparation process can undergo any type of treatment such as surface treatments to improve its mechanical, aesthetic and optical properties or even its wettability properties.

[0195] According to one embodiment, as indicated above, the polymerizable composition according to the invention may further comprise at least one coloring agent, preferably at least one pigment and / or at least one organic dye.

[0196] Alternatively, the process for preparing the organic glass according to the invention may comprise an additional step consisting of adding at least one coloring agent, preferably at least one pigment, after obtaining the organic glass, that is to say after the polymerization step.

[0197] The organic glass obtained following this process has good mechanical, aesthetic and optical properties.

[0198] The optical quality of the organic glasses according to the invention can be evaluated by determining in particular at least one of the following parameters:

[0199] - the refractive index (n D 2o) measured with an Abbe refractometer (standardized method ASTM D-542),

[0200] - the yellowing index (YI) by spectroscopic means (standardized method ASTM E313) using a spectrocolorimeter according to the CIE 1976 Standard according to the following equation:

[0201] [Math 1]

[0202] YI = 100 / Y(1.277X-LÔ6Z)

[0203] Equation in which X, Y and Z are trichromatic coordinates of the sample, measured by the spectrophotometer over the entire spectrum between 380 and 780 nanometers.

[0204] The mechanical properties of the organic glasses according to the invention can be evaluated by determining in particular at least one of the following parameters:

[0205] - Rockwell hardness measured using a Rockwell hardness tester (standardized method ASTM D-785), - Shore D hardness measured using a portable durometer type HPE II Shore D (standardized method ASTM D 2240),

[0206] - the modulus of elasticity, or

[0207] - the coefficient of friction.

[0208] Preferably, the mechanical properties of the organic glasses according to the invention can be evaluated from the hardness.

[0209] The following examples serve to illustrate the invention without, however, being limiting in nature.

[0210] Examples

[0211] The following examples illustrate the invention without limiting it.

[0212] A. Example of preparation of peroxyesters

[0213] Synthesis of peroxyesters

[0214] Tertiary alkyl peroxyesters are generally prepared by reaction between a hydroperoxide and an acid chloride or an anhydride in the presence of a base such as sodium hydroxide or a tertiary amine (see D. Swern - Organic Peroxides Vol 1 p 74 - Wiley Editions 1970).

[0215] 1.1 Preparation of tert-butyl peroxy-n-heptanoate (also called tert-butylperoxy-n-heptanoate)

[0216] In a glass reactor equipped with a double jacket, a condenser and a stirring system, 74g of a tert-butyl hydroperoxide solution (70%) are mixed with 116g of a potash solution (30%) at a temperature of 5-10°C. Then 70g of n-heptanoic acid chloride (99.7%) are added to this solution in a controlled manner in order to maintain the temperature between 5°C and 10°C. After 45 min of reaction at 5-10°C, the temperature is raised to 20-25°C for 15 min. After reaction, the two phases are allowed to settle. The organic phase is washed with a sodium hydroxide solution (10%), then a sodium metabisulfite solution (10%), then with water. 67g of a tert-butyl peroxy-n-heptanoate solution is recovered. 1.2 Preparation of tert-amyl peroxy-n-heptanoate (also called tert-amylperoxy-n-heptanoate)

[0217] In a glass reactor equipped with a double jacket, a condenser and a stirring system, 32g of a tert-amyl hydroperoxide solution (85%) are mixed with 59g of a potash solution (30%) at a temperature of 5-10°C. Then 35g of n-heptanoic acid chloride (99.7%) are added to this solution in a controlled manner in order to maintain the temperature between 5°C and 10°C. After 45 min of reaction at 5-10°C, the temperature is raised to 20-25°C for 15 min. After reaction, the two phases are allowed to settle. The organic phase is washed with a sodium hydroxide solution (10%), then a sodium metabisulfite solution (10%), then with water. 26g of a tert-amyl peroxy-n-heptanoate solution are recovered.

[0218] 1.3 Preparation of tert-butyl peroxy-n-octanoate (also called tert-butylperoxy-n-octanoate)

[0219] In a glass reactor equipped with a double jacket, a condenser and a stirring system, 52g of a tert-butyl hydroperoxide solution (70%) are mixed with 83g of a potash solution (30%) at a temperature of 5-10°C. Then 52g of n-octanoic acid chloride (98.8%) are added to this solution in a controlled manner in order to maintain the temperature between 5°C and 10°C. After 45 min of reaction at 5-10°C, the temperature is raised to 20-25°C for 15 min. After reaction, the two phases are allowed to settle. The organic phase is washed with a sodium hydroxide solution (10%), then a sodium metabisulfite solution (10%), then with water. 52g of a tert-butyl peroxy-n-octanoate solution is recovered.

[0220] 1.4 Preparation of tert-amyl peroxy-n-octanoate (also called tert-amylperoxy-n-octanoate)

[0221] In a glass reactor equipped with a double jacket, a condenser and a stirring system, 38g of a tert-amyl hydroperoxide solution (85%) are mixed with 66g of a potash solution (30%) at a temperature of 5-10°C. Then 47g of n-octanoic acid chloride (98.8%) are added to this solution in a controlled manner in order to maintain the temperature between 5°C and 10°C. After 45 min of reaction at 5-10°C, the temperature is raised to 20-25°C for 15 min. After reaction, the two phases are allowed to settle. The organic phase is washed with a sodium hydroxide solution (10%), then a sodium metabisulfite solution (10%), then with water. 39g of a tert-amyl peroxy-n-octanoate solution is recovered. B. Example of preparation of a polymerizable composition

[0222] A polymerizable composition is prepared from diethylene glycol bis-allyl carbonate (CAS 142-22-3), marketed under the trade name CR-39® by PPG, and each organic peroxide as described below.

[0223] The organic peroxides tested are as follows (The proportions of organic peroxides represent 0.23% of active oxygen in the composition, which corresponds to the mass proportions in the table below): [Table 1] Tl

[0224] C. Example of preparation of an organic glass

[0225] Each previously obtained composition is then poured into a mold having a concave part and a convex part. Once poured, the convex part is closed over the concave part of the mold and then the whole thing is heated to a temperature less than or equal to 110°C.

[0226] The thermal crosslinking cycle is adapted according to the decomposition temperature of the organic peroxides used (half-life temperatures (HLT) at 1h and 10h) according to the following scheme: rise in 14h to the half-life temperature at 10h (HLT 10h) of the peroxide used, then rise in 4h to the HLT to the half-life temperature at 1h (HLT 1h) of the peroxide used, then cooling to a temperature of 70°C, the temperature at which demolding is carried out.

[0227] The polymerized product thus obtained is annealed for a period which can vary from 1 to 20 hours at temperatures which can reach 130°C.

[0228] The organic glass is then recovered.

[0229] D. Biplane system for measuring optical properties

[0230] Different optical properties, namely Shore D hardness and Yellowing Index (YI) were measured for different organic glasses. These organic glasses were prepared according to the protocol described above, except for the polymerization which was carried out between flat glass plates of 10*15cm of thickness 4 mm, arranged vertically, separated by a silicone rubber joint of 4 mm in diameter, the mechanical cohesion of the assembly being achieved by a clamp at constant pressure. All tests were carried out with an air intake at the top of the mold.

[0231] The yellowness index YI is obtained with a Spectro-colorimeter from the manufacturer X-RITE, type SP60, according to the CIE 1976 Standard (color chain). The trichromatic coordinates are those of Lab Hunter. The measurement is calibrated every day with a standard calibration plate (white and black), serial number: 20609 D65:10° of 02 / 18 / 2010 WO A89274.

[0232] The YI measurement is carried out in their 4 mm glass thickness and is expressed by difference with the YI measured on the white area of ​​the Leneta Eorm 2A card (whose yellowing index measurement is 10.48 after calibration of the spectrophotometer).

[0233] Shore D hardness is measured using a portable durometer type HPE II Shore D (Manufacturer: BAREISS, device standardized to NE T51-174; DIN EN ISO 868; ISO 7619; ASTM D 2240; BS 903 Part A26).

[0234] For each organic glass, the organic hardness was measured five times and the average of these measurements was taken.

[0235] The results on the hardness of the organic glasses obtained are grouped in the following table:

[0236] [Table 2] The organic glasses obtained with the peroxyesters according to the invention have a significantly higher hardness than that obtained with organic peroxides not corresponding to formula (I) according to the invention (tert-butyl peroxy-2-ethylhexanoate and tert-amyl peroxy-2-ethylhexanoate).

[0237] Diisopropyl peroxydicarbonate is not storable or transportable at room temperature.

[0238] The results on the yellowing index (YI) of organic glasses obtained with the tested organic peroxides are grouped in the following table:

[0239] [Table 3]

[0240] The organic glasses obtained with the peroxyesters according to the invention have a lower yellowing index (YI) and / or allow storage and transport at room temperature of the organic peroxides compared to the organic glasses obtained with an organic peroxide, not corresponding to formula (I) according to the invention.

Claims

CLAIMS 1. Use of one or more peresters of the following formula (I): [Chem 5] Formula (I) in which: • Ri represents a linear or branched, non-aromatic, C1-C10 alkyl group, • R2 and R3 represent a hydrogen atom, • R4 represents a hydrogen atom or a linear or branched C1-C16 alkyl group; for the polymerization of one or more allylic monomers and / or allylic copolymers.

2. Use according to claim 1, characterized in that, in formula (I), Ri represents a linear alkyl group, C1-C6, preferably C1-C5, more preferably C1-C4, even more preferably C1-C3, even more preferably is a CH3 group.

3. Use according to claim 1 or 2, characterized in that, in formula (I), R4 represents a linear or branched alkyl group, C1-C11, more preferably C3-C11, even more preferably C5-C10, preferably R4 represents a linear alkyl group, C1-C11, more preferably C3-C11, even more preferably C5-C10, even more preferably C1-C10, and even more preferably C5.

4. Use according to any one of the preceding claims, characterized in that the perester(s) is or are chosen from the group consisting of tert-butylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-hexylperoxy-n-heptanoates, tert-heptylperoxy-n-heptanoates, tert-octylperoxy-n-heptanoates, tert-butylperoxy-n-octanoate, tert-amylperoxy-n-octanoate, tert-hexylperoxy-n-octanoates, tert-heptylperoxy-n-octanoates, tert-octylperoxy-n-octanoates, tert-butyl-3,5,5-trimethylhexaneperoxoate, tert-amyl-3,5,5-trimethylhexaneperoxoate, and mixtures thereof, preferably at least one perester selected from the group consisting of tert-butylperoxy-n-heptanoate, tert-butylperoxy-n-octanoate, and mixtures thereof, more preferably is a tert-butylperoxy-n-heptanoate.

5. Use according to any one of the preceding claims, characterized in that the perester(s) has (or have) a 10-hour half-life temperature (HLT 100) greater than or equal to 75°C.

6. Use according to any one of the preceding claims, characterized in that the perester(s) has (or have) a self-accelerating decomposition temperature (SADT) greater than or equal to 50°C, preferably greater than or equal to 60°C.

7. Use according to any one of the preceding claims, characterized in that the allylic monomer is chosen from the group consisting of bis(allyl carbonate) monomers.

8. Use according to any one of the preceding claims, characterized in that the allylic monomer is chosen from the group consisting of the bis(allyl carbonate) monomers of the following formula (II): Formula (II) in which: • R a and R c , identical or different, represent an allyl group of the following formula: [Chem 7] î d H2C=C — CH — Formula in which Ra is chosen from: a hydrogen atom, a halogen atom, preferably a fluorine or chlorine atom, a linear or branched C1-C4 alkyl group, • Rb is selected from the group consisting of alkylene groups, alkylene ether groups, aromatic alkylene ether groups, alkylene polyether groups, alkylene carbonate groups and mixtures thereof.

9. Use according to any one of the preceding claims, characterized in that the allylic monomer is chosen from the group consisting of ethylene glycol bis allyl carbonate, diethylene glycol bis 2-methyl carbonate, diethylene glycol bis (allyl carbonate), ethylene glycol bis (2-chloro allyl carbonate), triethylene glycol bis (allyl carbonate), 1,3-propane bis (allyl carbonate), propylene glycol bis (2-ethyl allyl carbonate), 1,3-butene bis (allyl carbonate), 1,4-butene bis (2-bromo allyl carbonate), dipropylene glycol bis (allyl carbonate), trimethylene glycol bis (2-ethyl allyl carbonate), pentamethylene glycol bis (allyl carbonate), isopropylene bis phenol-A bis (allyl carbonate) and mixtures thereof.

10. Use according to any one of the preceding claims, characterized in that the allylic monomer is diethylene glycol bis(allyl carbonate).

11. Polymerizable composition comprising at least one perester, as defined according to any one of claims 1 to 6 and at least one allylic monomer, as defined according to any one of claims 1, 7 to 10, and / or at least one allylic copolymer.

12. Composition according to claim 11, characterized in that it further comprises at least one additional organic peroxide different from the peresters as defined according to any one of claims 1 to 6.

13. Use of the composition as defined according to claim 11 or 12 for the manufacture of an organic glass, preferably an ophthalmic lens.

14. Polymer composition characterized in that it is obtained by polymerization of the polymerizable composition as defined according to claim 11 or 12.

15. Organic glass obtained by polymerization of a polymerizable composition as defined according to claim 11 or 12, preferably chosen from the group consisting of instrument windows, optical detectors and ophthalmic lenses.

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