CS252224B1 - Hydrophilic copolymer suitable eapecially for contact lenses and medicinal utilization and method of its producion - Google Patents

Abstract

A hydrophilic copolymer suitable for contact lenses and medical applications is prepared by copolymerization of 10 to 90 wt.%, advantageously 40 to 80 wt.%, of the monomer with general formula I <IMAGE> where n = 1 or 2,with 90 - 10 wt.% of 2-hydroxyethyl methacrylate and 0.01 to 2 wt.% of at least one crosslinking agent having at least two olefinic double bonds, in the presence of radical initiators. Copolymerization may be carried out in bulk or in a polar solvent.

Description

The present invention relates to hydrophilic copolymers suitable in particular for contact lenses and for medical use and to a process for the preparation thereof.

Strong swellable elastomers are known for a variety of measuring purposes, contact lens manufacturing and other applications. However, these materials will not be useful for some applications due to their insufficient mechanical properties. Therefore, thinly crosslinked copolymers of strong hydroline N-vinylpyrrolidone with a hydrophobic alkyl methacrylate (Brit. Pat. No. 1,514,810) have been developed which have more convenient low properties in addition to high swelling. However, they have an undesirable extractable content and their hydrophobic comonomers, especially methyl ether, are very volatile.

Therefore, these materials cannot be used to cast in open molds, such as in the production of films or contact lenses by centrifugal casting. Also, the cross-linked trichloride microfiber, known from U.S. Pat. No. 3,220,960, which is also highly swellable, does not possess sufficiently eechalogenic properties, and therefore cannot be worn for a long time in some applications such as contact lenses. It is an attempt for these lenses to develop hygroscopic copolymers which will be highly swellable, while maintaining good elastic properties, especially strength, tainoot, and modulus of elasticity.

The above disadvantages are eliminated by a hygroscopic copolymer suitable especially for contact lenses and epithelial applications, which contains in its chain structure 10 to 90% by weight, preferably to 80% by weight, of units derived from the monoimers of the general formula I wherein:

η = 1 or 2, ai 10% hmmt, units derived from 2-hydroxyldyleedaacrlate and 0.01 and 2% units derived from at least one crosslinker having at least two olefin double bonds.

The cross-linked units are preferably derived from polyfunctional esters or amides of acrylic or acrylic acid.

The hydrous copolymer of the invention is prepared by copolymerizing 10 to 90% by weight of a monomer of formula I with 90 to 10% by weight. % Of 2-hydroxyldyleedaacyllate and 0.01 to 2% by weight of acrylic or meearyl acrylic esters or amides in at least two olefinic double bonds in the free radical phase. The copolymerization may also be carried out in the presence of polar solvents, such as preferably glycerol, glycols and derivatives thereof, water, ethyl oleate, diluent, dimethoxyethers, isopropanol, or their simes, the solvent to monomer ratio being from 1 to 100. : 99 monom! measured to a ratio of 50:50 (% by weight).

The radical iiicittfil are selected from the group of azo compounds, peroxides, percarbonates, photo-initiators based on benzo-ethers and its derivatives or redox systems, such as preferably persulfate-pyrosulphate, persulfate-alkylamines, benzooyperoxide-alkylamines at a concentration of 0.0-3% hmmt.

If ropolyeeraid is used in the absence of a polar solvent or a mixture of polar solvents, a block copolymer is obtained which is particularly suitable for those apliaid which will give subsequent treatment. However, some block products can also be used to produce some products directly.

In the presence of the aforementioned polar solvents of the foregoing, or mixtures thereof, a copolymer is prepared having a suitably selected solvent content suitable for casting, e.g., centrifugal casting of contact lenses. On the other hand, the solvent used, which in the first case would prevent mechanical machining, favorably influences the swelling pressures occurring during the swelling of the finished product.

Copolymers of 2-hydroxyethyl methacrylate with diethylene glycol methacrylate or 2-hydroxyytyl methacrylate with triethylene glycol methacrylate in the presence of diethylene glycol dimethacrylate retp were prepared. triethylene glycol dimethylene glycol and ethylene glycol methacrylate, or in the presence of only one crosslinking component, which may be any meeacrylic or acrylic acid diethyl ether, if the starting monomers are deprived of their very own dietary diets resulting from their synthesis, or as using methylene-bitrcrllamide, ttl-bis-ettacrllaeid, hexamethylether-bit-methacrylamide and the like, or a combination thereof, each with at least 3 comonomers entering the polymerization, two of which are moonoethers and the third is a titrator; one ee of the two mmn ethers is always 2-hydroxyethyl ether and the other of the mono-ser is either dittytenglynol-methacrylate or triethyeglyknleonosethacrylate. When prepared from ethyl oxide and methyl methacrylate, the 2-hydroxyl ethyl ether acylate may contain up to 0.190% hmmt. ectaarylic acid, which is beneficial for further processing into contact lenses. Pou

Only at the aforementioned ratio of the said moneoethers and maintaining the permeability, a concentration of < 31 -? - 1? Retp. diethyl or triethyl ethers of acrylic or ethoxyaryl, or diamide retp. The acrylic or meearyl acrylic diamides are capable of tightening the resulting hydropolymer or terpolymer to such properties that it can be used for the preparation of contact lenses or for technical purposes. With an increasing ratio of dittye-nglkOolmo-nonethacrylate (DEGMA) resp. tert-gglkol · mesoacetyl acrylate (TEGMA) versus 2-hydroxyyl-ethyl-arylate (HEMA) under constant retp dittt coating. their darkness continuously increases the water content of the final tripleemene hydrogel, and with the proportions of these components according to the invention, hydrogels with good mcC activity are obtained. properties at equilibrium water circulation of 55 to 76%.

It is also possible and advantageous in the case of the production of multicellular turned contact lenses, a solvent or a solvent. The water-soluble, low-molecular-weight scavengers contained in the forged copolymer in the presence of the above-mentioned polar solvents are extracted with water and the copolymer is thereafter until constant. The soft xerogel is well suited for milling work. In this case, the drying can advantageously be carried out in a saturated steam environment above the glass transition temperature Tg of the prepared copolymer.

The advantage of this process is that, in addition to the method used to prepare contact lenses from different types of xerogels, the method not only allows perfect washing of the low-viscosity components as mentioned above, but is also tightened in terms of the internal tension of the cross-links during polymerization of their lenses. A more uniform structure, which is retained during hunching, and upon re-swelling of the contact lens produced from the xerogels thus prepared as a result of the arrangement of the cross-linking structure, is also obtained without intrinsic light, which is evident in the semi-crisscross light. In this process, the volatilization of the oletizing component is also ensured at the time of preparation of the solvent-free xerogel pellets.

A further advantage of this process is that each percent of washed and low-alcohol fractions increases the glass transition temperature Tg by about 6 degrees C, which has a beneficial effect on turning and polishing the final shape of the contact lens.

The advantage of suspending the water-swellable prefabricated parts for turned contact lenses in superheated steam is that the removal ^{of the} lye-stabilizing solvent, i.e. water, from the diverse structure, occurs under conditions that are perfect ^{in the size of the} polymer chains and its side segments (i.e., above the temperature of the copolymer), thereby ensuring rapid solvent removal without disturbing the three-dimensional structure, while maintaining the external dimensions and angles of the prefabricated prefabricated component relative to the swollen, given the initial composition of the polythesis strand.

The copolymers according to the invention have surprisingly higher yield values than the homo polymers of the above-mentioned DEGME and TEGMA monomers even at low elastic modulus. The copolymers according to the invention are practically free of water-soluble extracts for all known hydrophilic polymers used for the production of contact lenses, in particular vinylpyrrolidone-based. The copolymers of the present invention do not contain hydrophilic domains or ionogenesis groups in their structures, and therefore significantly lower eye protein depots are expected compared to known copolymers. The copolymers of the present invention also provide a sufficiently high equilibrium water content in the final copolymers so that they can be used to make contact lenses for permaanene (longer) wear.

In the following, the invention is explained in more detail by way of examples of a specific embodiment:

Example 1 wt.%, Composition with 70 wt. % Of 2 - hydroxydtyl methacrylate (hereinafter HEMA) and% by weight of riethylncyclomonomeththrylate (hereinafter DEGMA) containing 0.45 wt. % ethylene glycol trimethacrylate and 0.2 wt%. % of rietdl · englycolrimethacrylate as the crosslinking agent was mixed with 40 wt. 8 glycerin. This mixture was polymerized with 0.5 wt. 8 of benzoonyl ether per total monommer mass for 15 minutes under UV radiation. The resulting maternal after swelling contained 49.6 wt. % of water, at the shear modulus G = 103 kPa and кое ^ ог ^: for linear expansion Kv = 1.09 for swelling in I ^ O and К = 1.08 for swelling in the iyzioogical solution. Izerο ^ ία ^ η: Lizarial expansion is defined as the ratio of the swollen test specimen diameter to its polymer diameter.

Example 2 wt. HEMA and 40 wt. 8 DEGMA containing 0.45 wt. % of etdldgldktlrimethacrylate and 0.2 wt. 8% of the tacrylate was mixed with 40 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzene methyl ether on the total monomer mass for 15 minutes exposed to UV light. The resulting material contains 53.6 hmmt after swelling. 8 of water, at the shear modulus G = 85 kPa, and the linear expansion coefficients K _v = 1.12, Kf = 1.12.

Example 3 hmmt. % composition of 50 hmmt. % HEMA and 50 hmmt. 8 DEGMA containing 0.45 hmmt. % etdlfigldktlrieetakkylate a 0,2 hmmt. 8 riftylezglyctlzetacrylate was mixed with 40 hmmt. 8 glycerin. This mixture was polymerized with 0.5 hmmt. % of beniophenethyl ether to the total monomer mass for 15 miz. UV radiation. The resulting swelling material contains 59.5 hmoo. 8 water, ductility is 120 8, strength 150 kPa, G = 73 kPa (K _v = 1.15, K i = 1.15.

ÍkladExample4 hmoo. % of a composition of 40 wt. % HEMA and 60 wt. % DEGMA containing 0.2 wt. 8 of riftylgizktlrizethacrylate and 0.7 wt. 8 triglyceride cordimide was mixed with 40 masses of 8 glycerin. This mixture was polymerized with 0.5 wt. 8 benizone ethyl ether per total monomer mass for 15 min. UV radiation. Exclusive malatial after swelling contains 63.1 masses. 8 water, at G = 63 kPa and K _v = 1.21, K _f = 1.20.

Example 5 pots. % composition 30 hmmt. % HEMA and 70 hmmt. 8 DEGMA containing 0.6 hmmt. % ^ П п п gly 0,1 ^ 0,1 0,1 0,1 0,1 0,1 0,1 0,1 0,1 and 0.15 hmmt. % of ethyl glyceryl isocrylate was mixed with 40 wt. % glycerin. This mixture was polymerized with 0.5 hmmt. 8 of benzene isopropyl ether per total mass of the mono for 15 min. UV radiation. Výledný materá :! after swelling it contains 68 hmmt. 8 water, at G = 57 kPa, Ky = 1.24, Kf = 1.23.

Example 6 wt. % of a 70 wt. % And 30 wt. % DEGMA containing 0.3 wt. % ethylene glycol dimethacrylate, 0.20 wt. % diethylene glycol dimethacrylate and 0.3 wt. % of triethylene glycol dimethacrylate was mixed with 30 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting swelling material contains 50.1 wt. % water, at G = 119 kPa; K _v = 1.14; K _f = 1.14.

Example 7 wt. % of a mixture of 60 wt. % And 40 wt. % DEGMA containing 0.5 wt. % ethylene glycol dimethacrylate was mixed with 30 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting swelling material contains 54.2 wt. % water, at G = 97 kPa; K _v = 1.17; K _f = 1.17.

Example 8 wt. % blend of 40 wt. % And 60 wt. % DEGMA containing 0.6 wt. % of diethylene glycol dimethacrylate and 0.15 wt. % ethylene glycol methacrylate was mixed with 30 wt. From glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting swelling material contains 63.1 wt. % water, at G = 75 kPa; K _v = 1.25; = 1.25.

Example 9 wt. % of composition 30 wt. And 70 wt. % DEGMA containing 0.6 wt. % of diethylene glycol dimethacrylate and 0.15 wt. % ethylene glycol dimethacrylate was mixed with 30 wt. § glycerine. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting swelling material contains 67.4 wt. % water, at G = 67 kPa; K _v = 1.29; = 1.28.

Example 10 wt. % of a 70 wt. % And 30 wt. % DEGMA containing 0.45 wt. % ethylene glycol dimethacrylate and 0.2 wt. % diethylene glycol dimethacrylate was mixed with wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting swelling material contains 49.6 wt. % water, at G = 39 kPa; vigor 110%; strength 220 kPa; K _v = 1.18; K _f = 1.17.

Example 11 wt. % of a mixture of 60 wt. % And 40 wt. % DEGMA containing 0.45 wt. % ethylene glycol dimethacrylate and 0.2 wt. % diethylene glycol methacrylate was mixed with 20 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting swelling material contains 53.6 wt. % water, at G = 122 kPa; K _v = 1.22; K _f = 1.21.

Example 12 wt. % of a 50 wt. % And 50 wt. % DEGMA containing 0.45 wt. % ethylene glycol dimethacrylate and 0.2 wt. % of diethylene glycol dimethacrylate was mixed with 20 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting swelling material contains 58.9 wt. % water, at G = 108 kPa; K _v = 1.23; K _f = 1.21.

Example 13 wt. % blend of 40 wt. % HEMA and 60 wt. % DEGMA containing 0.6 wt. % of diethylene glycol dimethacrylate and 0.15 wt. % ethylene glycol dimethacrylate was mixed with 20 wt% glycerin. This mixture was polymerized with 0.5 wt. % of benzoonney ether per total monommer, for 15 min by UV radiation. The resulting material after swelling contains 60.1 wt. % water, at G = 94 kPa; K _v = 1.27; K _f = 1.26.

Example 14 wt. 30 wt. % HEMA and 70 wt. % DEGMA containing 0.5 wt. % of ethylene glycol dimethacetylate was mixed with 20 wt. % glycerin. This mixture was polymerized with 0.5 wt. % bennoinney ether per total monommer mass, for 15 min by UV radiation. The resultant spinner contains 63.7 wt. % water, at G = 82 kPa; K _v = 1.31;

K _f = 1.30.

Example 15 wt. % smmsi on fold:! 60 wt. % HEMA and 40 wt. % DEGMA containing 0.45 wt. % ethylene glycol dimethacrylate and 0.2 wt. % of diltyl glycildimethacrylate was mixed with 10 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoonney ether to total monomer mass for 15 min. UV radiation. The resulting maternal after swelling contains 50.7 wt. % water, at G = 143 kPa; K _y = 1.23; Kf = 1.21.

Example 16 hmmo. % by weight of a composition of 50 wt. % HEMA and 50 wt. % DEGMA containing 0.5 wt. % of ethylene glycol dimethacetylate was mixed with 10 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoinelyl ether on total monomer mass for 15 min. UV radiation. The resulting maaeeial after swelling contained 53.6 hmmt. % water, at G = 121 kPa; strength 180 kPa; tensile ≥ 80%; K _v = 1.26 and K _f = 1.24.

Example 77 hmo. % smmsi on fold:! 40 wt. % HEMA and 60 wt. % DEGMA containing 0.6 wt. % diltyllzglykildimethacrylate and 0.15 wt. % of ethylene glycildimethacrylate was mixed with 10 with 10 wt. % glycerin. This mixture was polymerized with 0.5 hmmt. % benzoinels in summer to a total weight of mono-t for 15 min. UV radiation. The resulting swelling after swelling contained 58.3 wt. % water, at G = 108 kPa; К _у = 1.31; K _f = 1.28.

Example 18 wt. 30 wt. % HEMA and 70 hmmt. % DEGMA containing 0.6 hmmt. % d diltyl glycildimethacrylate and 0.15 hmmt. The% ethyl glycildieetacrylate was mixed with 10 hmmt. % glycerin. This mixture was polymerized with 0.5 hmmt. % benzoinelyl lithium on the total monomer mass for 15 min by UV radiation. The resulting material! after swelling it contains 63.1 hmmt. % water, at G = 94 kPa; K _v = 1.37; Kf - 1.33.

He said a d 19 hm ^ o. % smmsi with a composition of 60 hmmt. % HEMA and 40 hmmt. % DEGMA containing 0.6 hmmt. % diltyllzglykildimeth acrylate and 0.15 hmmt. % Methylene glycol · d: L-methacrylate was mixed with 40 wt. % glycerin. This smss was polymerized with 0.5 hmmt. % benzoinelyl ether to total mono? T mass for 15 min. UV radiation. The resulting measure! after swelling contains hmmt. % water, at G = 85 kPa; strength 215 kPa; tensile ≥ 220%; = Kf = 1.10.

Example 20 wt. % of a mixture of 60 wt. % HEMA and 40 wt. % DEGMA containing 0.20 wt. % ethylene glycol dimethacrylate and 0.15 wt. % diethylene glycol dinol acrylate was mixed with 40 wt.% glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting material contains 54 wt. % water, at G = 75 kPa; strength 210 kPa; elongation at break 230%; K _v = 1.14.

Example 21 wt. % of a mixture of 60 wt. % HEMA and 40 wt. % DEGMA containing 0.6 wt. % ethylene glycol methacrylate and 0.6 wt. % of diethylene glycol dimethacrylate was mixed with 40 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoethyl ether to total monomer mass for 15 min. UV radiation. The resulting swelling material contains 49 wt. % water, at G = 110 kPa; ductility 150% and strength 240 kPa.

Example 22 wt. % mixture 50 wt. % HEMA and 50 wt. DEGMA containing 0.15 wt. % ethylene glycol dimethacrylate was mixed with 15 wt. % glycerin. This mixture was polymerized with 0.5 to 0.5 wt. % benzoinether on total monomer mass for 15 min. UV radiation. The resulting swelling material contains 55 wt. % water, at G = 110 kPa; strength 260 kPa; 160%.

Example 23 wt. % blend of 40 wt. % HEMA and 60 wt. % DEGMA containing 0.20 wt. % ethylene glycodimethacrylate and 0.15 wt. % diethylene glycol methacrylate was mixed with 15 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting material contains 62 wt. % water, at G = 70 kPa; strength 160 kPa; elongation 135 'i.

Example 24 wt. % blend of 40 wt. % HEMA and 60 wt. % DEGMA containing 0.6 wt. % of diethylene glycol dimethacrylate and 0.15 wt. % ethylene glycol dimethacrylate was mixed with 15 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation. The resulting swelling material contains 62 wt. % water, at G = 74 kPa; strength 185 kPa; 150%.

Example 25 wt. % blend of 30 wt. % HEMA and 70 wt. % DEGMA containing 0.6 wt. % d diethylene glycol dimethacrylate and 0.15 wt. % ethylene glycol dimethacrylate was mixed with 15 wt. % ethylene glycol dimethacrylate was mixed with 15 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min. UV radiation.

The resulting swelling material contains 64 wt. % water, at G = 82 kPa; strength 260 kPa; ductility 205%.

Example 26 wt. % of a mixture of 60 wt. % HEMA and 40 wt. % DEGMA containing 0.20 wt. % ethylene glycol dimethacrylate and 0.15 wt. % of diethylene glycol dimethacrylate was mixed with 40 wt. % 40 wt. % glycerin. This mixture was polymerized with 0.1 wt. % diisopropyl percarbonate on the total amount of monomers for 16 h at 60 ° C. The resulting material contains 55 wt. % water, at G = 70 kPa.

Example 27 wt. % of a mixture of 60 wt. % And 40 wt. % DEGMA containing 0.20 wt. % ethylene glycol dimethacrylate and 0.15 wt. % diethylene glycol dimethacrylate was mixed with 20 wt. % glycerin. This mixture was polymerized with 0.1 wt. % diisopropyl percarbonate on the total amount of monomers for 16 h at 60 ° C. The resulting material contains mass after swelling. % water, at G = 101 kPa.

Example 28 wt. % of a 50 wt. % And 50 wt. % DEGMA containing 0.15 wt. % ethylene glycol dimethacrylate was mixed with 40 wt. % glycerin. This mixture was polymerized with 0.1 wt.% Of diisopropyl percarbonate to a total amount of monomers for 16 h at 60 ° C. The resulting material contains 60.6 wt.% Of water after swelling at G = 62 kPa.

Example 29 wt. % of a 50 wt. % And 50 wt. % DEGMA containing 0.15 wt. % ethylene glycol dimethacrylate was mixed with 20 wt. % glycerin. This mixture was polymerized with 0.1 wt. % diisopropyl percarbonate on the total amount of monomers, for 16 at 60 ° C. The resulting material contains 58.9 wt. % water, at G = 105 kPa.

Example 30 wt. % blend of 40 wt. % And 60 wt. % DEGMA containing 0.20 wt. % ethylene glycol dimethacrylate and 0.15 wt. % of diethylene glycol dimethacrylate was mixed with 40 wt. % of glycerin, this mixture was polymerized with 0.1 wt. % diisopropyl percarbonate on the total amount of monomers for 16 h at 60 ° C. The resulting material contains 65.7 wt. % water, at G = 50 kPa.

J r. . i and d 31 wt. % blend of 40 wt. % And 60 wt. % DEGMA containing 0.20 wt. % ethylene glycol dimethacrylate and 0.15 wt. % diethylene glycol dimethacrylate was mixed with 20 wt. % glycerin. This mixture was polymerized with 0.1 wt. % diisopropyl percarbonate on the total amount of monomers for 16 h at 60 ° C. The resulting material contains 64.3 wt. % water, at G = 75 kPa.

Example 32 wt. 60% by weight of the mixture of 60. % НЕМА а 40 nmot. % DEGMA containing 0.15 wt. % ethylene glycol dimethacrylate was mixed with wt. % glycerin. This mixture was polymerized with 0.2%. <j: ιζο. ^ν η collected from the total amount of monomers for 16 h at 60 ° C. The resulting swelling rial contains 54.7 masses of water at G = 75 kPa.

Example 33 wt. % of a mixture of 60 wt. % HEMA and 40 wt. % DEGMA containing 0.20 wt. % ethylene glycol dimethacrylate and 0.15 wt. % of diethylene glycol dimethacrylate was mixed with 40 wt. % glycerin. This mixture was polymerized with 0.2 wt. % ammonium persulfate for 1 hour at 78 ° C. The resulting swelling material contains 54.9 wt. % water, at G = 75 kPa.

Example 34 wt. % of a mixture of 60 wt. % And 40 wt. % DEGMA containing 0.20 wt. % ethylene glycol dimethacrylate and 0.15 wt. % of diethylene glycol dimethacrylate was mixed with 40 wt. %

G = 70 kPa.

glycerin. This mixture was polymerized with 0.5 wt. % benzoin methyl ether for 15 min. UV radiation. The resultant diet contains 55 wt. % water at

Example 35 containing 0.6 wt. % was mixed hmmt. 20 wt. % HEMA and 80 wt. % DEGMA with the addition of 0.15 wt.% And 0.15 wt. % ttlltngllkoldimettkryláeu with 15 wt. % glycerin. This mixture was polymerized with 0.5 hmmt. % benzoineeyl ether for 15 min by UV radiation. The resulting maaeeial contains 70 pots after wrapping. % water, at G = 38 kPaa; tažneos! 160% and a strength of 103 kPa.

He said a

15 min. % smmsi with a composition of 10 hmmt. % HEMA and 90 wt. % DEGMA containing 0.6 wt. % of diyl tzgllkildietacrylate and 0.15 hmmt. % of ttyltoglycildieett acrylate was mixed with 15 wt. % glycerin. This mixture was polymerized with 0.5 h. % benzoethylether after radiation. The resulting mare! contains 74 hmmt. % water, at G 160% and a strength of 100 kPa.

She said

Mixture of 60 hmmt. % Of 2-hydroxyeeyl meeaarylate (hereinafter HEMA); % By weight of glyceroilImtetrrlaeu (hereinafter DEGMA) containing 0.20 wt. % ethyl acetate and acrylate and 0.15 hmmt. % ditellteglildieetacrylate was polymerized with 0.1 wt%. % Diizipiipylptrtartonátu on duties oviu ^r ^ ^h after motu monommru to ^B in ^{16 h} at ⁶⁰ DEG C. s. The resultant m ^^ ^s obotn only after it contains. 49.1 wt. % of water, at shear modulus G = 325 kPa. (Suitable for contra-cont. Lenses).

Ex

and

50 wt. % HEMA and 50 wt. % DEGMA containing 0.15 wt. % diethyl aryl was polymerized with 0.1 wt. % diOio ^p ro ^p ll ^p erktrbieáeu to the total mass monommri po at G = 290 to ^b u kPa.

¹⁶ H ^P s ⁶⁰ (suitable for ° C. Results The matel · ^ y ^^ ^b of Sahu ^{j p} m e ⁿ u bot ^{for 52 2h} MMT.% Aq ^ souusr, contacts, lenses).

P Peak and composition of 40 wt.

dieeeatryláeu and 0.15 wt. § ⁱ⁰ iopropylperkabizá d u ^e to the total mass after dot monommru> ul containing ⁶ at ⁶⁰ after

Mixture of% HEMA and 60 hmmt. % DEGMA containing 0.20 wt.%. ° C. The ultimate swelling 56.2 wt. % water, at G = 270 kPa.

Example 40 of 30 wt. % HEMA and 70 wt. % DEGMA containing 0.6 wt. Mixture of dimethatrylate and 0.15 hmmt. % glycol glyceride acrylate was polymerized with 0.1 wt. % Of di ^and oipiip lpei ^{y r e} trbiná on the total mmtu monommru ^h after ^{d b} in the following obotnání contains 60 wt. % water at G. = 232 kPa.

P ad Rikli 41 ^h at ¹⁶ ° C for ⁶⁰ s. ^In ýsle ^d Nu eate ^I Al

20 wt. % HEMA and 80 wt. % DEGMA with dieetatrylate and 0.15 wt. % Dieelltzgllrildieettkryláeu d ^io ioprip lptrkarbizá ^l u ^e to ^h ceUovou motu monommru to ^b after ¹⁶ h at ⁶⁰ after eateeiál oЬotzálzí contains 63.7 hmmt. % water, at G = 143 kPa.

content 0.20 wt. % by weight was polymerized with 0.1 wt. ° C. Resultant

Example 42

Mixture of 10 wt. And 90 wt. % DEGMA containing 0.15 wt. % ethylene glycol dimethacrylate was polymerized with 0.1 wt. % diisopropyl percarbonate on the total monomer mass for 16 h at 60 ° C. The resulting swelling material contains 66.6 wt. % water, at G = 113 kPa.

Example 43

Mixture of 40 wt. % And 60 wt. DEGMA containing 0.5 wt. % ethylene glycol dimethacrylate was polymerized with 0.2 wt. % azobisisibutyronitrile per total monomer mass for 16 h at 60 ° C. The resulting swelling material contains 54.7 wt. % water, at G = 290 kPa.

Example 44

Mixture of 40 wt. % And 60 wt. % DEGMA containing 0.6 wt. % ethylene glycol dimethacrylate was polymerized with 0.2 wt. % azobisisobutyronitrile per total mass mc '

meters for 16 h at 60 ° C. at G = 305 kPa. The resulting swelling material contains 53 wt. % water, Example 1 a d 45 Mixture o composition 40 wt. % HEMA ³ a 60 wt. % DEGMA containing 0.20 wt. % ethylene glycol

dimethacrylate and 0.15 wt. % of diethylene glycol dimethacrylate was polymerized with 0.1 wt. % diisopropyl percarbonate on the total amount of monomers for 16 h at 60 ° C. The resulting swelling material contains 56.2 wt. % water, at G = 270 kPa.

Example 46

Mixture of 40 wt. % And 60 wt. % DEGMA containing 0-3 wt. % ethylene glycol dimethacrylate, 0.20 wt. % diethylene glycol dimethacrylate and 0.3 wt. % triethylene glycol dimethacrylate with 0.2 wt. % ammonium persulphate on the total monomer mass for 1 hour at 78 ° C. The resulting swelling material contains 56 wt. % water, at G = 272 kPa.

Example 47

Mixture of 40 wt. НЕМА and 60 wt. % DEGMA containing 0.20 wt. % ethylene glycol dimethacrylate and 0.15 wt. % of diethylene glycol dimethacrylate was polymerized with 0.5 wt. % benzoethylether for 15 min by UV radiation. The resulting material contains 56.3 wt. % water, at G = 272 kPa.

Example 48

Mixture of 40 wt. % And 60 wt. % DEGMA containing 0.20 wt. % ethylene glycol dimethacrylate and 0.15 wt. % of diethylene glycol dimethacrylate was polymerized with 0.5 wt. % benzoin methyl ether for 15 minutes by UV radiation. The resulting material contains 56.2 wt. % water, at G = 270 kPa.

Example 49

Mixture of 90 wt. % 2-hydroxyethyl methacrylate (NAM) and 10 wt. % triethylene glycol methacrylate (hereinafter DEGMA) containing 0.4 wt. % ethylene glycol dimethacrylate and 0.20 wt. % of triethylene glycol dimethacrylate as the crosslinking agent was polymerized with 0.5 wt. % benzoethylether on total monomer mass for 15 min by UV radiation. The resulting swelling material contained 48 wt. % water.

Example 50 wt. % of a mixture of 80 wt. % HEMA and 20 wt. % TEGMA containing 0.4 wt. and 0.20 wt. % erretyrzngtykoУdicretkrtláeu was mixed.

with 20 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzotneryltrium on total mass of water, monornmers for 15 min by UV radiation. The resulting swelling material contains 53 wt. § at shear module G - 133 kPa.

P Example 51 wt. % of the composition of 50 wt%. % HEMA and 50 wt. % TEGMA containing 0.3 wt. % of ethyl tert-dimethyl dimethacrylate and 0-6 wt. % of Htu was mixed with 20 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzoic acid to the total monornm mass for 15 min by UV radiation. The resulting cattrial by mass. % of water, at shear modulus G = 50 kPa.

swelling contains

P Example 52 contains 0.3 wt. % mixed

This mixture was polymerized with 0.5 wt. % of benzotryryltrium over a 15 wt. % blend of 85 wt. % TEGMA and 15 wt. % HEMA with ethylene glycol dimethacrylate and 0.6 wt. % eretetyrengl · kkoldimretkiyláeu with 20 wt. % glycerin. mass of monornm by weight. % water.

min UV radiation. The resulting material after swelling contains

Example 53 composed:!

ethylene glycol dimethacrylate and 0.6 with 30 wt. % glycerin. This mixture was polymerized with 0.5 wt. % benzotrans: for a total weight of monorimers for 15 min by UV radiation. The resulting mart ^ á! after swelling it contained 76 wt. % of water, at shear modulus G = 45 kPa.

wt. % srnmsi wt. % HEMA and 60 wt. % TEGMA containing 0.3 wt. wt. % tréetlrenglykoldimretkryláeu was mixed

He said 54 wt. % of a 50 wt. % HEMA and 50 wt. % TEGMA containing 0.5 wt. % ethylene glycol dimethacrylate was mixed with 40 wt. % glycerin. This mixture was polymerized with 0.5 wt. The resulting swelling material contains 69 wt. % water.

min UV radiation.

Example 55 wt. % srnsi. Composed: 30 wt. % HEMA and 70 wt. % DEGMA with rhtylbis-acrylate and 0.2 wt. % Of the glycol glycine was glycerine. This mixture was polymerized with 0.5 wt. % Ьenzotryryltrium on total hooeu monornmer for water, at G = 56 content of 0.3 wt. % mixed with 40 wt. % min. UV radiation. The resulting swelling contains 67.5 wt. % kPa, K - 1.24, K к = 1.225.

'v' 'f'

Example ad mass. % mixture of:! 60 wt. % DEGMA and 40 wt. % HEMA containing 0.4 wt. % hexaactyteezbis-acrylamide and 0.35 wt. % of meryl-bis-acrylamide was mixed with 30 wt. % glycerin. This mixture was polymerized with 0.1 wt. % to c ^ lk. diSsoprtpylprrkarbtzátu mixture at 60 ° ^{C when} a ^B to I ⁵ minutes. The resulting matte contains ⁶³ wt. Vody.p% ^P and G = ⁷⁵ Pa ^to K = 1.25, KF = 1.25.

Claims (7)

A hydrophilic copolymer comprising in the structure of its chains 10 to 90, preferably 40 to 80% by weight, of units derived from monomer I сн ₂ = C - COO- ₍₂ сн сн о _{2) п} ~ ₂ сн сн -он ₂ (I) wherein n = 1 or 2, 90 to 10% by weight, units derived from 2-hydroxyethyl methacrylate and 0.01 to 2% units derived from at least one crosslinker having at least two olefinic double bonds. 2. Hydrophilic copolymer according to claim 1, characterized in that the crosslinker units are derived from multifunctional esters or amides of acrylic or methacrylic acid. 3. A process for the preparation of a hydrophilic copolymer according to claim 1 or 2, characterized in that 10 to 90% by weight of the monomer of the formula I as defined in item 1 is copolymerized with 90 to 10% by weight. % Of 2-hydroxyethyl methacrylate and 0.01 to 2% by weight of polyfunctional esters or amides of acrylic or methacrylic acid having at least two olefinic double bonds in the presence of radical initiators. Method according to claim 3, characterized in that the radical initiators are selected from the group of azo compounds, percarbonates, persulphates, peroxides, benzoinether-based photoinitiators and their derivatives or initiation redox systems, such as preferably persulfate-pyrosulfite, persulfate-alkylamines, benzol peroxide alkylamines, in a concentration of 0.01 to 3% by weight, based on the monomer mixture. 5. The process according to claim 3, wherein the copolymerization is carried out in the presence of at least one polar solvent, such as preferably glycerin, glycols and derivatives thereof, water, dimethylformamide, dimethylsulfoxide, dimethylacetamide, diacetamide, isopropanol, or mixtures thereof. wherein the ratio of solvent to monomer mixture is from 1 wt%, solvent: 99 wt%, monomer blend to 50:50. 6. The process of claim 4 wherein the solvent or water-soluble low molecular weight constituents contained in the cross-linked copolymer are extracted with water, and the copolymer is dried to constant weight. 7. Process according to claim 4, characterized in that the drying is carried out in a saturated steam environment above the glass transition temperature Tg of the prepared copolymer.