EP1664136A2 - Hydrogel - Google Patents

Hydrogel

Info

Publication number
EP1664136A2
EP1664136A2 EP04765406A EP04765406A EP1664136A2 EP 1664136 A2 EP1664136 A2 EP 1664136A2 EP 04765406 A EP04765406 A EP 04765406A EP 04765406 A EP04765406 A EP 04765406A EP 1664136 A2 EP1664136 A2 EP 1664136A2
Authority
EP
European Patent Office
Prior art keywords
polyethylene glycol
hydrogels
water
glycol dimethacrylate
polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04765406A
Other languages
German (de)
English (en)
French (fr)
Inventor
Werner Siol
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1664136A2 publication Critical patent/EP1664136A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses

Definitions

  • the invention relates to hydrogels based on polyethylene glycol dimethacrylate and their preparation and the use of these hydrogels as contact lenses, electrophoresis gels, membrane materials and anti-drumming compounds.
  • polyacrylic acid poly-methacrylic acid and their derivatives such as e.g. Poryacrylamide or polyhydroxyethyl methacrylate as well as polyvinyl alcohol or polyvinyl pyrrolidone.
  • polyethylene glycol hydrogels can be produced by the action of high-energy radiation on an aqueous polyethylene glycol solution. Because of the good tolerability and low irritancy of the methacrylates, there is a tendency within the group of poly (meth) acrylates to replace acrylates with methacrylates. However, the higher rigidity of the polymethacrylate chains is a hindrance in many applications.
  • the stiffness of the polymethacrylate chain also causes problems in the area of contact lens materials. It is known from DE 38 00 529 that hydrogel contact lenses and intraocular lenses are best tolerated if they are softer than the living tissue. Polyhydroxyethyl methacrylate can be mixed with 60-90% water Adjust swelling equilibrium very softly, however, this high content of water as a plasticizer requires a low mechanical strength. In addition, the low refractive index of the highly water-containing material requires particularly thick lenses. The longer diffusion path makes the penetration of atmospheric oxygen to the cornea difficult.
  • hydrogels with a high content of polyethylene glycol dimethacrylate should be suitable for the construction of very soft hydrogels, since the polyethylene glycol chain with a glass transition temperature of approx. -50 ° C is very flexible. It is therefore incomprehensible at first glance that e.g. Even in the production of hydrogels for contact lenses, polyethylene glycol dimethacrylates can only be used in minor amounts. JP 61166516 describes contact lenses with up to 3% by weight of polyethylene glycol dimethacrylate. This restriction to small amounts of polyethylene glycol dimethacrylate in the hydrogel formulations, which can be observed in many applications, can be derived from the polymerization behavior of the polyethylene glycol dimethacrylates. Here is e.g.
  • this complex course of polymerization can be controlled by adding plasticizers or solvents.
  • plasticizers or solvents for example, the rich Polyethylene glycol dimethyl ether or propylene carbonate as a plasticizer.
  • polyoxyethylene pressure-sensitive adhesives are described which are made up of polyethylene oxide dimethacrylate and polyethylene glycol as plasticizers.
  • polyethylene glycol dimethacrylate and ethylene glycol are used after sealing with ammonium persulfate to seal water leaks, for example in tunnels. This material is non-toxic and shows excellent elasticity.
  • hydrogels have good optical and mechanical properties
  • Polyethylene glycol dimethacrylates which is known for many nonionic surfactants
  • cloud points are caused by small additions of water-insoluble components, e.g. water-insoluble regulators such as dodecanethiol, significantly reduced.
  • water-insoluble regulators such as dodecanethiol
  • Mixtures of very short-chain polyethylene glycol dimethacrylates have a similar effect.
  • the polymerization is carried out at least 40 ° C. or preferably at least 60 ° C. below the cloud point of the 10% solution.
  • this information is Averages.
  • a certain distribution width of the chain length is definitely an advantage. It is therefore possible to use polyethylene glycol dimethacrylates whose ethylene oxide content is within the abovementioned range, including corresponding commercial products, polyethylene glycol, in some cases polyethylene oxide, correspondingly also being called PEG or PEO.
  • Commercial products from Degussa / Röhm Methacrylate are of particular interest:
  • Particularly high quality hydrogels are obtained if the chain length of the polymethacrylate blocks is limited by the addition of polymerization regulators or by a high radical current (i.e. a high concentration of initiator or activator). This is a particularly effective measure to reduce the tendency to segregate in the course of the polymerization.
  • free radicals can be generated by thermal, redox or photochemical processes or by the action of high-energy radiation.
  • Suitable thermal initiators include Azo compounds, peroxides and persulfates. If peroxides and persulfates are used in combination with a reducing agent such as ascorbic acid or a bisulfite compound and optionally a transition metal salt such as iron, the redox generation of radicals can even take place below room temperature.
  • ammonium peroxodisulfate / N, N, N, N-tetramethylethylene diamine is of particular interest as a radical generator.
  • the initiator is used in an amount corresponding to 0.1-10% by weight, based on the amount of the polyethylene glycol dimethacrylate used. If no polymerization regulators are used, the rule applies that the molar ratio of polyethylene glycol dimethacrylate to initiator is ⁇ 200 to 1, preferably ⁇ 50 to 1.
  • polymerization regulators deserve special attention.
  • chain transfer regulators are connections with a mobile H atom, e.g. To mention cumene, but halogen-containing compounds can also be used.
  • Sulfur-containing polymerization regulators are preferred, especially mercaptans, and water-soluble mercaptans are particularly preferred.
  • mercaptans with only one SH group are used, such as mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-l, 2-propanediol, but the use of polyvalent mercaptans is also possible in principle, e.g.
  • the regulators are preferably used in proportions of 0 to 30 mol% based on the polyethylene glycol dimethacrylates used. Despite this sometimes high regulator content, the hydrogels produced in this way are generally completely odorless. This may be due to the fact that in this complex network, at least towards the end of the polymerization, the chain regulators are the most mobile components of the polymerization mixture and are therefore completely incorporated into the network.
  • the chain length of the methacrylate chains can be controlled quite well by using the mercaptans. It has been found that, in particular in the case of short-chain polyethylene glycol dimethacrylates (ie small n according to formula (1)), a high content of regulator is required in order to obtain a transparent, elastic hydrogel, while in the case of longer-chain polyethylene glycol dimethacrylates (ie large n according to formula (1)) the regulator content may be lower.
  • the molar ratio of polyethylene glycol dimethacrylate to mercaptan should at most be as large as the number of ethylene oxide groups in the polyethylene glycol dimethacrylate, So n.
  • hydrogels are obtained when the molar ratio of polyethylene glycol dimethacrylate / mercaptan is ⁇ 0.5n, in general the molar ratio of polyethylene glycol dimethacrylate / sulfur atoms is therefore ⁇ 0.5n.
  • the abovementioned high radical flow or the content of regulators enables hydrogels to be produced, as are shown schematically in FIG. 1.
  • the polymerized methacrylate chain is advantageously so short that these methacrylate oligomers do not form their own phase.
  • the elasticity and mobility of the hydrogel according to FIG. 1 is essentially determined by the length of the polyethylene glycol blocks.
  • mercaptans for methacrylic acid esters generally have a transfer constant of 1 or slightly less than 1 (for example 0.6-0.9 for the 3-mercapto-1,2-propanediol / MMA system)
  • the amount of mercaptan used can be determined by in relation to the amount of polyethylene glycol dimethacrylate used, estimate the length of the polymethacrylate blocks quite well.
  • the polymethacrylate blocks are very short, in principle down to dimers, trimers etc. Such short blocks guarantee the homogeneity and optical clarity of the hydrogels according to the invention.
  • type B monomers The content of type B monomers is generally limited to 0-20 parts by weight to 100 parts by weight of polyethylene glycol dimethacrylate.
  • monomers B amides and / or esters of methacrylic acid with 1-18 carbon atoms, eg methyl methacrylate or glycerol monomethacrylate in question.
  • polymerizable stabilizers or methacrylic acid derivatives with reactive groups such as, for example, glycidyl methacrylate, or monomers with aryl groups, which make it possible to increase the refractive index of the hydrogel.
  • hydrogels with excellent mechanical and optical properties, e.g. good elasticity, excellent clarity (haze ⁇ 30%, preferably ⁇ 10% according to ASTM 1003), light transmittance> 90% (DIN 5306) and low coloring (yellowness index ⁇ 500, preferably ⁇ 200 and very particularly preferably ⁇ 100 APHA). These hydrogels can also be easily heated above the original separation temperatures (cloud points) without losing the good optical and mechanical properties.
  • the invention therefore also relates to hydrogels containing in polymerized form
  • hydrogels that have a light transmission> 90%.
  • the invention relates to hydrogels which have a weight ratio of water to polyethylene glycol dimethacrylate in the range from 1 to 1 to 1 to 0.5n.
  • Hydrogels are preferred which contain sulfur atoms and in which the molar ratio of polyethylene glycol dimethacrylate / sulfur is ⁇ 0.5n.
  • the proportion of polyethylene glycols of the type HO - (- CH 2 -CH 2 -O-) n -H n 1- 100 ⁇ 5% by weight, preferably ⁇ 2% by weight.
  • hydrogels are suitable as contact lens material, and very soft lenses in particular can be produced.
  • the refractive index can be determined using the
  • Electrophoresis gels should also be mentioned.
  • the high chain mobility of the polyethylene glycol chain as well as the possibility of almost any architecture of the network density over the length of the polyethylene glycol blocks or the water content are to be mentioned.
  • preference will be given to networks with a high solids content and small values for n, but for the separation of large molecules, preference is given to more extensive networks.
  • membranes or constituents of membranes e.g. Dialysis membranes.
  • hydrogels according to the invention the great possibility of varying the network density and the high, possible content of water also allow the use of these hydrogels as insulating materials, eg. B. as anti-droning compounds.
  • the hydrogels can be synthesized directly by the user, for example by pouring the aqueous solutions into an appropriate form.
  • the hydrogel can be removed from the mold after the polymerization process or, as with large-area anti-drumming applications, for example, can remain directly in the mold, for example between two glass panes.
  • the aqueous solutions of the polyethylene glycol dimethacrylates are oligomeric formulations, the polymerizable fraction, i.e. essentially the methacrylic group, is relatively small.
  • the lowest possible stabilized polyethylene glycol dimethacrylates will be used.
  • the level of polymerization inhibitor e.g. Hydroquinone monomethyl ether, ⁇ 400ppm or preferably 200ppm based on the polyethylene glycol dimethacrylate used or ⁇ 100ppm or preferably ⁇ 20ppm based on the total formulation.
  • the hydrogel is annealed to complete the polymerization or left in the mold for a few minutes to, for example, 24 hours at room temperature.
  • the initiator ammonium peroxodisulfate is used as a 10% solution in water.
  • the information in the examples relates to the solid used.
  • the information on the ratio of polyethylene glycol dimethacrylate (DMA) / water is weight, the information on the ratio of polyethylene glycol dimethacrylate (DMA) / regulator is molar.
  • the haze is given in% (ASTM 1003).
  • the light transmittance is determined in accordance with DIN 5036.
  • the yellowness index APHA is determined in accordance with DIN 53409. Comparative example (not according to the invention)
  • 3-Mercapto-1,2-propanediol (0.3 mmol) is mixed with 0.028 g of N, N, N, N-tetramethylethylenediamine at about 5 ° C., degassed and polymerized at 5 ° C. under argon.
  • Electrophoresis gel is suitable.
  • Ammonium peroxodisulfate and 0.091g 3-mercapto-l, 2-propanediol (0.84mmol) in 7.825 g of water is mixed at about 5 ° C with 0.022 g of N, N, N, N-tetramethylethylenediamine, degassed and polymerized at 5-10 ° C under argon as a protective gas.
  • a colorless, crystal-clear hydrogel is obtained which shows good strength and elasticity. This hydrogel is easy to cut, it is suitable as an electrophoresis gel and for optical applications. It has a light transmission> 90% »and Haze ⁇ 10%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Eyeglasses (AREA)
  • Polymerisation Methods In General (AREA)
EP04765406A 2003-09-25 2004-09-20 Hydrogel Withdrawn EP1664136A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10344411A DE10344411A1 (de) 2003-09-25 2003-09-25 Hydrogel
PCT/EP2004/010519 WO2005030820A2 (de) 2003-09-25 2004-09-20 Hydrogel

Publications (1)

Publication Number Publication Date
EP1664136A2 true EP1664136A2 (de) 2006-06-07

Family

ID=34384273

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04765406A Withdrawn EP1664136A2 (de) 2003-09-25 2004-09-20 Hydrogel

Country Status (10)

Country Link
US (2) US8329763B2 (xx)
EP (1) EP1664136A2 (xx)
JP (1) JP4383452B2 (xx)
KR (1) KR101149778B1 (xx)
CN (1) CN100400561C (xx)
CA (1) CA2539770C (xx)
DE (1) DE10344411A1 (xx)
HK (1) HK1093994A1 (xx)
RU (1) RU2368627C2 (xx)
WO (1) WO2005030820A2 (xx)

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RU2006113639A (ru) 2007-11-10
CN100400561C (zh) 2008-07-09
RU2368627C2 (ru) 2009-09-27
CA2539770A1 (en) 2005-04-07
US20120145942A1 (en) 2012-06-14
JP2007506823A (ja) 2007-03-22
WO2005030820A3 (de) 2005-08-18
CN1856517A (zh) 2006-11-01
KR101149778B1 (ko) 2012-06-08
DE10344411A1 (de) 2005-04-28
JP4383452B2 (ja) 2009-12-16
CA2539770C (en) 2011-06-14
US20060264571A1 (en) 2006-11-23
US8329763B2 (en) 2012-12-11
HK1093994A1 (en) 2007-03-16
WO2005030820A2 (de) 2005-04-07
KR20060094971A (ko) 2006-08-30

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