CN120152995A

CN120152995A - Composition based on allyl monomers and peroxides for the manufacture of organic glass

Info

Publication number: CN120152995A
Application number: CN202380078851.5A
Authority: CN
Inventors: B·范赫梅里克; S·胡布
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2022-11-18
Filing date: 2023-11-17
Publication date: 2025-06-13
Also published as: JP2025538447A; MX2025005304A; WO2024105341A1; KR20250117385A; EP4619448A1

Abstract

本发明涉及一种或多种式(I)的过酸酯用于至少一种烯丙基单体和/或至少一种烯丙基共聚物的聚合的用途。本发明还涉及包含至少一种烯丙基单体和/或至少一种烯丙基共聚物和至少所述过酸酯的可聚合组合物。本发明还涉及如上定义的可聚合组合物用于有机玻璃、优选眼科镜片的制造的用途。本发明还涉及由如上定义的可聚合组合物的聚合获得的有机玻璃。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. The present invention also relates to the use of the polymerizable composition as defined above for the manufacture of organic glasses, preferably ophthalmic lenses. The present invention also relates to organic glasses obtained by the polymerization of the polymerizable composition as defined above.

Description

Allyl monomer and peroxide-based composition for the manufacture of organic glass

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.

The invention also relates to a polymerizable composition comprising at least one allyl monomer and/or at least one allyl copolymer and at least the perester.

The invention also relates to the use of a polymerizable composition as defined above for the manufacture of a plexiglass, preferably an ophthalmic lens.

The invention also relates to a plexiglass obtained by polymerization of a polymerizable composition as defined above.

Plexiglas, such as instrument or optical detector windows or ophthalmic lenses, may be prepared by free radical polymerization of one or more allyl monomers and/or allyl copolymers in the presence of one or more polymerization initiators, in particular organic peroxides.

Such free-radical polymerization can be carried out in particular by pouring the polymerizable composition based on allyl monomers and/or allyl copolymers and organic peroxides into a mold (in particular a mold made of mineral glass) having a geometry suitable for the desired application.

The mould is typically an assembly that may be made up of two glass parts, in particular mineral glass parts, which are separated by a recess and held together by the presence of a sealing seal made of elastomeric and/or thermoplastic material, located at the periphery. Thus, the polymerizable composition is poured into the cavity formed between the two glass parts of the mold so as to undergo therein a suitable thermal cycle during which the temperature may be raised more or less gradually, while optionally one or more stable temperature phases are observed.

During such thermal cycling, the composition polymerizes and hardens in the mold to produce a plexiglass after removal from the mold, which may then undergo various types of processing, depending upon the desired application. The mold is typically reused in many thermal cycles.

Organic peroxides commonly used as polymerization initiators are entities that are generally highly unstable when heated. This is because, in the case of uncontrolled increases in temperature, some organic peroxides may undergo self-accelerating exothermic decomposition with the risk of ignition and/or severe decomposition. Thus, where it is intended for the production of plexiglas, this behaviour proves difficult to make it compatible with the current regulations regarding the transportation and storage of hazardous materials.

It has therefore proved to be particularly advantageous to formulate such organic peroxides in liquid form in solvents (also known as phlegmatizers), i.e. in a diluted state, in order to reduce their thermal instability, thereby ensuring that they can be stored and transported under safer conditions.

For this purpose, the use of diisopropyl peroxydicarbonate (commonly known as IPP) for the free radical polymerization of allyl monomers and/or allyl copolymers (diisopropyl peroxydicarbonate is dissolved in allyl monomers, for example diethylene glycol bis (allyl carbonate), in a content of 27% by weight relative to the total weight of the composition) makes it possible to obtain organic glasses with good optical properties, in particular in terms of transparency and weak coloration, aesthetic properties and mechanical properties. In other words, the organic glass obtained with such an organic peroxide composition has the following advantages, is transparent and colorless, and exhibits good mechanical properties, for example, in terms of hardness and abrasion. For example, such compositions may be sold by Arkema under the trade name Luperox IPP27 or by Nouryon under the trade name Perkadox IPP-NS 27.

Nevertheless, such compositions based on diisopropyl peroxydicarbonate show a too large risk of uncontrolled decomposition during storage and transport in the event of uncontrolled increases in temperature.

This is because diisopropyl peroxydicarbonate is a "cold" peroxide, that is to say it shows, alone or as a mixture with other peroxides and/or phlegmatizers, a maximum transport temperature set at-20 ℃, also called control temperature, according to UN Recommendations for Transportation of Dangerous Goods, 19 th edition, section 2.5.3.2.4, related to organic peroxides.

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 ℃.

Thus, despite the dilution of diisopropyl peroxydicarbonate in allyl monomers, continuous exposure to very low temperatures, in particular temperatures below 20 ℃, during storage and movement of products such as Luperox IPP27 or Perkadox IPP-NS27, in particular during marine transport, proves necessary in order to minimize the risk of decomposition thereof, which greatly complicates its use.

Furthermore, in order to reduce the risk of starting polymerization of allyl monomers having the function of desensitizing organic peroxides, the temperature of these products during transportation and storage must be controlled.

In addition, diisopropyl peroxydicarbonate also exhibits the disadvantage of being too reactive to be stored and transported in allyl monomers at concentrations of more than 30% by weight.

To overcome these numerous difficulties, it has been envisaged to replace diisopropyl peroxydicarbonate with organic peroxides, such as diacyl aromatic peroxides or peresters, which can be stored and transported at ambient temperature.

However, such organic peroxides present the drawback of leading to high polymerization temperatures, which may be greater than 120 ℃, indeed even greater than 125 ℃, instead of around 80 ℃ for diisopropyl peroxydicarbonate. Thus, such polymerization temperatures tend to damage the surface geometry of the glass mold and to damage the elastomer and/or thermoplastic seals more or less rapidly, preventing their re-use in many subsequent thermal cycles on the one hand, and on the other hand leading to mechanical and optical defects in the formed organic glass.

In particular, it was observed that the degree of breakage increased significantly upon removal of the organic glass formed with such organic peroxide from the mold.

Furthermore, such high polymerization temperatures promote the risk of organic glass yellowing. This is because this type of organic peroxide, in particular benzoyl peroxide, can cause intense yellowing of the organic glass, which requires recourse to colorants capable of compensating, if possible, for this yellowing. However, their presence is not always effective for most of the time, or acceptable when wearing corrective lenses.

Finally, thermal cycling, during which the polymerization temperature is at least 40 ℃ higher than that of the diisopropyl peroxydicarbonate generally used, results in a significant excess of energy consumption, resulting in the additional costs associated with annual production of organic glass.

In other words, the low reactivity of these organic peroxides, which can be stored and transported at ambient temperature, proves to be incompatible with the molding materials, thus leading to deterioration of the molds and of the elastomer and/or thermoplastic seals employed, promoting the formation of mechanical and optical defects of the organic glasses obtained, in particular reflected by aggravating their yellowing, and increasing the production costs.

As a result, while such peroxides allow for operation under safer conditions, they generally result in organic glass having significantly poorer mechanical and optical properties than organic glass obtained with cold peroxides.

In view of the above, one of the objects of the present invention is to overcome the above drawbacks, that is to say to replace the organic peroxides commonly used during the polymerization of allyl monomers and/or allyl copolymers with other polymerization initiators which can be stored and transported alone or as a mixture at ambient temperature, in order to obtain organic glasses with good optical, aesthetic and mechanical properties, without deteriorating the industrial equipment used during their manufacture.

In other words, it is therefore actually necessary to use other polymerization initiators which can be stored and transported at ambient temperature, i.e. therefore under safe conditions, alone or as a mixture, while at the same time being able to produce organic glasses which have particularly good properties in terms of transparency, color (in particular yellowing), hardness and abrasion resistance.

In particular, one of the objects of the present invention is to improve the safety conditions for obtaining organic glasses without changing their optical, aesthetic and mechanical properties and without deteriorating the glass moulds, in particular their geometrical parameters, such as their surface geometry, and the elastomer and/or thermoplastic seals necessary for their manufacture.

The subject of the present invention is therefore in particular the use of one or more peresters corresponding to the following formula (I) for the polymerization of one or more allyl monomers and/or allyl copolymers:

[ chemical 1]

Wherein formula (I):

R ₁ represents a linear or branched, non-aromatic C ₁-C₁₀ alkyl group, preferably R ₁ represents a linear C ₁-C₃, more preferably a C ₁-C₂ alkyl group, more preferably a CH ₃ group,

R ₂ and R ₃ represent a hydrogen atom,

R ₄ represents a hydrogen atom or a linear or branched C ₁-C₁₆ alkyl group, preferably R ₄ represents a linear C ₁-C₁₁, more preferably C ₃-C₁₁, still more preferably C ₅-C₁₀, still more preferably C ₅-C₆ and more preferably C ₅ alkyl group.

The one or more peresters according to the invention are thus one or more non-aromatic tertiary alkyl peroxyesters.

The peresters according to the invention have the advantage that they can be stored and transported alone or as a mixture with other peroxides and/or phlegmatizers which are reactive or non-reactive at ambient temperature, i.e. under better safety conditions.

The term "ambient temperature" is understood to mean a temperature which may be in the range of 21 ℃ to 30 ℃.

The peresters according to the invention thus have the advantage of exhibiting, alone or as a mixture with other peroxides and/or phlegmatizers (reactive or non-reactive), a maximum transport temperature (also called control temperature) strictly above 20 ℃, according to UN Recommendations for Transportation of Dangerous Goods, 19 th edition, 2.5.3.2.4 in relation to organic peroxides.

Thus, the safety conditions with respect to transportation and storage are improved compared to the use of cold peroxides as defined above, in particular with respect to organic peroxides belonging to the dialkyl peroxydicarbonates, in particular diisopropyl peroxydicarbonate dissolved in diethylene glycol bis (allyl carbonate) and sold under the name Luperox IPP27 or under the name Perkadox IPP-NS 27.

The peroxyesters according to the invention are in fact easier to handle, they present the advantage of significantly reducing the costs associated with their transportation and with their storage, and can be distributed more widely worldwide under safe conditions, including distribution in the least accessible places.

The peresters also present the advantage of being able to be used alone, i.e. in an undiluted state, which makes it possible to dispense with the use of non-polymerizable solvents, for example oils, which are necessary for safety reasons and which tend to negatively affect the optical and mechanical quality of the organic glass obtained, on the one hand, and polymerizable solvents, for example allyl monomers, which tend to increase the risk of starting polymerization at unregulated temperature during transport or storage, on the other hand.

More generally, the peresters according to the invention make it possible to dispense with the installation of any type of storage device (or devices intended to store the solvent) dedicated to polymerizable or non-polymerizable solvents at the site where the peroxide is produced, which results in a significant space saving and reduced maintenance costs.

In other words, the peroxide according to the invention makes it possible to avoid any type of problem associated with the use of polymerizable or non-polymerizable solvents.

More particularly, the peresters according to the invention allow to dispense with the usual phlegmatizers for peroxides (e.g. hydrocarbons, such as isododecane, mineral oil, esters, such as liquid phthalates, ethylbenzene or allyl monomers).

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

Furthermore, the peresters according to the invention exhibit sufficient reactivity to cause a significantly lower polymerization temperature than previously used organic peroxides storable and transportable at ambient temperature without damaging the industrial equipment used in the molding process and without degrading the optical, aesthetic and mechanical properties of the organic glass.

The term "polymerization temperature" is understood to mean the highest temperature reached during the thermal polymerization cycle.

In particular, the peresters according to the invention do not reduce the geometric constants of the glass mold, such as their surface geometry, and the quality of the elastomer and/or thermoplastic seal, which makes it possible to ensure that the glass mold is reused for subsequent thermal cycles.

In other words, the peresters according to the invention present the advantage of being compatible with glass molding techniques and with elastomeric and/or thermoplastic seals.

The use of peresters according to the invention can additionally improve growth on an industrial scale of organic glass, in particular minimize the rate of breakage after the organic glass is removed from the mould, and reduce any excessive energy consumption associated with its production.

The organic glass thus obtained is in particular transparent, weakly colored, indeed even colorless, and has good mechanical properties, in particular in terms of hardness and abrasion resistance.

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

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

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

The composition according to the invention is therefore polymerizable or polymerizable.

The invention also relates to the use of a composition as defined above for the manufacture of organic glass.

Another subject-matter according to the invention relates to a plexiglass obtained by polymerizing a composition as defined above.

The organic glass exhibits good aesthetic, optical and mechanical properties.

The organic glass in particular exhibits improved hardness compared to organic glasses obtained with other organic peroxides which can be stored and transported at ambient temperature.

Other features and advantages of the invention will become more apparent from a reading of the following description and examples.

In the following, and unless otherwise indicated, the limits of the ranges of values are included in this document.

The expression "at least one" is equivalent to the expression "one (species) or a plurality of (species)".

Within the meaning of the present invention, the terms "perester" and "peroxyester" are used indifferently.

Use of the same

As indicated 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 allyl monomers and/or allyl copolymers.

The term "non-aromatic" within the meaning of the present invention is understood to mean that R ₁ does not contain an aromatic ring.

In other words, R ₁ represents an aliphatic C ₁-C₁₀ alkyl group.

Preferably, in formula (I), R ₁ represents a linear or branched non-aromatic C ₁-C₆, still more preferably C ₁-C₅, still better C ₁-C₄, still more preferably C ₁-C₃ alkyl.

Advantageously, in formula (I), R ₁ represents a linear C ₁-C₃, more preferably a C ₁-C₂, alkyl group, more preferably a CH ₃ group.

Advantageously, in formula (I), R ₄ represents a hydrogen atom or a linear C ₁-C₁₆ alkyl group.

Preferably, in formula (I), R ₄ represents a linear or branched C ₁-C₁₁, more preferably C ₃-C₁₁, still more preferably C ₅-C₁₀, still more preferably C ₅-C₆ and more preferably C ₅ alkyl.

Preferably, in formula (I), R ₄ represents a linear C ₁-C₁₁, more preferably C ₃-C₁₁, still more preferably C ₅-C₁₀, still more preferably C ₅-C₆ and more preferably C ₅ alkyl.

Advantageously, in formula (I):

R ₁ represents a linear C ₁-C₃, more preferably a C ₁-C₂ alkyl, more preferably a CH ₃ group,

-R ₂ and R ₃ represent a hydrogen atom, and

R ₄ represents a linear or branched C ₁-C₁₁, more preferably C ₃-C₁₁, still more preferably C ₅-C₁₀ alkyl group, preferably R ₄ represents a linear C ₁-C₁₁, more preferably C ₃-C₁₁, still more preferably C ₅-C₁₀, still more preferably C ₅-C₆ and more preferably C ₅ alkyl group.

The one or more peresters are preferably selected from the group consisting of t-butyl peroxy-n-heptanoate, t-amyl peroxy-n-heptanoate, t-hexyl peroxy-n-heptanoate, t-heptyl peroxy-n-heptanoate, t-octyl peroxy-n-octanoate, t-amyl peroxy-n-octanoate, t-hexyl peroxy-n-octanoate, t-heptyl peroxy-n-octanoate, t-octyl peroxy-n-octanoate, t-butyl 3, 5-trimethylhexane peroxy-t-amyl 3, 5-trimethylhexane peroxy-t-hexyl 3, 5-trimethylhexane peroxy-t-heptyl 3, 5-trimethylhexane peroxy-t-octyl and mixtures thereof.

Preferably, the one or more peresters are selected from the group consisting of t-butyl peroxy-n-heptanoate, t-amyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate, t-amyl peroxy-n-octanoate, t-butyl 3, 5-trimethylhexane peroxyate, t-amyl 3, 5-trimethylhexane peroxyate, and mixtures thereof.

Advantageously, the one or more peresters are selected from the group consisting of t-butyl peroxy-n-heptanoate, t-amyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate, t-amyl peroxy-n-octanoate and mixtures thereof, more preferably, the one or more peresters according to the invention are selected from the group consisting of t-butyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate and mixtures thereof, still more preferably t-butyl peroxy-n-heptanoate.

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

Preferably, the peresters according to the invention are obtained in particular from the reaction between tert-butyl or tert-amyl hydroperoxide and an acyl halide, preferably an acyl chloride, in particular n-heptanoyl chloride or n-octanoyl chloride.

Preferably, the one or more peresters according to the invention have a10 hour half life temperature, expressed as HLT 10h, of greater than or equal to 75 ℃.

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

The 10 hour half life temperature of the peroxyesters according to the invention, expressed as HLT 10h, is preferably measured in isododecane solution.

Preferably, the peresters according to the invention have a 10 hour half life temperature, expressed as HLT 10h, of less than or equal to 110 ℃.

Preferably, the peresters according to the invention have a10 hour half life temperature between 70 ℃ and 110 ℃, more preferably between 75 ℃ and 105 ℃.

Preferably, the peresters according to the invention have a 10 hour half life temperature (HLT 10 h) ranging from 95 ℃ to 105 ℃.

The peresters according to the invention additionally exhibit Self Accelerated Decomposition Temperatures (SADT) of greater than or equal to 50 ℃, preferably greater than or equal to 60 ℃.

The term "self-accelerating decomposition temperature" (SADT) is understood to mean the lowest temperature at which uncontrolled reactions, i.e. self-accelerating decomposition, occur in its packaging. Preferably, the self-accelerating decomposition is measured in 25kg HDPE packaging. In other words, self-accelerating decomposition temperature means the temperature at which a chemical process leading to uncontrolled decomposition begins, possibly accompanied by spontaneous combustion and explosion phenomena. The self-accelerating decomposition temperature is, for example, measured according to the 7 th revision of standard UN H.3 of the United Nations Manual of TESTS AND CRITERIA, 2019.

Advantageously, the peresters according to the invention exhibit a half life temperature in 10 hours (HLT 10 h) greater than or equal to 75 ℃ and a Self Accelerated Decomposition Temperature (SADT) greater than or equal to 50 ℃, preferably greater than or equal to 60 ℃.

Preferably, the peresters according to the invention correspond to formula (I), wherein R ₄ represents a linear C ₁-C₇, in particular C ₅ or C ₆ alkyl, exhibiting a 10 hour half life temperature (HLT 10 h) ranging from 95 ℃ to 105 ℃.

Again advantageously, the one or more peresters according to the invention are produced from bio-based starting materials.

The term "biobased" is understood to mean within the meaning of the present invention that the one or more peresters are produced from compounds of vegetable and/or animal origin, preferably of vegetable origin.

The one or more peresters according to the invention may comprise bio-based (i.e. carbon of plant and/or animal origin, in particular carbon of plant origin) carbon in an amount of at least 20 wt%, preferably at least 50 wt%, more preferably 100 wt%, relative to the total weight of carbon present in the perester compound.

Advantageously, the one or more peresters according to the invention may comprise a carbon content produced from renewable raw materials of greater than or equal to 50wt%, preferably ranging from 55 wt% to 70 wt%, more preferably ranging from 60 wt% to 65 wt%, relative to the total weight of carbon present in the perester compound.

¹⁴ The content of C is substantially constant from the extraction of the renewable starting material until the copolymer according to the invention is manufactured and even until the end of life of the manufactured object made of said copolymer.

Thus, the presence of ¹⁴ C in the material (this is the case regardless of its amount) gives an indication as to the source of the molecules that make up it, i.e. they originate from renewable starting materials rather than from fossil materials.

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

The standard includes three methods of measuring the organic carbon produced from renewable starting materials, which is denoted as "biobased carbon". The proportions shown for the peresters of the invention are preferably measured according to mass spectrometry or in liquid scintillation spectrometry described in this standard, and very preferably by mass spectrometry.

These measurement methods evaluate the ratio of ¹⁴C/¹² C isotopes in the sample and compare it to the ratio of ¹⁴C/¹² C isotopes in the bio-derived material giving 100% standards to measure the percentage of organic carbon in the sample.

Preferably, the one or more peresters according to the invention are liquid at ambient temperature, i.e. at a temperature in the range from 21 ℃ to 30 ℃.

The allyl monomer may be selected from bis (allyl carbonate) monomers.

Advantageously, the allyl monomer is selected from the group consisting of bis (allyl carbonate) monomers of formula (II):

[ chemical 2]

Wherein formula (II):

R _a and R _c, which are identical or different, represent allyl groups of the formula:

[ chemical 3]

Wherein formula R _d is selected from:

The radical of a hydrogen atom,

Halogen atoms, preferably fluorine or chlorine atoms,

Linear or branched C ₁-C₄ alkyl groups,

R _b is selected from the group consisting of alkylene, alkylene ether groups, aromatic alkylene ether groups, polyalkylene ether groups, alkylene carbonate groups, and mixtures thereof.

Preferably, in formula (II), R _a and R _c are the same.

Preferably, R _a and R _c are the same and represent allyl, wherein R _d represents a hydrogen atom, a chlorine atom, a fluorine atom or a methyl or ethyl group.

Still more preferably, R _a and R _c are the same and represent allyl groups, wherein R _d represents a hydrogen atom.

Preferably, R _b represents an alkylene group, an alkylene ether group or an aromatic alkylene ether group.

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

More preferably, R _b represents an alkylene or alkylene ether group.

Still more preferably, R _b represents an alkylene ether group, in particular a group of the formula:

[ chemical 4]

In formula (II), R _b is preferably aliphatic, that is to say it does not represent an aromatic alkylene ether group. In other words, the allyl monomer is preferably selected from bis (allyl carbonate) monomers of formula (II).

The allyl monomer is preferably selected from 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-butylene bis (allyl carbonate), 1, 4-butylene bis (2-bromoallyl carbonate), dipropylene glycol bis (allyl carbonate), trimethylene glycol bis (2-ethylallyl carbonate), pentamethylene glycol bis (2-ethylallyl carbonate), isopropylidene bisphenol a bis (allyl carbonate), and mixtures thereof.

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

Other allyl monomers may be used alone or in combination with the above-described bis (allyl carbonate) monomers, such as bis (allyl monocarbonate) monomers.

The allyl copolymer may be obtained from the polymerization of the above-described bis (allyl carbonate) monomer.

The allyl copolymer is preferably selected from the group consisting of polyol poly (allyl carbonate).

Poly (allyl carbonate) is obtained from the polymerization of a polyol and a bis (allyl carbonate) monomer.

Among the polyols involved in the preparation of the polyol poly (allyl carbonate), mention may be made in particular of polyols selected from the group consisting of 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, polylactone glycol, polyethoxylated glycerol glycol, xylene- α, α -diol, 1, 4-bis (hydroxyethyl) toluene, 2-bis (4- (hydroxyethyl) phenyl) propane, pentaerythritol, trimethylolpropane, dipentaerythritol, ditrimethylolpropane, tris (hydroxyethyl) isocyanurate.

Allyl copolymers selected from the group consisting of polyol poly (allyl carbonates) may be used in combination with the allyl monomers described above, in particular the bis (allyl carbonate) monomers of formula (II).

Allyl copolymers may also be obtained from the polymerization of bis (allyl carbonate) monomers and glycol polyethers.

The glycol polyether is preferably selected from homopolymers, copolymers or block polymers of polyether glycols, such as those described in patent application US 6 506 864.

Preferably, the present invention relates to the use of at least one peroxyester of formula (I) for the free radical polymerization of one or more allyl monomers and/or allyl copolymers, preferably one or more allyl monomers, in particular those selected from bis (allyl carbonate) monomers of formula (II).

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

Composition and method for producing the same

As indicated above, the composition according to the invention is a polymerizable composition comprising one or more peresters of the above formula (I) and one or more allyl monomers and/or allyl copolymers as defined above.

Preferably, the composition comprises at least one allyl monomer selected from bis (allyl carbonate) monomers.

Advantageously, the composition comprises:

-at least one perester of formula (I), wherein:

R ₁ represents a linear or branched C ₁-C₃, more preferably a C ₁-C₂ alkyl, more preferably a CH ₃ group,

R ₂ and R ₃ represent a hydrogen atom, and

R ₄ represents a linear or branched C ₁-C₁₁, more preferably C ₃-C₁₁, still more preferably C ₅-C₁₀ alkyl group, preferably R ₄ represents a linear C ₁-C₁₁, more preferably C ₃-C₁₁, still more preferably C ₅-C₁₀, still more preferably C ₅-C₆ and more preferably C ₅ alkyl group, and

-At least one allyl monomer selected from bis (allyl carbonate) monomers.

Preferably, the composition comprises at least one allylic monomer selected from the bis (allyl carbonate) monomers of formula (II) described above.

More preferably, the composition comprises at least one allyl monomer selected from bis (allyl carbonate) monomers of formula (II), wherein R _a and R _c are the same and represent allyl groups, wherein R _d represents a hydrogen atom and R _b represents an alkylene or alkylene ether group.

Preferably, the composition according to the invention comprises:

At least one perester selected from the group consisting of t-butyl peroxy-n-heptanoate, t-amyl peroxy-n-heptanoate, t-hexyl peroxy-n-heptanoate, t-heptyl peroxy-n-heptanoate, t-octyl peroxy-n-octanoate, t-amyl peroxy-n-octanoate, t-hexyl peroxy-n-octanoate, t-heptyl peroxy-n-octanoate, t-octyl peroxy-n-octanoate, t-butyl 3, 5-trimethylhexane peroxy-t-amyl 3, 5-trimethylhexane peroxy-t-hexyl 3, 5-trimethylhexane peroxy-t-heptyl 3, 5-trimethylhexane peroxy-t-octyl and mixtures thereof, preferably at least one perester selected from the group consisting of t-butyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate and mixtures thereof, more preferably t-butyl peroxy-n-heptanoate,

At least one allyl monomer, preferably chosen from bis (allyl carbonate) monomers, more preferably from aliphatic bis (allyl carbonate) monomers of formula (II) as defined above.

Advantageously, the composition according to the invention comprises:

At least one perester chosen from t-butyl peroxy-n-heptanoate, t-amyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate, t-amyl peroxy-n-octanoate, t-butyl 3, 5-trimethylhexane peroxy-t-amyl and mixtures thereof, preferably at least one perester chosen from t-butyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate and mixtures thereof, more preferably t-butyl peroxy-n-heptanoate, and

Diethylene glycol bis (allyl carbonate) (ADC).

The perester present in the composition according to the invention may be present in the composition in a content ranging from 0.1 to 20wt%, preferably in a content ranging from 1 to 16 wt%, preferably in a content ranging from 2 to 15 wt%, relative to the total weight of allyl monomers and/or allyl copolymers present in the composition.

Preferably, the active oxygen content is from 0.1% to 0.5% by weight, preferably from 0.15% to 0.4% by weight, more preferably from 0.2% to 0.35% by weight, relative to the total weight of the composition. The expression "active oxygen content" (also referred to as "active O", "AO") is understood to mean the weight percentage of oxygen radicals (one oxygen atom per perester function) with respect to the total weight of the composition. In other words, the active oxygen content in% can be calculated as the molar mass of 16/organic peroxide x the weight concentration of organic peroxide in the composition.

The composition according to the invention may additionally comprise at least one polymerization initiator different from the peroxyesters according to the invention.

In this case, the polymerization initiator may be a further organic peroxide or a non-peroxide compound other than the perester according to the invention, preferably a further organic peroxide other than the perester according to the invention.

Preferably, the composition according to the invention comprises at least one perester as defined above, at least one further organic peroxide, which is different from the perester or peresters according to the invention, and the allyl monomer(s) and/or allyl copolymer(s).

The composition according to the invention may also comprise one or more photoinitiators, for example chosen from acetophenone and benzophenone derivatives.

The composition according to the invention may also comprise one or more further monomers in addition to the allyl monomers.

The additional monomer is selected from acrylic monomers or methacrylic monomers, such as those selected from methyl acrylate, methyl methacrylate, phenyl methacrylate, vinyl acetate, iso-allyl isophthalate, diallyl terephthalate and diallyl adipate.

The composition according to the invention may also comprise at least one pigment and/or at least one organic dye, i.e. at least one colorant.

In this case, the composition may further comprise at least one dispersant having the effect of dispersing the pigment in the composition.

According to a preferred embodiment, the composition comprises:

Diethylene glycol bis (allyl carbonate),

At least one perester selected from the group consisting of t-butyl peroxy-n-heptanoate, t-amyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate, t-amyl peroxy-n-octanoate, t-butyl 3, 5-trimethylhexane peroxy-t-amyl and mixtures thereof, preferably at least one perester selected from the group consisting of t-butyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate, t-amyl peroxy-n-octanoate and mixtures thereof, more preferably t-butyl peroxy-n-heptanoate, and mixtures thereof

-At least one pigment and/or one organic dye and optionally at least one dispersant.

Preferably, the colorant is a pigment.

Pigments that may be present in the composition may be organic or inorganic.

Among the inorganic pigments, mention may be made in particular of mineral pigments which may optionally be surface-treated.

The mineral pigment is preferably selected from titanium oxides, in particular titanium dioxide, iron oxides, such as iron oxide red or yellow, and zirconium oxide.

The organic pigment may be selected from the group consisting of phthalocyanine blue, phthalocyanine green, dioxazine (cromophtal) violet, and dioxazine oxide green.

Among the pigments, mention may be made in particular of phthalocyanine pigments, in particular copper phthalocyanine pigments, especially blue copper phthalocyanine pigments, and iron oxides.

Advantageously, the polymerizable composition is free of pigments.

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

The composition according to the invention is in particular a liquid in a temperature range which may extend from 10 ℃ to 30 ℃, more preferably from 15 ℃ to 25 ℃.

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

Organic glass

Preferably, the polymerizable composition according to the invention yields a plexiglass after polymerization.

The invention therefore also relates to a plexiglass obtained by polymerization of a composition as defined above.

More specifically, the invention also relates to an organic glass obtained by free radical polymerization of the composition as defined above.

The plexiglass is preferably selected from the group consisting of instrument windows, optical detectors and ophthalmic lenses.

Preferably, the plexiglass is selected from ophthalmic lenses.

Within the meaning of the present invention, the term "ophthalmic" refers to a lens capable of fitting into eyeglasses and whose function is to protect the eye from sunlight, in particular ultraviolet light (sunglasses) or to correct vision. In the latter case, the ophthalmic lens is preferably afocal, monofocal, bifocal, trifocal or progressive.

Thus, the ophthalmic lens may be of the multifocal or progressive multifocal type, that is to say a multifocal lens with variable intensity.

The ophthalmic lenses obtained may be covered with a coating or treated at their surface.

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

According to one embodiment, an ophthalmic lens is obtained from the polymerization of a composition comprising at least one perester selected from t-butyl peroxy-n-heptanoate, t-amyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate, t-amyl peroxy-n-octanoate, t-butyl 3, 5-trimethylhexane peroxy-t-amyl 3, 5-trimethylhexane peroxy-and mixtures thereof and at least one allylic monomer selected from bis (allylcarbonate) monomers of formula (II) above, in particular diethylene glycol bis (allylcarbonate).

Products obtained from polymerizable compositions

Another subject of the 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.

Thus, the product is a polymer composition (or polymer product) resulting from the free radical 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.

In other words, the polymer composition corresponds to a resin that can be used as a base substance for manufacturing any type of object that is used for its good mechanical, aesthetic and optical properties, in particular its optical quality.

Preferably, the polymer product or polymer composition can be shaped to obtain a plexiglass or any other object used for its good mechanical and optical properties, in particular for its transparency and its weak coloration, indeed even for its colourless nature.

The polymer composition is in particular in solid form in a temperature range between 10 ℃ and 30 ℃, more preferably between 15 ℃ and 25 ℃.

Polymerization process

The invention likewise relates to a process for the polymerization of a polymerizable composition as defined above, comprising at least one polymerization stage of the polymerizable composition as defined above, preferably at one or more temperatures less than or equal to 110 ℃.

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

Method for preparing organic glass

The process for the preparation of the organic glass comprises at least one polymerization stage of the composition as defined above in an apparatus comprising at least one mould, preferably at one or more temperatures less than or equal to 110 ℃.

According to one embodiment, a method for preparing organic glass comprises at least the following stages:

Stage of introducing the polymerizable composition as defined above into a device comprising at least one mold,

The polymerization stage of the composition is preferably carried out at one or more temperatures of less than or equal to 110 ℃, preferably the polymerization stage is a series of stages at different temperatures, so that shrinkage and polymerization can be controlled,

-A stage of collection of the plexiglas.

According to this embodiment, the introduction phase is a phase of pouring 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 biplane mold, a mold comprising a concave portion and a convex portion, or a mold of concave shape.

Preferably, the device comprises at least one mould comprising at least one concave portion and at least one convex portion.

More generally, the apparatus includes at least one mold whose geometry exhibits the desired final geometry of the plexiglas.

The device may also comprise at least one mould having one face with a geometry corresponding to the final geometry of the desired organic glass and another face which is not modelled as a function of the final geometry of the organic glass, but which allows the preparation of a second face of the organic glass which can then be processed.

Preferably, the introduction phase comprises pouring the polymerizable composition between two molds having the desired surface geometry, e.g., one mold having a concave shape and one mold having a convex shape.

The polymerization stage is in particular radical polymerization.

The polymerization stage may be carried out by performing the thermal cycle at a temperature range of less than or equal to 110 ℃ for a period of time sufficient to cause polymerization, in particular a period of time which may range from 10 hours to 30 hours, preferably a period of time of 30 hours.

Thus, the temperature may be gradually increased during the polymerization stage.

The polymerization stage makes it possible to produce the desired organic glass.

The preparation process for the organic glass may comprise, after the polymerization stage, a stage of annealing the organic glass, which aims to eliminate possible residual stresses in the glass. The annealing stage may be carried out at a temperature in the range of 60 ℃ to 130 ℃, preferably 70 ℃ to 100 ℃, for a period of time in the range of 1 hour to 20 hours.

The stage of harvesting the plexiglas may be a stage comprising opening the mold and collecting the plexiglas.

Thus, the preparation method for a plexiglass preferably comprises a stage of pouring or injecting the composition according to the invention into a device comprising at least one mould having at least one concave portion and at least one convex portion, a stage comprising closing the mould, a polymerization stage comprising the composition as defined above, and a stage comprising opening the mould and collecting the plexiglass.

The method according to the invention in particular makes it possible to prepare the ophthalmic lenses described above.

The organic glass obtained after this preparation process can be subjected to any type of treatment, for example surface treatment, in order to improve its mechanical, aesthetic and optical properties, or also its wettability properties.

According to one embodiment, as indicated 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.

Alternatively, the preparation process for organic glass according to the invention may comprise a further stage comprising the addition of at least one colorant, preferably at least one pigment, after the organic glass has been obtained, i.e. after the polymerization stage.

The organic glass obtained according to this method exhibits good mechanical, aesthetic and optical properties.

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 normalization method),

-A Yellowness Index (YI) according to standard CIE 1976 using a spectrocolorimeter (ASTM E313 standardized method) according to the following equation:

[ mathematics 1]

In this equation X, Y and Z are the tristimulus coordinates of the sample, measured by a spectrophotometer over the entire spectrum between 380 and 780 nanometers.

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

Rockwell hardness, measured using a Rockwell hardness tester (ASTM D-785 standardization method),

Shore D hardness, measured using an HPE II Shore D portable durometer (ASTM D2240 standardized method),

Modulus of elasticity, or

-Coefficient of friction.

Preferably, the mechanical properties of the plexiglas according to the invention can be evaluated by hardness.

The following examples are illustrative of the invention and are not to be construed as limiting.

Examples

The following examples illustrate the invention, but do not limit it.

A. preparation example of peroxyesters

Synthesis of peroxyesters

Tertiary alkyl peroxy esters are generally prepared by reaction between a hydroperoxide and an acyl chloride or anhydride in the presence of a base, such as sodium hydroxide or a tertiary amine (see d.swern-Organic Peroxides, volume 1, page 74-published by Wiley, 1970).

1.1 Preparation of tert-butyl peroxy-n-heptanoate

74G of t-butyl hydroperoxide solution (70%) and 116g of potassium hydroxide solution (30%) were mixed at a temperature of 5-10℃in a glass reactor equipped with a jacket, condenser and stirring system. 70g of n-heptanoyl chloride (99.7%) was then added to the solution in a controlled manner to maintain the temperature between 5 ℃ and 10 ℃. After 45 minutes of reaction at 5-10 ℃, the temperature was raised to 20-25 ℃ over 15 minutes. After the reaction, the two phases were separated by sedimentation. The organic phase is washed with sodium hydroxide solution (10%), then sodium metabisulfite solution (10%) and then with water. 67g of t-butyl peroxy-n-heptanoate solution was recovered.

1.2 Preparation of tert-amyl peroxy-n-heptanoate

32G of t-amyl hydroperoxide solution (85%) and 59g of potassium hydroxide solution (30%) were mixed at a temperature of 5-10℃in a glass reactor equipped with a jacket, condenser and stirring system. Then 35g of n-heptanoyl chloride (99.7%) was added to the solution in a controlled manner to maintain the temperature between 5 ℃ and 10 ℃. After 45 minutes of reaction at 5-10 ℃, the temperature was raised to 20-25 ℃ over 15 minutes. After the reaction, the two phases were separated by sedimentation. The organic phase is washed with sodium hydroxide solution (10%), then sodium metabisulfite solution (10%) and then with water. 26g of a t-amyl peroxy n-heptanoate solution was recovered.

1.3 Preparation of tert-butyl peroxy-n-octoate

52G of t-butyl hydroperoxide solution (70%) and 83g of potassium hydroxide solution (30%) were mixed at a temperature of 5-10℃in a glass reactor equipped with a jacket, condenser and stirring system. 52g of n-octanoyl chloride (98.8%) were then added to the solution in a controlled manner to maintain the temperature between 5 and 10 ℃. After 45 minutes of reaction at 5-10 ℃, the temperature was raised to 20-25 ℃ over 15 minutes. After the reaction, the two phases were separated by sedimentation. The organic phase is washed with sodium hydroxide solution (10%), then sodium metabisulfite solution (10%) and then with water. 52g of t-butyl peroxy-n-octoate solution were recovered.

1.4 Preparation of tert-amyl peroxy-n-octanoate

38G of t-amyl hydroperoxide solution (85%) and 66g of potassium hydroxide solution (30%) were mixed at a temperature of 5-10℃in a glass reactor equipped with a jacket, condenser and stirring system. 47g of n-octanoyl chloride (98.8%) was then added to this solution in a controlled manner to maintain the temperature between 5 and 10 ℃. After 45 minutes of reaction at 5-10 ℃, the temperature was raised to 20-25 ℃ over 15 minutes. After the reaction, the two phases were separated by sedimentation. The organic phase is washed with sodium hydroxide solution (10%), then sodium metabisulfite solution (10%) and then with water. 39g of a t-amyl peroxy n-octanoate solution were recovered.

B. examples of preparation of polymerizable compositions

The polymerizable composition was prepared starting from diethylene glycol bis (allyl carbonate) (CAS 142-22-3) sold under the trade name CR-39 by PPG and each of the organic peroxides described below.

The organic peroxides tested were as follows (proportion of organic peroxide is 0.23% active oxygen in the composition, which corresponds to the weight proportion of the table below):

TABLE 1

C. examples for the preparation of organic glasses

Each of the compositions obtained above was then poured into a mold having concave portions and convex portions. Once poured, the male portion is closed over the female portion of the mold, and then the assembly is heated to a temperature of less than or equal to 110 ℃.

The thermal crosslinking cycle is adjusted as a function of the decomposition temperature of the organic peroxide used (half-life temperature (HLT) of 1 hour and 10 hours) according to the protocol of increasing to the half-life temperature of the peroxide used (HLT 10 h) within 14 hours, then increasing to the half-life temperature of the peroxide used (HLT 1 h) within 4 hours under HLT, then cooling to a temperature of 70 ℃ at which the removal from the mould takes place.

The polymerization product thus obtained is annealed at a temperature ranging up to 130 ℃ for a period of time, which may vary from 1 to 20 hours.

The plexiglas is then harvested.

D. Biplane 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 above scheme, except for polymerization, which was carried out at 1015Cm, 4mm thick, with the flat glass sheets aligned vertically and separated by a 4mm diameter silicone rubber seal, the mechanical cohesion of the assembly being produced by the clamping fixture under constant pressure. All tests were performed with air intake on top of the mold.

The yellowness index YI was obtained according to the standard CIE 1976 (color sequence) using a spectral colorimeter of the SP 60 type from the manufacturer X-Rite. The tristimulus coordinates are of Hunter Lab. Measurements were calibrated daily with standard calibration tiles (black and white), serial No. 20609D 65:10, 18/02/2010, WO A89274.

YI measurements were made in 4mm thick glass and are represented by the difference from YI measured on the white area of the Leneta Form2A chart (its yellowness index measurement after calibration of the spectrophotometer is 10.48).

Shore D hardness was measured using an HPE II Shore D portable durometer (manufacturer: bareiss, apparatus for Standard NF T51-174; DIN EN ISO 868;ISO 7619;ASTM D2240;BS 903 Part A26).

For each organic glass, the hardness of the organic glass was measured five times, and the average of these measurements was retained.

The results concerning the hardness of the obtained organic glass are incorporated in the following table:

TABLE 2

The hardness of the organic glass obtained with the peroxy esters according to the invention is significantly greater than that obtained with the organic peroxides (tert-butyl peroxy-2-ethylhexanoate and tert-amyl peroxy-2-ethylhexanoate) not corresponding to formula (I) according to the invention.

Diisopropyl peroxydicarbonate is not storable and transportable at ambient temperature.

The results with respect to Yellowness Index (YI) of the organic glasses obtained with the tested organic peroxides are incorporated in the following table:

TABLE 3

The organic glass obtained with the peroxyesters according to the invention exhibits a lower Yellowness Index (YI) and/or allows storage and transportation of the organic peroxide at ambient temperature compared to organic glasses obtained with organic peroxides not corresponding to formula (I) according to the invention.

Claims

1. Use of one or more peresters having the following formula (I) for the polymerization of one or more allyl monomers and/or allyl copolymers:

[ chemical 5]

(I)

Wherein formula (I):

R ₁ represents a linear or branched, non-aromatic C ₁-C₁₀ alkyl group,

R ₂ and R ₃ represent a hydrogen atom,

R ₄ represents a hydrogen atom or a linear or branched C ₁-C₁₆ alkyl group.

2. Use according to claim 1, characterized in that in formula (I), R ₁ represents a linear C ₁-C₆, preferably C ₁-C₅, more preferably C ₁-C₄, still more preferably C ₁-C₃ alkyl, more preferably a CH ₃ group.

3. Use according to claim 1 or 2, characterized in that in formula (I), R ₄ represents a linear or branched C ₁-C₁₁, more preferably C ₃-C₁₁, still more preferably C ₅-C₁₀ alkyl, preferably R ₄ represents a linear C ₁-C₁₁, more preferably C ₃-C₁₁, still more preferably C ₅-C₁₀, still more preferably C ₅-C₆ and more preferably C ₅ alkyl.

4. Use according to any of the preceding claims, characterized in that the one or more peresters are selected from t-butyl peroxy-n-heptanoate, t-amyl peroxy-n-heptanoate, t-hexyl peroxy-n-heptanoate, t-heptyl peroxy-n-heptanoate, t-octyl peroxy-n-octanoate, t-amyl peroxy-n-octanoate, t-hexyl peroxy-n-octanoate, t-heptyl peroxy-n-octanoate, t-octyl peroxy-n-octanoate, t-butyl 3, 5-trimethylhexane peroxy-and mixtures thereof, t-amyl 3, 5-trimethylhexane peroxy-and mixtures thereof, preferably the at least one perester is selected from t-butyl peroxy-n-heptanoate, t-butyl peroxy-n-octanoate and mixtures thereof, more preferably t-butyl peroxy-n-heptanoate.

5. Use according to any one of the preceding claims, characterized in that the one or more peresters have a 10 hour half life temperature (HLT 10 h) greater than or equal to 75 ℃.

6. Use according to any one of the preceding claims, characterized in that the one or more peresters have a Self Accelerated Decomposition Temperature (SADT) of greater than or equal to 50 ℃, preferably greater than or equal to 60 ℃.

7. Use according to any of the preceding claims, characterized in that the allyl monomer is selected from bis (allyl carbonate) monomers.

8. Use according to any one of the preceding claims, characterized in that the allyl monomer is selected from bis (allyl carbonate) monomers having the following formula (II):

[ chemical 6]

(II)

Wherein formula (II):

R _a and R _c, which are identical or different, represent allyl of the formula:

[ chemical 7]

Wherein formula R _d is selected from:

The radical of a hydrogen atom,

Halogen atoms, preferably fluorine or chlorine atoms,

Linear or branched C ₁-C₄ alkyl groups,

R _b is selected from the group consisting of alkylene, alkylene ether, aromatic alkylene ether, polyalkylene ether, alkylene carbonate, and mixtures thereof.

9. Use according to any of the preceding claims, characterized in that the allyl monomer is selected from 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-butylene bis (allyl carbonate), 1, 4-butylene bis (2-bromoallyl carbonate), dipropylene glycol bis (allyl carbonate), trimethylene glycol bis (2-ethylallyl carbonate), pentamethylene glycol bis (allyl carbonate), isopropylidene bisphenol a bis (allyl carbonate) and mixtures thereof.

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

11. A polymerizable composition comprising at least one perester as defined in any one of claims 1 to 6, and at least one allyl monomer as defined in any one of claims 1 and 7 to 10, and/or at least one allyl copolymer.

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

13. Use of a composition as defined in claim 11 or 12 for the manufacture of plexiglas, preferably ophthalmic lenses.

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

15. A plexiglass, obtained by polymerization of a polymerizable composition as defined in claim 11 or 12, preferably selected from the group consisting of instrument windows, optical detectors and ophthalmic lenses.