Material based on crosslinked silicone polymer comprising an attached photoinitiator, process for the preparation thereof, hydrophilic polymeric product obtained from this material and process for the preparation thereof, and novel photoinitiators

This invention pertains to a process for the manufacture of a hydrophilic polymeric product, consisting in causing a material comprising a crosslinked silicone polymer matrix and photoinitiator groups dispersed and immobilized within the polymer matrix to swell in a swelling solution comprising a solvent for swelling the crosslinked silicone polymer of the matrix of the material, a photopolymerizable hydrophilic monomer and optionally a crosslinking agent and a proton- or electron-donating coinitiator compound, when the material comprises photoactivable photoinitiator groups and does not comprise proton- or electron-donating coinitiator groups causing the photopolymerizable hydrophilic monomer to diffuse into the swollen material, and polymerizing, by irradiation, the photopolymerizable hydrophilic monomer.

The present invention relates to a material based on crosslinked silicone
 polymer comprising a crosslinked silicone polymer matrix and
 photoinitiator groups which are dispersed and attached within the silicone
 matrix, and to a process for the preparation thereof.
 The invention also relates to hydrophilic polymeric products obtained from
 the material based on silicone polymer, to a process for the preparation
 thereof and to the application thereof in the manufacture of hydrophilic
 contact lenses.
 Finally, the invention relates to novel photoinitiators especially suited
 to being incorporated in the above material based on crosslinked silicone
 polymer and to the use of the process resulting in the hydrophilic
 polymeric products.
 Materials based on silicone or polysiloxanes are well known for their very
 high permeability to oxygen, in particular polydimethylsiloxanes (PDMS).
 However, the use of pure polysiloxanes cannot be envisaged for the
 preparation of contact lenses because this material has the disadvantage
 of being hydrophobic and thus exhibits an absence of surface wettability
 which causes splitting of the lacrymal film. Furthermore, contact lenses
 made of pure silicone lead to suction effects (adhesion to the cornea of
 the eye).
 Various techniques have already been provided in order to make silicone
 lenses compatible with the eye.
 Some techniques are targeted at treating the surface of the lens in order
 to render it hydrophilic.
 For example, a process for rendering contact lenses made of silicone
 hydrophilic at the surface is known in French Patent FR 2,073,034, which
 process consists in swelling the silicone matrix using a monomer of
 monoester or monoamide of acrylic or methacrylic acid type forming a
 hydrophilic polymer.
 The contact lenses thus obtained exhibit a very low level of acrylic or
 methacrylic polymer incorporated at the surface of the silicone matrix.
 Other techniques are targeted at obtaining hydrophilic materials of the
 interpenetrating polymer network (IPN) type from hydrophobic
 organosiloxane prepolymers and hydrophilic monomers of the monoester or
 monoamide of acrylic or methacrylic acid type. The material of IPN type is
 a material in which the hydrophobic prepolymers and the hydrophilic
 monomers are mixed together and react simultaneously in order to form two
 interwoven networks by an independent polymerization of the hydrophobic
 prepolymers and of the hydrophilic monomers, respectively.
 This technique exhibits disadvantages because there are problems of
 solubility of the hydrophilic monomer in the hydrophobic prepolymer. It is
 thus difficult to obtain homogeneous materials and this technique is not
 suited to the production of materials with a high concentration of
 hydrophilic polymer and thus with high contents of water in the final
 material.
 French Patent FR 2,709,756, on behalf of the Applicant Company, discloses a
 process for producing a hydrophilic silicone material of IPN type
 consisting, in a first stage, in swelling a polymer of PDMS type in a
 composition comprising acrylic acid, a photoinitiator, a crosslinking
 agent and a solvent for swelling the PDMS polymer and in then bringing
 about the polymerization of the acrylic acid by subjecting the swollen
 PDMS polymer to UV irradiation. It is thus possible to obtain materials
 which are hydrophilic to the core, with high levels of hydrophilicity.
 Although this process gives satisfactory results, it can still be
 improved, however. In particular, there exists a possibility of
 heterogeneity in the photoinitiator/hydrophilic monomer distribution
 within the matrix, insofar as these compounds diffuse at different rates,
 which can result in physical and mechanical heterogeneities.
 Moreover, it would be desirable further to increase the level of
 hydrophilicity of the final material.
 Finally, it is also desirable to simplify the implementation of the process
 disclosed in French Patent FR 2,709,756, for its industrial exploitation
 and for its application to the manufacture of contact lenses.
 In order to solve these technical problems, the preparation has been
 carried out of a material based on crosslinked silicone polymer comprising
 a crosslinked silicone polymer matrix, that is to say in which the polymer
 network is three-dimensional, the distinguishing feature of which is to
 comprise photoinitiator groups which are dispersed and immobilized within
 the silicone matrix.
 The processes for the subsequent treatment of this material based on
 crosslinked silicone polymer, which are targeted at rendering it
 hydrophilic to the core, are greatly simplified thereby and the
 hydrophilic products obtained exhibit particularly interesting and
 advantageous characteristics.
 The material based on crosslinked silicone polymer comprising immobilized
 initiator groups and the process for the preparation thereof will now be
 described in more detail.
 According to the invention, the crosslinked silicone matrix comprises
 photoinitiator groups or fragments distributed homogeneously throughout
 its volume and to the very heart of the matrix.
 The photoinitiator groups can be attached by the following techniques:
 According to a first technique, the photonitiator groups are attached to
 the silicone matrix ia a covalent chemical bond.
 To this end, a photoinitiator functionalized by an SiH silyl group or by an
 unsaturated C.dbd.C double bond is prepared.
 This double bond can be of vinyl, (meth)acrylic or allyl type.
 The photoinitiator compound is introduced into a crosslinkable liquid
 composition comprising:
 an oil A of a polysiloxane monomer or oligomer carrying Si-vinyl groups;
 an oil B of a polysiloxane monomer or oligomer carrying Si--H groups;
 a metal catalyst for the hydrosilylation reaction.
 During the crosslinking by a hydrosilylation reaction carried out by the
 thermal route, the photoinitiator compound is grafted to the polysiloxane
 network via an Si--C covalent bond.
 According to a second immobilization technique, use is made of a long-chain
 photoinitiator compound. This chain is preferably a polysiloxane chain on
 which the photoinitiator group(s) is (are) grafted. This photoinitiator
 compound is, in the same way as in the preceding technique, introduced
 into the liquid mixture of the polysiloxane precursors.
 During the crosslinking of the mixture, the polysiloxane chain of the
 photoinitiator compound is physically immobilized within the crosslinked
 silicone polymer matrix obtained.
 In this case, in contrast to the preceding technique, there is no chemical
 bond between the photoinitiator compound and the silicone matrix but a
 simple retention of physical nature, due in particular to the
 three-dimensional character of the network of the crosslinked silicone
 polymer of the matrix.
 However, whatever the immobilization technique used, the photoinitiator
 groups remain attached in the polysiloxane matrix, even when the latter is
 subjected to extraction treatments with solvents. In other words, it is
 impossible to separate the photoinitiator groups from the matrix by
 extraction with solvents, whether these groups are grafted to the polymer
 forming the matrix or simply grafted to a long-chain compound physically
 immobilized within the matrix.
 Thus, at the end of the hydrosilylation reaction, there is obtained a
 material based on crosslinked silicone polymer comprising a crosslinked
 silicone polymer matrix, in which matrix are distributed photoinitiator
 groups capable of generating free radicals by light irradiation.
 The liquid silicone compositions used to produce the silicone polymer
 matrix are preferably polydimethylsiloxane oils with two constituents, the
 essential constituent units of which are represented below:
 ##STR1##
 These silicone oils are crosslinked by virtue of a hydrosilylation
 catalyst. Such catalysts are well known to the person skilled in the art.
 They are, for example, platinum, hexachloroplatinic acid,
 platinum-hydrocarbon complexes and rhodium complexes.
 Platinum-based catalysts are generally used at concentrations of 10 ppm to
 500 ppm, preferably of 50 to 300 ppm.
 The reaction temperatures vary from room temperature to 250.degree. C.
 according to the concentration and the type of catalyst used. The
 preferred temperatures vary from 50.degree. C. to 150.degree. C.
 The constituents A and B are used in proportions such that their mixture
 includes from 0.8 to 1.9 SiH bonds per 1 Si-vinyl bond.
 The polydimethylsiloxane (PDMS) polymer is preferably prepared by mixing
 two siloxane prepolymers developed by Rhone-Poulenc under the reference
 RTV 141 A and B and the functionalized photoinitiator in the desired
 proportions.
 The oil A is composed of mono- and divinyl PDMS and of a platinum catalyst.
 This part comprises approximately 3.10.times.10.sup.-4 vinyl functional
 groups per gram of RTV 141 A and its number-average molecular mass is
 31,200.
 The oil B is preferably a hydromethyl PDMS and comprises
 4.07.times.10.sup.-3 SiH functional groups per gram of RTV 141 B and its
 number-average molecular mass is 1770.
 In order to obtain the polymer, 10 parts by weight of oil A and 1 part by
 weight of oil B and the photoinitiator are mixed and then the crosslinking
 is carried out as mentioned above.
 The photoiniators, by means of which the photoinitiator groups can be
 introduced into the crosslinkable liquid compositions described above,
 will now be described in more detail.
 The photoinitiator compounds comprise, on the one hand, a functional group
 intended to react with the SiH or Si-vinyl groups of the PDMS oils and, on
 the other hand, a photoinitiator group.
 Such compounds can be obtained by functionalizing conventional
 photoinitiators, namely: any compound which produces free radicals under
 irradiation, whether by itself or by interaction with another proton- or
 electron-donating compound. That is to say that the photoinitiators used,
 or photopolymerization initiators, can equally well be of photo-cleavable
 type as of photoactivable type, with, however, a preference for those
 which are active in initiating the photopolymerization of the monomer for
 irradiation wavelengths lying in the UV region.
 A photocleavable photoinitiator comprises one or more compounds which
 function by directly generating one or more polymerization-initiating free
 radicals, whereas a photoactivable photoinitiator is formed of a system
 producing such radicals by photoassisted oxidation/reduction reaction
 between a light-absorbing compound and a hydrogen or electron donor, both
 present in the system. Of course, mixtures of the two types of
 photoinitiators can also be used.
 Examples of photocleavable compounds known per se are chosen from
 alkoxyacetophenone derivatives, benzoin ethers, phosphine oxides or
 benzoyloxime derivatives. Examples of known photoactivable photoinitiators
 comprise an absorber which produces free radicals, chosen from
 benzophenones, benzyls, xanthones, anthrones, thioxanthones, fluorenones,
 suberones or acridones, in combination with, as proton donor, a compound
 of the type of ethers, alcohols, amines or amino acids, or organometallic
 compounds.
 Such photoinitiators can be functionalized by techniques known to the
 person skilled in the art.
 Reference may usefully be made to the teaching of the following documents:
 U.S. Pat. No. 4,507,187, which describes the manufacture of a photoiniator
 of aryoyl [sic] formate type functionalized by alkene or acetylene groups;
 U.S. Pat. No. 4,477,326 and U.S. Pat. No. 4,587,276, which describe the
 production of photoinitiators of benzoin type functionalized by allyl
 groups;
 U.S. Pat. No. 4,536,265, which describes the production of acetophenones
 with olefinic or acetylenic functionality; and
 the document "Photoinitiator with functional group", J.M.S.--Pure
 Appl--Chem [sic] A 31 (3) pp 305-318 (1994)--Kolar, Grube and Greber,
 which describes photoinitiators functionalized by a silyl group, namely
 2-hydroxy-(or 2-methoxy)-2-methyl-1-[(4-dimethylsilyl)phenyl]propane-1-one
 [sic].
 Among the photoinitiators of use in the present invention, those
 corresponding to the formula:
 ##STR2##
 in which:
 R represents a hydrogen atom or a methyl group,
 Z is a divalent hydrocarbon-comprising chain comprising from 1 to 10 carbon
 atoms which can be interrupted by 1 to 3 atoms chosen from --O--, or
 ##STR3##
 where R' is independently a hydrogen atom or an alkyl group, preferably a
 C.sub.1 -C.sub.6 alkyl group and better still a methyl group, and
 A.sub.m is a group comprising a
 ##STR4##
 functional group, are more particularly recommended.
 Z preferably represents the following divalent chains:
 ##STR5##
 in which R" and R"' represent, independently of one another, an alkyl
 group, preferably a C.sub.1 -C.sub.6 alkyl group and in particular a
 methyl group, n.sub.1 and n.sub.2 are integers from 1 to 6, n.sub.3 and
 n.sub.5 are integers from 0 to 4, n.sub.4 is equal to 0 or 1, and n.sub.6
 is an integer from 0 to 5.
 The A.sub.m group is preferably chosen from the groups corresponding to the
 formulae:
 ##STR6##
 provided that Z comprises at least two carbon atoms;
 ##STR7##
 in which R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which are identical or
 different, are chosen from hydrogen and alkyl groups having from 1 to 6
 carbon atoms, preferably a methyl group.
 Other photoinitiators of use in the present invention correspond to the
 following formulae:
 ##STR8##
 The photoinitiators corresponding to the above formula (I) and for which
 the A.sub.m group is chosen from the groups of formulae (II) to (IV) are
 novel, as well as the compounds of formulae (Vb) to (Vf).
 The present invention thus also relates to these novel photoinitiators
 especially suited to being incorporated in the material based on
 crosslinked silicone polymer according to the invention and to the use of
 the process resulting in the hydrophilic polymeric products of the present
 invention.
 The photoinitiators preferably correspond to one of the following formulae:
 ##STR9##
 in which R, R", R"', R.sup.1, R.sup.2, R.sup.3, R.sup.4, n.sub.2, n.sub.3,
 n.sub.4, n.sub.5 and n.sub.6 have the same meanings as above.
 The photoinitiators preferably used in the context of the invention are:
 4-allylbenzophenone (ALBP)
 ##STR10##
 4-(allyloxymethyl)benzophenone (ALOBP)
 ##STR11##
 Such photoinitiators are introduced as mentioned above into the mixture of
 the siloxane prepolymers in a proportion of more than 0.1% by weight,
 preferably 0.5 to 10% by weight and better still from 0.5 to 4% by weight.
 The photoinitiator will thus be attached by covalent bonding to the final
 silicone.
 It is also possible to use long-chain photoinitiators obtained by reacting
 one of the photoinitiators mentioned above with a polysiloxane oil,
 preferably with a linear chain, by hydrosilylation reaction. The
 polysiloxane oil is preferably a PDMS oil with a molecular mass of between
 132 and 50,000 g/mol, preferably between 250 and 10,000 g/mol.
 The preparation of such photoinitiators is described in the article by
 Kolar, Grube and Greber mentioned above, as well as in the article
 "Functional polysiloxanes with benzophenone side groups: a photochemical
 application as radical polymerisation macroinitiators", Lydie Pouliquen,
 Xavier Coqueret, Alain Lablache-Combier and Claude Loucheux, Makromol.
 Chem., 113, 1273-1282 (1992).
 The long-chain photoinitiator is introduced into the PDMS oil at a
 concentration such that the fraction by weight of the photoinitiating
 functional groups is equal to that: used for the conventional
 photoinitiators, typically from 0.05 to 5% by weight of photoinitiator
 functional groups, preferably from 0.05 to 2% by weight. When use is made
 of photoactivable photoinitiators, the hydrogen- or electron-donating
 compound can be introduced into the swelling solution used in the first
 stage of the hydrophilization process.
 The donating compound can also be attached to the network of the PDMS
 matrix, that is to say introduced into the mixture of the siloxane
 prepolymers, insofar as the donating compound has been functionalized
 beforehand.
 In this case, the donating compound will be attached to the network of the
 silicone matrix via a covalent bond.
 This functionalized donating compound can also be fixed to a polysiloxane
 chain by hydrosilylation reaction and a donating compound with a long
 polysiloxane chain, preferably a PDMS chain, can thus be obtained which,
 introduced into the mixture of the siloxane prepolymers, will be
 physically retained in the final silicone matrix. The same polysiloxane
 oil is used for the preparation of the donating compound with a long
 polysiloxane chain as that defined for the preparation of the
 photoinitiator compound with a long polysiloxane chain.
 One example of donating compound or coinitiator is ethyl
 4-(dimethylamino)benzoate (EDMAB)
 ##STR12##
 One functionalized coinitiator which can be used is
 4-dimethylvinylsilane-N,N-dimethylaniline [sic].
 ##STR13##
 The amount of coinitiator used is generally a function of the amount of
 photoinitiator used. Use is made of concentrations of coinitiating units
 chosen within the same concentration ranges as the photoinitiators.
 The novel photoinitiators according to the invention can be prepared by
 conventional processes well known to the person skilled in the art.
 Examples of the preparation of photoinitiators according to the invention
 have been shown below.
 Synthesis of
 ##STR14##
 (Darocur.RTM. methacrylate)
 20 g (0.122 mol) of Darocur.RTM. 1173
 ##STR15##
 are introduced into a 250 ml, three-necked, round-bottomed flask equipped
 with a thermometer, a nitrogen inlet and a dropping funnel. 250 ml of
 ether, distilled once over sodium, and 20.4 ml (0.146 g) of distilled
 triethylamine are added. After purging with argon, methacrylic acid
 chloride is added dropwise with stirring. The temperature of the reaction
 medium increases and cooling is carried out from time to time by means of
 a cold water bath. The reaction medium immediately turns cloudy, the
 opacity increasing in step with the addition, and increases further after
 the end of the addition of the acid chloride. Once all the acid chloride
 has been added (13.1 ml, 0.134 mol), the reaction mixture is left stirring
 at room temperature for 2 hours. The mixture obtained is subsequently
 washed with 100 ml of water to which a few milliliters of HCl have been
 added, then with 100 ml of water and finally with 100 ml of water to which
 a few grams of NaHCO.sub.3 have been added. The product obtained is dried
 over MgSO.sub.4, filtered and evaporated to dryness to produce 23.5 g of
 expected product (Yield: 83%).
 The product obtained is Darocur.RTM. methacrylate of formula:
 ##STR16##
 Synthesis of
 ##STR17##
 (Irgacure.RTM. vinylsilane or IVS)
 150 ml of anhydrous tetrahydrofuran (THF) and 9.37 g (4.18.times.10.sup.-2
 mol) of Irgacure.RTM. 2959
 ##STR18##
 are introduced into a 500 ml, multi-neck, round-bottomed flask which is
 purged with argon and equipped with a dropping funnel for THF, a
 thermometer, an argon inlet, a dropping funnel for triethylamine (TEA) and
 a dropping funnel for chlorovinyldimethylsilane. The Irgacure.RTM. 2959
 rapidly dissolves. 3.82 ml of TEA, distilled over CaH.sub.2, are then
 added and, finally, the chlorovinyldimethylsilane is added dropwise. The
 temperature of the reaction mixture rises and it is cooled by means of an
 ice bath. A cream-white precipitate is immediately formed. At the end of
 the addition of the chlorovinyldimethylsilane [sic] (5.04 g,
 4.18.times.10.sup.-2 mol), the reaction mixture is left stirring for 4
 hours. The solution obtained is filtered on sintered glass (porosity 4).
 The THF is driven off from the filtered product and the residue is taken
 up in cyclohexane. The mixture becomes cloudy, which cloudiness is removed
 by filtration. The solvent is then driven off in order to collect 12.44 g
 of a yellow oil. After distillation under reduced pressure at 175.degree.
 C., two fractions of 5.13 g and 3.27 g respectively of the expected
 product are collected, i.e. a yield of 65%.
 The product obtained is Irgacure.RTM. vinylsilane of formula:
 ##STR19##
 Synthesis of
 ##STR20##
 (3-butene-4-acyloxymethylbenzophenone)
 a. Preparation of 4-(bromomethyl)benzophenone
 ##STR21##
 30 g (0.153 mol) of 4-methylbenzophenone are introduced into a 250 ml
 three-necked flask equipped with a reflux condenser and a dropping funnel
 containing 8.7 ml (0.168 mol) of bromine. In a first step, the reaction
 medium is heated to 70.degree. C. and then, after complete dissolution of
 the solid, to 150.degree. C. The bromine is then added dropwise over a
 period of 3 hours. The reaction is exothermic. The initially colorless
 solution becomes orange-yellow. Heating is maintained at 150.degree. C.
 for 15 hours. At the end of the reaction, the temperature of the reaction
 medium is allowed to return to room temperature. The solution is brown in
 color. 75 ml of benzene and 35 ml of diethyl ether are added. Washing is
 carried out with a saturated Na.sub.2 CO.sub.3 solution, then with a
 saturated Na.sub.2 S.sub.2 O.sub.3 solution and finally with a saturated
 NaCl solution, in order to remove the salts formed and to bring the
 solution to a pH of the order of 6-7. The organic phase is recovered and
 the solvents are evaporated. A caramel-colored paste is obtained. It is
 recrystallized from 100 ml of ethanol. The cream-colored crystals are
 collected and dried under vacuum. The mother liquors are collected and a
 second crystallization is carried out. The crystals obtained are dried
 under vacuum. The yield of expected product is 50%, m=20.81 g.
 b. Synthesis of 4-hydroxymethylbenzophenone:
 The 4-bromomethylbenzophenone obtained in the preceding stage (2 g, 7.27
 mmol) is introduced into a three-necked flask equipped with a reflux
 condenser and with magnetic stirring. A 15% by volume solution of water
 and of N-methyl-2-pyrrolidone (5.6/31.5 ml) is prepared in an Erlenmeyer
 flask. Slight warming is observed. This solution is subsequently
 introduced into a dropping funnel and it is added dropwise over 1 h 45 to
 the 4-bromomethylbenzophenone while heating the reaction medium to
 80.degree. C. At the end of the addition, the temperature of the solution
 is gradually raised to 110.degree. C. Heating is maintained for 18 hours.
 At the end of the reaction, the temperature of the reaction medium returns
 to room temperature. 70 ml of water are added and the reaction medium
 becomes white after mixing. The organic phase is extracted three times
 with 70 ml of diethyl ether. The organic phases are then combined, washed
 3 times with 150 ml of water and dried over MgSO.sub.4. After evaporating
 the solvents on a rotary evaporator, 1.43 g of crude product are obtained
 (crude yield=93%).
 Purification is carried out by distillation in a bulb oven. 1.16 g of the
 expected product are then obtained (final yield=75%).
 c. Condensation of 4-hydroxymethylbenzophenone with 4-pentenoic [sic] acid
 chloride:
 4-Pentenoic [sic] acid chloride (0.77 g, 6.5 mmol) and
 4-hydroxymethylbenzophenone (1.16 g, 5.5 mmol) are introduced into 20 ml
 of anhydrous THF in a round-bottomed flask. Pyridine (0.56 g, 7 mmol) is
 added dropwise. A white precipitate is formed in step with the addition
 (pyridinium salt). The reaction is continued for 3 hours with magnetic
 stirring. At the end of the reaction, the salt is filtered off and washed
 with ether. The filtrate is then recovered and water is added. The aqueous
 phase is washed and then extracted 3 times with 30 ml of ether. The
 organic phases are combined, an aqueous K.sub.2 CO.sub.3 solution is added
 and the organic phase is brought back to neutrality by addition of a
 saturated aqueous NaCl solution. Drying is subsequently carried out over
 MgSO.sub.4 and the solvents are removed. 1.28 g of the expected product
 are obtained (yield=79%).
 The photoinitiator compound obtained corresponds to the formula:
 ##STR22##
 Synthesis of 4-allylbenzophenone (ALBP)
 ##STR23##
 The scheme for the preparation of allylbenzophenone is shown below.
 ##STR24##
 1) Protection of the Carbonyl Functional Group by Synthesis of an Acetal
 The first stage consists in protecting the carbonyl functional group of the
 bromobenzophenone by the formation of a cyclic acetal. This reaction is
 carried out experimentally in solution in benzene by using a Dean-Stark
 device in order to remove the water released in the process.
 The operating conditions are as follows:
 The following are introduced into a 250 ml round-bottomed flask surmounted
 by a Dean-Stark device and by a condenser:

4-Bromobenzophenone 80.0 g i.e. 0.306 mol
 Ethylene glycol 18.8 ml i.e. 0.337 mol
 (10% excess)
 Benzene 130 ml
 p-Toluenesulfonic acid 100 mg
 The reaction mixture is heated to 110.degree. C. by means of an oil bath.
 The theoretical amount of water released in the process in the case of a
 quantitative yield is 5.15 ml. The reaction is continued for 56 hours. The
 initially cloudy reaction mixture is clear and exhibits a light yellow
 coloring. 9.478 g of water were collected in total, although the reaction
 only releases 5.15 g of it. The difference is attributed to the presence
 of water in the crude benzene used. The solvent is subsequently evaporated
 at 60.degree. C. by means of a rotary evaporator. Microdrops of residual
 water or ethylene glycol seem to be present in the medium.
 An additional devolatilization is carried out by using an oil bath,
 thermostatically controlled at 50.degree. C., coupled to the vacuum of a
 vane pump.
 Finally, the structure of the compound obtained was confirmed by .sup.1 H
 and .sup.13 C NMR in CDCl.sub.3.
 However, there remains a small amount of unprotected benzophenone which has
 to be separated. This is because this compound would result in the
 formation of undesirable products by coupling with the organomagnesium
 compound which will be prepared during the following stage.
 At this point in the synthesis, the product is a slightly yellowish,
 viscous oil which is beginning to crystallize. After leaving for a day,
 the product has completely set solid. 100 ml of ethanol are then added and
 the product is dissolved therein at a temperature in the region of
 50.degree. C. No crystallization is induced during the cooling of the
 solution. A few crystals of 4-bromobenzophenone are then added and the
 mixture is placed in a refrigerator for about 30 minutes. This treatment
 makes it possible to obtain beautiful white crystals in the form of
 plates. Recrystallization is subsequently carried out according to the
 usual techniques and the purity of the compound thus obtained is confirmed
 by NMR.
 The samples collected at the end of recrystallization are analyzed by
 .sup.1 H NMR in order to confirm the purity thereof, before mixing them
 with the top fractions. It turns out that this purity is no longer
 satisfactory for the final two fractions collected.
 The total mass of pure acetal collected after recrystallization is 70.0 g.
 The synthetic yield, including recrystallization, calculated with respect
 to the starting amount of 4-bromobenzophenone charged is thus 74.9%.
 2) Synthesis of the Organomacrnesium Compound
 This second stage consists in reacting the acetal of 4-bromobenzophenone
 with magnesium turnings, in order to prepare the intermediate
 organomagnesium derivative which will subsequently be used during the
 coupling reaction with allyl bromide.
 The operating conditions are as follows:
 The reaction is carried out under a slight argon flow in a 250 ml,
 three-necked, round-bottomed flask equipped with a bulb condenser
 surmounted by a CaCl.sub.2 tube, with a 100 ml dropping funnel and with a
 Y-shaped fitting equipped with a thermometer and an argon inlet.
 The reaction is exothermic; however, when additional heating will be
 necessary, the latter will be achieved with a water bath thermostatically
 controlled at 45.degree. C.

Acetal of 4-BrPh 20.097 g dissolved in 40 ml of an-
 hydrous THF (0.0686 mol)
 Mg turnings 1.71 g in 10 ml of anhydrous THF
 (0.0704 mol)
 Iodine one crystal
 In a first step, the reactor is purged with argon for approximately 15
 minutes. The magnesium, 10 ml of anhydrous THF and an iodine crystal are
 introduced. The acetal solution is prepared in an Erlenmeyer flask and
 decanted into the dropping funnel, and then the latter is mounted on the
 reactor. The reactor is again purged with argon for a few minutes.
 Approximately 5 ml of acetal solution are subsequently poured into the
 reactor, then, without stirring, this mixture is subsequently heated using
 a hairdryer until the appearance of bubbles at the surface of the
 magnesium turnings; a slight cloudiness is observed in the reaction
 medium, followed by the rapid appearance of the blood-red color of the
 organomagnesium compound formed. Stirring is then started and the acetal
 solution added dropwise.
 As the reaction is exothermic, the rate of addition is adjusted so as to
 maintain the temperature of the reaction medium in the vicinity of
 45.degree. C. If necessary, the thermostatically-controlled water bath can
 be used.
 The total duration of the addition is 90 minutes and then the reaction is
 further continued under these conditions for an additional 90 minutes. At
 the end of the reaction, there still remains a small amount of unconsumed
 magnesium turnings in the medium and the solution thus obtained is
 blood-red in color.
 3) Coupling Reaction
 Before carrying out the coupling reaction with allyl bromide, the reaction
 mixture is allowed to cool to room temperature.
 The operating conditions are as follows:
 A solution of allyl bromide in THF is prepared in a 100 ml dropping funnel
 by dissolution of 5.8 ml of the bromide (8.108 g, i.e. 0.0671 mol) in 25
 ml of anhydrous THF. The funnel is subsequently mounted on the reactor and
 the addition is begun dropwise.
 The appearance of an insoluble compound in the reaction medium is very
 quickly observed. The latter is in principle the magnesium bromide which
 is released during the progression of the reaction. The total duration of
 the addition is one hour and then the stirring is further continued under
 the same conditions for an additional hour.
 At the end of the reaction, the reaction mixture, which is orangey in
 color, is diluted with a small amount of THF and then filtration is
 carried out on a sintered glass in order to separate therefrom the
 residual magnesium as well as the precipitated salt formed during
 synthesis. The THF is subsequently evaporated using a rotary evaporator.
 The residue thus obtained is oily and comprises a not insignificant
 proportion of an insoluble compound, probably a magnesium bromide residue.
 The residue is taken up in 250 ml of dichloromethane (clear orangey-yellow
 solution) and then extraction is carried out successively three times with
 50 ml of distilled water.
 During the first extraction, the phase separation is not sharp but is
 composed of an emulsion which is very difficult to break down. A
 significant amount of the synthesized compound is very probably trapped in
 this emulsion and has to be recovered. The aqueous and emulsified phases
 are thus reextracted with a small amount of dichloromethane.
 Finally, the organic phase is filtered on a sintered glass of porosity 4
 and then drying is carried out over magnesium sulfate before removing the
 dichloromethane. The orangey residue isolated is characterized by NMR.
 15.25 g of crude product are thus obtained.
 4. Deprotection Reaction
 Several routes for deprotection of the carbonyl are possible. Mention may
 be made of acid hydrolysis and dioxolane exchange by acid catalysis. It is
 the latter route which will be used here.
 The deprotection reaction was carried out on all the product collected
 during the two syntheses carried out. (The second synthesis is described
 below).

Functionalized acetal 29.92 g
 Acetone 150 ml
 95% H.sub.2 SO.sub.4 0.05 ml
 The reaction temperature is set by the boiling temperature of the acetone.
 The total duration of the reaction is 2 hours. The solution, initially
 orangey-yellow, turns red. The solvent is evaporated using a rotary
 evaporator and then an additional devolatilization is carried out using a
 vane pump at a temperature in the vicinity of 45.degree. C. 26.92 g of an
 opaque brown-colored oil are thus collected.
 A small amount of crystalline product was separated using a mixture
 consisting of 450 ml of ethanol and 50 ml of benzene. After filtration and
 characterization of the crystals by .sup.1 H NMR, it turned out that this
 was 4-bromobenzophenone. The filtrate is then concentrated until only
 approximately 50 to 100 ml of solution remains and then it is cooled to
 0.degree. C. A paste settles out at the bottom of the round-bottomed
 flask. The crystallization process is repeated but few crystals settle
 out. 24 g of oil remain.
 23.24 g of oil are distilled in a bulb oven under a vacuum of 10.sup.-2
 mmHg in a temperature range from 175 to 250.degree. C. 11.94 g of a
 slightly yellow oil consisting of two phases are collected. The minor
 phase is attributed to ethylene glycol which would result from a thermal
 deprotection, catalyzed by sulfuric acid, of an acetal residue present in
 the oil.
 The distillate is centrifuged in order to separate therefrom the ethylene
 glycol (30 minutes at 10,000 r/min) and then redistillation is carried out
 at 185.degree. C. under 10.sup.-2 mmHg. A small amount of ethylene glycol
 is again released and the distillate is slightly yellow.
 The three fractions (top, middle, tail) are characterized by NMR and then
 the top and middle fractions are combined (11.02+0.58=11.60 g).
 Due to the presence of the ethylene glycol, the whole mixture is taken up
 in 100 ml of benzene, three spatulafuls of silica gel are added and
 stirring is carried out with the aim of promoting the adsorption of the
 ethylene glycol on the silica. After filtration on sintered glass and
 evaporation of the solvent, analysis by .sup.1 H NMR shows that the amount
 of ethylene glycol present has been reduced by half.
 2nd Synthesis of 4-allylbenzophenone
 The equipment and the operating conditions are similar.
 Synthesis of the Organomagnesium Derivative
 The following is placed in the dropping funnel: Acetal of
 bromobenzophenone: 20.0 g (0.0683 mol) in 75 ml of anhydrous THF.
 The following are placed in the round-bottomed flask:

Mg turnings 1.63 g (0.0671 mol)
 Anhydrous THF 15 ml
 one iodine crystal
 5 to 10 ml of the acetal solution are added and then, without stirring,
 this mixture is heated until the appearance of a release of gas at the
 surface of the metal. Stirring is then started and the acetal is slowly
 added dropwise. The blood-red coloring of the organomagnesium derivative
 develops virtually instantaneously in the reaction medium.
 A thermostatically-controlled water bath is used as additional heating and
 the rate of addition is adjusted so as to maintain the temperature between
 43 and 47.degree. C.
 The total duration of the addition is 2 hours, after which there still
 remains an unconsumed magnesium residue. The reaction is continued under
 the same conditions for an additional 2 hours.
 Coupling Reaction with Allyl Bromide:
 An allyl bromide solution is prepared by dilution of 6.0 ml of allyl
 bromide (0.0692 mol) in 50 ml of anhydrous THF.
 After cooling the organomagnesium solution to room temperature, the allyl
 bromide solution is slowly added dropwise over approximately 2 hours. A
 precipitate rapidly appears in the reaction medium.
 At the end of the reaction, this solution is diluted with a small amount of
 THF and then filtration is carried out on sintered glass of porosity 4, in
 order to separate therefrom the insoluble salt as well as the residual
 magnesium. The filtrate is subsequently evaporated at 50.degree. C. using
 a rotary evaporator and an orangey-colored pasty residue is isolated which
 is taken up in approximately 250 ml of dichloromethane and then extracted
 several times with distilled water. The formation of a very stable
 emulsified phase is once again observed during the first extraction. The
 organic phase, which is orangey-yellow in color, is subsequently dried
 over magnesium sulfate and then the solvent is evaporated.
 15.65 g of an orange-colored oil are collected.
 Monitoring .sup.1 H NMR confirms the nature of the compound thus prepared,
 as well as the presence of impurities which it will be necessary to remove
 after the stage of deprotection of the carbonyl functional group.
 Preparation of 4-(allyloxymethyl)benzophenol [sic]
 ##STR25##
 5 g of bromomethylbenzophenone are dissolved in 20 ml of anhydrous THF and
 the solution obtained is placed in a dropping funnel.
 40 ml of THF are introduced into a 500 ml round-bottomed flask equipped
 with a thermometer, a dropping funnel for the initiator, a dropping funnel
 for introduction of allyl alcohol and the dropping funnel containing the
 bromomethylbenzophenone solution. The impurities of the solvent are
 neutralized with 2 to 3 drops of naphthalene-potassium
 ##STR26##
 1.2 ml (1.82.times.10.sup.-2 mol) of distilled allyl alcohol are then
 introduced. 20.2 ml of naphthalene-potassium are then added. A white
 precipitate is formed during the addition. The contents of the dropping
 funnel containing the bromomethylbenzophenone solution are added. The
 temperature increases by 5 to 10.degree. C. The precipitate increases in
 scale and becomes brown-red. The mixture is left stirring for 3 hours. The
 color of the reaction medium lightens and the temperature decreases. The
 THF is then driven off and the residue is taken up in benzene. A
 significant precipitate remains. Washing is carried out with water and the
 organic phase is filtered. Drying is carried out and then the benzene is
 removed.
 5.69 g of a dark-yellow liquid are collected. The liquid obtained is placed
 in a sublimator for 5 hours at 100.degree. C. The liquid residue obtained
 represents 3.40 g (74%). 1.7 g of this residue are distilled in a bulb
 oven and 0.7 g (57%) of product, distilling at 175.degree. C. under
 10.sup.-2 mmHg, is collected.
 The remaining 1.7 g are distilled under the same conditions and 0.61 g
 (41%) of product is collected.
 The distillate comprises a portion which is solid at room temperature. The
 distillate is filtered through a Millipore filter (0.5 .mu.m) and 1.05 g
 (23%) of the expected product are finally collected, which product
 corresponds to the formula:
 ##STR27##
 Preparation of 2-hydroxy-1-phenyl-2-methyl-5-hexene-1-one [sic]
 ##STR28##
 5 ml (3.72 g, 37.5 mmol) of trimethylsilyl cyanide (withdrawn using a dry
 syringe) are added to a solution of 3.98 g (37.5 mmol) of freshly
 distilled benzaldehyde and 20 mg of AlCl.sub.3 in THF.
 The assembly is placed under an inert argon atmosphere and the mixture is
 heated under reflux to 90.degree. C. After stirring for 10 hours, the
 solvent is evaporated and the residue is distilled at 80.degree. C. (0.1
 mmHg) in a bulb oven.
 The expected product is obtained with a yield of 95%.
 The structure of the product obtained was confirmed by IR spectrometry
 (Perkin-Elmer spectrometer) and NMR spectrometry (AC 200 MHz).
 c) Synthesis of 2-hydroxy-1-phenyl-2-methyl-5-hexene-1-one [sic]
 A solution of tert-butyllithium in hexane (tert-BuLi/hexane) (1.6M, 20 ml,
 31.8 mmol) is slowly added, under an argon atmosphere, to a solution of
 diisopropylamine (3.23 g, 31.9 mmol) in THF (20 ml) at -78.degree. C.
 The mixture is maintained at this temperature for 45 minutes. A solution of
 phenyltrimethylsiloxyacetonitrile (6.54 g, 31.8 mmol) in THF (50 ml) is
 then added dropwise.
 Stirring is maintained for 45 minutes and then a solution of 5-hexene-2-one
 [sic] (3.26 g, 31.8 mmol) in THF is slowly added to the intense brown
 solution.
 The mixture is kept stirring. After 2 hours at -78.degree. C., the ice bath
 is removed. When the temperature of the round-bottomed flask reaches
 0.degree. C., 300 ml of water are added. The solution obtained is
 introduced into a separating funnel and extracted with 400 ml of CH.sub.2
 Cl.sub.2 after shaking several times.
 The organic solution recovered is concentrated.
 Deprotection of the alcohol group: 5.4 g of benzyltrimethylammonium
 fluoride, 20 ml of THF and 1 ml of H.sub.2 O are added to the organic
 solution recovered. After stirring for 4 hours, the solution is washed
 with 4.times.300 ml of water and then extracted with ether. The ethereal
 solution is concentrated and distilled in a bulb oven (115.degree. C. at
 0.1 mmHg).
 The expected product is obtained with a yield of 35%.
 The structure of the product was confirmed by IR spectrometry and NMR
 spectrometry.
 Preparation of 1-(o-allylphenyl)-2-trimethylsiloxy-2-methyl-1-butanone.
 ##STR29##
 0.8 ml (600 mg, 6.04 mmol) of trimethylsilyl cyanide is added to a solution
 of 883 mg of distilled allylbenzaldehyde and 5 mg of anhydrous AlCl.sub.3
 in THF.
 The assembly is placed under an inert argon atmosphere and the mixture is
 heated under reflux to 90.degree. C. After stirring for 10 hours, the
 solvent is evaporated and the residue is distilled at 130.degree. C. (0.1
 mmHg) in a bulb oven.
 The expected product is obtained with a yield of 85%.
 The structure of the product was confirmed by IR spectrometry and NMR
 spectrometry.
 c) Synthesis of 1-(o-allylphenyl)-2-trimethylsiloxy-2-methyl-1-butanone
 A solution of tert-BuLi/hexane (1.6M, 2.38 ml, 3.81 mmol) is slowly added,
 under an argon atmosphere, to a solution of diisopropylamine (395 mg, 3.9
 mmol) in THF (20 ml) at -78.degree. C.
 The mixture is maintained at this temperature for 15 minutes. A solution of
 o-allylphenyltrimethyl-siloxyacetonitrile (938 mg, 3.81 mmol) in THF (50
 ml) is then added dropwise.
 Stirring is maintained for 10 minutes and then a solution of butanone (274
 mg, 3.81 mmol) in THF is slowly added to the intense brown solution.
 The mixture is kept stirring. After 3 hours at -78.degree. C., the ice bath
 is removed. When the temperature of the round-bottomed flask reaches
 0.degree. C., 100 ml of water are added. The solution obtained is
 introduced into a separating funnel and extracted with 400 ml of CH.sub.2
 Cl.sub.2 after shaking several times.
 The organic solution recovered is concentrated and then distilled at
 125.degree. C. (0.1 mmHg) in a bulb oven.
 The expected product is obtained with a yield of 35%. The structure of the
 product was confirmed by IR spectrometry and NMR spectrometry.
 Preparation of 1-(o-allylphenyl)-2-trimethylsiloxy-2-methyl-5-hexene-1-one
 [sic]
 ##STR30##
 b) Synthesis of 1-(o-allylphenyl)-2-trimethylsiloxy-2-methyl-5-hexene-1-one
 [sic]
 A solution of tert-BuLi/hexane (1.5M, 3.1 ml, 4.7 mmol) is slowly added,
 under an argon atmosphere, to a solution of diisopropylamine (486 mg, 4.8
 mmol) in THF (50 ml) at -78.degree. C.
 The mixture is maintained at this temperature for 15 minutes. A solution of
 o-allylphenyltrimethylsiloxyacetonitrile (1.152 g, 4.7 mmol) in THF (50
 ml) is then added dropwise.
 Stirring is maintained for 5 minutes and then a solution of 5-hexene-2-one
 [sic] (471 mg, 4.8 mmol) in THF is slowly added to the intense black
 solution.
 The mixture is kept stirring. After 3 hours at -78.degree. C., the ice bath
 is removed. When the temperature of the round-bottomed flask reaches
 0.degree. C., 400 ml of water are added. The solution obtained is
 introduced into a separating funnel and extracted with 400 ml of CH.sub.2
 Cl.sub.2 after shaking several times.
 The organic solution recovered is concentrated and then distilled at
 150.degree. C. (0.1 mmHg) in a bulb oven.
 The expected product is obtained with a yield of 45%.
 The structure of the product was confirmed by IR spectrometry and NMR
 spectrometry.
 Preparation of 2-trimethylsiloxy-1-phenyl-2-(3-butene)-5-hexene-1-one [sic]
 ##STR31##
 A solution of tert-BuLi/hexane (1.55M, 13 ml, 20 mmol) is slowly added,
 under an argon atmosphere, to a solution of diisopropylamine (2.12 g, 21
 mmol) in THF (20 ml) at -78.degree. C.
 The mixture is maintained at this temperature for 45 minutes. A solution of
 5-hexene-2-one [sic] (1.96 g, 20 mmol) in THF (20 ml) is then added
 dropwise.
 Stirring is maintained for 60 minutes and then 1.8 ml of allyl bromide are
 slowly added to the colorless solution. Stirring is maintained for 12
 hours at room temperature.
 The resulting red solution is filtered through 2 cm of silica. A yellow
 solution is then obtained which is concentrated. The residue is distilled
 in a bulb oven (50.degree. C., 2 mmHg).
 The expected product is obtained with a yield of 65%.
 The structure was confirmed by IR spectrometry and NMR spectrometry.
 c) Synthesis of 2-trimethylsiloxy-1-phenyl-2-(3-butene)-5-hexene-1-one
 [sic]
 A solution of tert-BuLi/hexane (1.55M, 4.1 ml, 6.3 mmol) is slowly added,
 under an argon atmosphere, to a solution of diisopropylamine (648 g, 6.4
 mmol) in THF (20 ml) at -78.degree. C.
 The mixture is maintained at this temperature for 15 minutes. A solution of
 phenyltrimethylsiloxyacetonitrile (1.29 g, 6.3 mmol) in THF (50 ml) is
 then added dropwise.
 Stirring is maintained for 20 minutes and then a solution of
 1,8-nonadiene-5-one [sic] (867 mg, 6.3 mmol) in THF is slowly added to the
 intense brown solution.
 The mixture is kept stirring. After 3 hours at -78.degree. C., the ice bath
 is removed.
 When the temperature of the round-bottomed flask reaches 0.degree. C., 200
 ml of water are added. The solution obtained is introduced into a
 separating funnel and extracted with 400 ml of CH.sub.2 Cl.sub.2 after
 shaking several times.
 The organic solution recovered is concentrated and then distilled at
 150.degree. C. (0.1 mmHg) in a bulb oven.
 The expected product is obtained with a yield of 30%.
 The structure was confirmed by IR spectrometry and NMR spectrometry.
 Preparation of
 ortho-di[2-(o-trimethylsiloxy)-2-(3-butene)-5-hexene-1-one]-1-phenyl [sic]
 ##STR32##
 3.565 g (36 mmol) of liquid trimethylsilyl cyanide (withdrawn using a dry
 syringe) is [sic] added to a solution of 2.41 g (36 mmol) of
 orthophthaldicarboxyaldehyde [sic] and 20 ml of AlCl.sub.3 in THF.
 The assembly is placed under an inert argon atmosphere and the mixture is
 heated under reflux to 900C. After stirring for 10 hours, the solvent is
 evaporated and the residue is distilled at 175.degree. C. (0.1 mmHg) in a
 bulb oven.
 The expected product is obtained with a yield of 75%.
 The structure of the product was confirmed by IR spectrometry and NMR
 spectrometry.
 c) The Continuation of the Synthesis of the Compound (Vd) is Carried Out
 from Ortho-phthal Di(trimethylsiloxyacetonitrile) [sic] as Above.
 Preparation of a Macrophotoinitiator of the Irgacure.RTM.
 Vinylsilane-polydimethylsiloxane-Irgacure.RTM. Vinylsilane Type
 0.61 g (8.1.times.10-4 mol) of a PDMS with silyl endings having a
 number-average molar mass M.sub.n of approximately 750 and 0.5 g of
 Irgacure.RTM. vinylsilane of formula:
 ##STR33##
 dissolved beforehand in 5 ml of cyclohexane (anionic grade), are placed in
 a 100 ml round-bottomed flask. 0.12 ml (6.646.times.10-3 mol) of a
 solution of H.sub.2 PtCl.sub.6.6H.sub.2 O in 50 ml of isopropanol is added
 and the mixture is heated at 70.degree. C. for 8 hours. It is left
 standing overnight and then filtered through a Millipore.RTM. filter (0.45
 .mu.m).
 The expected product is thus obtained, which product corresponds to the
 formula:
 ##STR34##
 Preparation of a Compound (Va)--Polydimethylsiloxane--Compound (Va)
 Difunctional Macrophotoinitiator
 ##STR35##
 b) Procedure
 1.53 g (4.08 mmol) of .alpha.,.omega.-dihydropolydimethylsiloxane (PDMS)
 and then 833 mg (8.16 mmol) of 2-hydroxy-1-phenyl-2-methyl-5-hexene-1-one
 [sic] are successively added to a 250 ml three-necked flask. After three
 vacuum/argon operations, 50 ml of anhydrous toluene are introduced,
 followed by 2 ml of a solution of H.sub.2 PtCl.sub.6 in isopropanol (6.646
 mmol), and then the mixture is heated to 80.degree. C.
 After stirring for 24 hours, the solvent is evaporated. The viscous residue
 obtained is precipitated from 100 ml of MeOH and dried. In order to remove
 the traces of catalyst, the filtrate (MeOH) is evaporated and filtered
 through 2 cm of SiO.sub.2 (treated with a cyclohexane solution having 5%
 of triethylamine, eluent CH.sub.2 Cl.sub.2), and then dried under vacuum.
 Preparation of a Compound (Ve)--Polydimethylsiloxane--Compound (Ve)
 Difunctional Macrophotoinitiator
 ##STR36##
 397 mg (0.53 mmol) of .alpha.,.omega.-dihydropolydimethylsiloxane (PDMS)
 and then 307 mg (1.06 mmol) of
 1-(o-allylphenyl)-2-trimethylsiloxy-2-methyl-1-butanone are successively
 added to a 250 ml three-necked flask. After three vacuum/argon operations,
 50 ml of anhydrous toluene are introduced, followed by 1.6 ml of a
 solution of platinum divinyltetramethyldisiloxane in toluene (0.392 mmol).
 After stirring for 24 hours at room temperature, the solvent is evaporated.
 The viscous residue obtained is precipitated from 150 ml of methanol and
 dried. In order to remove the traces of catalyst, the filtrate (MeOH) is
 evaporated and filtered through 2 cm of SiO.sub.2 (treated with a
 cyclohexane solution having 5% of triethylamine, eluent CH.sub.2
 Cl.sub.2), and then dried under vacuum.
 Preparation of Multifunctional Macrophotoinitiators
 I. From 2-trimethylsiloxy-1-phenyl-2-(3-butene)-5-hexene-1-one [sic]
 ##STR37##
 b) Procedure
 681 mg (0.9 mmol) of .alpha.,.omega.-dihydropolydimethylsiloxane (PDMS) and
 then 287 mg (0.9 mmol) of
 2-trimethylsiloxy-1-phenyl-2-(3-butene)-5-hexene-1-one [sic] are
 successively added to a 250 ml three-necked flask.
 After three vacuumn/argon operations, 50 ml of anhydrous toluene are
 introduced, followed by 2.73 ml of a solution of platinum
 divinyltetramethyldisiloxane in toluene (0.392 mmol/l).
 After stirring for 48 hours at room temperature, the solvent is evaporated.
 The viscous residue obtained is precipitated from 100 ml of methanol.
 After separation by settling for 3 days, the methanol is removed and the
 precipitate is dried. The organic phase (MeOH) is evaporated and filtered
 through 2 cm of SiO.sub.2 (treated with a cyclohexane solution having 5%
 of triethylamine, eluent CH.sub.2 Cl.sub.2), and then dried under vacuum.
 II. From 1-(o-allylphenyl)-2-trimethylsiloxy-2-methyl-5-hexene-1-one [sic]
 1.8 g (2.4 mmol) of .alpha.,.omega.-dihydropolydimethylsiloxane (PDMS) and
 then 760 mg (2.4 mmol) of
 1-(o-allylphenyl)-2-trimethylsiloxy-2-methyl-5-hexene-1-one [sic] are
 successively added to a 250 ml three-necked flask. After three
 vacuum/argon operations, 50 ml of anhydrous toluene are introduced,
 followed by 5 ml of a solution of platinum divinyltetramethyldisiloxane in
 toluene (0.392 mmol/l).
 After stirring for 48 hours at room temperature, the solvent is evaporated.
 The viscous residue obtained is precipitated from 100 ml of methanol.
 After separation by settling for 4 days, the methanol is removed and the
 precipitate is dried. The organic phase (MeOH) is evaporated and filtered
 through 2 cm of SiO.sub.2 (treated with a cyclohexane solution having 5%
 of triethylamine, eluent CH.sub.2 Cl.sub.2), and then dried under vacuum.
 ##STR38##
 (ALBP-PDMS-ALBP).
 5.06 g (6.75.times.10.sup.-3 mol) of polydimethylsiloxane oil with silyl
 endings, Mn=750, and 3.0 g (1.35.times.10.sup.-2 mol) of
 4-allylbenzophenone are weighed directly in a 250 ml, three-necked,
 round-bottomed flask equipped with a bulb condenser. After three
 successive purges with argon, 50 ml of anhydrous benzene and 1.023 ml of a
 catalyst solution (H.sub.2 PtCl.sub.6.6H.sub.2 O-6.646.times.10.sup.-3 M
 solution in isopropanol) are introduced. The mixture is subsequently
 heated at 70.degree. C. for 8 hours.
 At the end of the reaction, the solution is clear. The solvent is
 evaporated and the presence is then observed of a few solid particles
 (catalyst) which are removed by filtration through a 0.5 .mu.m
 Millipore.RTM. filter. 8.01 g of the expected product are collected.
 Syntheses of a Functionalized Coinitiator and of a Long-chain Coinitiator
 ##STR39##
 Procedure:
 All the materials must be purified before beginning the synthesis. The THF
 is distilled under argon, over sodium wire, at atmospheric pressure. The
 4-bromo-N,N-dimethylaniline (Aldrich) is conditioned under argon. The
 chlorodircethylvinylsilane (Aldrich) is distilled at atmospheric pressure
 under a slight argon flow (bp=81.degree. C.). A solution of anhydrous THF
 (66 ml, 2/3 of the total volume of THF in the reaction medium) and of
 4-bromo-N,N-dimethylvinylaniline (m=20.01 g, n=0.1 mol) is subsequently
 prepared in a dropping funnel under argon.
 2.673 g (0.11 mol) of magnesium and an iodine crystal are introduced into a
 reactor equipped with a mechanical stirrer, a reflux condenser and a
 thermometer. The assembly is then conditioned under argon. 30 ml of THF
 are introduced under an argon flow. The solution then becomes
 brown-yellow. At most 1/10 of the bromine/THF [sic] solution is then added
 under argon. After reacting for 1/2 hour, the solution becomes
 colorless-cloudy and then, after 3/4 hour, purple. A slight warming is
 then observed and reflux occurs.
 The brominated [sic] solution is subsequently added dropwise under argon.
 At the end of the addition, the reaction medium is heated at 50.degree. C.
 for two hours. The temperature of the solution is allowed to return to
 room temperature.
 13.81 ml (0.1 mol) of silane chloride are subsequently added dropwise. A
 warming of the reaction medium is observed. At the end of the addition,
 stirring is continued for 15 minutes and then 8 ml of water are added. A
 white emulsion is produced and refluxing occurs. After having allowed the
 temperature of the reaction medium to return to room temperature, 100 ml
 of H.sub.2 O and 100 ml of ether are added. The solution is filtered. The
 organic phase is separated from the aqueous phase and washed with a
 saturated NaCO.sub.3 solution. The solution, which is yellow in color, is
 dried over MgSO.sub.4 and the solvents are driven off.
 Crude yield=91%
 Crude mass=18.7 g
 The crude product is distilled under vacuum, bp .sub.0.1 =79.degree. C.,
 yield=50%.
 ##STR40##
 Procedure:
 1 g (0.0049 mol) of the product obtained in the preceding stage and then
 1.8293 g (0.0024 mol) of PDMS (Mn=750) are introduced into a three-necked
 flask, conditioned under argon, equipped with a magnetic stirrer. Dry
 toluene, 50% by mass, and 3.3 ml of the H.sub.2 PtCl.sub.6 catalyst
 (5.times.10.sup.-4 mol/SiH functional group) are subsequently added. The
 reaction medium is heated at 80.degree. C. for 8 hours. The solution
 becomes black and refluxing occurs. At the end of the reaction, the
 temperature of the reaction medium returns to room temperature. A portion
 of the solution is then precipitated from a minimum amount of ethanol and
 a portion of the crude is characterized.
 Quantitative determination of the residual hydrosilane functional groups of
 the polymer shows that the functionalization is virtually quantitative.
 Preparation of the Hydrophilic Ppolymers According to the Invention
 The polymeric products which are hydrophilic to the core and transparent,
 according to the invention, are prepared according to a process comprising
 the following stages:
 a) The material based on crosslinked silicone olymer comprising the
 photoinitiator, for example PDMS, obtained above is diffused and swollen
 in a solution comprising a photopolymerizable hydrophilic monomer, a
 solvent for swelling the material based on crosslinked silicone polymer
 and preferably a crosslinking agent; and
 b) the hydrophilic monomer is polymerized by irradiation and optionally the
 crosslinking agent is polymerized,
 in order to obtain the final hydrophilic polymeric product.
 There exists no specific limitation with respect to the hydrophilic monomer
 to be used, provided that the latter is soluble in a solvent for swelling
 the material based on silicone polymer and that it is, furthermore,
 photopolymerizable.
 Use may be made, in particular, of acrylic or methacrylic acid or
 hydroxyalkyl (meth)acrylates, such as hydroxyethyl methacrylate (HEMA).
 Some monomers which make it possible to avoid lipid or protein deposits can
 be incorporated, such as, for example, glyceryl methacrylate and
 (meth)acrylate derivatives of glucuronic or galacturonic acid.
 In the swelling solution, the
 [hydrophilic monomer]/[solvent]
 ratio is preferably less than 0.5 and better still less than 0.2.
 The solvent used must be able, at least partially, to dissolve the
 hydrophilic monomer and be an agent for swelling the silicone material. It
 is preferably low in volatility. Use will be made, for example, of
 toluene, cyclohexane, tetrahydrofuran, dodecane or a fluorinated solvent.
 The crosslinking agent used must, like the hydrophilic monomer, be
 photopolymerizable and at least partially soluble in the solvent. Use will
 be made, for example, of ethylene glycol dimethacrylate (EGDMA).
 Two preferred embodiments of the process for the preparation of the
 hydrophilic products, according to the invention, will now be described:
 The first process consists in carrying out the photopolymerization stage b)
 by compressing the disk of material based on crosslinked silicone polymer
 in a mold which is transparent to UV radiation and which corresponds to
 the irradiation region of the photoinitiator.
 The reverse diffusion reactions of the swelling solution are then limited.
 The second process, which is preferably used, in particular for industrial
 exploitation, consists in irradiating the swollen material while the
 latter is immersed in the swelling solution.
 It is found, in this case, that polymeric products are obtained with a
 higher level of hydrophilicity than in the process of the prior art where
 the photoinitiator is present in the swelling solution.
 The hydrophilic polymeric products obtained have different final structures
 which depend in particular on the nature of the photoinitiator group used
 and, incidentally, whether the photoinitiator groups are or are not
 attached to silicon atoms of the crosslinked silicone polymer of the
 matrix via covalent bonds and whether the photoinitiating entity formed
 during the photopolymerization remains attached or not to the silicone
 polymer of the matrix.
 When the photoinitiating entity remains attached chemically to the silicone
 polymer of the matrix, the polymer resulting from the photopolymerization
 of the hydrophilic monomer is, at least partially, grafted to this
 silicone polymer.
 In general, when the photoinitiator groups are not grafted to the silicone
 polymer of the matrix or when the photoinitiating entities created during
 the photopolymerization are free, the hydrophilic polymeric products
 obtained exhibit a structure mainly and sometimes even solely of IPN type.
 Thus, when Irgacure.RTM. vinylsilane is used as photoinitiator, this
 photoinitiator is grafted via the vinyl functional groups to the
 crosslinked PDMS of the matrix during the crosslinking. During the
 irradiation, the photoinitiator forms a C(Me.sub.2)OH free radical while
 the photoinitiating entity
 ##STR41##
 remains attached to the crosslinked PDMS of the matrix. For this reason,
 the hydrophilic polymer resulting from the photopolymerization of the
 hydrophilic monomer, for example acrylic acid, will be, at least
 partially, grafted to the crosslinked PDMS of the matrix via the
 photoinitiating entities grafted to this crosslinked PDMS.
 The invention thus also relates to a hydrophilic polymeric product obtained
 by the process described above, in which photoinitiator groups are
 attached via covalent bonds to Si atoms of the crosslinked silicone
 polymer of the matrix and the hydrophilic polymer obtained by
 photopolymerization of the photopolymerizable hydrophilic monomer is, at
 least partially, grafted to the crosslinked silicone polymer of the
 matrix.
 The hydrophilic polymeric products are particularly suited to the
 manufacture of ophthalmic items, such as contact lenses.

EXAMPLES
 I--Preparation of Disks or [sic] Material Based on Crosslinked Silicone
 Polymers Incorporating the Photoinitiator.
 Silicone disks (incorporating the photoinitiator) with a diameter of 14 mm
 and a thickness of 0.2 mm are prepared.
 The photoinitiator is added to the mixture of siloxane prepolymers (10% by
 weight oil A+1% by eight oil B) mentioned above.
 The mixture is degassed and poured into
 either polyamide molds (PAm)
 or polypropylene molds (PPm).
 The molds are subsequently heated under pressure for 8 hours at 64.degree.
 C. and 15 hours at 83.degree. C.
 The disks obtained are transparent, flexible and elastic.
 The disks obtained are subsequently extracted with cyclohexane, so as to
 remove the unreacted constituents.
 The disks, after extraction, are subsequently characterized by confirming,
 by a UV spectrum of the sample, the presence of the absorption bands
 characteristic of the photoinitiator.
 In all cases, it was found that the photoinitiator was thoroughly
 immobilized within the crosslinked silicone polymer matrix of the disks.
 The following photoinitiators were tested:
 Darocure.RTM. methacrylate
 Ivs
 IVS-PDMS-IVS
 ALBP
 ALOBP.
 II--Preparation of the Hydrophilic Polymeric Products
 II.1--Process by Molding
 The disks obtained above are swollen in a solution containing:
 the hydrophilic monomer
 the mixed solvent for the hydrophilic monomer and the silicone material
 the crosslinking agent EGDMA.
 When the diffusion equilibrium is reached, the sample is dried and placed
 between two quartz mold parts (in order to avoid the reverse diffusion of
 solvent and monomer) covered with a polyethylene film (in order to avoid
 adhesion of the hydrophilic polymer, in particular poly(acrylic acid), to
 the glass).
 The irradiation source is a mercury vapor lamp (100 W) maintained at a
 distance of 12 to 13 cm.
 Continuous rotation of the sample makes it possible to irradiate each face
 of the disk alternately.
 Irradiation is maintained for 15 minutes.
 After irradiation, the sample is dried in order to remove the solvent. It
 is then extracted with water in order to remove the monomer and oligomers.
 The sample is then hydrated in distilled water until equilibrium is
 reached.
 II.2--Vessel Process.
 The disk made of silicone material is introduced into a quartz vessel with
 a thickness of 0.4 mm containing the hydrophilic monomer, the crosslinking
 agent and the solvent.
 Irradiation is carried out after swelling and after the diffusion
 equilibrium has been obtained.
 Irradiation lasts 30 minutes. The irradiation source-sample distance is
 from 12 to 13 cm.
 EXAMPLES 1 to 16

PDMS-Coinit- Swelling in the
 ALBP solution % % PAA % H.sub.2 O
 Example 27 71 27 28
 Example 28 75 30 30
 After photopolymerization the samples remain transparent and relatively
 flexible.
 The percentage of polymer was obtained by initially determining the mass m
 of the disks made of material based on crosslinked silicone polymer before
 the photopolymerization stage.
 After the photopolymerization, the sample is extracted in chloroform and
 then dried and its mass m' determined. It is possible, from the values of
 m and m' to calculate the percentage of polymer (for example PAA)
 incorporated:
 ##EQU3##
 However, a certain amount of polymer may have polymerized at the surface of
 the disk. This polymer can be removed by extraction in an appropriate
 medium, for example distilled water in the case of PAA. After dehydration,
 the new mass m" of the disk is determined, and the true amount of polymer
 incorporated and the amount of polymer polymerized at the surface which
 has been extracted.
 The degrees of hydration are determined after swelling in distilled water
 or physiological serum (hydrated mass=m.sub.H) from the relationship:
 ##EQU4##