Compositions based on allylic monomers and peroxides for the production of organic glasses

Abstract

The present invention relates to the use of one or more peresters of formula (I) for the polymerization of at least one allylic monomer and / or at least one allylic copolymer. The present 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. Similarly, the present invention relates to the use of the polymerizable composition as defined above for the production of organic glass, preferably ophthalmic lenses. The present invention also relates to organic glass obtained from the polymerization of the polymerizable composition as defined above.

Description

[Technical Field]

[0001] The present invention relates to the use of one or more peresters, as defined below, for the polymerization of at least one allyl monomer and / or at least one allyl copolymer.

[0002] The present invention also relates to a polymerizable composition comprising at least one allyl monomer and / or at least one allyl copolymer and at least said perester.

[0003] Likewise, the present invention relates to the use of a polymerizable composition as defined above for the production of organic glasses, preferably ophthalmic lenses.

[0004] The present invention also relates to an organic glass obtained from the polymerization of the polymerizable composition defined above. [Background technology]

[0005] Organic glasses, such as instrument or optical detector windows, or ophthalmic lenses, can be prepared by radical polymerization of one or more allylic monomers and / or allylic copolymers in the presence of one or more polymerization initiators, especially organic peroxides.

[0006] Such radical polymerization can be carried out in particular by injecting a polymerizable composition based on allylic monomers and / or allylic copolymers and organic peroxides into a mold, in particular a mold made of mineral glass, having a geometry suited to the desired application.

[0007] A mold is generally an assembly that may consist of two glass parts, in particular mineral glass parts, separated by a recess and held together by the presence of a leak-proof seal made of an elastomer and / or thermoplastic material located at the periphery. A polymerizable composition is then injected into the cavity formed between the two glass parts of the mold and subjected to a suitable thermal cycle, during which the temperature may be generally gradually increased, optionally observing one or more steady temperature phases.

[0008] During such thermal cycling, the composition polymerizes and hardens within the mold, yielding an organic glass that, after removal from the mold, can then be subjected to various processes depending on the desired application. The mold is typically reused for many thermal cycles.

[0009] Organic peroxides commonly used as polymerization initiators are generally substances that become very unstable when heated. This is because, in the event of an uncontrolled increase in temperature, some organic peroxides undergo self-accelerating exothermic decomposition that carries the risk of fire and / or violent decomposition. This behavior has proven difficult to comply with current regulations regarding the transport and storage of hazardous materials in places intended for the production of organic glass.

[0010] It has therefore been found to be particularly advantageous to formulate organic peroxides in such solvents (also called viscosity reducers) in a liquid, i.e., diluted state, which reduces thermal instability and allows for storage and transportation under safer conditions. Summary of the Invention

[0011] Thus, the use of diisopropyl peroxydicarbonate (IPP) dissolved in an allyl monomer, such as diethylene glycol bis(allyl carbonate), in a content of 27 wt. % based on the total weight of the composition in the radical polymerization of allyl monomer(s) and / or allyl copolymer(s) makes it possible to obtain organic glasses with good optical properties (especially transparency and low coloration), aesthetic properties, and mechanical properties. In other words, organic glasses obtained using such organic peroxide compositions have the advantage of being colorless and transparent and exhibiting good mechanical properties, such as hardness and abrasion resistance. For example, such compositions are sold by Arkema under the trade name Luperox® IPP27 or by Nouryon under the trade name Perkadox® IPP-NS27.

[0012] Nevertheless, such compositions based on diisopropyl peroxydicarbonate are at great risk of uncontrolled decomposition if the temperature rises uncontrollably during storage and transportation.

[0013] This is because diisopropyl peroxydicarbonate is a "cold" peroxide, i.e., it exhibits a maximum transport temperature (also called the controlled temperature), set at -20°C, either alone or in mixtures with other peroxides and / or viscosity reducers, reactive or non-reactive, in accordance with section 2.5.3.2.4 on organic peroxides of the United Nations Recommendations on the Transport of Dangerous Goods (19th edition, 2015).

[0014] More generally, within the meaning of the present invention, the term "cold peroxide" is understood to mean any peroxide-based composition having a maximum transport temperature of 20°C.

[0015] Therefore, despite the dilution of diisopropyl peroxydicarbonate in the allyl monomer, it has been found that during storage and transport, especially during sea transport, products such as Luperox® IPP27 or Perkadox® IPP-NS27 must always be kept at very low temperatures, in particular temperatures below 20°C, in order to minimize the risk of decomposition which would make their use significantly more difficult.

[0016] Furthermore, it is necessary to control the temperature during shipping and storage of these products to reduce the risk of initiating polymerization of the allylic monomer, which has the effect of desensitizing organic peroxides.

[0017] Furthermore, diisopropyl peroxydicarbonate exhibits the disadvantage that at concentrations above 30% by weight in allyl monomer it is too reactive, making storage and transportation difficult.

[0018] To overcome many of these difficulties, it has been envisioned to replace diisopropyl peroxydicarbonate with organic peroxides such as diacyl-type aromatic peroxides or peresters, which can be stored and transported at ambient temperatures.

[0019] However, such organic peroxides present the drawback of causing high polymerization temperatures that can exceed 120° C., and in some cases even 125° C., as opposed to around 80° C. in the case of diisopropyl peroxydicarbonate. Such polymerization temperatures therefore tend to more or less rapidly damage the surface geometry of the glass mold and also the elastomeric and / or thermoplastic seals, on the one hand preventing their subsequent reuse in many thermal cycles, and on the other hand causing mechanical and optical defects in the organic glass formed.

[0020] In particular, organic glasses formed using such organic peroxides have been observed to suffer significantly increased levels of breakage upon removal from the mold.

[0021] Furthermore, such high polymerization temperatures increase the risk of yellowing of organic glasses, since this type of organic peroxide, especially benzoyl peroxide, can induce significant yellowing of organic glasses, making it necessary to use colorants that can correct this yellowing as much as possible, but their presence is often not always effective or acceptable when wearing corrective glasses.

[0022] Finally, thermal cycling at polymerization temperatures at least 40°C higher than those typically applied with diisopropyl peroxydicarbonate leads to significant excess energy consumption, resulting in additional costs to the annual production of organic glass.

[0023] In other words, these organic peroxides, which can be stored and transported at room temperature, have low reactivity and are therefore known to be incompatible with molding materials, resulting in deterioration of the molds used and the elastomeric and / or thermoplastic seals, which in turn promotes the formation of mechanical and optical defects in the resulting organic glass, particularly yellowing, and increases production costs.

[0024] As a result, such peroxides allow operation under safer conditions, but generally produce organic glasses with significantly inferior mechanical and optical properties than those obtained using cold peroxides.

[0025] In light of the above, one of the objectives of the present invention is to overcome the above-mentioned drawbacks, i.e., to replace the organic peroxides commonly used during the polymerization of allyl monomers and / or allyl copolymers with other polymerization initiators that can be stored and transported at room temperature, either alone or in mixtures, to obtain organic glasses with good optical, aesthetic, and mechanical properties, without degrading the industrial equipment used during their production.

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

[0027] In particular, one of the aims of the present invention is to improve the safety conditions for obtaining organic glasses without modifying their optical, aesthetic and mechanical properties and without deteriorating the geometric parameters of the glass mold, in particular its surface shape and the elastomeric and / or thermoplastic seals required for its production. DETAILED DESCRIPTION OF THE INVENTION

[0028] The subject of the present invention is therefore in particular a process for the polymerization of one or more allyl monomers and / or allyl copolymers of the following formula (I): [C1] TIFF2025538447000001.tif40170[In formula (I), R1 is a linear or branched non-aromatic C1-C 10 represents an alkyl group, preferably R represents a linear C1-C3, more preferably a C1-C2 alkyl group, more preferably a CH3 group; R2 and R3 represent hydrogen atoms; R4 is a hydrogen atom or a linear or branched C1-C 16 preferably R represents a linear C-C alkyl group; 11 , more preferably C3-C 11 , and more preferably C5-C 10 , and more preferably a C5-C6, and even more preferably a C5 alkyl group. The use of one or more peresters corresponding to

[0029] Thus, the one or more peresters according to the present invention are one or more non-aromatic tert-alkyl peroxyesters.

[0030] The peresters according to the invention have the advantage that they can be stored and transported, alone or in mixtures with other reactive or non-reactive peroxides and / or viscosity reducers, at ambient temperatures, i.e. under safer conditions.

[0031] The term "normal temperature" is understood to mean a temperature which may range from 21°C to 30°C.

[0032] The peresters according to the invention therefore have the advantage, alone or in mixtures with other reactive or non-reactive peroxides and / or viscosity reducers, of exhibiting a maximum transport temperature (also called control temperature) strictly higher than 20°C in accordance with section 2.5.3.2.4 on organic peroxides of the UN Recommendations on the Transport of Dangerous Goods (19th edition, 2015).

[0033] Thus, safety conditions regarding transport and storage are improved compared to the use of cold peroxides as defined above, particularly for organic peroxides belonging to the dialkylperoxydicarbonate class, in particular diisopropyl peroxydicarbonate dissolved in diethylene glycol bis(allyl carbonate) (sold under the names Luperox® IPP27 or Perkadox® IPP-NS27).

[0034] The peroxyesters according to the invention are indeed easy to handle and present the advantage of significantly reducing the costs associated with transportation and storage, allowing them to be distributed more widely around the world, including in the most difficult to access areas, under safe conditions.

[0035] The peresters also present the advantage that they can be used alone, i.e. undiluted, which makes it possible, on the one hand, to dispense with the use of non-polymerizable solvents such as oils, which are required for safety reasons and which may have a negative effect on the optical and mechanical qualities of the resulting organic glass, and, on the other hand, to dispense with the use of polymerizable solvents such as allylic monomers, which tend to increase the risk of initiation of uncontrolled temperature polymerization during transport or storage.

[0036] More generally, the peresters according to the invention make it possible to eliminate the need for any type of storage means dedicated to polymerizable or non-polymerizable solvents at the peroxide production site (or in devices intended for storing solvents), resulting in significant space savings and reduced maintenance costs.

[0037] In other words, the peroxides according to the invention make it possible to overcome all kinds of problems associated with the use of polymerizable or non-polymerizable solvents.

[0038] More specifically, the peresters according to the present invention eliminate the need for conventional viscosity reducers for peroxides, such as hydrocarbons such as isododecane, mineral oil, esters such as liquid phthalates, ethylbenzene, or allyl monomers.

[0039] Thus, peresters can be packaged in a wider variety of containers or devices than conventional peroxides, which are thermally unstable and prone to decomposition during uncontrolled temperature increases.

[0040] Furthermore, the peresters of the present invention are sufficiently reactive to induce polymerization temperatures significantly lower than conventional organic peroxides, allowing them to be stored and transported at ambient temperatures without damaging the industrial equipment used in molding and without degrading the optical, aesthetic, and mechanical properties of the organic glass.

[0041] The term "polymerization temperature" is understood to mean the maximum temperature reached during the thermal polymerization cycle.

[0042] In particular, the peresters according to the invention do not degrade the geometric constants of the glass molds, such as their surface shape, and the quality of the elastomeric and / or thermoplastic seals, thus making it possible to ensure that the glass molds can be reused in the next thermal cycle.

[0043] In other words, the peresters according to the invention exhibit the advantage of being compatible with glass molding techniques and with elastomeric and / or thermoplastic sealants.

[0044] In addition, the use of peresters according to the invention makes it possible to improve the industrial-scale growth of organic glasses, minimizing the breakage rate of organic glasses, especially after removal from the mold, and reducing the excessive energy consumption associated with their production.

[0045] The organic glasses thus obtained are particularly transparent, slightly colored or even colorless and have good mechanical properties, especially with regard to hardness and wear resistance.

[0046] Finally, the peresters according to the invention are obtained in particular from bio-based starting materials, which makes their production more environmentally friendly and sustainable.

[0047] Another subject of the present invention is a polymerizable composition comprising one or more peresters corresponding to formula (I) above and one or more allyl monomers and / or allyl copolymers.

[0048] The composition according to the invention makes it possible, after polymerization, to obtain organic glasses having good optical, aesthetic and mechanical properties.

[0049] Thus, the compositions according to the present invention are polymerizable or polymerizable.

[0050] The present invention also relates to the use of the composition defined above for the manufacture of an organic glass.

[0051] Another subject of the invention relates to an organic glass obtained by polymerization of the composition defined above.

[0052] This organic glass exhibits good aesthetic, optical, and mechanical properties.

[0053] This organic glass exhibits improved hardness, particularly compared to organic glasses obtained using other organic peroxides, and can be stored and transported at room temperature.

[0054] Other characteristics and advantages of the invention will become more apparent on reading the description and examples that follow.

[0055] In the following description, unless otherwise indicated, numerical range limits are included herein.

[0056] The phrase "at least one" is synonymous with the phrase "one or more."

[0057] Within the meaning of the present invention, the terms "perester" and "peroxyester" are used interchangeably.

[0058] use As mentioned above, the present invention relates to the use of one or more peresters corresponding to formula (I) above for the polymerization of one or more allylic monomers and / or allylic copolymers.

[0059] The term "non-aromatic" is understood within the meaning of the present invention to mean that R1 does not contain an aromatic ring.

[0060] In other words, R1 is an aliphatic C1-C 10 represents an alkyl group.

[0061] Preferably, in formula (I), R1 represents a linear or branched, non-aromatic, C1-C6, even more preferably C1-C5, even better still C1-C4, and even more preferably C1-C3 alkyl group.

[0062] Advantageously, in formula (I), R1 represents a linear C1-C3, more preferentially C1-C2 alkyl group, and more preferentially a CH3 group.

[0063] Advantageously, in formula (I), R4 represents a hydrogen atom or a linear C1-C 16 represents an alkyl group.

[0064] Preferably, in formula (I), R4 is a linear or branched C1-C 11 , more preferably C3-C 11 , and more preferably C5-C 10 , and even more preferably represents a C5-C6, and even more preferably a C5 alkyl group.

[0065] Preferably, in formula (I), R4 is a linear C1-C 11 , more preferably C3-C 11 , and more preferably C5-C 10 , and even more preferably represents a C5-C6, and even more preferably a C5 alkyl group.

[0066] Advantageously, in formula (I), R1 represents a linear C1-C3, more preferably C1-C2 alkyl group, more preferably a CH3 group; R2 and R3 represent hydrogen atoms; - R4 is a linear or branched C1-C 11 , more preferably C3-C 11 , and more preferably C5-C 10 R represents an alkyl group, preferably a linear C1-C 11 , more preferably C3-C 11 , and more preferably C5-C 10 , and even more preferably represents a C5-C6, and even more preferably a C5 alkyl group.

[0067] The perester or peresters according to the invention are preferably tert-butyl peroxy-n-heptanoate, tert-amyl peroxy-n-heptanoate, tert-hexyl peroxy-n-heptanoate, tert-heptyl peroxy-n-heptanoate, tert-octyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, tert-hexyl peroxy-n-octanoate, peroxy-n tert-heptyl 3,5,5-trimethylhexaneperoxyate, tert-octyl peroxy-n-octanoate, tert-butyl 3,5,5-trimethylhexaneperoxyate, tert-amyl 3,5,5-trimethylhexaneperoxyate, tert-hexyl 3,5,5-trimethylhexaneperoxyate, tert-heptyl 3,5,5-trimethylhexaneperoxyate, tert-octyl 3,5,5-trimethylhexaneperoxyate, and mixtures thereof.

[0068] Preferably, the one or more peresters according to the present invention are selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-amyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, tert-butyl 3,5,5-trimethylhexaneperoxyate, tert-amyl 3,5,5-trimethylhexaneperoxyate, and mixtures thereof.

[0069] Advantageously, the perester(s) are selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-amyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, and mixtures thereof, more preferentially the perester(s) according to the invention are selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, and mixtures thereof, even more preferentially tert-butyl peroxy-n-heptanoate.

[0070] The peresters according to the invention are obtained in particular from the reaction of tert-alkyl hydroperoxides with acid halides, especially acid chlorides, in particular in the presence of one or more alkaline agents.

[0071] Preferably, the peresters according to the invention are obtained in particular from the reaction of tert-butyl or tert-amyl hydroperoxide with an acid halide, preferably an acid chloride, in particular n-heptanoyl or n-octanoyl chloride.

[0072] Preferably, the perester(s) according to the invention have a half-life temperature at 10 hours (denoted HLT10 hours) of 75° C. or higher.

[0073] The "10-hour half-life temperature" is the temperature at which half of the peroxide decomposes in 10 hours. In other words, it is the temperature at which the loss of half of the active oxygen content of the peroxide occurs after 10 hours.

[0074] The half-life temperature at 10 hours (denoted HLT10 hours) of the peroxyesters according to the invention is preferably measured in isododecane solution.

[0075] Preferably, the peresters according to the invention have a half-life temperature at 10 hours (denoted HLT10 hours) of 110° C. or less.

[0076] Preferably, the peresters according to the invention have a 10 hour half-life temperature between 70°C and 110°C, more preferably between 75°C and 105°C.

[0077] Preferably, the peresters according to the invention have a half-life temperature at 10 hours (HLT10h) in the range of 95°C to 105°C.

[0078] The peresters according to the invention may further exhibit a self-accelerating decomposition temperature (SADT) of 50°C or higher, preferably 60°C or higher.

[0079] The term "self-accelerating decomposition temperature" (SADT) is understood to mean the lowest temperature at which an uncontrolled reaction, i.e., self-accelerating decomposition, occurs in the package. Preferably, this self-accelerating decomposition is measured in a 25 kg HDPE package. In other words, the self-accelerating decomposition temperature represents the temperature at which a chemical reaction begins that leads to uncontrolled decomposition, possibly accompanied by self-combustion and explosion phenomena. The self-accelerating decomposition temperature is measured, for example, in accordance with standard UN H.3 of the United Nations Manual of Test Methods and Criteria (7th revised edition, 2019).

[0080] Advantageously, the peresters according to the invention have a half-life temperature at 10 hours (HLT10h) of 75°C or higher and a self-accelerating decomposition temperature (SADT) of 50°C or higher, preferably 60°C or higher.

[0081] Preferably, the peresters according to the invention correspond to formula (I) where R4 represents a linear C1-C7, in particular C5 or C6 alkyl group, and exhibit a half-life temperature at 10 hours (HLT10h) ranging from 95°C to 105°C.

[0082] Also advantageously, the perester(s) according to the invention are obtained from bio-based starting materials.

[0083] The term "bio-based" is understood within the meaning of the present invention to mean that the perester(s) are obtained from compounds of plant and / or animal origin, preferably of plant origin.

[0084] The perester(s) according to the invention may comprise a content of bio-based carbon, i.e. carbon of plant and / or animal origin, in particular plant origin, of at least 20% by weight, preferably at least 50% by weight, more preferentially 100% by weight, relative to the total weight of carbon present in the perester compound.

[0085] Advantageously, the perester(s) according to the invention may comprise a carbon content derived from renewable starting materials of 50% by weight or more, preferably in the range of 55% to 70% by weight, more preferably in the range of 60% to 65% by weight, relative to the total weight of carbon present in the perester compound.

[0086] 14 The C content remains substantially constant from extraction from renewable starting materials through to the production of the copolymers according to the invention and to the end of the life of the articles made from said copolymers.

[0087] Therefore, in a material 14 The presence of C, regardless of its amount, is an indicator of the origin of the molecules that make it up, i.e., that they come from renewable starting materials rather than fossil materials.

[0088] In the material 14 The amount of C can be determined by one of the methods described in the ASTM D6866-06 standard (Standard Test Methods for Determination of Biobased Content of Natural Substances Using Radiocarbon and Isotope Ratio Mass Spectrometry).

[0089] This standard includes three methods for measuring organic carbon derived from renewable starting materials, called "biobased carbon." The percentages shown for the peresters of the present invention are preferably measured by mass spectrometry or liquid scintillation spectrometry as described in this standard, and most preferably by mass spectrometry.

[0090] These measurement methods 14 C / 12 C isotope ratios in biological materials, providing a 100% standard for measuring the proportion of organic carbon in a sample. 14 C / 12 Compare with the C isotope ratio.

[0091] Preferably, the perester(s) according to the invention are liquid at ambient temperature, i.e. at a temperature in the range of 21°C to 30°C.

[0092] The one or more allyl monomers may be selected from the group consisting of bis(allyl carbonate) monomers.

[0093] Advantageously, the one or more allyl monomers are bis(allyl carbonate) monomers of formula (II): [Case 2] TIFF2025538447000002.tif17170 [In formula (II), R a and R c are the same or different and are allyl groups of the formula: [C3] TIFF2025538447000003.tif18170 [where, formula R d teeth, - hydrogen atoms, a halogen atom, preferably a fluorine or chlorine atom, - linear or branched C1-C4 alkyl groups Select from represents R b is selected from alkylene groups, alkylene ether groups, aromatic alkylene ether groups, polyalkylene ether groups, alkylene carbonate groups, and mixtures thereof. is selected from the group consisting of:

[0094] Preferably, in formula (II), R a and R c are identical.

[0095] Preferentially, R a and R c are identical and represent an allyl group, where R d represents a hydrogen atom, a chlorine atom, a fluorine atom, or a methyl or ethyl group.

[0096] Even more preferentially, Ra and R c are identical and represent an allyl group, where R d represents a hydrogen atom.

[0097] Preferably, R b represents an alkylene group, an alkylene ether group, or an aromatic alkylene ether group.

[0098] The term "alkylene group" is understood to mean an alkyl group having unsaturation.

[0099] More preferentially, R b represents an alkylene group or an alkylene ether group.

[0100] Even more preferentially, R b represents an alkylene ether group, more particularly a group of the formula: [C4] TIFF2025538447000004.tif15170

[0101] In formula (II), R b is preferably aliphatic, i.e. does not represent an aromatic alkylene ether group. In other words, the allyl monomer(s) are preferentially selected from bis(allyl carbonate) monomers of formula (II):

[0102] The one or more allyl monomers 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-chloroallyl carbonate), triethylene glycol bis(allyl carbonate), 1,3-propane bis(allyl carbonate), propylene glycol bis(2-ethylallyl carbonate), 1,3-butene bis(allyl carbonate), 1,4-butene bis(2-bromoallyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis(2-ethylallyl carbonate), pentamethylene glycol bis(allyl carbonate), isopropylene bisphenol A bis(allyl carbonate), and mixtures thereof.

[0103] Preferably, the allylic monomer is diethylene glycol bis(allyl carbonate) (also known as ADC).

[0104] Other allylic monomers can be used alone or in combination with the bis(allylic carbonate) monomers described above, such as, for example, bis(allylic monocarbonate) monomers.

[0105] One or more allyl copolymers may result from the polymerization of the bis(allyl carbonate) monomers described above.

[0106] The one or more allyl copolymers are preferably selected from polyol poly(allyl carbonate).

[0107] The poly(allyl carbonate)(s) result from the polymerization of a polyol and a bis(allyl carbonate) monomer.

[0108] Among the polyols involved in the preparation of the polyol poly(allyl carbonate), mention may in particular be made of polyols chosen from 1,6-hexanediol, 1,4-cyclohexanedimethanol, polylactonediols, polyethoxylated glyceroldiols, xylene-α,α-diol, 1,4-bis(hydroxyethyl)toluene, 2,2-bis(4-(hydroxyethyl)phenyl)propane, pentaerythritol, trimethylolpropane, dipentaerythritol, ditrimethylolpropane, tris(hydroxyethyl)isocyanurate.

[0109] One or more allylic copolymers selected from polyol poly(allyl carbonate)s can be used in combination with allylic monomers, particularly bis(allyl carbonate) monomers of formula (II).

[0110] The allylic copolymer(s) may also result from the polymerization of a bis(allyl carbonate) monomer with a diol polyether.

[0111] The diol polyether is preferably selected from homopolymers, copolymers, or block polymers of polyether diols, such as those described in US Pat. No. 6,506,864.

[0112] Preferably, the present 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 selected from the group consisting of bis(allyl carbonate) monomers of formula (II).

[0113] More preferably, the present invention relates to the use of at least one peroxyester selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-amyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, tert-butyl 3,5,5-trimethylhexaneperoxyate, and mixtures thereof for the polymerization of diethylene glycol bis(allyl carbonate) (ADC).

[0114] composition As stated above, the composition according to the present invention is a polymerizable composition comprising one or more peresters corresponding to formula (I) above and one or more allylic monomers and / or allylic copolymers as defined above.

[0115] Preferably, the composition comprises at least one allylic monomer selected from the group consisting of bis(allyl carbonate) monomers.

[0116] Advantageously, the composition comprises: at least one perester of formula (I), R1 represents a linear or branched C1-C3, more preferably C1-C2 alkyl group, more preferably a CH3 group; R2 and R3 represent hydrogen atoms, and ○ R4 is a linear or branched C1-C 11 , more preferably C3-C 11 , and more preferably C5-C 10 Preferably, R4 represents a linear C1-C 11 , more preferably C3-C 11 , and more preferably C5-C 10 , and more preferably a C5-C6, more preferably a C5 alkyl group; at least one perester of formula (I), and - at least one allylic monomer selected from the group consisting of bis(allyl carbonate) monomers Includes:

[0117] Preferably, the composition comprises at least one allylic monomer selected from the group consisting of bis(allyl carbonate) monomers of formula (II) above.

[0118] More preferably, the composition comprises at least one allylic monomer selected from the group consisting of bis(allyl carbonate) monomers of formula (II), wherein R a and R c are identical and represent an allyl group, where R d represents a hydrogen atom, and R b represents an alkylene group or an alkylene ether group.

[0119] Preferably, the composition according to the invention comprises: at least one perester, such as tert-butyl peroxy-n-heptanoate, tert-amyl peroxy-n-heptanoate, tert-hexyl peroxy-n-heptanoate, tert-heptyl peroxy-n-heptanoate, tert-octyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, tert-hexyl peroxy-n-octanoate, tert-heptyl peroxy-n-octanoate, tert-octyl peroxy-n-octanoate, tert-butyl 3,5,5-trimethylhexaneperoxyate; , at least one perester selected from the group consisting of tert-amyl 3,5,5-trimethylhexaneperoxyate, tert-hexyl 3,5,5-trimethylhexaneperoxyate, tert-heptyl 3,5,5-trimethylhexaneperoxyate, tert-octyl 3,5,5-trimethylhexaneperoxyate, and mixtures thereof, preferably at least one perester selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, and mixtures thereof, more preferably tert-butyl peroxy-n-heptanoate, at least one allylic monomer, preferably selected from the group consisting of bis(allyl carbonate) monomers, more preferentially selected from the group consisting of aliphatic bis(allyl carbonate) monomers of formula (II) as defined above; Includes:

[0120] Advantageously, the composition according to the invention comprises: at least one perester selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-amyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, tert-butyl 3,5,5-trimethylhexaneperoxyate, tert-amyl 3,5,5-trimethylhexaneperoxyate, and mixtures thereof, preferably at least one perester selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, and mixtures thereof, more preferably tert-butyl peroxy-n-heptanoate, and - Diethylene glycol bis(allyl carbonate) (ADC) Includes:

[0121] 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 monomers and / or allylic copolymers present in the composition.

[0122] Preferably, the active oxygen content of the composition is between 0.1% and 0.5% by weight, preferably between 0.15% and 0.4% by weight, more preferably between 0.2% and 0.35% by weight, based on the total weight of the composition. The expression "active oxygen content" (also called "active O", "AO") is understood to mean the percentage by weight of oxygen radicals (one oxygen atom per perester functional group) based on the total weight of the composition. In other words, the active oxygen content expressed in % can be calculated as follows: 16 / molar mass of organic peroxide × weight concentration of organic peroxide in the composition.

[0123] The composition according to the invention may additionally comprise at least one polymerization initiator other than the peroxyester according to the invention.

[0124] In this case, the polymerization initiator can be an additional organic peroxide other than the peresters according to the invention or a non-peroxide compound, preferably an additional organic peroxide other than the peresters according to the invention.

[0125] Preferably, the composition according to the invention comprises at least one perester as defined above, at least one additional organic peroxide other than the one or more peresters according to the invention, and one or more allyl monomers and / or allyl copolymers.

[0126] The compositions according to the invention may also comprise one or more photoinitiators, such as those selected from acetophenone and benzophenone derivatives.

[0127] The compositions according to the present invention may also include one or more additional monomers other than the allylic monomer.

[0128] The one or more additional monomers are selected from acrylic or methacrylic monomers, such as those selected from methyl acrylate, methyl methacrylate, phenyl methacrylate, vinyl acetate, isoallyl isophthalate, diallyl terephthalate, and diallyl adipate.

[0129] The composition according to the invention may also comprise at least one pigment and / or at least one organic dye, ie at least one colorant.

[0130] In this case, the composition may also comprise at least one dispersant whose role is to disperse the pigment or pigments within the composition.

[0131] According to a preferred embodiment, the composition comprises: - diethylene glycol bis(allyl carbonate), at least one perester selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-amyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, tert-butyl 3,5,5-trimethylhexaneperoxyate, tert-amyl 3,5,5-trimethylhexaneperoxyate, and mixtures thereof, preferably at least one perester selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, and mixtures thereof, more preferably tert-butyl peroxy-n-heptanoate, and - at least one pigment and / or organic dye, and optionally at least one dispersant Includes:

[0132] Preferably, the colorant is a pigment.

[0133] The pigments that may be present in the composition may be organic or inorganic.

[0134] Inorganic pigments include in particular mineral pigments which may optionally be surface treated.

[0135] The mineral pigment(s) is preferably selected from titanium oxide, especially titanium dioxide, iron oxide, for example red iron oxide or yellow iron oxide, and zirconium oxide.

[0136] The organic pigment may be selected from phthalocyanine blue, phthalocyanine green, chromophthalic violet, and chromophthalic green oxide.

[0137] Mention may in particular be made, among other pigments, of phthalocyanine pigments, especially copper phthalocyanine pigments, in particular blue copper phthalocyanine pigments, and iron oxides.

[0138] Advantageously, the polymerizable composition is pigment-free.

[0139] The composition according to the invention may also contain one or more release agents, such as the agent sold under the trade name Zelec® UN by Stepan.

[0140] The compositions according to the invention are in particular liquid in a temperature range that may range from 10°C to 30°C, more preferentially from 15°C to 25°C.

[0141] The compositions according to the invention as defined above are polymerizable compositions, ie capable of polymerizing under the action of heat.

[0142] The present invention also relates to the use of a polymerizable composition as defined above for the production of organic glasses, preferably ophthalmic lenses.

[0143] organic glass Preferably, the polymerizable composition according to the present invention yields an organic glass after polymerization.

[0144] The present invention therefore also relates to an organic glass obtained from the polymerization of the composition defined above.

[0145] More particularly, the invention also relates to an organic glass obtained from the radical polymerization of the composition defined above.

[0146] The organic glass is preferably selected from the group consisting of instrument windows, photodetectors, and ophthalmic lenses.

[0147] Preferably, the organic glass is selected from the group consisting of ophthalmic lenses.

[0148] Within the meaning of the present invention, the term "ophthalmic" refers to glasses that can be worn in spectacles and have the function of protecting the eyes from sunlight, in particular UV rays (sunglasses), or of correcting vision. In the latter case, the ophthalmic lenses are preferably afocal, monofocal, bifocal, trifocal or progressive.

[0149] Thus, the ophthalmic lens may be of the multifocal or progressive or regressive power type, ie a variable power multifocal lens.

[0150] The resulting ophthalmic lens may be covered with a coating or may be surface treated.

[0151] Advantageously, the invention relates to an ophthalmic lens obtained from the polymerization of the composition defined above.

[0152] According to one embodiment, the ophthalmic lens is obtained from the polymerization of a composition comprising at least one perester according to the invention, selected from the group consisting of tert-butyl peroxy-n-heptanoate, tert-amyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, tert-butyl 3,5,5-trimethylhexaneperoxyate, tert-amyl 3,5,5-trimethylhexaneperoxyate, and mixtures thereof, with at least one allylic monomer selected from the group consisting of bis(allyl carbonate) monomers of formula (II) as defined above, in particular diethylene glycol bis(allyl carbonate).

[0153] Products Obtained from Polymerizable Compositions Another subject of the present invention relates to the products resulting from the polymerization of one or more allyl monomers and / or one or more allyl copolymers in the presence of one or more peresters according to the invention as defined above.

[0154] The product is therefore 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 above.

[0155] The polymer composition is thus obtained by polymerization of the polymerizable composition defined above, more particularly by polymerization of the different components of the polymerizable composition.

[0156] In other words, the polymer composition corresponds to a resin that can serve as a base material for the manufacture of any type of object used for its excellent mechanical, aesthetic and optical properties, in particular its optical properties.

[0157] Preferably, the polymer product or polymer composition can be molded to obtain organic glasses or other objects that are used for their excellent mechanical and optical properties, particularly their transparency and light coloring, or even colorless nature.

[0158] The polymer composition is in particular in solid form in the temperature range between 10°C and 30°C, more preferentially between 15°C and 25°C.

[0159] Polymerization Process Likewise, the present invention also relates to a process for polymerizing the polymerizable composition defined above, comprising at least one stage of polymerization of the polymerizable composition defined above at one or more temperatures preferably below 110°C.

[0160] The present invention also relates to a process for preparing the polymer composition defined above, comprising at least one stage of polymerization of the polymerizable composition defined above, preferably at one or more temperatures below 110°C.

[0161] Process for preparing organic glass The process for preparing the organic glass comprises at least one stage of polymerization of the composition defined above in a device equipped with at least one mold, at one or more temperatures preferably below 110°C.

[0162] According to one embodiment, the process for preparing an organic glass comprises at least the following steps: - introducing the polymerizable composition defined above into a device comprising at least one mold, - polymerizing said composition at one or more temperatures, preferably up to 110°C (preferably the polymerization steps are a series of steps at different temperatures allowing for control of shrinkage and polymerization), - Recovering organic glass Includes:

[0163] According to this embodiment, the introducing step is a step of pouring or injecting the polymerizable composition according to the invention into a device comprising at least one mold.

[0164] The device can include at least one mold having a complex shape, such as a two-plane mold, a mold having a concave and a convex portion, or a concave mold.

[0165] Preferably, the device comprises at least one mold comprising at least one recess and at least one protrusion.

[0166] More generally, the device comprises at least one mold that represents the final shape of the desired organic glass.

[0167] The device may also include at least one mold having one surface with a shape corresponding to the final shape of the desired organic glass and another surface that is not modeled as a function of the final shape of the organic glass but allows for the preparation of a second surface of organic glass that can then be processed.

[0168] Preferably, the introducing step consists of injecting the polymerizable composition between two molds having the required surface shapes (e.g., one mold having a concave shape and the other having a convex shape).

[0169] The polymerization step is in particular a radical polymerization.

[0170] The polymerization step can be carried out by carrying out a thermal cycle at a temperature range of up to 110° C. for a time sufficient to effect polymerization, specifically in the range of 10 to 30 hours, preferably 30 hours.

[0171] Thus, the temperature can be gradually increased during the polymerization stage.

[0172] The polymerization step makes it possible to obtain the desired organic glass.

[0173] The process for preparing the organic glass can include, after the polymerization step, an annealing step of the organic glass aimed at eliminating any residual stresses in the glass, which can be carried out at a temperature ranging from 60°C to 130°C, preferably from 70°C to 100°C, for a time period ranging from 1 hour to 20 hours.

[0174] The step of recovering the organic glass may comprise opening the mold and collecting the organic glass.

[0175] Thus, the process for preparing the organic glass preferably comprises the steps of pouring or injecting the composition according to the invention into a device comprising at least one mold having at least one recess and at least one protrusion, closing the mold and polymerizing the composition defined above, and opening the mold and collecting the organic glass.

[0176] The process according to the invention makes it possible in particular to prepare the ophthalmic lenses described above.

[0177] The organic glass obtained according to this preparation process can be subjected to any type of treatment, such as a surface treatment, in order to improve its mechanical, aesthetic and optical properties, or even its wettability properties.

[0178] According to one embodiment, as mentioned above, the polymerizable composition according to the invention may additionally comprise at least one colorant, preferably at least one pigment and / or at least one organic dye.

[0179] Alternatively, the process for preparing the organic glass according to the invention can comprise an additional step consisting of adding at least one colorant, preferably at least one pigment, after obtaining the organic glass, i.e. after the polymerization step.

[0180] The organic glasses obtained according to this process exhibit good mechanical, aesthetic and optical properties.

[0181] The optical quality of the organic glass according to the invention can be evaluated in particular by determining at least one of the following parameters: - Refractive index (n D 20 ), measured with an Abbe refractometer (ASTM D-542 standard method), - Yellowness Index (YI), measured spectrophotometrically using a spectrophotometer according to the CIE 1976 standard (method according to ASTM E313 standard) according to the following formula: [Number 1] TIFF2025538447000005.tif10170 where X, Y, and Z are the trichromatic coordinates of the sample measured on a spectrophotometer across the entire spectrum between 380 and 780 nanometers.

[0182] The mechanical properties of the organic glass according to the invention are determined in particular by the following parameters: - Rockwell hardness, measured using a Rockwell hardness tester (method according to ASTM D-785 standard); - Shore D hardness, measured using a portable durometer, HPE II Shore D type (method of ASTM D 2240 standard); - modulus of elasticity, or - Friction coefficient The evaluation can be performed by determining at least one of:

[0183] Preferably, the mechanical properties of the organic glass according to the present invention can be evaluated from the hardness.

[0184] The following examples are intended to illustrate, but not limit, the present invention. [Example]

[0185] The following examples illustrate the invention without limiting it.

[0186] A. Example of Peroxyester Preparation Synthesis of peroxyesters Tertiary alkyl peroxyesters are generally prepared by the reaction of a hydroperoxide with an acid chloride or anhydride in the presence of a base such as sodium hydroxide or a tertiary amine (see D. Swern - Organic Peroxides, Vol. 1, p. 74 - Published by Wiley, 1970).

[0187] 1.1 Preparation of tert-butyl peroxy-n-heptanoate 74 g of tert-butyl hydroperoxide solution (70%) is mixed with 116 g of potassium hydroxide solution (30%) in a glass reactor equipped with a jacket, condenser, and stirring system at a temperature of 5-10°C. Next, 70 g of n-heptanoic acid chloride (99.7%) is added to this solution in a controlled manner to maintain the temperature between 5 and 10°C. After 45 minutes of reaction at 5-10°C, the temperature is increased to 20-25°C over 15 minutes. After the reaction, the two phases are allowed to settle and separate. The organic phase is washed with sodium hydroxide solution (10%), then with sodium metabisulfite solution (10%), and then with water. 67 g of tert-butyl peroxy-n-heptanoate solution is recovered.

[0188] 1.2 Preparation of tert-amyl peroxy-n-heptanoate 32 g of tert-amyl hydroperoxide solution (85%) is mixed with 59 g of potassium hydroxide solution (30%) in a glass reactor equipped with a jacket, condenser, and stirring system at a temperature of 5-10°C. Next, 35 g of n-heptanoic acid chloride (99.7%) is added to this solution in a controlled manner to maintain the temperature between 5 and 10°C. After 45 minutes of reaction at 5-10°C, the temperature is increased to 20-25°C over 15 minutes. After the reaction, the two phases are allowed to settle and separate. The organic phase is washed with sodium hydroxide solution (10%), then with sodium metabisulfite solution (10%), and then with water. 26 g of tert-amyl peroxy-n-heptanoate solution is recovered.

[0189] 1.3 Preparation of tert-butyl peroxy-n-octanoate 52 g of tert-butyl hydroperoxide solution (70%) is mixed with 83 g of potassium hydroxide solution (30%) at a temperature of 5-10°C in a glass reactor equipped with a jacket, condenser, and stirring system. Next, 52 g of n-octanoic acid chloride (98.8%) is added to this solution in a controlled manner to maintain the temperature between 5 and 10°C. After 45 minutes of reaction at 5-10°C, the temperature is increased to 20-25°C over 15 minutes. After the reaction, the two phases are allowed to settle and separate. The organic phase is washed with sodium hydroxide solution (10%), then with sodium metabisulfite solution (10%), and then with water. 52 g of tert-butyl peroxy-n-octanoate solution is recovered.

[0190] 1.4 Preparation of tert-amyl peroxy-n-octanoate 38 g of tert-amyl hydroperoxide solution (85%) is mixed with 66 g of potassium hydroxide solution (30%) at a temperature of 5-10°C in a glass reactor equipped with a jacket, condenser, and stirring system. Next, 47 g of n-octanoic acid chloride (98.8%) is added to this solution in a controlled manner to maintain the temperature between 5 and 10°C. After 45 minutes of reaction at 5-10°C, the temperature is increased to 20-25°C over 15 minutes. After the reaction, the two phases are allowed to settle and separate. The organic phase is washed with sodium hydroxide solution (10%), then with sodium metabisulfite solution (10%), and then with water. 39 g of tert-amyl peroxy-n-octanoate solution is recovered.

[0191] B. Examples of Preparation of Polymerizable Compositions The polymerizable compositions are prepared starting from diethylene glycol bis(allyl carbonate) (CAS 142-22-3) sold by PPG under the trade name CR-39® and the following organic peroxides:

[0192] The organic peroxides tested were as follows (the proportion of organic peroxides corresponds to 0.23% of the active oxygen in the composition, which corresponds to the weight proportions in the table below): [Table 1] TIFF2025538447000006.tif172170

[0193] C. Preparation of Organic Glass Next, each of the compositions obtained above is poured into a mold having a recessed portion and a protruding portion. After pouring, the recessed portion of the mold is covered with the protruding portion to close it, and then this assembly is heated to a temperature of 110°C or less.

[0194] The thermal crosslinking cycle is adjusted according to the decomposition temperature (half-life temperature (HLT) at 1 hour and 10 hours) of the organic peroxide used, according to the following scheme: the temperature is raised to the 10-hour half-life temperature (HLT 10 hours) of the peroxide used over 14 hours, then raised to the 1-hour half-life temperature (HLT 1 hour) of the peroxide used over 4 hours at HLT, then cooled to a temperature of 70°C and removed from the mold at that temperature.

[0195] The polymerized product thus obtained is annealed at a temperature that can range up to 130° C. for a time that can vary from 1 to 20 hours.

[0196] The organic glass is then recovered.

[0197] D. Biplanar system for measuring optical properties Different optical properties, namely Shore D hardness and Yellowness 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 performed between 10 x 15 cm flat glass sheets, 4 mm thick, arranged vertically and separated by a 4 mm diameter silicone rubber seal. Mechanical bonding of this assembly was achieved by a constant-pressure grip clamp. All tests were performed with an air intake at the top of the mold.

[0198] The yellowness index YI is obtained according to the CIE 1976 standard (color arrangement) with a spectrophotometer model SP60 from the manufacturer X-Rite. The trichromatic coordinates are from Hunter Lab. The measurements are calibrated daily with a standard calibration tile (black and white): 20609 D65:10°, 18 / 02 / 2010, WO A89274.

[0199] The YI measurement was made on a glass thickness of 4 mm and expressed as the difference from the YI measured in the white zone of the Leneta Form 2A chart (yellowness index measurement of 10.48 after calibration of the spectrophotometer).

[0200] The Shore D hardness is measured using a portable durometer, HPE II Shore D type (manufacturer: Bareiss, equipment conforming to the standards NF T51-174; DIN EN ISO 868; ISO 7619; ASTM D 2240; BS 903 Part A26).

[0201] For each organic glass, the organic hardness was measured five times and the average value was retained.

[0202] The results regarding the hardness of the obtained organic glasses are summarized in the following table: [Table 2] TIFF2025538447000007.tif56170

[0203] The organic glasses obtained using the peroxyesters according to the invention have significantly higher hardness than the glasses obtained using organic peroxides not corresponding to formula (I) according to the invention (t-butylperoxy-2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate).

[0204] Diisopropyl peroxydicarbonate cannot be stored or transported at room temperature.

[0205] The results regarding the yellowness index (YI) of the organic glasses obtained with the tested organic peroxides are summarized in the following table: [Table 3] TIFF2025538447000008.tif35170

[0206] The organic glass obtained using the peroxyester according to the present invention exhibits a lower yellowness index (YI) and / or allows the storage and transportation of the organic peroxide at room temperature compared to the organic glass obtained using the organic peroxide not corresponding to formula (I) according to the present invention.

Claims

1. For the polymerization of one or more allyl monomers and / or allyl copolymers, the following formula (I): [5] [In formula (I), ・R １ is a linear or branched non-aromatic C １ -C １０ represents an alkyl group, ・R ２ and R ３ represents a hydrogen atom, ・R ４ is a hydrogen atom or a linear or branched C １ -C １６ represents an alkyl group] Use of one or more peresters of

2. In formula (I), R １ But linear C １ -C ６ , preferably C １ -C ５ , more preferably C １ -C ４ , and more preferentially C １ -C ３ and more preferably represents an alkyl group of the formula CH ３ 2. The use according to claim 1, characterized in that the aryl group is a aryl group.

3. In formula (I), R ４ is a linear or branched chain C １ -C １１ , more preferably C ３ -C １１ , and more preferably C ５ -C １０ preferably represents an alkyl group represented by R ４ But linear C １ -C １１ , more preferably C ３ -C １１ , and more preferably C ５ -C １０ , and more preferably C ５ -C ６ , more preferably C ５ 3. Use according to claim 1 or 2, characterized in that it represents an alkyl group of the formula:

4. The one or more peresters are tert-butyl peroxy-n-heptanoate, tert-amyl peroxy-n-heptanoate, tert-hexyl peroxy-n-heptanoate, tert-heptyl peroxy-n-heptanoate, tert-octyl peroxy-n-heptanoate, tert-butyl peroxy-n-octanoate, tert-amyl peroxy-n-octanoate, tert-hexyl peroxy-n-octanoate, tert-heptyl peroxy-n-octanoate, tert-octyl peroxy-n-octanoate, 4. Use according to any one of claims 1 to 3, characterized in that the perester is selected from the group consisting of tert-butyl peroxyn-n-heptanoate, tert-butyl peroxyn-n-octanoate, tert-amyl peroxyn-n-trimethylhexaneperoxyate, and mixtures thereof, preferably the at least one perester is selected from the group consisting of tert-butyl peroxyn-n-heptanoate, tert-butyl peroxyn-n-octanoate, and mixtures thereof, more preferentially tert-butyl peroxyn-n-heptanoate.

5. 5. Use according to any one of claims 1 to 4, characterized in that the perester or peresters have a half-life temperature at 10 hours (HLT 10h) of 75°C or higher.

6. Use according to any one of claims 1 to 5, characterized in that the perester or peresters have a self-accelerating decomposition temperature (SADT) of 50°C or more, preferably 60°C or more.

7. 7. Use according to any one of claims 1 to 6, characterized in that the allyl monomer is selected from the group consisting of bis(allyl carbonate) monomers.

8. The allylic monomer is a bis(allyl carbonate) monomer of formula (II): [6] [In formula (II), ・R ａ and R ｃ are the same or different and are allyl groups of the formula: [7] [wherein formula R ｄ teeth, - hydrogen atom, a halogen atom, preferably a fluorine or chlorine atom, - Linear or branched C １ -C ４ Alkyl group Selected from represents ・R ｂ is selected from the group consisting of alkylene groups, alkylene ether groups, aromatic alkylene ether groups, polyalkylene ether groups, alkylene carbonate groups, and mixtures thereof. Use according to any one of claims 1 to 7, characterized in that it is selected from the group consisting of:

9. 9. Use according to any one of claims 1 to 8, characterized in that the allyl monomer is selected 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-chloroallyl carbonate), triethylene glycol bis(allyl carbonate), 1,3-propane bis(allyl carbonate), propylene glycol bis(2-ethylallyl carbonate), 1,3-butene bis(allyl carbonate), 1,4-butene bis(2-bromoallyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis(2-ethylallyl carbonate), pentamethylene glycol bis(allyl carbonate), isopropylene bisphenol A bis(allyl carbonate), and mixtures thereof.

10. 10. Use according to any one of claims 1 to 9, characterized in that the allylic monomer is diethylene glycol bis(allyl carbonate).

11. 11. A polymerizable composition comprising at least one perester according to any one of claims 1 to 6 and at least one allylic monomer and / or at least one allylic copolymer according to any one of claims 1 and 7 to 10.

12. 12. Composition according to claim 11, characterized in that it also contains at least one additional organic peroxide other than the perester according to any one of claims 1 to 6.

13. 13. Use of a composition according to claim 11 or 12 for the production of organic glasses, preferably ophthalmic lenses.

14. A polymer composition obtained by polymerization of the polymerizable composition according to claim 11 or 12.

15. 13. An organic glass obtained by polymerization of the polymerizable composition according to claim 11 or 12, preferably selected from the group consisting of instrument windows, photodetectors and ophthalmic lenses.

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