Method for preparing polyalkyl-functional prepolymer composition, and method for manufacturing optical article using said prepolymer composition

Abstract

The present invention relates to a process for preparing a polyallyl functional prepolymer composition, the process comprising: (a) providing a reaction mixture comprising:-at least one polyallyl functional monomer; 0.5 to 3.0 wt.% of at least one aromatic peroxide compound as radical initiator, the weight percentages being based on the total weight of the polyallyl functional monomers; (b) heating the reaction mixture at a temperature in the range of 12 to 3 degrees Celsius (DEG C) lower than the 10 hour half-life temperature of the aromatic peroxide compound to form a prepolymer composition having a viscosity at 25 DEG C in the range of 40 to 350 mm2 / s (40 to 350 cSt). The invention also relates to a method of manufacturing an optical article using the prepolymer composition.

Description

Technical Field

[0001] The present invention relates to a method for preparing a polyallyl functional prepolymer composition, and a method for manufacturing optical articles using the prepolymer composition. Background Technology

[0002] Polyallyl functional monomers are polymerized using free radical initiators to prepare rigid polymers. Many of these polymers are substantially transparent to visible light, substantially colorless, have a refractive index of about 1.45 to about 1.6, and exhibit good mechanical strength. For these reasons, these monomers are widely used as precursors for optical articles such as optical lenses and lens blanks, protective lenses, and flat or curved transparent sheets. Light transmission properties can be altered by introducing dyes, light-absorbing compounds, pigments, etc., into the polymeric composition containing the monomers prior to polymerization, or by dyeing the polymer.

[0003] Polymerization of polyallyl functional monomers is typically carried out in the presence of peroxide initiators, particularly dialkyl percarbonate esters such as, for example, diisopropyl percarbonate (IPP) or a mixture of IPP and disec-butyl percarbonate, which enables the production of rigid polymers with excellent optical properties, particularly transparency and low tinting.

[0004] However, dialkyl percarbonate initiators, especially IPP, are very expensive and extremely thermally unstable, with the disadvantage of explosive decomposition, thus requiring rather harsh transportation and storage conditions. Even when formulated in diluted form using, for example, polyallyl functional monomers for dilution, they still require transportation and storage temperatures as low as approximately -20°C to -10°C.

[0005] In the prior art, peroxide initiators are also known to be stable at ambient temperatures (also known as environmentally stable initiators - ASI), and therefore have the potential to overcome the aforementioned disadvantages of dialkyl percarbonate initiators. As used herein, environmentally stable initiators are free radical initiator compounds that do not require refrigeration, i.e., they can be stored at temperatures ranging from 20 to 36°C without substantially decomposing. As used herein, ASI initiators therefore have a “high” 10-hour half-life temperature, where “high” means a 10-hour half-life temperature of at least about 55°C.

[0006] However, ASI compounds such as certain diacid peroxides, alkyl peroxides, alkyl peroxy ketals, and peroxy monocarbonates also have some drawbacks that have so far limited their use in practice as initiators for the polymerization of polyallyl functional monomers.

[0007] For example, some ASI compounds have low solubility in polyallyl functional monomers, resulting in unsatisfactory curing levels in rigid polymers. Furthermore, rigid polymers obtained using ASI compounds such as diacyl peroxide initiators (e.g., benzoyl peroxide) exhibit considerable yellowing and poor UV resistance. Moreover, materials polymerized using ASI compounds typically exhibit relatively high hardness and brittleness, as well as high shrinkage levels, compared to rigid polymer materials obtained using IPP as an initiator.

[0008] As used herein, the term "shrinkage" (S) refers to the following ratio Among them, D pol D represents the density of the final thermosetting polymer at 23°C. mon This refers to the density of the monomer-containing liquid polymerizable composition at 23°C before polymerization. The term "shrinkage percentage (%)" is equal to shrinkage multiplied by one hundred.

[0009] High shrinkage levels are particularly detrimental in casting processes, such as those commonly used to prepare ophthalmic lenses and ophthalmic lens blanks, in which a liquid monomer composition is introduced into a mold and then polymerized into a thermosetting final polymer.

[0010] When polymerization is carried out in the presence of an ASI compound as an initiator, the liquid polymerizable composition must, in practice, be heated to a relatively high initial temperature to initiate the curing cycle of the polymerization reaction. For example, for benzoyl peroxide with a 10-hour half-life temperature of 73°C, the initial temperature is approximately 60°C, which is much higher than that of IPP with a 10-hour half-life temperature of 45°C (its initial temperature is approximately 40°C). However, this initial heating step is accompanied by volume expansion of the polymerizable composition within the mold, resulting in a non-negligible decrease in its density. Because the initial volume expansion when cured with an ASI compound is greater than that when the same polymerizable composition is cured with IPP or other non-ASI initiators, the shrinkage observed in rigid polymers cured with ASI initiators is significantly greater than the shrinkage of rigid polymers obtained by curing with IPP or other non-ASI initiators.

[0011] This high level of shrinkage within the mold introduces numerous defects into rigid polymers, such as variations in size and internal stress, and material detachment from the mold walls. This results in surfaces with insufficient smoothness and can lead to breakage of the polymer or the mold. Due to these negative aspects, manufacturing processes using ASI initiators are characterized by low yields.

[0012] The aforementioned drawbacks particularly affect the fabrication of semi-finished lenses (also known as “blanks”) with complex designs and geometries, such as blanks with high radii of curvature (6-base or higher) and bifocal semi-finished blanks (e.g., semi-finished lenses with bifocal correction on the front surface to compensate for both myopia and hyperopia simultaneously).

[0013] In fact, in bifocal blanks, the mechanical stress generated by shrinkage differs in each of the two power segments, often leading to lens damage during demolding, such as fragmentation, pitting, or complete breakage along the separation surface of the two power segments. Fracture problems are particularly relevant in the casting of flat-top bifocal blanks (characterized by two power segments separated by a flat separation surface).

[0014] In the prior art, it is known that shrinkage can be reduced by using specific formulations of polyallyl functional monomers. For example, when the polyallyl functional monomer is diethylene glycol bis(allyl carbonate) having the following formula (II), shrinkage can be reduced by including one or more mono- or polyene-bonded unsaturated compounds of non-poly(allyl carbonate) functional monomers in the formulation of the polymerizable composition. The aforementioned diethylene glycol bis(allyl carbonate) is one of the most commonly used polyallyl functional monomers for the preparation of optical articles. Where n is a positive integer (e.g., in the range of 1-10).

[0015] Examples of these mono- or polyene-bonded unsaturated compounds (also known as comonomers or reactive diluents) are mono- or polyene-bonded unsaturated compounds such as vinyl esters of versatic acid 9 and 10. The comonomer can be a liquid component with a lower density of polymerizable double bonds (i.e., the number of double bonds per unit mass of the compound) compared to diethylene glycol bis(allyl carbonate) monomers. These comonomers enable the production of hard polymers with lower levels of crosslinking (i.e., lower term D in the aforementioned shrinkage equation) compared to diethylene glycol bis(allyl carbonate) monomers without comonomers. pol The value of the final rigid polymer is thus lower and therefore has a lower shrinkage.

[0016] Alternatively, or in addition to the effects described above, the comonomer may have a higher density (i.e., mass / volume ratio) than the diethylene glycol bis(allyl carbonate) monomer, so that the cast polymerizable composition containing the polyallyl functional monomer and the comonomer has an increased density (i.e., a higher D in the above shrinkage equation). monThe value of the term), and therefore a lower final shrinkage. This is the case, for example, with compounds disclosed in US 4144262 that have high molar mass or multifunctional structures, i.e., three or more olefinic unsaturated functional groups per molecule, in which these compounds are also used as a single monomer in place of diethylene glycol bis(allyl carbonate) monomer.

[0017] This approach of using comonomers to reduce shrinkage is described in WO 2004090002A1, US 2021 / 0263197A1, EP3381951A1 and EP 0241997.

[0018] In an alternative approach, when the polyallyl functional monomer is diethylene glycol bis(allyl carbonate) of formula (II) above, the polymerizable composition can contain a relatively high content of oligomers, i.e., substances of formula (II) above where n is an integer equal to 2 or more. Since these oligomers have a lower polymerizable double bond density compared to linear substances of diethylene glycol bis(allyl carbonate) monomers (i.e., substances of formula (II) with n=1), they enable the production of substances with a lower level of crosslinking (i.e., a lower term D in the shrinkage equation). pol (value) and therefore have lower shrinkage rigid polymers.

[0019] This pathway to reduce shrinkage is described in WO 00 / 27794 and WO 2017 / 168325A1. Summary of the Invention

[0020] The problem that the invention aims to solve Another method known in the art to mitigate shrinkage is based on introducing a liquid prepolymer composition into a mold and then polymerizing it to obtain the final thermosetting polymer.

[0021] Prepolymer compositions (hereinafter also referred to as "prepolymers") are typically prepared by partially polymerizing polyallyl functional monomers to consume a portion of the allyl groups. However, partial polymerization (hereinafter also referred to as "prepolymerization") is stopped before more than a small amount of gelation occurs, so that the prepolymer composition can be introduced into a mold as a liquid with an increased density than the initial polyallyl functional monomers.

[0022] Prepolymerization requires precise control. Typically, a small amount of initiator is added to control the prepolymerization reaction, ensuring that only the desired portion of the allyl double bond in the initial polyallyl functional monomer reacts to form the prepolymer composition. Furthermore, this small amount of initiator ensures that it is completely consumed at the end of the prepolymerization reaction, so that the liquid prepolymer composition is stable at ambient temperature and has sufficient shelf life—that is, it can be stored for a considerable period without gelling before being used to produce rigid polymer articles.

[0023] Furthermore, the prepolymerization reaction is controlled by adjusting the heat supplied to the reaction mixture of monomer and initiator in the reactor. In particular, once the desired viscosity of the prepolymer is reached, it may be necessary to cool the reaction mixture to stop the reaction and prevent subsequent gelation, which may be caused by the thermal inertia of the prepolymer material (the so-called "bulk effect").

[0024] To prepare rigid polymers, a liquid prepolymer composition is subsequently added along with an initiator and subjected to a thermosetting cycle to polymerize the composition. The initiator (which can be the same as or different from the initiator used to prepare the prepolymer composition) is added to the prepolymer composition in an amount sufficient to substantially polymerize the allyl double bonds of the prepolymer. However, when initiators with low 10-hour half-life temperatures (i.e., non-ASI initiators, such as IPP) are used in the curing cycle, the resulting liquid polymerizable formulation must be used rapidly once mixed with the monomers due to their short shelf life. If not used immediately, the formulation must be refrigerated (resulting in high energy consumption) for later use. This disadvantage forces manufacturers to prepare small batches of polymerizable formulations.

[0025] To increase the shelf life of a formulation, the concentration of the initiator in the formulation can be increased, and casting can be performed at a low temperature, i.e., below 10°C. However, this method has the disadvantage of increasing the viscosity of the prepolymer after cooling, which leads to longer and less efficient mold filling operations, and thus limits productivity, especially in the manufacture of lenses with complex designs and geometries.

[0026] According to another known method, the prepolymer composition can be prepared by solution polymerization. The monomer composition is dissolved in a substantially inert organic solvent that also dissolves some of the monomers to be polymerized, and then heated in the presence of a small amount of initiator. At the end of the prepolymerization, the solvent is removed, for example by evaporation or distillation, and the liquid prepolymer composition is polymerized after the addition of a fresh initiator to prepare a rigid polymer.

[0027] US 4623708 discloses a method for preparing a prepolymer, wherein the prepolymerization step includes: adding a small amount of a free radical initiator, which may be the same as or different from the initiator to be used before casting; and heating to a temperature higher than the 1-hour half-life temperature of the initiator. In this way, most of the added initiator is consumed, and the prepolymerization produces the highest achievable conversion rate while preventing overpolymerization.

[0028] US 6057411 discloses a method for forming a polymerizable, liquid, substantially gel-free poly(allyl carbonate) functional prepolymer composition, comprising: heating a net composition comprising at least one poly(allyl carbonate) functional monomer and a radical initiator having a 10-hour half-life temperature of at least 85°C in a temperature ranging from 5°C lower than the 10-hour half-life temperature of the radical initiator to 150°C to form a reaction mixture having an increased 25°C viscosity in the range of 25 to 10,000 centipoise and at least 3% utilization of olefinic double bonds; and cooling the reaction mixture to a temperature at least 20°C lower than the 10-hour half-life temperature of the initiator over a period of less than 90 minutes.

[0029] The aforementioned prior art monomer and prepolymer compositions are used to reduce shrinkage; however, they result in high costs due to the use of additional raw materials and complex preparation processes (i.e., comonomers and the provision of specific polyallyl monomer and prepolymer compositions).

[0030] In particular, known methods for preparing prepolymer compositions and their applications are impractical for several reasons. First, the precise control of several variables, namely the initiator dosage and reaction temperature, during prepolymerization makes it difficult to obtain the desired properties of the prepolymer in a reproducible manner. Second, the addition of the initiator to the liquid prepolymer composition is required before casting to prepare the final polymer product, resulting in a short shelf life for the polymerizable composition and making the manufacturing process quite complex and inefficient. Third, when preparing prepolymers via solution polymerization, complete solvent removal is time-consuming and expensive, and also dangerous if the solvent is toxic or flammable.

[0031] Therefore, there is a need for new methods for the preparation and use of polyallyl functional monomers (especially in the form of prepolymer compositions) that can overcome the shortcomings of existing technologies.

[0032] Methods for solving problems Methods have been discovered that allow the preparation of allyl-based rigid polymers using environmentally stable polymerization initiators, which possess mechanical and optical properties substantially equivalent to those of rigid polymers that can be cured with highly efficient initiators such as IPP or other conventional peroxide carbonate initiators.

[0033] This method is based on preparing a liquid prepolymer composition by partially polymerizing a polyallyl functional monomer in the presence of a selected set of environmentally stable free radical initiators, wherein the free radical initiator is mixed with the polyallyl functional monomer in an amount such that the initiator is not completely consumed during the prepolymerization reaction; the prepolymerization reaction is carried out by heating the resulting mixture at a temperature close to but below the 10-hour half-life temperature of the initiator (and therefore also below its 1-hour half-life temperature) for a period of time sufficient to obtain a prepolymer composition with the desired increased viscosity.

[0034] Because a sufficient amount of initiator is retained in the prepolymer composition, its ability to generate free radicals is utilized in the subsequent steps of thermosetting the prepolymer composition, thus avoiding any further steps of incorporating additional initiator into the prepolymer composition before casting into the mold.

[0035] The environmentally stable free radical initiator is an aromatic peroxide compound (e.g., benzoyl peroxide) that is highly soluble in polyallyl functional monomers and thus can be formulated in effective amounts to convert liquid prepolymer compositions into rigid polymers under conventional curing cycles (e.g., at temperatures up to 80 to 120°C and over approximately 24 to 30 hours).

[0036] Furthermore, since the initiator is stable at ambient temperature, the i.e., cast liquid prepolymer compositions have a fairly long shelf life (approximately 1-2 weeks) at ambient temperature (i.e., 25°C), and even longer (months) if stored under refrigerated conditions, for example, in the range of 0 to 4°C. In particular, the shelf life is significantly longer than that of i.e., cast liquid prepolymer compositions containing IPP (1 hour at ambient temperature) or similar non-ASI initiators.

[0037] The prepolymer compositions prepared as described herein effectively control shrinkage during the polymerization step that forms the rigid polymer, with observed shrinkage values ​​being substantially the same as those of rigid polymers obtained using the IPP initiator (less than about 12%).

[0038] Furthermore, the methods described herein enable the highly efficient and convenient preparation of rigid polymers and thus optical articles using environmentally stable initiators such as benzoyl peroxide. The rigid polymers exhibit mechanical and optical properties comparable to those of rigid polymers cured using IPP, while overcoming the drawbacks associated with handling and using IPP and other non-ASI initiators. Moreover, thanks to effective control of material shrinkage, the methods described herein enable the manufacture of lenses with complex designs and geometries (e.g., semi-finished lenses with high radii of curvature and bifocal semi-finished lenses) using ASI initiators, with improved manufacturing yields.

[0039] Because the total amount of aromatic peroxide initiator used to prepare the prepolymer and subsequently the final polymer product is lower than that typically used for the direct conversion of the same polyallyl functional monomer composition, the method described herein has the additional advantage of reducing the negative effects associated with the use of relatively high amounts of aromatic peroxide initiator, such as adjustment of lens refractive index, increased hardness and brittleness, inherent yellowing, and yellowing caused by exposure to UV light.

[0040] The benefits of this invention can be achieved using a variety of polyallyl functional monomers without particular limitation. However, the method described herein is particularly advantageous when the starting material supplied for prepolymerization is a polyallyl functional monomer with low viscosity and density, because these are obtained through a simpler and more cost-effective preparation process compared to monomers intentionally prepared to have inherently reduced shrinkage properties.

[0041] Therefore, according to a first aspect, the present invention relates to a method for preparing a polyallyl functional prepolymer composition, the method comprising: (a) Providing a reaction mixture comprising: - At least one polyallyl functional monomer; - 0.5 to 3.0 wt.% of at least one aromatic peroxide compound as a free radical initiator, the weight percentage being based on the total weight of the polyallyl functional monomer; (b) Heating the reaction mixture at a temperature 12 to 3 degrees Celsius (°C) lower than the 10-hour half-life temperature of the aromatic peroxide compound to form a viscosity of 40 to 350 mm at 25°C. 2 Prepolymer compositions in the range of / s (40 to 350 cSt).

[0042] According to a third aspect, the present invention relates to a method for manufacturing optical articles, the method comprising: (i) Providing a reaction mixture, the reaction mixture comprising: - At least one polyallyl functional monomer; - 0.5 to 3.0 wt.% of at least one aromatic peroxide compound as a free radical initiator, the weight percentage being based on the total weight of the polyallyl functional monomer; (ii) Heating the reaction mixture at a temperature 12 to 3 degrees Celsius (°C) lower than the 10-hour half-life temperature of the aromatic peroxide compound to form a viscosity of 40 to 350 mm at 25°C. 2 Prepolymer compositions in the range of / s (40 to 350 cSt); (iii) Cast the prepolymer composition into a mold; (iv) Curing the prepolymer composition in a mold to form an optical article.

[0043] Further features of the invention are the subject of the dependent claims appended to this specification.

[0044] The compositions of the present invention may comprise, and be substantially composed of, or consist of, the basic components described herein and optional ingredients. In this document, “substantially composed of” means that the composition or components may include other ingredients, provided that such other ingredients do not substantially alter the essential characteristics and novel features of the claimed composition or method.

[0045] As used herein, the articles “a,” “an,” and “the” should be understood to include one or more, and the singular includes the plural unless there is an obvious other meaning. This is done for convenience and to give a general meaning to the published content.

[0046] Except as provided in the embodiments, or as otherwise specified, all figures used in the specification and claims to indicate the amounts of ingredients, reaction conditions, etc., should be understood to be modified by the term "about" in all cases. Detailed Implementation

[0047] Polyallyl functional monomers To prepare the prepolymer composition according to the invention, a reaction mixture comprising at least one polyallyl functional monomer and at least one aromatic peroxide compound as a free radical initiator is provided. The mixture may contain two or more polyallyl functional monomers.

[0048] Polyallyl functional monomers can be selected from a variety of liquid polyallyl compounds, which may include monomers and oligomers having at least two allyl groups as polymerizable functional groups.

[0049] Polyallyl functional monomers may include, for example, compounds containing two or more allyl groups, such as diallyl esters, diallyl carbonates, and diallyl phthalates.

[0050] In one embodiment, the polyallyl functional monomer comprises a liquid poly(allyl carbonate) of a polyhydroxy organic material. Examples of such monomers include poly(allyl carbonate) of linear or branched aliphatic polyols, poly(allyl carbonate) of alicyclic polyols, and poly(allyl carbonate) of aromatic polyhydroxy compounds. These monomers are known in themselves and can be prepared by processes well known in the art.

[0051] In one embodiment, the polyallyl functional monomer is selected from: diethylene glycol bis(allyl carbonate), ethylene glycol bis(allyl carbonate), oligomers of diethylene glycol bis(allyl carbonate), oligomers of ethylene glycol bis(allyl carbonate), bisphenol A bis(allyl carbonate), diallyl phthalates, such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl phthalate, and mixtures thereof.

[0052] Polyallyl functional monomers are liquid products at ambient temperature, with kinematic viscosities ranging from 10 to 1000 mmHg measured at 25°C. 2 / s (10 to 1000 cSt).

[0053] In one embodiment, the polyallyl functional monomer has a 10 mm 2 / s to 300 mm 2 / s (10 cSt to 300 cSt), preferably 10 to 100 mm 2 / s (10 to 100 cSt), more preferably 10 to 40 mm 2 Kinematic viscosity in the range of / s (10 to 40 cSt).

[0054] As used herein, the kinematic viscosity of compounds containing polyallyl functional monomers or prepolymer compositions is determined according to ASTM D446 using a KPG Ubbelohde viscometer (capillary type 1C, 2C, or 3C).

[0055] Preferably, the polyallyl functional monomer has a density at 25°C in the range of 1.10 g / ml to 1.30 g / ml, more preferably 1.11 g / ml to 1.20 g / ml.

[0056] Compound (A) containing two or more allyloxycarbonyl groups. In one embodiment, the polyallyl functional monomer can be represented as a compound (A) comprising two or more allyloxycarbonyl groups according to formula (1): In this formula, n is an integer from 2 to 6, R1 represents a hydrogen atom or a methyl group, and multiple R1s may be the same or different. X is a divalent to hexavalent organic group a derived from a linear or branched aliphatic polyol having 3 to 12 carbon atoms that may have an oxygen atom, a divalent to hexavalent organic group b derived from an alicyclic polyol having 5 to 16 carbon atoms that may have an oxygen atom, or a divalent to hexavalent organic group c derived from an aromatic compound having 6 to 12 carbon atoms, and organic group a or organic group b forms an allyl carbonate group by bonding to an allyloxycarbonyl group via an oxygen atom derived from a hydroxyl group.

[0057] These polyols typically contain 2 to 6 hydroxyl groups in their molecules, and it is preferred that they contain 2 to 4 hydroxyl groups in their molecules.

[0058] Examples of aliphatic polyols a1 include diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, glycerol, trimethylolpropane, tris(hydroxyethyl)isocyanurate, pentaerythritol, dipentaerythritol, etc.

[0059] Examples of alicyclic polyols b1 include 1,4-dihydroxymethylcyclohexane, 4,8-di(hydroxymethyl)-[5.2.1.0] 2,6 Tricyclodecane, etc.

[0060] Examples of aromatic compounds C1 include benzene, toluene, xylene, naphthalene, etc.

[0061] Specific examples of compounds containing two or more allyloxycarbonyl groups include allyl carbonate polymeric compounds (A1), allyl ester polymeric compounds (A2), and polymeric compounds containing at least one of allyl carbonate and allyl ester groups (A3).

[0062] A compound (A) containing two or more allyloxycarbonyl groups may contain its oligomers.

[0063] Compounds containing two or more allyloxycarbonyl groups are liquid products at ambient temperature, with kinematic viscosities ranging from 10 to 1000 mm² measured at 25°C. 2 / s (10 to 1000 cSt), and the oligomer content can be varied over a wide range (e.g., from 0% to about 80% by weight).

[0064] In one embodiment, the compound comprising two or more allyloxycarbonyl groups has a 10 mm diameter.2 / s to 300 mm 2 / s (10 cSt to 300 cSt), preferably 10 to 100 mm 2 / s (10 to 100 cSt), more preferably 10 to 40 mm 2 The kinematic viscosity is in the range of / s (10 to 40 cSt). Preferably, the density of the compound containing two or more allyloxycarbonyl groups at 25°C is in the range of 1.10 g / ml to 1.30 g / ml, more preferably 1.11 g / ml to 1.20 g / ml.

[0065] Allyl carbonate polymeric compound (A1) Allyl carbonate polymeric compound (A1) can be represented by formula (2): In formula (2), X represents a divalent to hexavalent group derived from a linear or branched aliphatic polyol having 3 to 12 carbon atoms, or a divalent to hexavalent group derived from an alicyclic polyol having 5 to 16 carbon atoms, and n represents an integer from 2 to 6.

[0066] The allyl carbonate polymerizable compound (A1) of formula (2) may include its oligomers. The oligomers are allyl carbonates in which two or more molecules of a polyol are linked via carbonate groups generated by an ester exchange reaction between the allyl carbonate produced in the preparation step and the polyol.

[0067] Allyl carbonate polymerizable compounds are poly(allyl carbonate) compounds of linear or branched aliphatic polyols having 3 to 12 carbon atoms. Poly(allyl carbonate) compounds of alicyclic polyols having 5 to 16 carbon atoms in the molecule are also suitable for this purpose. These polyols typically have 2 to 6 hydroxyl groups in the molecule, and it is preferred that these polyols have 2 to 4 hydroxyl groups in the molecule. Mixed poly(allyl carbonate) compounds can also be used, i.e., compounds derived from at least two polyols and obtainable by mechanical mixing of the corresponding polyol poly(allyl carbonate) compounds, or compounds obtained directly by a chemical reaction starting from a mixture of polyols and diallyl carbonate.

[0068] Ultimately, all these poly(allyl carbonate) compounds can be in the form of monomers, or mixtures of monomers and oligomers.

[0069] Typically, allyl carbonate polymers are liquid products at ambient temperature, with kinematic viscosities ranging from 10 to 1000 mmHg when measured at 25°C. 2 / s (10 to 1000 cSt), and the oligomer content can be varied over a wide range (e.g., from 0% to about 80% by weight).

[0070] In one embodiment, the allyl carbonate polymeric compound has a 10 mm diameter. 2 / s to 300 mm 2 / s (10 cSt to 300 cSt), preferably 10 to 100 mm 2 / s (10 to 100 cSt), more preferably 10 to 40 mm 2 The kinematic viscosity is in the range of / s (10 to 40 cSt). Preferably, the density of the allyl carbonate polymerizable compound at 25°C is in the range of 1.10 g / ml to 1.30 g / ml, more preferably 1.11 g / ml to 1.20 g / ml.

[0071] Specific examples of polyols forming X in general formula (2) include diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dihydroxymethylcyclohexane, 4,8-di(hydroxymethyl)-[5.2.1.0] 2,6 Tricyclodecane, glycerol, trimethylolpropane, tri(hydroxyethyl)isocyanurate, pentaerythritol, dimeric glycerol, bis(trimethylolpropane), dipentaerythritol, etc.

[0072] The polyol that forms X in general formula (2) can also be a chain-extended polyol, such as a lactone-extended polyol and an alkyl oxygen-extended polyol. A chain-extended polyol is a reaction product that has a terminal hydroxyl group of the polyol and a suitable reactant such as a lactone or an alkyl oxygen.

[0073] Examples of polyols with ε-caprolactone chain extension include: diethylene glycol with ε-caprolactone chain extension, dipropylene glycol with ε-caprolactone chain extension, triethylene glycol with ε-caprolactone chain extension, tetraethylene glycol with ε-caprolactone chain extension, pentaerythritol with ε-caprolactone chain extension, and trimethylolpropane with ε-caprolactone chain extension.

[0074] Examples of alkylated oxygen-extended polyols include: diethylene glycol extended from ethylene oxide or propylene oxide, dipropylene glycol extended from ethylene oxide or propylene oxide, triethylene glycol extended from ethylene oxide or propylene oxide, tetraethylene glycol extended from ethylene oxide or propylene oxide, pentaerythritol extended from ethylene oxide or propylene oxide, and trimethylolpropane extended from ethylene oxide or propylene oxide.

[0075] Therefore, examples of allyl carbonate compounds include at least one selected from the group consisting of diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dihydroxymethylcyclohexane, and 4,8-di(hydroxymethyl)-[5.2.1.0] 2,6 The following are compounds: bis(allyl carbonate) compounds of at least one diol selected from tricyclodecane; tri(allyl carbonate) compounds of at least one triol selected from glycerol, trimethylolpropane, and tri(hydroxyethyl)isocyanurate; tetra(allyl carbonate) compounds of at least one tetraol selected from pentaerythritol, dipropylene glycol, and bis(trimethylolpropane); dipentaerythritol hexa(allyl carbonate) compounds; and mixed poly(allyl carbonate) compounds of at least two compounds selected from diols, triols, tetraols, and dipentaerythritol.

[0076] For example, when the glycols are diethylene glycol and neopentyl glycol, "bis(allyl carbonate) of a mixture of at least two glycols" is obtained as a mixture of the following monomeric and oligomeric components: Monomer components: (1) Diethylene glycol bis(allyl carbonate); (2) Neopentyl glycol bis(allyl carbonate); Oligomer components: (3) Oligomers containing only hydrocarbons (and ethers) derived from diethylene glycol (compounds having the following structure: in which two hydroxyl groups of a compound in which diethylene glycol is linearly oligomerized via carbonate bonds are replaced by allyl carbonate groups). (4) Oligomers containing only hydrocarbons derived from neopentyl glycol (compounds having the following structure: in which two hydroxyl groups of a compound in which neopentyl glycol is linearly oligomerized via carbonate bonds are replaced by allyl carbonate groups). (5) A complex oligomer of both a hydrocarbon (and ether) derived from diethylene glycol and a hydrocarbon derived from neopentyl glycol in the same molecule (a compound having the following structure: wherein two hydroxyl groups of a compound in which diethylene glycol and neopentyl glycol are linearly oligomerized in the same molecule via carbonate bonds in any order are replaced by allyl carbonate groups).

[0077] The following are preferred examples of allyl carbonate polymerizable compounds (A1) suitable for the purposes of this invention: (i) A mixture of diethylene glycol bis(allyl carbonate) and its oligomers, wherein the diethylene glycol bis(allyl carbonate) can be defined by formula (I). Furthermore, oligomers of diethylene glycol bis(allyl carbonate) can be defined by formula (II). In equation (II), n is equal to or greater than 2 and equal to or less than 10.

[0078] For example, as described in "Encyclopedia of Chemical Technology", Kirk-Othmer, 3rd edition, Vol. 2, pp. 111-112, compound (I) can be prepared by reacting diethylene glycol bis(chloroformate) with allyl alcohol. For example, as described in EP35304, a mixture of diethylene glycol bis(allyl carbonate) (formula (I)) and its oligomers (formula (II)) can be readily prepared by ester substitution between diallyl carbonate and diethylene glycol in the presence of a basic catalyst. These mixtures typically contain up to about 80% oligomers by weight; (ii) A mixture of diethylene glycol and neopentyl glycol in the form of bis(allyl carbonate) compounds and their oligomers. Except for replacing diethylene glycol with a mixture of diethylene glycol and neopentyl glycol, this bis(allyl carbonate) compound is the same as the bis(allyl carbonate) compound in aspect (i) above. (iii) A mixture of diethylene glycol and tris(hydroxyethyl) isocyanurate poly(allyl carbonate) compounds and their oligomers For example, as described in US4,812,545, poly(allyl carbonate) compounds can be obtained by ester substitution of diallyl carbonate in a mixture of diethylene glycol and tris(hydroxyethyl) isocyanurate.

[0079] (iv) A mixture of diethylene glycol and trimethylolpropane, a poly(allyl carbonate) compound and its oligomers.

[0080] Except for replacing tri(hydroxyethyl) isocyanurate with trimethylolpropane, this poly(allyl carbonate) compound is the same as the poly(allyl carbonate) compound in aspect (iii) above.

[0081] (v) A mixture of diethylene glycol and pentaerythritol, a poly(allyl carbonate) compound and its oligomers.

[0082] Except for replacing tris(hydroxyethyl) isocyanurate with pentaerythritol, this poly(allyl carbonate) compound is the same as the poly(allyl carbonate) compound in aspect (iii) above.

[0083] (vi) A mixture of poly(allyl carbonate) compounds and their oligomers, consisting of a mixture of diethylene glycol, neopentyl glycol, and pentaerythritol.

[0084] Except for the substitution of diethylene glycol with diethylene glycol and neopentyl glycol, this poly(allyl carbonate) compound is the same as the poly(allyl carbonate) compound in aspect (v) above.

[0085] (vii) Poly(allyl carbonate) mixtures comprising: a mixture of poly(allyl carbonate) compounds and their oligomers comprising a mixture of diethylene glycol, neopentyl glycol and pentaerythritol, and a mixture of diethylene glycol bis(allyl carbonate) compounds and their oligomers.

[0086] In one embodiment, the polyallyl functional monomer comprises or is a diethylene glycol bis(allyl carbonate) compound of general formula (II): In equation (II), n is equal to or greater than 1 and equal to or less than 10.

[0087] Preferably, the polyallyl functional monomer comprises 70 wt.% or more, preferably 80 wt.% or more of a diethylene glycol bis(allyl carbonate) compound of formula (II) with n equal to 1 (i.e., the monomeric compound of formula (I) above), the weight percentage being based on the weight of the polyallyl functional monomer.

[0088] The wt.% relative concentrations of the monomeric substances (n=1) and oligomeric substances (n=2-10) of Formula (II) in the polyallyl functional monomer can be determined by known methods. In particular, the concentration values ​​can be determined by HPLC or GPC analysis under conditions that yield sufficiently separated peaks corresponding to the monomeric substances and each oligomeric substance, followed by calculation of the percentage area of ​​the chromatographic peaks associated with each monomeric substance and oligomeric substance.

[0089] In one embodiment, the polyallyl functional monomer comprises, or is a reaction product (RP) of, the following components: diallyl carbonate (A); one or more linear or branched aliphatic diols (B) containing 3 to 10 carbon atoms in a molecule; and optionally, a linear or branched aliphatic polyol (C) containing 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in a molecule; wherein the molar ratio A / (B+C) is in the range of 4 / 1 to 20 / 1, and the amount of the optional component (C) in the mixture (B+C) is equal to or less than 5 wt.% relative to the weight of the mixture (B+C).

[0090] Preferably, the molar ratio A / (B+C) is in the range of 5 / 1 to 10 / 1, and the amount of (C) in the mixture (B+C) is equal to or less than 3 wt.% relative to the weight of the mixture (B+C).

[0091] The diol (B) is a linear or branched aliphatic diol, preferably containing 3 to 10 carbon atoms in the molecule.

[0092] Examples of suitable diols (B) are: diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol, neopentyl glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, and 1,4-cyclohexanediol.

[0093] Preferably, the diol (B) is selected from diethylene glycol, neopentyl glycol, and combinations thereof.

[0094] The polyol (C) is a linear or branched aliphatic polyol, preferably containing 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in the molecule.

[0095] Examples of suitable polyols (C) are: pentaerythritol, trimethylolpropane, dipentaerythritol, bis(trimethylolpropane) and tri(hydroxyethyl)isocyanurate.

[0096] Preferably, the polyol (C) is selected from pentaerythritol, trimethylolpropane and combinations thereof.

[0097] As described, for example, in WO 2004 / 090002, polyallyl functional monomers can be obtained as reaction products (RPs) by reacting diallyl carbonate (A) with diol (B) or a mixture of diol (B) and polyol (C) under transesterification conditions in the presence of a basic catalyst.

[0098] The reaction product (RP) is a liquid product at ambient temperature, and its kinematic viscosity, measured at 25°C, ranges from 10 to 1000 mmHg. 2 / s (10 to 1000 cSt).

[0099] In one embodiment, the reaction product (RP) has a 10 mm diameter at 25°C. 2 / s to 300 mm 2 / s (10 cSt to 300 cSt), more preferably 10 to 100 mm 2 / s (10 to 100 cSt), more preferably 10 to 40 mm 2 The kinematic viscosity is in the range of / s (10 to 40 cSt). Preferably, the density of the reaction product RP at 25°C is in the range of 1.10 g / ml to 1.30 g / ml, more preferably 1.11 g / ml to 1.20 g / ml.

[0100] The reaction product (RP) is typically obtained as a mixture of allyl carbonate substances in monomeric and oligomeric forms, components (B) and (C) (if present), and as a mixture of mixed oligomeric allyl carbonate substances in the form of said components (B) and (C), the relative amounts of said allyl carbonate substances depending primarily on the selected proportions of reagents (A), (B) and (C).

[0101] Allyl ester polymerizable compounds (A2) and (A3) Examples of allyl ester polymerizable compounds (A2) include: diallyl phthalate represented by general formula (3) and oligomers thereof; and allyl ester compounds represented by general formula (4) and oligomers thereof, which are obtained by transesterification of a mixture of diallyl phthalate and a polyol. Examples of polymerizable compounds (A3) include polymerizable compounds represented by general formula (5) containing at least one of allyl ester group and allyl carbonate group, and oligomers thereof.

[0102] Polymerizable compounds represented by general formula (5) include: allyl ester compounds, allyl carbonate compounds, and mixtures of compounds having allyl ester groups and allyl carbonate groups, which are obtained by transesterification of a mixture of dialkyl phthalate, allyl alcohol, diallyl carbonate and polyol.

[0103] In this embodiment, the compounds of general formulas (3) to (5) include positional isomers.

[0104] The diallyl phthalate represented by general formula (3) is selected from at least one of diallyl isophthalate, diallyl terephthalate and diallyl phthalate.

[0105] In formula (4), X represents a divalent group derived from a linear or branched aliphatic diol having 2 to 8 carbon atoms, or a trivalent to hexavalent group derived from a linear or branched aliphatic polyol having 3 to 10 carbon atoms and 3 to 6 hydroxyl groups, and n is an integer from 2 to 6.

[0106] In formula (5), X represents a divalent group derived from a linear or branched aliphatic diol having 2 to 8 carbon atoms, or a trivalent to hexavalent group derived from a linear or branched aliphatic polyol having 3 to 10 carbon atoms and 3 to 6 hydroxyl groups, m and n represent integers from 0 to 6, and the sum of m and n is an integer from 2 to 6.

[0107] Specific examples of polyols (aliphatic diols, aliphatic polyols) forming X in formulas (4) and (5) include: ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol and di,4-dihydroxymethylcyclohexane; glycerol and trimethylolpropane; and tri(hydroxyethyl)isocyanurate, pentaerythritol, diglycerol, bis(trimethylolpropane) and dipentaerythritol.

[0108] The compounds of formulas (4) and (5) may contain their oligomers. The oligomer in formula (4) is prepared by transesterification of an allyl ester compound generated in the preparation step with a polyol. The oligomer in formula (5) is prepared by transesterification of an allyl ester compound or an allyl carbonate compound generated in the preparation step with a polyol.

[0109] Therefore, the allyl ester polymerizable compound (A2) or polymerizable compound (A3) includes at least one selected from the following substances, such as: diallyl phthalate compounds selected from diallyl isophthalate, diallyl terephthalate, and diallyl phthalate; diallyl ester compounds and oligomers thereof, which are formed by reacting a diallyl phthalate compound with a compound selected from ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1 The polyallyl polyol is obtained by transesterification of a mixture of at least one diol selected from the following: 2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, and 1,4-dihydroxymethylcyclohexane. Ester compounds and their oligomers obtained by transesterification reaction between diallyl phthalate and at least one polyol selected from glycerol and trimethylolpropane, tris(hydroxyethyl)isocyanurate, pentaerythritol, dimeric glycerol, bis(trimethylolpropane), dipentaerythritol, etc.; and allyl ester compounds, allyl carbonate compounds, compounds having allyl carbonate groups and allyl ester groups, and their oligomers obtained by transesterification reaction of the following mixtures, the mixture having at least one dialkyl phthalate having 1 to 3 carbon atoms selected from dimethyl isophthalate, dimethyl terephthalate, dimethyl phthalate, diethyl isophthalate, diethyl terephthalate, diethyl phthalate, dipropyl isophthalate, dipropyl terephthalate and dipropyl phthalate, allyl alcohol, diallyl carbonate and the above diols or polyols.

[0110] More specifically, the allyl ester polymerizable compound (A2) or polymerizable compound (A3) preferably comprises at least one selected from the following: (i) diallyl terephthalate, and a mixture of diethylene glycol bis(allyl carbonate) compound and oligomers thereof, which are 30% by weight relative to the diallyl terephthalate; (ii) an allyl ester compound obtained by transesterification of a mixture of diallyl terephthalate and propylene glycol; (iii) the allyl ester compound in (ii), and a mixture of diethylene glycol bis(allyl carbonate) compound and oligomers thereof, which are 30% by weight relative to the diallyl terephthalate. (iv) A mixture of 20% by weight of a diethylene glycol bis(allyl carbonate) compound and its oligomers; (v) A mixture of an allyl ester compound, an allyl carbonate compound and a compound having allyl ester and allyl carbonate groups, obtained by transesterification of a mixture of dimethyl terephthalate, allyl alcohol, diallyl carbonate and diethylene glycol; and (v) A mixture obtained in (iv) with 10% by weight of a diethylene glycol bis(allyl carbonate) compound and its oligomers relative to the mixture.

[0111] The following are preferred examples of allyl ester polymerizable compounds (A2) or polymerizable compounds (A3) suitable for the purposes of this invention: mixtures of allyl ester compounds, allyl carbonate compounds, and compounds having allyl ester groups and allyl carbonate groups, which are obtained by transesterification of a mixture of dimethyl terephthalate, allyl alcohol, diallyl carbonate, and diethylene glycol.

[0112] The above-mentioned allyl ester polymerizable compound (A2) or polymerizable compound (A3) can be defined by formulas (III) to (V), wherein diallyl terephthalate of formula (III) is its main component and each contains an oligomer obtained by transesterification reaction with a polyol.

[0113] According to the present invention, the compound (A) comprising two or more allyloxycarbonyl groups may be selected as follows: allyl ester polymeric compound (A2) and / or polymeric compound (A3) and its oligomers, or a mixture with allyl carbonate polymeric compound (A1) and its oligomers.

[0114] Polymerizable comonomers The reaction mixture may also contain an olefinically unsaturated compound (as a monomer or oligomer) capable of polymerizing with the aforementioned polyallyl functional monomer. Here, this optional olefinically unsaturated compound is also referred to as a "comonomer". Examples of suitable comonomers include: aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, chloromethylstyrene, and divinylbenzene; and mono(meth)acrylate alkyl groups such as methyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, glycidyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-phenoxy-2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. Esters; such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 2,2-bis[4-((methyl)]acrylate Di(meth)acrylates of [acryloyloxyethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, and 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane; tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate and tetramethylolmethane tri(meth)acrylate; tetra(meth)acrylates such as tetramethylolmethane tetra(meth)acrylate. These comonomers can be used alone or in combination of two or more. In the above description, "(meth)acrylate" means "methacrylate" or "acrylate", and "(meth)acryloyloxy" means "methacryloyloxy" or "acryloyloxy".

[0115] With regard to the total amount of comonomer in the reaction mixture according to the invention, based on the total weight of the reaction mixture, it may be 1% to 80% by weight, particularly 1% to 50% by weight, more particularly 2% to 20% by weight, and even more particularly 3% to 10% by weight.

[0116] In a preferred embodiment, the reaction mixture does not contain olefinically unsaturated compounds, which means that no polymerizable comonomers have been added to the reaction mixture; therefore, the only polymerizable compound present in the reaction mixture is a polyallyl functional monomer.

[0117] In a preferred embodiment, the reaction mixture comprises a polyallyl functional monomer of a diethylene glycol bis(allyl carbonate) compound of general formula (II) where n is an integer equal to or greater than 1 and equal to or less than 10, and does not contain an olefinically unsaturated compound as a comonomer; therefore, the only polymerizable compound present in the reaction mixture is the diethylene glycol bis(allyl carbonate) compound of general formula (II).

[0118] In one embodiment, the reaction mixture comprises a polyallyl functional monomer of the above-described reaction product (RP) comprising diallyl carbonate (A), one or more aliphatic diols (B) and optionally aliphatic polyols (C), and the reaction mixture does not contain olefinically unsaturated compounds as comonomers; therefore, the only polymerizable compound present in the reaction mixture is the reaction product (RP) of components A, B and optionally C.

[0119] Free radical polymerization initiators The free radical initiator is an aromatic peroxide compound. Preferably, the aromatic peroxide compound has the following general formula (F1). Wherein, X is selected from: hydrogen, C1 to C 12 Alkoxy, chlorine, and bromine. In one embodiment, X is selected from hydrogen, C... l To C4 alkoxy or bromine. Examples of suitable aromatic peroxide initiators include benzoyl peroxide (BPO), bis(p-methoxybenzoyl) peroxide, bis(p-ethoxybenzoyl) peroxide, bis(p-propoxybenzoyl) peroxide, bis(p-isopropoxybenzoyl) peroxide, bis(p-butoxybenzoyl) peroxide, and bis(p-chlorobenzoyl) peroxide. A particularly preferred initiator is benzoyl peroxide [CAS 94-36-0].

[0120] The half-life of a free radical initiator at any given temperature is defined as the time it takes for the initiator to lose half of its activity. It is determined by studying the decomposition kinetics of the initiator. The 10-hour half-life temperature of an initiator is the temperature at which half of the initially present initiator will decompose within 10 hours.

[0121] The half-life temperature is determined by periodically sampling a peroxide solution maintained at several selected constant temperatures and determining the amount of undecomposed peroxide remaining in the sampled solution using conventional iodometric titration. This measurement, in turn, measures the decomposition rate of the initiator in the aromatic solvent monochlorobenzene, thereby determining the half-life temperature. Such half-life measurement techniques are well known to those skilled in the art. Suitable techniques for determining this half-life temperature in the same solvent using differential scanning calorimetry, which provides a direct measurement of the desired half-life temperature, are also known to those skilled in the art and can replace iodometric measurements. Both techniques provide equivalent results for the same solvent within the expected standard experimental deviation of the procedure. It is known in the art that the half-life temperature depends on the solvent in which the determination is made; therefore, to accurately compare the half-life temperatures of one peroxide with those of another, a solvent must be selected for determining the half-life in which it is made.

[0122] The aromatic peroxide initiator suitable for use in this invention has a 10-hour half-life temperature equal to or greater than 55°C, preferably equal to or greater than 60°C. For example, the 10-hour half-life temperature of the initiator can be in the range of 55°C to 100°C, preferably 60°C to 95°C, and more preferably 60°C to 85°C. In one embodiment, the 10-hour half-life temperature of the initiator is in the range of 60°C to 80°C. A particularly preferred aromatic peroxide is benzoyl peroxide, which has a 10-hour half-life temperature of 73°C.

[0123] In one embodiment, the reaction mixture comprises only one aromatic peroxide compound as a free radical polymerization initiator. However, when desired, combinations of two or more aromatic peroxide compounds having the same or different 10-hour half-life temperatures can be used.

[0124] Based on the weight of the polyallyl functional monomer to be prepolymerized, the total amount of individual radical initiators or combinations of initiators in the reaction mixture is in the range of 0.5 to 3.0 wt.%, preferably 1.0 to 2.0 wt.%, more preferably 1.3 to 1.8 wt.% (the above wt.% refers to the amount of initiator excluding any solid or liquid diluent components). An amount of initiator higher than 3.0 wt.% is disadvantageous because they generate excessive heat, thus increasing the risk of potential cracks and optical defects in the rigid polymer; furthermore, they can lead to higher yellowness index and hardness, which may be undesirable for ophthalmic lenses.

[0125] Aromatic peroxide initiators are typically commercially available in the form of compositions containing desensitizers and / or stabilizers (such as alkyl benzoate desensitizers, phthalate desensitizers, and cresol desensitizers, or water as a stabilizer). It has been observed that the use of initiators containing phthalate and cresol desensitizers can result in optical articles with defects (so-called "dots"), which become particularly noticeable on coated lenses. Furthermore, phthalate and cresol desensitizers have relatively low solubility in polyallyl functional monomers and their prepolymers, which is reflected in higher haze in optical articles.

[0126] The use of water-stabilized peroxides can also have some disadvantages in the manufacturing process if the water content in the prepolymer composition exceeds a certain concentration before casting. For example, the presence of more than 0.5 wt% residual water based on the weight of the prepolymer composition may actually lead to premature detachment of optical articles from the mold during the curing cycle, or to uneven conversion of polyallylic functional monomers in different molds. However, since water can be more easily removed from the polymerizable composition before casting the prepolymer composition into the mold (e.g., by degassing or purging with an inert gas), in one embodiment, water-stabilized aromatic peroxides are preferred.

[0127] A particularly preferred initiator is water-stabilized benzoyl peroxide, which is commercially available as a wet powder. Preferably, the water content is equal to or less than 50 wt%, more preferably equal to or less than 25 wt%, based on the weight of the water-stabilized aromatic peroxide (e.g., benzoyl peroxide).

[0128] Therefore, in one embodiment, the step of preparing the reaction mixture includes adding an aromatic peroxide compound, preferably benzoyl peroxide, in a water-stabilized form.

[0129] Other components The reaction mixture and prepolymer composition may also contain other additive compounds, such as internal release agents, UV and / or HEV light absorbers, resin modifiers (e.g., chain extenders, crosslinking agents, light stabilizers), antioxidants, fillers, adhesion promoters, bleaching agents, etc.

[0130] As an internal release agent, acidic phosphate esters or non-reactive silicone oils can be used, for example. Examples of acidic phosphate esters include monophosphate esters and diesters, and these substances can be used alone or in combination of two or more.

[0131] Examples of resin modifiers include olefin compounds containing cyclic sulfides, alcohol compounds, amine compounds, epoxy compounds, organic acids and their anhydrides, (meth)acrylate compounds, etc.

[0132] Examples of suitable bleaching agents are those based on inorganic pigments or organic dyes dispersed in an allyl resin, such as those disclosed in WO 2021095774A1 and WO 2022224928A1 under the same applicant.

[0133] Examples of UV and / or HEV light absorbers include benzotriazole, benzophenone, triazine, and oxaloylaniline.

[0134] These additional compounds can be introduced into either or both of the reaction mixture and the prepolymer composition, in the latter case, before being cast into the mold.

[0135] In one embodiment, the reaction mixture and the prepolymer composition are solvent-free, meaning they do not contain any inert organic solvents that need to be removed from the prepolymer composition at the end of the prepolymerization reaction.

[0136] Preparation of prepolymer compositions According to the present invention, the prepolymer composition is prepared by heating a reaction mixture comprising at least one polyallyl functional monomer, at least one free radical polymerization initiator, and optional components.

[0137] The mixing and prepolymerization of the components can be carried out in a reactor (such as a stainless steel reactor) equipped with heating and cooling devices to regulate the temperature of the reaction mixture.

[0138] The prepolymerization reaction is carried out by heating the reaction mixture at a temperature 12 to 3°C lower than the 10-hour half-life temperature of the aromatic peroxide compound. Preferably, the reaction mixture is heated at a temperature 10 to 5°C lower than the 10-hour half-life temperature of the aromatic peroxide compound. For example, when benzoyl peroxide is used as an initiator (10-hour half-life temperature equals 73°C), the temperature of the prepolymerization reaction can be selected in the range of 61°C to 70°C, for example 63°C to 70°C, or 65°C to 68°C.

[0139] When maintained at the above-mentioned temperature, it is preferable to degas the reaction mixture to substantially remove all oxygen and water present therein. Degassing can be carried out in any suitable manner, for example by treating the reaction mixture under reduced pressure (e.g., below 50 mbar) or by bubbling with a non-reactive gas such as nitrogen, helium, or argon.

[0140] In one embodiment, based on the weight of the prepolymer composition, at the end of the prepolymerization reaction, the prepolymer composition has a water content equal to or less than 0.5 wt%.

[0141] When maintained at the above temperature, the reaction mixture can remain still or can be stirred.

[0142] The viscosity of the reaction mixture increases as it is heated and polymerization proceeds. The reaction mixture is heated to form a viscosity ranging from 40 to 350 mmHg, measured at 25°C. 2 A prepolymer composition in the range of / s (40 to 350 cSt). Preferably, the reaction mixture is heated until the formed prepolymer composition reaches a viscosity of 60 to 200 mmHg, measured at 25°C. 2 / s (60 to 200 cSt), more preferably 70 to 120 mm 2 The reaction rate is in the range of 70 to 120 cSt. At the end of the prepolymerization reaction, the prepolymer composition is liquid and substantially free of gel. By being liquid, it means that the prepolymer composition is suitable for casting into molds.

[0143] The duration of the prepolymerization reaction can depend to a great extent on the prepolymerization temperature, the type of polyallyl functional monomer, and the desired increase in viscosity. Typically, the duration of the prepolymerization reaction ranges from 0.5 to 15 hours, and in most cases from 1 to 10 hours.

[0144] As described above, when needed, a combination of two or more aromatic peroxide compounds having the same or different 10-hour half-life temperatures can be used. In this case, if the 10-hour half-life temperatures are the same, the prepolymerization temperature is selected according to the principles of the invention, i.e., 12 to 3°C lower than the 10-hour half-life temperature, or as described above in its preferred range. If the 10-hour half-life temperatures of the two or more initiators are different, the prepolymerization temperature is preferably 12 to 3°C lower than the lowest 10-hour half-life temperature among the combined initiators, or as described above in its preferred range.

[0145] In a preferred embodiment, the reaction mixture and its prepolymer composition comprise only one aromatic peroxide compound as an initiator.

[0146] Once the prepolymer composition has been formed, i.e., the reaction mixture has the desired increased viscosity, the prepolymer composition can be cast into a mold or cooled to, for example, ambient temperature for storage.

[0147] Therefore, in one embodiment, the preparation method includes the step of cooling the prepolymer composition to ensure that the polymerization reaction does not proceed further. This is advantageous, for example, when preparing large quantities of prepolymer, as it avoids undesirable viscosity increases occurring before or during the casting operation.

[0148] In one embodiment, the method includes the step of cooling the prepolymer composition to a temperature at least 20°C lower than the 10-hour half-life temperature of the initiator. For example, when benzoyl peroxide is used as the initiator, the prepolymer composition may be cooled to a temperature below 53°C.

[0149] Cooling can be completed in a period of less than 90 minutes, preferably less than 60 minutes, and more preferably less than 30 minutes.

[0150] The prepolymer composition exhibits relatively high stability at normal ambient temperatures. Despite containing a portion of the initiator initially formulated and not consumed during the prepolymerization reaction, the prepolymer composition possesses a considerably long shelf life and working shelf life. For the shelf life, it can be, for example, up to approximately more than 20 weeks, depending on the amount of initiator used and the viscosity increase achieved at the end of the prepolymerization reaction.

[0151] Prepolymer compositions can be polymerized into a thermosetting state, i.e., a rigid polymer, using known conventional techniques for polymerizing formulations containing polyallyl functional monomers.

[0152] In one embodiment, a prepolymer composition is placed in a mold, such as a glass mold, and polymerized to form a molded article, such as a lens preform or a lens. This method is particularly advantageous for preparing ophthalmic lens preforms and ophthalmic lenses.

[0153] According to the present invention, it is not necessary to introduce any additional amount of free radical initiator into the mold before casting the prepolymer composition into the mold. However, when needed, a prepolymer formulation comprising the prepolymer composition and other optional components (e.g., UV absorbers and bluing agents) can be prepared.

[0154] The prepolymer composition can be cast immediately after the prepolymerization reaction is complete, for example, at the end of a cooling step that reaches a temperature at least 20°C lower than the 10-hour half-life temperature of the initiator. For example, in the case of benzoyl peroxide, prepolymerization can be interrupted at about 50°C or lower, and the prepolymer composition can be cast into a mold at that temperature. Alternatively, the prepolymer composition can be cooled to ambient temperature or refrigerated (e.g., at a temperature in the range of 0°C to 6°C) and stored for later use.

[0155] The cast prepolymer composition can be polymerized by heating it in a mold, for example in an oven or water bath.

[0156] As a curing cycle, i.e., the temperature-time profile used to polymerize the prepolymer composition into a rigid polymer, conventional curing cycles, such as those commonly used for curing allyl polymers with IPP, can be used.

[0157] Typically, polymerization is carried out at temperatures ranging from about 80°C to about 120°C for 10 to 48 hours to achieve complete polymerization of the optical article. Complete polymerization is considered to have been achieved when the liquid prepolymer composition has been converted into a rigid polymer suitable for demolding.

[0158] After obtaining the rigid polymer, it is typically cooled before demolding. Preferably, the rigid polymer within the mold is cooled to a temperature in the range of 40 to 80°C, more preferably 50 to 70°C. For this purpose, the mold containing the polymerized optical material can be left to stand at ambient temperature outside the heating device.

[0159] Post-curing allows for the removal of molded optical materials, i.e., heating at or above the highest temperature of the curing cycle, but below those temperatures where the material might undergo thermal degradation. Post-curing neutralizes free radicals from polymerization initiators that may still be present in the optical material and eliminates internal stresses.

[0160] When a bleach containing tetrazaporphyrin (TAP) dye is added to a polymerizable formulation to compensate for the yellowing of optical articles (e.g., caused by the presence of UV-absorbing compounds or by an initiator), post-curing can also be used to improve the efficiency of the TAP dye, as disclosed in WO 2022224928 A1.

[0161] In most cases, post-curing is performed at temperatures ranging from 90°C to 130°C.

[0162] The polymerization of the prepolymer composition can be carried out in conventional equipment such as a convection oven or a water bath. The mold can be a conventional mold, for example, made of two mold parts forming a cavity and a gasket, which defines the shape and size of the final optical material. The mold parts can be made of glass, metal, or plastic.

[0163] The optical materials of this invention can be used in a variety of applications, particularly ophthalmic lenses, protective face mask lenses, optical filters, etc. Ophthalmic lenses are defined herein as lenses designed to fit within eyeglass frames to protect the eyes and / or correct vision. These ophthalmic lenses can be uncorrected ophthalmic lenses (also known as plano or afocal lenses) or corrective ophthalmic lenses. Corrective lenses can be monofocal, bifocal, trifocal, or progressive lenses.

[0164] Optical materials can be coated with one or more functional coatings selected from the group consisting of anti-abrasion coatings, anti-reflective coatings, anti-fouling coatings, antistatic coatings, anti-fog coatings, polarizing coatings, coloring coatings, and photochromic coatings.

[0165] The invention will now be described in more detail through the following embodiments, which are given for illustrative purposes only and are not intended to limit the scope of the invention in any way: Example Characterization methods Optical materials are evaluated using the following methods.

[0166] Density / Specific Gravity : The densities of polyallyl functional monomers and different prepolymerized resins were determined as follows: using a volume-calibrated glass hydrometer (25 ml), the hydrometer was immersed in a constant-temperature water bath at 23°C, and the resin volume was adjusted to reach a meniscus. Density ρ (g / cm³) 3 The value is defined as: the weight of the weighed monomer / 25.

[0167] Polymer density / specific gravity (ASTM D-792) : The density of the polymer was determined by displacement method according to ASTM D-792. The balance used to determine the buoyancy increment was a Gibertini SRL model E42.

[0168] Kinematic viscosity (ASTM D-446): The viscosity at 25°C was determined using a KPG Ubbelohde viscometer according to ASTM D-446, wherein capillary type 1C was used for polyallyl functional monomers, or alternatively 2C / 3C for prepolymer compositions.

[0169] Shrinkage percentage : Use the following formula to determine contraction. Among them, D pol D represents the density of the final thermosetting polymer at 23°C. mon The density of a liquid polymerizable composition containing monomers at 23°C before polymerization.

[0170] Yellowness Index (YI) (ASTM D-1925) : Taking into account the standard light source C and the observer (2° angle), YI was determined using a GretagMacbeth 1500 Plus spectrophotometer on an optical material in the form of a 4 mm plano mirror. YI was defined as: YI = (100 / Y)(1.277X - 1.06Z).

[0171] Total transmittance and haze value : According to ASTM D 1003, the total transmittance and haze value of an optical material in the form of a flat plate with a thickness of 2 mm were determined using a BYK-Gardner digital haze-gard plus.

[0172] transmittance at a specified wavelength : The transmittance at a specified wavelength of a 2 mm thick plate-shaped optical material was measured using an Agilent Cary 60 UV-Vis spectrophotometer.

[0173] The terms “UV-cutoff” and “HEV-cutoff” used in this article refer to the highest wavelength in the UV region (280 nm to 380 nm) and HEV region (380 nm to 500 nm) of an optical material with a transmittance of less than 1% as measured according to ASTM D 1003, respectively.

[0174] Coloration test of 2mm plano lens : The ability of a material to absorb dye on its surface was demonstrated by applying a neutral plano 2mm lens to a dyeing bath at 93°C using a BPI dyeing apparatus (model COLORADO Electronic, from ORGANIZZAZIONE GF). TM The lens was immersed in a gray solution for 15 minutes for measurement. After rinsing with demineralized water, the lens transmittance was determined by measuring the total transmittance as described above. In addition, the uniformity / non-uniformity of the stained lens was visually evaluated by exposing it to a backlit observer (model Professional 20-5000K, from LUPO DAYLIGHT).

[0175] Refractive index nD20 : The polymer refractive index was measured at 20°C using an ATAGO Abbe refractometer, model NAR-3T.

[0176] Mechanical properties - Rockwell hardness M Evaluate the Rockwell hardness M (ASTM D-785) of optical materials on a flat sheet of 5 mm thickness.

[0177] Material In the examples, the following compounds were used.

[0178] Polyallyl functional monomers The polyallyl functional monomer is prepared by reacting diallyl carbonate (component A), diethylene glycol as a diol (component B), and pentaerythritol as a polyol (component C) in a molar ratio of A / (B+C) equal to 7.2 and a ratio of C / (B+C) equal to 2.29 wt.%.

[0179] The following compound was packed into a three-necked jacketed flask equipped with a thermometer and a magnetic stirrer, and topped with a distillation column containing 10 perforated plates with a diameter of 30 mm: - Pentaerythritol (PE): 5 g (approximately 0.04 mol); - Diethylene glycol (DEG): 213 g (approximately 2.01 mol); - Diallyl carbonate (DAC): 2100 g (approximately 14.80 mol); - 20% by weight solution of sodium methoxide in methanol: 1.0 ml.

[0180] The reaction was carried out at a temperature of 85°C to 120°C and a reduced pressure of 200 to 130 mbar for 3 hours by distilling off allyl alcohol (total 242 g, approximately 285 ml; purity >99%) during the formation of allyl alcohol.

[0181] After cooling, the reaction mixture was washed with two equal 500 ml portions of demineralized water.

[0182] Excess DAC was distilled off at a pressure of approximately 1 mbar by operating at an elevated temperature of up to 130°C: the resulting product was filtered through a 0.45 m membrane filter.

[0183] A liquid product of 512 g was obtained, which had the following characteristics: - Viscosity (25°C): 17 mm 2 / s (17 cSt); - Density (20°C): 1.152 g / ml; - Refractive index nD20: 1.453; - Apha chromaticity: 1.

[0184] The above-mentioned polyallyl functional monomers are obtained in the form of monomers and oligomers of diethylene glycol bis(allyl carbonate), monomers and oligomers of pentaerythritol tetra(allyl carbonate), and mixtures of the above-mentioned diols and polyols in the form of poly(allyl carbonate).

[0185] Based on the weight of the mixture of monomers and oligomers, the amount of diethylene glycol bis(allyl carbonate) compound of formula (II) with n=1 is approximately 83 wt%. This amount was determined by HPLC analysis of the reaction product under the following conditions: temperature = 25 °C; sample of the reaction product for analysis in the form of a 10% by weight solution of acetonitrile; injected sample = 5 μL; eluent: a mixture of acetonitrile / water (45 / 55% by volume); UV detector.

[0186] UV absorber - BP6 (2,2'-dihydroxy-4,4'-dimethoxybenzophenone, prepared by MFCI).

[0187] - Addivant produces Lowilite 20: 2-dihydroxy-4-methoxybenzophenone.

[0188] Peroxide radical polymerization initiator - ARKEMA Luperox A75 (registered trademark); water-stabilized benzoyl peroxide (25 wt.% water), in granular wet powder form.

[0189] - Nouryon PERKADOX CH50-L; benzoyl peroxide (50 wt.% alkyl phthalate ester) stabilized in granular wet powder form.

[0190] - NOURYON manufactures Trigonox ADC-NS30 (registered trademark); this commercially available product contains approximately 70% by weight of diethylene glycol bis(allyl carbonate) and 30% by weight of a mixture of isopropyl dicarbonate, sec-butyl, and isopropyl / sec-butyl dicarbonate.

[0191] TAP dyes (bleaching agents) The bleaching agent used is FDG-005, a commercially available product manufactured by Yamada Chemicals (a Pd-containing TAP compound with a main absorption peak at 583 nm). FDG-005 is used as a masterbatch, i.e., pre-dispersed in polyallyl functional monomers at a concentration of 0.05 wt. based on the monomer weight.

[0192] UV&Blue cutoff MB TM (bleach) Bleaching masterbatch provided by Acomon SRL, based on a proprietary composition of pigments dispersed in polyallyl functional monomers (approximately 2.0 wt.% pigments in the polyallyl functional monomers based on the weight of the monomers).

[0193] Prepolymerization method The polyallyl functional monomer is loaded into a three-necked jacketed flask equipped with a magnetic stirrer and a thermocouple. Optional additives, such as light stabilizers, UV absorbers, antioxidants, and bleaching agents, are also introduced into the flask at this stage, if required in the formulation.

[0194] In vigorous mixing and decompression (P abs The monomer (or formulation containing optional additives) is heated to the prepolymerization temperature (T<50 mbar) under these conditions. p Once the set T is reached... p The atmospheric pressure in the flask was restored by purging nitrogen. The BPO initiator was then introduced into the flask. The pressure was reduced again (<50 mbar), and mixing continued until the desired viscosity was achieved due to the polymerization reaction. The increased viscosity of the prepolymer composition was measured based on a series of reaction mixture samples taken from the reaction flask at predetermined time intervals.

[0195] The prepolymer composition is discharged from the flask and cast directly into a glass mold (i.e., without pre-cooling).

[0196] Example 1. Preparation of prepolymer compositions The prepolymer composition is prepared by mixing 100 parts by weight (pbw) of a polyallyl functional monomer with a BPO initiator, or for comparative purposes with a peroxide dicarbonate initiator Trigonox ADC-NS30 and optional additives in the ratios recorded in Table 1.

[0197] The shelf life of each prepolymer composition was evaluated by measuring the viscosity trends at different prepolymerization temperatures and during prepolymerization. Here, shelf life at a given temperature refers to the period during which a prepolymer composition can remain at that temperature until its viscosity increases to the point that its use for mold filling operations becomes impractical.

[0198] In Comparative Example CC1, the polyallyl functional monomer was prepolymerized using the following conventional procedure cured with a dicarbonate peroxide initiator. The polymerization was carried out at a temperature T = 80°C. p A small amount of initiator (0.1 parts by weight) is added to the monomer, and the mixture is then subjected to reduced pressure (P) abs Degas for 3 hours at <50 mbar. Select a temperature T of 80℃. p At a temperature higher than the 1-hour half-life temperature of the initiator (equivalent to 66°C for ADC NS-30). Small amounts of initiator and relatively high T0 p This enables the production of prepolymer compositions with the desired increase in viscosity (and thus density) and also provides a good shelf life due to the complete consumption of the initiator compound.

[0199] To obtain an immediate-cast polymerizable formulation, the prepolymer composition CC1 was mixed with the same major amount of initiator (comparative sample CC2). However, as shown in Table 1, the immediate-cast CC2 composition exhibited a significantly reduced shelf life at ambient temperature compared to CC1 (approximately 1 hour at 25°C). Such a short shelf life makes cryogenic storage a virtually indispensable operation for manufacturing optical articles using these compositions (shelf life exceeds 6 months at 4°C).

[0200] As shown in Table 1, the prepolymer compositions (PP1 to PP3) of the present invention are ready-to-cast compositions exhibiting good processability and a very satisfactory shelf life. Samples PP1-PP3 exhibit increased viscosity, which effectively ensures that the shrinkage level is comparable to that when cured using a peroxide carbonate initiator, without increasing so rapidly over time, thus enabling proper casting operations even in the presence of sufficient initiator.

[0201] 2. Optical items EX2 and EX3, and comparison with EX1 and EX1-PP Preparation The cast-polymerizable formulations (EX2 and EX3) according to the invention are converted into rigid polymers. For comparison, a rigid polymer (EX1) is prepared by curing a non-prepolymerized polyallylic functional monomer using a conventional dicarbonate peroxide ADC NS-30.

[0202] EX2 and EX3 formulations were prepared by loading polyallyl functional monomers, initiators, and additives into a jacketed stainless steel reactor equipped with a mechanical stirrer, thermocouples, and a bottom drain line for mold filling. The reaction mixture was mixed and degassed at 65°C (P...). abs <50 mbar) 3 hours (90 mm at 25°C) 2 The final viscosity was determined to be 90 cSt. The prepolymerization process was carried out under the conditions described in point 1 above for prepolymer PP3. At the end of the reaction period, the prepolymer composition was cooled to 50°C. Then, nitrogen (P...) was used... abs =1.2 bar) displacement vacuum. Before casting, the prepolymer composition is filtered by passing it through a stainless steel disc holder containing a 0.45-micron PTFE membrane (47 mm diameter) located on the discharge line, and then used to fill the glass mold.

[0203] Mix and degas at ambient temperature for 2 hours (P) abs <50mbar), except that the comparative formulation EX1 was prepared in the same manner as EX2 and EX3.

[0204] According to one of the curing cycles recorded in Tables 2 and 3, polymerization to form a rigid polymer is completed by heating a mold containing a polymerizable composition in a forced air circulation oven.

[0205] At the end of the curing cycle, remove the mold from the oven and allow it to cool. Demold at a temperature ranging from 50 to 70°C. Then, post-cur the polymer product in a forced air circulation oven under the following conditions: - For EX1, the temperature is 100℃ for 1 hour. - For EX2 and EX3, the temperature is 120℃ for 2 hours.

[0206] To determine the total transmittance, haze%, and dyeability tests (T% after coloring and uniformity of dye absorption), polymeric compositions EX1 to EX3 were cast into glass molds in the form of plano mirrors with a thickness of 2 mm and cured; to determine YI and Rockwell hardness, they were cast into flat sheets with a thickness of 5 mm.

[0207] The characterization data recorded in Tables 4 and 5 are based on measurements taken with post-cured lenses.

[0208] Lenses with complex designs and geometries were also prepared to evaluate the manufacturing yield of the compositions of the present invention under more particularly demanding conditions. Lenses prepared for each casting test were: - 10 semi-finished blanks, namely front mold and rear mold with curvature base 6 and base arc 8 (5 pieces for each curvature), with a center thickness of 10 mm; - Five bifocal lenses with an additional power equal to +2.00 and a curvature base curve of 6 for the front and rear lenses.

[0209] Process yield is evaluated by determining the ratio of the number of defective items exhibiting defects (i.e., cracks, flow lines, or defective sections in bifocal lenses) to the total number of cast items (regardless of design type).

[0210] The data in Table 4 show that the prepolymerization method according to the present invention, using BPO (EX2 and EX3), can yield optical articles with good mechanical and optical properties comparable to those of composition EX1 polymerized using dicarbonate peroxide ADC NS-30 initiator, with limited differences in refractive index. EX2 exhibits slightly higher yellowness than the comparative material EX1; however, this can be easily compensated for by adding a small amount of TAP-based bleaching agent without adversely affecting other characteristics.

[0211] Furthermore, both EX2 and EX3 exhibit similar T% and tinting properties to the comparative material EX1 (when the difference in the total T% value of the lenses is within + / - 5 units, the two lenses can be considered to have the same ability to absorb dye hues).

[0212] Furthermore, thanks to the shrinkage control achievable through the prepolymerization method of this invention, lenses EX2 and EX3 exhibited excellent manufacturing yields. In fact, compared to curing polyallylic functional monomers with standard dicarbonate peroxide ADC NS-30 initiator, no lenses with early peeling, cracks, or flow lines were observed in any of the prepared semi-finished blanks; moreover, all bifocal lenses were successfully cast without defective segment lines.

[0213] Comparative example EX1-PP in Table 4 As shown, this is the same effect that can be obtained by prepolymerization of polyallyl functional monomers with peroxydicarbonate ADC NS-30 initiator, but the significant improvement is that the prepolymer composition according to the invention is a cast-ready composition with improved shelf life and requires no subsequent addition of initiator before casting.

[0214] 3. Optical items EX5, EX7, EX9 and comparison EX4 EX6 EX8 Preparation The polymerizable formulations (EX5, EX7, EX9) according to the invention are prepared by prepolymerizing polyallyl functional monomers under the same conditions described above for prepolymer PP3. UV absorber compounds and bluing agents are formulated into the prepolymerized formulations to obtain final lenses with different cutoff ratios. For comparative purposes, a formulation containing non-prepolymerized polyallyl functional monomers and optional components is cured using a dicarbonate peroxide ADC NS 30 initiator (compare EX4). EX6 EX8 ).

[0215] The compositions of each formulation, along with the characterization data, are recorded in Table 5. Curing and post-curing conditions are as described in point 2 above.

[0216] The polymerizable compositions EX4 to EX9 represent alternative UV and HEV compositions containing a significantly higher dose of the UV absorber BP6, introduced in powder form. The high dosage of UV absorber does not affect the results of the prepolymerization reaction, and the resulting prepolymer compositions exhibit 70-110 mmHg at 25°C. 2 The desired increase in viscosity is within the range of 70-110 cSt / s.

[0217] The data in Table 5 show that the prepolymerization method of the present invention can be advantageously used to prepare optical articles having optical and mechanical properties very similar to those of high-quality lenses obtained by curing non-prepolymerized monomers with dicarbonate ADC NS-30 initiator.

[0218] Regarding optical articles (EX6 to EX9) with cutoffs of 400 nm and 410 nm, regardless of the type of initiator used, it was observed that higher doses of UV absorber required to achieve the desired cutoff ratio resulted in higher yellowness in the optical articles. However, by appropriately incorporating a blue agent, the yellowness could be maintained at an acceptable level.

[0219] It is noteworthy that when using high doses of UV absorbers, i.e., in optical articles with higher cutoff values, the optical articles according to the present invention still exhibit better properties compared to comparative materials. In fact, compared to comparative articles (EX4) where a downward trend was observed... EX6 and EX8 Regarding the materials according to the invention (EX5, EX7 and EX9), stable hardness values ​​were observed in the lenses. Furthermore, with respect to the material according to the invention (EX9), better and more uniform dyeing properties were observed in the final lens, wherein the high UV absorber dosage did not affect the final uniformity of color absorption and hue. In contrast, the lower hardness of the TX ADCNS30 cured lens (EX8) was reflected in faster dye penetration and the presence of some uniformity defects.

[0220] Finally, when demolding the bifocal lens, the comparative compositions showed a high incidence of cracks, flow lines, and frequent defect segments. Conversely, thanks to the reduced polymerization shrinkage level, the formulation according to the invention showed excellent casting results.

Claims

1. A method for preparing a polyallyl functionalized prepolymer composition, the method comprising: (a) Providing a reaction mixture comprising: - At least one polyallyl functional monomer; - 0.5 to 3.0 wt.% of at least one aromatic peroxide compound as a free radical initiator, the weight percentage being based on the total weight of the polyallyl functional monomer; (b) Heating the reaction mixture at a temperature 12 to 3 degrees Celsius (°C) lower than the 10-hour half-life temperature of the aromatic peroxide compound to achieve a kinematic viscosity of 40 to 350 mm at 25°C. 2 A prepolymer composition in the range of / s (40 to 350 cSt), wherein the kinematic viscosity is determined according to ASTM D446.

2. The method according to claim 1, wherein, In step (b), the reaction mixture is heated at a temperature 10°C to 5°C lower than the 10-hour half-life temperature of the aromatic peroxide compound.

3. The method according to any one of claims 1 to 2, wherein, The prepolymer composition has a thickness of 60 to 200 mm. 2 / s (60 to 200 cSt), preferably 70 to 120 mm 2 Viscosity at 25°C in the range of / s (70 to 120 cSt).

4. The method according to any one of claims 1 to 3, wherein, The at least one aromatic peroxide compound has the following general formula (F1): Wherein, X is selected from: hydrogen, C1 to C 12 Alkoxy, chlorine, and bromine.

5. The method according to claim 4, wherein, The at least one aromatic peroxide compound is benzoyl peroxide.

6. The method according to any one of claims 1 to 5, wherein, Step (b) includes degassing the reaction mixture.

7. The method according to any one of claims 1 to 6, wherein, In step (a), the viscosity of the at least one polyallyl functional monomer at 25° is between 10 and 300 mm. 2 / s (10 to 300 cSt), preferably 10 to 100 mm 2 / s (10 to 100 cSt), more preferably 10 to 40 mm 2 Within the range of / s (10 to 40 cSt).

8. The method according to any one of claims 1 to 7, comprising: The prepolymer composition is cooled to a temperature at least 20°C lower than the 10-hour half-life temperature of the aromatic peroxide compound.

9. The method according to any one of claims 1 to 8, wherein, The at least one polyallyl functional monomer comprises a compound containing two or more allyloxycarbonyl groups according to formula (1): In this formula, n is an integer from 2 to 6, R1 represents a hydrogen atom or a methyl group, and multiple R1s may be the same or different, X is a divalent to hexavalent organic group (a) derived from a linear or branched aliphatic polyol having 3 to 12 carbon atoms that may have an oxygen atom, a divalent to hexavalent organic group (b) derived from an alicyclic polyol having 5 to 16 carbon atoms that may have an oxygen atom, or a divalent to hexavalent organic group (c) derived from an aromatic compound having 6 to 12 carbon atoms, and the organic group (a) or the organic group (b) forms an allyl carbonate group by bonding to an allyloxycarbonyl group via an oxygen atom derived from a hydroxyl group.

10. The method according to any one of claims 1 to 9, wherein, The at least one polyallyl functional monomer comprises a diethylene glycol bis(allyl carbonate) compound of general formula (II): In equation (II), n is an integer equal to or greater than 1 and equal to or less than 10.

11. The method according to claim 10, wherein, The diethylene glycol bis(allyl carbonate) compound of general formula (II) comprises 70 wt.% or more, preferably 80 wt.% or more of the diethylene glycol bis(allyl carbonate) compound of formula (II) with n equal to 1, the weight percentage being based on the total weight of the diethylene glycol bis(allyl carbonate) compound of general formula (II) with n equal to or greater than 1 and equal to or less than 10.

12. The method according to any one of claims 1 to 9, wherein, The at least one polyallyl functional monomer comprises a reaction product (RP) containing the following components: diallyl carbonate (A); one or more linear or branched aliphatic diols (B) containing 3 to 10 carbon atoms in a molecule; and optionally, a linear or branched aliphatic polyol (C) containing 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in a molecule; wherein the molar ratio A / (B+C) is in the range of 4 / 1 to 20 / 1, and the optional component (C) in the mixture (B+C) is equal to or less than 5 wt.%, preferably equal to or less than 3 wt.%, relative to the total weight of the mixture (B+C).

13. The method according to any one of claims 1 to 9, wherein, The at least one polyallyl functional monomer comprises a reaction product (RP) containing the following components: diallyl carbonate (A); one or more linear or branched aliphatic diols (B) containing 3 to 10 carbon atoms in a molecule; and linear or branched aliphatic polyols (C) containing 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in a molecule; wherein the molar ratio A / (B+C) is in the range of 4 / 1 to 20 / 1, preferably 5 / 1 to 15 / 1, and the amount of component (C) in the mixture (B+C) is equal to or less than 5 wt.%, preferably equal to or less than 3 wt.%, relative to the total weight of the mixture (B+C).

14. The method according to any one of claims 10 to 11, wherein, The reaction mixture does not contain any other olefinically unsaturated compounds of diethylene glycol bis(allyl carbonate) compounds of general formula (II) that are not equal to or greater than 1 and equal to or less than 10.

15. The method according to any one of claims 12 to 13, wherein, The reaction mixture is free from other olefinic unsaturated compounds that are not the reaction product (RP) of the following components, which include: diallyl carbonate (A); one or more linear or branched aliphatic diols (B) containing 3 to 10 carbon atoms in a molecule; and optionally, linear or branched aliphatic polyols (C) containing 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in a molecule; wherein the molar ratio A / (B+C) is in the range of 4 / 1 to 20 / 1, and the amount of the optional component (C) in the mixture (B+C) is equal to or less than 5 wt.% relative to the total weight of the mixture (B+C).

16. A method for manufacturing an optical article, the method comprising: (i) Providing a reaction mixture, the reaction mixture comprising: - At least one polyallyl functional monomer; - 0.5 to 3.0 wt.% of at least one aromatic peroxide compound as a free radical initiator, the weight percentage being based on the total weight of the polyallyl functional monomer; (ii) Heating the reaction mixture at a temperature 12 to 3 degrees Celsius (°C) lower than the 10-hour half-life temperature of the aromatic peroxide compound to achieve a kinematic viscosity of 40 to 350 mm at 25°C. 2 A prepolymer composition in the range of / s (40 to 350 cSt), wherein the kinematic viscosity is determined according to ASTM D446; (iii) Casting the prepolymer composition into a mold; (iv) Curing the prepolymer composition in a mold to form an optical article.

17. The method according to claim 16, wherein, The prepolymer composition was not added with any additional free radical initiator other than at least one aromatic peroxide before being cast into the mold.

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