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    • 专利摘要:
    Polyelectrolyte polymer composition comprising a water insoluble copolymer capable of forming hydrogels, the copolymer being formed by free radical polymerization of at least a first and second hydrophilic monomer, the first monomer being selected from vinylic sulfonic acids, vinylic phosphonic acids, or a water soluble salt of these and wherein the second monomer is at least one compound selected from the group consisting of monomers containing an acid group either in the free acid form or in the form of a water soluble salt, and whose logarithm of the acid dissociation constant (pKa ) in the free acid form has a value of less than 3.5.
    公开号:BE1022283B1
    申请号:E2014/0599
    申请日:2014-08-05
    公开日:2016-03-11
    发明作者:Geert Deroover；Els Mannekens
    申请人:Chemstream Bvba；
    IPC主号:
    专利说明:

    Polyelectrolyte polymer composition and its use
    The present invention relates to a polyelectrolyte composition with which a copolymer can be prepared that forms a water-insoluble hydrogel.
    The present invention also relates to a process for preparing the copolymer.
    The invention further relates to the resulting copolymer, in particular when used as a hydrogel.
    In particular, it relates to a polyelectrolyte composition and a copolymer formed therefrom that is negatively charged when fully dissociated in an aqueous medium.
    In this context, hydrogel is generally understood to be a cross-linked (cross-linked) or intertwined network of hydrophilic polymer chains that is capable of absorbing and retaining large amounts of water in proportion to its own mass. The water is hereby retained in the network by osmotic pressure.
    The term "hydrogel" is used herein in the broadest sense of the word and therefore also includes, for example, hydrogels that are in a dehydrated or anhydrous state, or in a state of partial hydration.
    The present invention particularly relates to polyelectrolyte compositions and copolymers formed therefrom which are suitable as a water-insoluble hydrogel and which can be used in various fields, for example, but not limited, in the treatment of water, in applications in oil extraction, in chemicals used in construction, for medical applications, personal hygiene, coatings, healing agents, as rheology enhancers, for protection of optical and electrical cables, etc.
    Polyelectrolyte polymer compositions based on hydrophilic co-monomers are commonly used in various industrial applications.
    For example, GB 1380807 from the Lubrizol Corporation teaches us a method of treating water, in particular a method of flocculating solids suspended in it, using water-soluble polymers of N-sulfo-hydrocarbon-substituted acrylamides . These polymers can be obtained by polymerization, either alone or in combination with other polymerizable vinyl monomers of the corresponding monomeric N-sulfo-hydrocarbon-substituted acrylamides, of which 2-acrylamidopropane sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid are typical examples. When used as flocculant, these polymers are used either in their acid form or in the form of a salt, the latter usually being an alkali metal or an ammonium salt, and preferably a sodium or potassium salt.
    However, when such polymers are cross-linked, they become insoluble in water. They can then be transformed into water super absorbent hydrogels. In demineralized or distilled water they are then able to swell and absorb several hundred times their own weight of water.
    Their total absorption and swelling capacity is, together with other factors, determined by the nature of the crosslinking agents and the degree of contamination used to make the gel, as K.Kabiri et al teach us in “Synthesis of fast-swelling superabsorbent hydrogels: effect of cross-linker type and concentration on porosity and absorption rate, 2003, European Polymer Journal 39 (7), p.1341-1348.
    Hydrogels with a low degree of contamination generally have a higher absorption capacity and show a stronger swelling. Gel formation tends to be softer and stickier. Polymers with a high degree of crosslinking, on the other hand, tend to exhibit a lower absorption capacity and lower swelling. However, their gel strength is firmer, and they are able to better retain their shape even when a modest pressure is exerted from the outside.
    These hydrogels are nowadays most widely used in personal hygiene products for single use, but are equally used to stop water penetration into underground electrical and data transmission cables, as water retention agents in horticulture, to control leaks or waste from aqueous liquids. in filtration and fire-retardant products, in wound dressing dressings, and in a wide variety of other large-scale and important industrial applications.
    In general, these and other hydrogels are made by polymerizing acrylic acid mixed with sodium hydroxide in the presence of an initiator to obtain a sodium polyacrylate. Other materials commonly used include polyacrylamide copolymer, ethylene maleic anhydride copolymer, crosslinked carboxymethylcellulose, polyvinyl alcohol copolymer, crosslinked polyethylene oxide, a starch and polyacrylonitrile copolymer and many more.
    In the vast majority of cases, starting from the reactive vinyl monomers, the polymers are produced by using a radical initiated polymerization under the influence of an appropriate energy source, in particular under the influence of heat, by using a thermal polymerization. initiator; by means of a photochemical reaction by using a photoinitiator and an appropriate light source such as UV radiation; or by exposing the monomer mixture to high energy radiation such as gamma or electron radiation.
    Three main methods are commonly used to make the polymers via radical polymerization: either by gel polymerization, suspension polymerization or solution polymerization, as taught for example by F. Buchholz, A. Graham and T. Andrew in "Modem Superabsorbent Polymer Technology", 1997 , John Wiley & Sons, ISBN 0-471-19411-5.
    In order to make end products that are provided with a coating (coating), the chemical technique of polymerization in solution can be applied immediately to wires and cables. This method has been specially optimized for use on components such as rolled goods or plate-shaped substrates.
    Substrates such as threads and cables, textile fibers, yarns, foils and the like can be easily coated using application techniques that are sufficiently known to those skilled in the art, such as, for example, immersion, the use of a spray head, the spraying, the application by means of transfer roles or by an equivalent technique.
    In these and similar cases, the coating formulation may contain effective amounts of additives and active ingredients that are well known to those skilled in the art, such as cross-linkers, polymerization rate modifiers, chain length regulators, polymerization initiators, rheology regulators, adhesion promoters, ingredients with chelating effect, corrosion inhibitors, film formers, plasticizers, wetting agents, anti-tack agents, anti-blocking agents, dyes and pigments, fillers, etc.
    In this context, EP 1 522 545 BI teaches from Vepetex B.V. us a method of making super-absorbent polymers, comprising supplying a reaction mixture comprising at least a first monomer and a second monomer and a radical-forming polymerization initiator, and then subjecting the monomers to a polymerization under the influence of an energy source, wherein the first monomer is neutralized with an inorganic base prior to polymerization.
    Furthermore, this relates to the manufactured super-absorbent polymers themselves, and additionally to a method of coating them on a support.
    In particular, this teaches us a process for producing super-absorbent polymers that comprises providing a non-aqueous reaction mixture comprising at least a first monomer and a second monomer and a radical-forming polymerization initiator, and then allowing the monomers to polymerize under influence of an energy source, whereby formation of radicals takes place and the polymerization is initiated.
    According to this invention of EP 1522545, the first monomer is a monomer containing an acrylic acid group corresponding to the formula H 2 C = CR 1 R 2, wherein R 1 = H or an alkyl group with 1-10 carbon atoms and R 2 = COOH. This monomer is always neutralized with an inorganic base before polymerizing. The radical-forming polymerization initiator is in this case a photo-initiator and the second monomer is a compound selected from: - a monomer containing an acrylic acid group having the formula H2C = CR3R4, wherein R3 = H or an alkyl group with 1-10 carbon atoms and R 4 represents an alkyl carboxyl group with 1-10 carbon atoms and is different from R 2; - a monomer containing an acrylamide group and having the formula H 2 C = CR 3 CONHR 5, wherein R 3 is defined as above, and R 5 is an alkyl group with 1-10 carbon atoms; - a compound selected from the group consisting of N, N dimethylacrylamide, diacetone acrylamide, methoxy (polyethylene glycol) methacrylate, ammonium sulphate, ethyl methacrylate, vinyl acetate, N-vinyl-2-pyrrolidone, N-vinyl-N-methylacetamide, vinyl cyanide, crotonic acid, 3 -amino-crotonamide, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate.
    In a preferred embodiment, the neutralization of the first monomer takes place in a liquid mixture of the first and the second monomer.
    Optionally, the second monomer is selected from the group consisting of methoxy (polyethylene glycol) methacrylate, N-isopropylacrylamide, and ammonium sulfate ethyl methacrylate.
    This publication also teaches us a super absorbent polymer made according to the method of the invention.
    It also teaches us a method of applying a super absorbent polymer coating of the invention to a support, which comprises impregnating the support with a reaction mixture comprising at least one monomer comprising a first acrylic acid group and neutralized with an inorganic base, and the formula has H 2 C = CR 1 R 2, wherein R 1 = H or an alkyl group of 1-10 carbon atoms, and R 2 = COOH, wherein this monomer is neutralized before the polymerization, and a second monomer and a radical-forming polymerization photo- initiator.
    It then learns to allow the monomers to be polymerized on the support under the influence of an energy source in which formation of radicals occurs and the polymerization is initiated. The second monomer contains an acrylate or acrylamide group or a compound such as higher. defined.
    Suitable energy sources can be gamma, electron or UV radiation.
    The disadvantages and inherent limitations are numerous and inter alia: - although desirable, the neutralization of the first monomer can often not be carried out in full because it depends on the solubility of the neutralized first monomer in the second monomer. (Description p.2 line 35-38.) For process technical reasons, it may therefore be necessary to opt for a lower degree of neutralization. - furthermore, we cannot rule out the possibility that the polymerization and subsequent swelling capacities in these poly-acrylic acid-containing super-absorbent copolymers are influenced by variation in monomer concentration, pH and ionic strength. Internal cyclization reactions occur in competition with cross-linking, making the final polymer structure inconsistent, as learned and discussed in the publication of Jeannine Elliott et al. In “Structure and swelling or poly (aciylic acid) hydrogels”, Polymer, volume 45, issue 5, March 2004, pages 1503-151 °. - during the processing processes of the polymers, high temperatures of 100-200 ° C (description p. 2 line 42) can occur that can give rise to degradation, discoloration, uncontrolled and undesired side reactions, etc. - as is clear from example 1. the temperature of the monomer mixture sometimes to be raised above 50 ° C during the neutralization step in order to obtain a clear mixture, and a few percentages of water must be added to keep the mixture liquid (description p.4 lines 50-54). - as becomes clear from Example 1, the pH of the reaction mixture should be kept between 4.5 and 5.5 with partial neutralization, which is still fairly acidic. Under these conditions, substantial amounts of acidic carboxyl groups are still present in the non-ionic state and do not contribute significantly to swelling. These polymers / hydrogels are in fact highly pH sensitive and show almost no swelling at low pH values.
    It can also be expected that this acidity will have a negative effect on the long-term behavior and stability of the dried as well as of the swollen polymer and also on other components, or for example, on an optical or electrical cable.
    Due to the large number and diversity of applications and the inherent limitations and shortcomings of the prior art methods and formulations, there is a constant demand for polyelectrolyte compositions containing hydrophilic polymers that can be converted to hydrogels by means of of simple, energy-saving, environmentally-friendly and renewable methods for production and application, and which exhibit longer-term stability and behavior while maintaining higher water absorption and swelling characteristics.
    The present invention is based on the surprising finding that the polyelectrolyte compositions of the invention are particularly suitable for forming hydrogels that have a longer-term stability, higher swelling rate and water-absorbing capacity, and this in a wider range of adverse conditions, in particularly in a wider range of pH values, than with compositions, it is the case today that are made according to the state of the art. With the invention, high swelling degrees have been obtained of more than 150, further 200 or more and even 300 or more.
    Moreover, it was surprisingly found that the copolymer can be efficiently produced from the polyelectrolyte composition of the invention under simple, safe, environmentally-friendly and energy-saving conditions.
    It is also important to mention that the copolymer composition can be made up of safe monomers (such as sodium vinyl sulfonate and the sodium salt of 2-acrylamido-2-methyl-1-propanesulfonic acid) and that the resulting copolymers do not appear to be harmful to the aquatic environment.
    Finally, it was found that substrates coated with the co-polymer (i.e., the hydrogel) of the invention, such as, for example, parts of optical or electrical cables, can be efficiently and at high speed produced on existing machines and according to well-established industrial techniques.
    The objectives outlined above are achieved and the disadvantages listed above as well as others are eliminated by providing a polyelectrolyte composition for forming a water insoluble copolymer for use as a hydrogel, the copolymer being formed by free radical polymerization of at least a first hydrophilic monomer and a second hydrophilic monomer, the first monomer being at least one selected from the group consisting of vinyl sulfonic acids, vinyl phosphonic acids, or a water-soluble salt of these as shown schematically in Formulas I-IV, wherein R 1, R 2 and R 3 represent a hydrogen, an optionally substituted alkyl or aryl group; Q represents an alkylene group and M represents a hydrogen or a cation.
    Suitable cations are, for example, alkali metal cations, in particular those of sodium, potassium or lithium.
    Obvious examples are vinyl sulfonic acid, also called ethylene sulfonic acid with EINECS number 214-676-1, the sodium salt of 2-methyl-2-propen-1-sulfonic acid with EINECS number 216-341-5 and vinyl phosphonic acid with EINECS number 217-123 -2.
    The second monomer is at least one compound selected from the group consisting of vinyl monomers containing an acid group that is separated from the double bond by an electron-withdrawing spacer, the acid group being present either in the form of the free acid or in the form of a water-soluble salt, and whose logarithm of the acid dissociation constant (pKa) in the free acid form has a value of less than 3.5. This second monomer is different from the first monomer.
    The objectives are further achieved with a method for applying the polyelectrolyte composition to a support, in particular as a coating and / or as impregnation of, for example, a fiber.
    It has been found that the copolymerization of the composition proceeds well due to the presence of the second monomer with the electron-withdrawing spacer group. This spacer group prevents mutual rejection of the negatively charged monomers, which was found when using purely first monomers. The electron-withdrawing spacer group moreover has a stimulating effect on the polymerization, so that it is brought to a successful conclusion.
    In this way it appears to be possible to carry out a polymerization without the use of the harmful acrylic acid and also without the use of likewise undesirable acrylamide, which has been used in the prior art. Incidentally, it is not excluded that acrylic acid or acrylamide is present in relatively small amounts, for example less than 10% by weight of the total amount of the first monomer. The acrylamide is also undesirable because it has no acid groups and therefore does not contribute to the swelling capacities of the resulting hydrogel.
    In the following, the operation, effects and characteristics of the present invention are explained in further detail.
    It is to be understood that the examples, options and preferred embodiments are intended only to illustrate the present invention, and that its actual scope will not be determined by it.
    The present invention also provides a hydrogel formed by that polyelectrolyte composition. The polyelectrolyte composition of the present invention can be used to be incorporated into or coated with a substrate.
    The present invention also provides a substrate in which the copolymer of the invention is used, either as a coating or as an important component.
    Preferably the acid group from the second monomer is selected from the group of monomers containing a sulfonic acid, phosphonic acid or phosphoric acid group, or a water-soluble salt of these. These acid groups have the desired pKa properties. They ensure that the acids occur under usual conditions such as a neutral or weak acid or basic environment. are in the form of the dissociated base, i.e. if anions are present.
    In a further preferred embodiment, the water-soluble salts of the first and the second monomer are formed by sodium, potassium, lithium, ammonium or amine salts, or from a combination thereof.
    The electron-withdrawing group of the second monomer preferably contains a group selected from a carbonyl, ether and / or mercapto. It is particularly advantageous if the group contains a carbonyl group, because it again contributes to the swelling degree.
    The second monomer preferably comprises an acrylamidoaryl or acrylamidoalkyl sulfonic acid or a salt thereof, in particular a compound corresponding to the formula (V)
    wherein n = 0 or 1; R 1, R 2 and R 3 represent hydrogen or an optionally substituted alkyl or aryl; Q represents an optionally substituted hydrocarbon or an arylene entity, and M represents hydrogen or a cation.
    Suitable cations are, for example, alkali metal cations, in particular those of sodium, potassium or lithium.
    In a further preferred embodiment, the second monomer comprises an n-sulfoaryl or n-sulfoalkyl or n-sulfoalkylene oxide (alkyl) acrylate or a salt thereof, in particular a compound corresponding to the formula (VI).
    wherein n = 0 or 1; R 1, R 2 and R 3 represent hydrogen or, an optionally substituted alkyl or aryl; Q represents an optionally substituted alkylene, arylene or alkylene oxide entity; and M represents hydrogen or a cation.
    Suitable catalysts are, for example, alkali metal cations, in particular those of sodium, potassium or lithium.
    In a further preferred embodiment, the second monomer comprises styrene sulfonic acid or a salt thereof, in particular a compound corresponding to the formula (VII)
    Wherein R 1, R 2 and R 3 represent a hydrogen or an optionally substituted alkyl or aryl group; and M represents hydrogen or a cation with n = 1 or 2. This sulfonic acid-substituted phenyl group also has good electron-sucking properties and is thereby very suitable as a spacer thanks to the sufficiently large phenyl ring.
    Suitable cations are, for example, alkali metal cations, in particular those of sodium, potassium or lithium.
    In a still further preferred embodiment, the second monomer comprises n-phosphoalkyl or n-phosphoaryl or n-phosphoalkylene oxide (alkyl) acrylate or a salt thereof, in particular a compound corresponding to the formula (VIII)
    wherein R 1, R 2 and R 3 represent hydrogen or an optionally substituted alkyl or aryl; Q represents an optionally substituted alkylene, arylene or alkylene oxide entity; M represents hydrogen or a cation and X = 1 or 2, and y = 3 - X.
    Suitable cations are, for example, alkali metal cations, in particular those of sodium, potassium or lithium.
    In a still further preferred embodiment, the second monomer comprises an allyloxyalkyl phosphonic acid, an allyloxyalkyl sulfonic acid, or a salt thereof, in particular a compound corresponding to the formulas (IX) or (X). wherein R 1, R 2 and R 3 represent hydrogen or an optionally substituted alkyl or aryl; M represents hydrogen or a cation; and Q represents an optionally substituted hydrocarbon entity.
    Suitable cations are, for example, alkali metal cations, in particular those of sodium, potassium or lithium.
    Optionally, the second monomer comprises 2-acrylamido-2-methylpropane sulfonic acid, or 3-acryloxypropane-1 sulfonic acid, or a water-soluble salt thereof, or a combination of any of these.
    Preferably, the first monomer comprises vinyl sulfonic acid, 2-methyl-2-propen-1-sulfonic acid, vinyl phosphonic acid, or a water-soluble salt thereof, or a combination of any of these. As can be seen from this, the alkylene group Q in the first monomer is preferably methylene. Ethylene or substituted methylene is also possible. Substitutions are, for example, alkyl, such as methyl or ethyl or halogen.
    The molar ratio between the first and the second monomer is at most 1, that is, there is as much or more second monomer than first monomer. Hereby it is obtained that there is sufficient second monomer to shield the mutually-repelling first monomer. Preferably the first monomer is present in a weight percentage of 1-40% of the total amount of monomer. More preferably, at least 5%, at least 7% or at least 10% of the first monomer is present.
    A third monomer can optionally be present, which deviates from the first and the second monomer and thus does not contribute to the swelling properties. It will be clear that such a third monomer will only be present in relatively small amounts, for example at most 10% by weight, or at most 5% or even at most 2%. Such a third monomer may, for example, be intended for optimization of physical properties and / or for improved adhesion to a support. The choice of the third monomer will also depend on the type of carrier.
    It is noted that US4,585,845 describes a copolymerization into a swellable copolymer with different monomers. In most examples, however, the primary monomer is acrylamide, which does not contribute to the swelling degree. The swelling degrees obtained are then also relatively low with respect to the swelling degrees obtained in the invention. However, in the examples where the amount of acrylamide is low, the amount of first monomer is much greater than the amount of second monomer. After-effects yielded that no copolymer could be formed.
    In a preferred embodiment, the polyelectrolyte composition of the invention contains a greasing monomer that has at least two polymerizable vinyl groups.
    Preferably, this cross-linking monomer is N, N'-methylenebisacrylamide.
    In a preferred embodiment, this cross-linking monomer is used in combination with a photoinitiator that polymerizes the first and second monomer to obtain the hydrophilic co-monomer compound present in the polyelectrolyte polymer composition of the invention.
    A suitable water-soluble photoinitiator is, for example, the photoinitiator 1 - (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propane-1-one, in particular IC2959 from BASF.
    The invention is described herein with reference to certain preferred embodiments. However, it is to be understood that these preferred embodiments are merely illustrations of the principles and applications of the present invention. It is therefore understood that numerous modifications can be made to these preferred embodiments, which are presented herein for illustrative purposes only, and that other embodiments thereof may be realized without prejudice to the spirit and scope of the present invention as set forth. .
    Without intending to limit the scope of the invention in any way, further preferred embodiments are described in more detail with reference to the following examples.
    The preparation of the Copolymers of the invention is illustrated by the following examples.
    Example 1: 3.94 g of a 25% aqueous solution of sodium vinyl sulfonate is mixed with 15.76 g of a 50% aqueous solution of the sodium salt of 2-acrylamido-2-methyl-1-propane sulfonic acid. To this mixture is added 0.006 g of Ν, Ν'-methylenebisacrylamide and 0.3 g of 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one and the mixture is further stirred at a temperature of 60 ° C until all ingredients are dissolved.
    The reaction mixture is brought to room temperature before transferring it with a pipette into a silicone mold having the dimensions of 8 cm in length, 1 cm in width and 0.5 cm in height, in order to make a beam-shaped casting of the final copolymer . The surface of the liquid is covered with a polypropylene film and the reaction mixture is then cured by simultaneously shining UV light of 254 nm and 365 nm on the top of the cover film for 20 minutes. The cured beam-shaped polymer casting is removed from the silicone mold and dried under atmospheric conditions until no weight loss can be detected.
    A small piece of the dry polymer, with dimensions of approximately 1 cm by 1 cm by 0.5 cm, is broken off from the bar-shaped casting and weighed as a dry mass in a 500 ml beaker. 300 ml of demineralized water are poured onto this piece of dry copolymer and the swelling process is allowed to continue undisturbed until equilibrium is reached. The swollen hydrogel is finally filtered on a screen with small openings and the hydrogel is re-weighed in the swollen state. The degree of swelling is then calculated using the following formula: (mass of the swollen hydrogel / dry mass). In this case a degree of swelling of 300 was achieved.
    Example 2:
    The same reaction mixture as described in Example 1 is applied as a very thin coating layer on a polyester fiber at a line speed of 20 m / min by using an immersion tank. The coated fiber is then cured on the line itself by using a mercury vapor UV lamp (UVAPRINT HPV, 200 W / cm), and dried in a 1.5 m long oven at a temperature of 260 ° C, and is then cured on a bobbin wounded. This inline coating process yielded a fiber that contained a dry water-swellable coating. After swelling for only 10 minutes in demineralized water, the coating had already absorbed 200 times its own weight in water.
    Example 3:
    A reaction mixture was made consisting of 1.98 g of a 25% aqueous solution of sodium vinyl sulfonate, 7.92 g of a 50% aqueous solution of potassium 3-sulfopropyl acrylate, 0.1 g of 1- [4- (2-hydroxyethoxy) phenyl] - 2-hydroxy-2-methyl-1-propan-1-one and 0.003 g of N, N'-methylenebisacrylamide, according to the same methodology as set forth in Example 1. The degree of swelling of this cured copolymer composition reached a value of 260.
    Example 4:
    Further compounds were prepared according to the method of Example 1 and Example 3, but with variation of the monomers and their ratios. Use was made of sodium vinyl sulfonate (SVS, 25% by weight aqueous solution) and disodium vinyl phosphonate (di-SVPA) as the first monomers. Use was made of the sodium salt of 2-acrylamido-2-methyl-1-propane sulfonate (SAMPS, 50 wt% aqueous solution) and of the potassium salt of 3-sulfopropyl acrylate (PSPAA) as second monomers. The Copolymers were prepared with the crosslinker (CL) of Examples 1 and 3. After preparation, the swell (SD) was measured (uptake of H 2 O in g H 2 O / gram of material).
    Table 1 - Amounts of reagents, crosslinker (GL) and obtained swell degrees (SD). The amounts relate to the amounts of the reagents in the commercially available form (i.e., either as 25% or as 50% aqueous solution, or as pure compound). Where no value is stated for the swell, it means that the polymer could not be formed or was not formed in a form suitable for water absorption.
    Comparative example 1:
    A reaction mixture was made using 4.99 g of 2-hydroxyethyl acrylate and 0.008 g of bis-acyl phosphinoxide (BAPO, Irgarcure 819), according to the same methodology as set forth in Example 1. The degree of swelling of this cured polymer composition reached only a value of 6 .
    Comparative example 2:
    A reaction mixture was made using 49.99 g of a 25% aqueous solution of sodium vinyl sulfonate, 49.99 g of 2-hydroxyethyl acrylate, 0.01 g of N, N'-methylenebisacrylamide and 2.04 g of 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, according to the same methodology as set forth in Example 1. The degree of swelling of this cured copolymer composition reached only a value of 20. /
    权利要求:
    Claims (19)
    [1]
    Conclusions
    An aqueous polyelectrolyte composition for forming a water insoluble copolymer suitable as a hydrogel, comprising at least a first hydrophilic monomer and a second hydrophilic monomer and a crosslinking monomer that has at least two polymerizable groups, which monomers form the copolymer by radical polymerization, characterized in that the first monomer is at least one selected from the group consisting of vinyl sulphonic acids, vinous phosphonic acids, or a water-soluble salt of these as represented in formulas I-IV, wherein R 1, R 2 and R 3 are hydrogen, a optionally substituted alkyl or aryl group; Q represents an alkylene group and M represents a hydrogen or cation,

    and that the second monomer is a vinylic monomer with an acid group separated from the double bond by an electron-withdrawing spacer group, which vinylic monomer is different from the first monomer, the acid group present either in the free acid form or in the form of a water-soluble salt, and the logarithm of the acid dissociation constant (pKa) in the free acid form having a value of less than 3.5.
    [2]
    The composition according to claim 1, characterized in that the molar ratio of the second monomer to the first monomer is at most one.
    [3]
    The composition according to claim 1 or 2, characterized in that the second monomer is at least one compound selected from the group of monomers containing a sulfonic acid, phosphonic acid or phosphoric acid group or a water-soluble salt thereof.
    [4]
    The composition according to any of the preceding claims 1 to 3, characterized in that the water-soluble salt is a salt of sodium, potassium, lithium, ammonium, or an amine salt, or of a combination of these.
    [5]
    The composition according to claim 1, characterized in that the second monomer comprises a compound corresponding to the formula (V)

    wherein n = 0 or 1; R 1, R 2 and R 3 represent hydrogen or an optionally substituted alkyl or aryl; Q represents an optionally substituted hydrocarbon or an arylene entity, and M represents hydrogen or a cation.
    [6]
    The composition according to claim 1, characterized in that the second monomer is a compound corresponding to the formula (VI)

    wherein n = 0 or 1; R 1, R 2 and R 3 represent hydrogen or an optionally substituted alkyl or aryl, Q represents an optionally substituted alkylene, arylene or alkylene oxide entity and M represents hydrogen or a cation.
    [7]
    The composition according to claim 1, characterized in that the second monomer comprises a compound corresponding to the formula (VII)

    wherein R 1, R 2 and R 3 represent hydrogen or an optionally substituted alkyl or aryl group and M represents hydrogen or a cation with n = 1 or 2.
    [8]
    The composition according to claim 1, characterized in that the second monomer comprises a compound corresponding to the formula (VIII)

    wherein R 1, R 2 and R 3 represent hydrogen or an optionally substituted alkyl or aryl, Q represents an optionally substituted alkylene, arylene or alkylene oxide entity, M represents hydrogen or a cation, and X = 1 or 2, and y = 3 - X.
    [9]
    The composition according to claim 1, characterized in that the second monomer comprises a compound corresponding to the formula (IX) or (X).

    wherein R 1, R 2 and R 3 represent hydrogen or an optionally substituted alkyl or aryl, M represents hydrogen or a cation, and Q represents an optionally substituted hydrocarbon entity.
    [10]
    The composition according to claim 1, characterized in that the first monomer comprises vinyl sulfonic acid, 2-methyl-2-propen-1-sulfonic acid, vinyl phosphonic acid, or a water-soluble salt thereof, or a combination of one of these.
    [11]
    The composition according to claim 1 or 10, characterized in that the second monomer comprises 2-acrylamido-2-methylpropane sulfonic acid, 3-acryloxypropane-1-sulfonic acid, or a water-soluble salt thereof, or a combination of one of these.
    [12]
    The composition according to any of the preceding claims, characterized in that the weight percentage of the first monomer is 5-40% by weight, preferably 7-40% by weight, more preferably 10-40% by weight.
    [13]
    The composition according to claim 1, characterized in that the crosslinking monomer is Ν, Ν'-methylenebisacrylamide.
    [14]
    The composition according to any of the preceding claims 1-12, characterized in that it additionally contains 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propane-1-one as a photo -initiator.
    [15]
    A method for applying a water-insoluble polyelectrolyte copolymer to a support wherein the composition according to any one of the preceding claims is used.
    [16]
    A carrier with the hydrogel available according to claim 14.
    [17]
    The use of the hydrogel according to claim 15 as a water blocking agent in the construction of wires and cables.
    [18]
    A substrate containing the hydrogel according to claim 14.
    [19]
    A substrate coated with the hydrogel of claim 14.
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    法律状态:
    优先权:
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    BE201300526|2013-08-05|
    BE20130526|2013-08-05|
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