COMPOSITION BASED ON ALLYL MONOMERS AND PEROXIDE(S) FOR THE MANUFACTURE OF ORGANIC GLASSES

Abstract

The present invention relates to the use of one or more specific organic peroxides for the polymerization of an allylic monomer and/or at least one allylic copolymer.

The invention also relates to a composition comprising at least one allylic monomer and/or at least one allylic copolymer and at least one specific organic peroxide.

The invention also relates to the use of the composition as defined above for the manufacture of an organic glass, preferably an ophthalmic lens, possibly optionally being tinted by means of pigments and/or organic dyes.

Claims

1-21. (canceled)

22. A process for polymerizing one or more allylic monomers and/or allylic copolymers comprising using one or more peroxides of the following formula (I):
1-alkoxy-1-t-alkylperoxycyclohexane(I) wherein in formula (I) the alkoxy group comprises from 1 to 4 carbon atoms, the t-alkyl group comprises from 4 to 12 carbon atoms, and the cyclohexane ring is optionally substituted by 1 or 3 alkyl groups, each comprising from 1 to 3 carbon atoms.

23. The process according to claim 22, wherein the peroxide(s) of formula (I) is/are selected from the group consisting of 1-methoxy-1-tert-amylperoxycyclohexane (TAPMC), 1-methoxy-1-t-butylperoxycyclohexane (TBPMC), 1-methoxy-1-t-amylperoxy-3,3,5-trimethylcyclohexane, 1-methoxy-1-t-butylperoxy-3,3,5-trimethylcyclohexane, 1-ethoxy-1-t-amylperoxycyclohexane (TAPEC), 1-ethoxy-1-t-butylperoxycyclohexane (TBPEC), 1-ethoxy-1-t-amylperoxy-3,3,5-trimethylcyclohexane and/or 1-ethoxy-1-t-butylperoxy-3,3,5-trimethylcyclohexane.

24. The process according to claim 22, wherein the peroxide of formula (I) is 1-methoxy-1-tert-amylperoxycyclohexane.

25. The process according to claim 22, wherein the allylic monomer(s) is/are chosen from bis(allyl carbonate) monomers.

26. The process according to claim 22, wherein the allylic monomer(s) is/are chosen from diol bis(allyl carbonate) monomers of the following formula (II): ##STR00003## wherein in formula (II): R.sub.a and R.sub.c, which are identical or different, represent an allyl group of the following formula: ##STR00004## wherein R.sub.d is selected from the group consisting of: a hydrogen atom, a halogen atom, and a linear or branched C.sub.1-C.sub.4 alkyl group, and R.sub.b is selected from the group consisting of alkylene groups, alkylene ether groups, aromatic alkylene ether groups, alkylene polyether groups, alkylene carbonate groups and mixtures thereof.

27. The process according to claim 22, wherein the allylic monomer(s) is/are selected from the group consisting of ethylene glycol bis(allyl carbonate), diethylene glycol bis(2-methyl carbonate), diethylene glycol bis(allyl carbonate), ethylene glycol bis(2-chloro allyl carbonate), triethylene glycol bis(allyl carbonate), 1,3-propanediol bis(allyl carbonate), propylene glycol bis(2-ethyl allyl carbonate), 1,3-butenediol bis(allyl carbonate), 1,4-butenediol bis(2-bromo allyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis(2-ethyl allyl carbonate), pentamethylene glycol bis(allyl carbonate), isopropylene bis phenol-A bis(allyl carbonate) and mixtures thereof.

28. The process according to claim 22, wherein the allylic monomer is diethylene glycol bis(allyl carbonate).

29. The process according to claim 22, wherein the allylic copolymer(s) is/are obtained from the polymerization of diol bis(allyl carbonate) monomers of the following formula (II): ##STR00005## wherein in formula (II): R.sub.a and R.sub.c, which are identical or different, represent an allyl group of the following formula: ##STR00006## wherein R.sub.d is selected from the group consisting of: a hydrogen atom, a halogen atom, and a linear or branched C.sub.1-C.sub.4 alkyl group, and R.sub.b is selected from the group consisting of alkylene groups, alkylene ether groups, aromatic alkylene ether groups, alkylene polyether groups, alkylene carbonate groups and mixtures thereof.

30. The process according to claim 22, wherein the allylic copolymer(s) is/are chosen from polyol poly(allyl carbonates).

31. The process according to claim 22, wherein the allylic copolymer(s) is/are obtained from the polymerization of a bis(allyl carbonate) monomer and a polyether diol.

32. A polymerizable composition comprising at least one peroxide of formula (I):
1-alkoxy-1-t-alkylperoxycyclohexane(I), wherein in formula (I), the alkoxy group comprises from 1 to 4 carbon atoms, the t-alkyl group comprises from 4 to 12 carbon atoms, and the cyclohexane ring is optionally substituted by 1 or 3 alkyl groups, each comprising from 1 to 3 carbon atoms, and at least one allylic monomer, wherein the allylic monomer(s) is/are selected from the group consisting of ethylene glycol bis(allyl carbonate), diethylene glycol bis(2-methyl carbonate), diethylene glycol bis(allyl carbonate), ethylene glycol bis(2-chloro allyl carbonate), triethylene glycol bis(allyl carbonate), 1,3-propanediol bis(allyl carbonate), propylene glycol bis(2-ethyl allyl carbonate), 1,3-butenediol bis(allyl carbonate), 1,4-butenediol bis(2-bromo allyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis(2-ethyl allyl carbonate), pentamethylene glycol bis(allyl carbonate), isopropylene bis phenol-A bis(allyl carbonate) and mixtures thereof, and/or at least one allylic copolymer, wherein the allylic copolymer(s) is/are obtained from the polymerization of diol bis(allyl carbonate) monomers, wherein the diol bis(allyl carbonate) monomers are selected from the group consisting of ethylene glycol bis(allyl carbonate), diethylene glycol bis(2-methyl carbonate), diethylene glycol bis(allyl carbonate), ethylene glycol bis(2-chloro allyl carbonate), triethylene glycol bis(allyl carbonate), 1,3-propanediol bis(allyl carbonate), propylene glycol bis(2-ethyl allyl carbonate), 1,3-butenediol bis(allyl carbonate), 1,4-butenediol bis(2-bromo allyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis(2-ethyl allyl carbonate), pentamethylene glycol bis(allyl carbonate), isopropylene bis phenol-A bis(allyl carbonate) and mixtures.

33. The composition according to claim 32, further comprising at least one additional peroxide other than the peroxides of formula (I).

34. The composition according to claim 33, wherein the ratio between the peroxide(s) of formula (I) and the at least one additional peroxide other than the peroxides of formula (I) is between 99:1 and 30:70.

35. The composition according to claim 32, further comprising at least one photoinitiator.

36. A process for preparing a polymer composition comprising at least one step of polymerization of a polymerizable composition as defined according to claim 32 at one or more temperatures ranging from 40 to 140 C.

37. A process for preparing an organic glass comprising at least the following successive steps: a step of introducing a polymerizable composition as defined according to claim 32 into a device comprising at least one mould, a step of polymerization of said composition at one or more temperatures ranging from 40 to 140 C., and a step of recovering the organic glass.

38. The composition according to claim 32, further comprising at least one additional peroxide other than the peroxides of formula (I), wherein the at least one additional peroxide is chosen from the peroxides of formula (III):
bis-t-alkylperoxycyclohexane(III), wherein in formula (III), each t-alkyl group comprises from 4 to 12 carbon atoms and the cyclohexane ring is optionally substituted by 1 or 3 alkyl groups, each comprising from 1 to 3 carbon atoms.

Description

EXAMPLES

A. Example of Synthesis of 1-methoxy-1-t-amylperoxycyclohexane (TAPMC)

[0211] A mixture of t-amyl hydroperoxide (TAHP), cyclohexanone and methanol is prepared and treated by means of 70% sulfuric acid at a temperature of between 6 C. and 4 C.

[0212] In fifteen minutes, an equilibrium mixture of 1-methoxy-1-t-amylperoxycyclohexane, 1,1-di-(t-amylperoxy)-cyclohexane and unreacted starting products, cyclohexanone and TAHP, is formed.

[0213] A small amount (approximately 2%) of cyclohexanone dimethyl ketal (CDMK) is also obtained in the reaction mixture.

[0214] The reaction mixture is treated with cold water, then the aqueous phase is separated from the organic phase, which is purified by rinsing.

[0215] This method for producing the main initiator of the method according to the invention is given here by way of example, it being understood that those skilled in the art may optionally be able to obtain it by other means well known to those skilled in the art. Moreover, it should be noted that organic peroxides belonging to the same family (close, or even very close, to TAPMC) have been produced and demonstrate the same technical effects obtained within the context of the present invention, namely for the polymerization of allylic monomers and/or allylic copolymers.

B. Example of Preparation of a Polymerizable Composition

[0216] A polymerizable composition based on diethylene glycol bis(allyl carbonate) (CAS 142-22-3), sold under the name CR-39 by PPG and on 1-methoxy-1-t-amylperoxycyclohexane (TAPMC) is prepared. The composition preferably comprises a mould-release agent, such as Zelec UN, available from Stepan.

[0217] The 1-methoxy-1-t-amylperoxycyclohexane is present at an amount of 4% by weight relative to the weight of diethylene glycol bis(allyl carbonate).

C. Example of Preparation of an Organic Glass

[0218] The previously obtained composition is subsequently poured into a mould having a concave portion and a convex portion. Once poured, the convex portion is closed over the concave portion of the mould, then the assembly is heated to a temperature of 90 C. Several steps with temperature gradients or stages ranging from 60 to 130 C. are carried out over a duration of 10 to 30 h.

[0219] The polymerized product obtained in this way is annealed for a duration which may range from 1 to 20 hours at temperatures which may range up to 130 C.

[0220] The organic glass is subsequently recovered.

[0221] The organic glass has good optical and mechanical properties in accordance with at least one of the parameters described above.

D. Biplanar System for Measuring the Optical Properties

[0222] Different optical properties, namely a yellowness index (YI), a haze measurement, and a Shore D hardness, were measured for different organic glasses. These organic glasses were prepared according to the protocol described above, with the exception of the polymerization which was carried out between two 10*15 cm flat sheets of glass, 4 mm thick, arranged vertically, separated by a silicone rubber seal 4 mm in diameter, with the mechanical cohesion of the assembly being produced by a clamping clip at constant pressure. All the tests were carried out with an air intake at the top of the mould.

[0223] The yellowness index YI is obtained with a type SP60 spectro-colorimeter from the manufacturer X-RITE, according to standard CIE 1976 (colour space). The trichromatic coordinates are those of Lab Hunter. The measurement is calibrated every day with a standard calibration tile (black and white), serial number: 20609 D65:10, of 18/02/2010, WO A89274.

[0224] The YI measurement is carried out in the thickness of the 4 mm glass, and is expressed as difference to the YI measured on the white zone of the Leneta Form 2A chart (the measurement of the yellowness index of which is 10.48, after calibration of the spectrophotometer).

[0225] The haze value is determined by means of a haze measurement device: the Haze-Gard plus apparatus, manufactured by BYK-GARDNER, according to standard ASTM D 1003 (Standard calibration (zero) no. 4733lightness calibration no. 4732).

[0226] The Shore D hardness is measured by means of a portable durometer of HPE II Shore D type (manufacturer: BAREISS, apparatus standardized according to NF T51-174; DIN EN ISO 868; ISO 7619; ASTM D 2240; BS 903 Part A26).

[0227] The following organic peroxides were tested: [0228] diisopropyl peroxydicarbonate (CAS 105-64-6) at 27% by weight in CR-39, sold by Arkema under the name Luperox IPP27 (comparative example 1); [0229] 1-methoxy-1-tert-amylperoxycyclohexane (TAPMC) as sold under the trade name LuperoxV10 by Arkema (example 2 according to the invention); [0230] a mixture of 70% by weight of 1-methoxy-1-tert-amylperoxycyclohexane (TAPMC) and of 30% by weight of 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane as sold under the trade name LuperoxV10 and Luperox231 by Arkema (example 3 according to the invention); [0231] a mixture of 70% by weight of 1-methoxy-1-tert-amylperoxycyclohexane (TAPMC) and of 30% by weight of 1,1-di(tert-amylperoxy)-cyclohexane as sold under the trade name LuperoxV10 and Luperox531M60 by Arkema (example 4 according to the invention); [0232] OO-tert-amyl-O-(2-Ethylhexyl)-monoperoxycarbonate sold by Arkema under the name Luperox TAEC (comparative example 5); [0233] OO-tert-butyl-O-(2-Ethylhexyl)-monoperoxycarbonate sold by Arkema under the name Luperox TBEC (comparative example 6).

[0234] The thermal crosslinking cycle is adapted as a function of the decomposition temperature of the organic peroxides used (half life temperatures (HLT) at 1 h and 10 h) according to the following scheme: rise in 14 h up to the 10 h half life temperature (HLT 10 h) of the peroxide used (in the case of a mixture of peroxides, up to the HLT 10 h of the peroxide having the highest HLT 10 h, i.e for example 3, that of Luperox 231, and for example 4, that of Luperox 531M60), then rise in 4 h to the 1 h half life temperature (HLT 1 h) of the peroxide used (in the case of a mixture of peroxides, up to the HLT 1 h of the peroxide having the highest HLT 1 h, i.e for example 3, that of Luperox 231, and for example 4, that of Luperox 531M60), then cooling down to a temperature of 70 C., at which temperature demoulding is carried out.

The results are presented in the table below:

TABLE-US-00001 References HLT 1 h HLT 10 h Active % by weight of Shore D Quality of (% by weight) in C. in C. Oxygen pure peroxide YI Haze hardness the sheets Ex 1 Luperox 75 46 0.230 2.97 0.45 0.50 74 + IPP27 Ex 2 TAMPC 108 87 0.12 1.67 1.08 0.39 67.4 + 0.230 3.33 1.07 0.32 74.8 + Ex 3 70% (Lup. 231) (Lup. 231) 0.131 1.67 1.03 0.46 73.1 + TAPMC-30% 115 96 0.262 3.33 1.38 0.57 78.4 + Luperox 231 Ex 4 70% (Lup. 531M60) (Lup. 531M60) 0.114 1.67 1.09 0.56 71.3 + TAPMC-30% 112 93 0.227 2.97 1.54 0.44 74.9 + Luperox 531M60 Ex 5 Luperox 117 98 0.149 2.57 3.27 1.06 80.3 * TAEC 0.223 3.85 8.00 1.32 80.2 * Ex 6 Luperox 121 100 0.15 2.27 8.32 1.39 76.2 ** TBEC 0.215 3.48 11.13 1.42 79.8 ** + Sheets not exhibiting any breakage upon demoulding. The silicone seal was always able to be removed from the sheets without any tearing zones arising. * Sheets sometimes broken upon demoulding, slight adhesion to the seal without tearing the seal during the removal thereof by manual pulling. ** Sheets always very brittle upon demoulding, adhering to the silicone seal, with tearing of the material during the manual removal of the seal following demoulding.

[0235] The active oxygen % is expressed in the following manner: A[O]=n*16*titre (%)/Mw, where n=number of peroxide functions present in the peroxide molecule, 16 is the molecular weight in g/mol of an atom of oxygen, and Mw is the molecular weight in g/mol of the peroxide.

It is noted that the use of TAPMC at a significantly higher temperature compared to the reference produced with IPP27 virtually does not adversely affect the yellowness index.
It is also noted that at an equivalent active oxygen content to example 1 (around 0.23%), the compositions of examples 3 and 4 do not substantially modify the YI value, despite a temperature in this case which is also higher than for example 1, and enables greater hardness, without thereby leading to sheets which are brittle upon demoulding.
It is also noted that at a lower dose, corresponding to an A[O] of around 0.12-0.13%, the addition of a bifunctional cyclic peroxide according to the invention (example 3) or of a tert-amyl perketal (example 4) makes it possible to come close to a hardness close to that of example 1.
It is possible to conclude from examples 5 and 6 that the mono tert-amyl percarbonate, Luperox TAEC, and the mono tert-butyl percarbonate Luperox TBEC lead to sheets which have a much higher yellowness index (YI) compared to the reference from example 1 and to examples 2 to 4. Moreover, for example 6, despite a hardness comparable to that of example 5, the sheets break upon demoulding after crosslinking and the sheet cannot be readily detached from the seal, which partially tears.

[0236] Examples 5 and 6 therefore show that the use of peroxides of percarbonate type does not make it possible to form sheets with a good yellowness index (YI), low haze and high hardness, without this being accompanied by breakage upon demoulding