EP2663627B1 - Hydrogele auf basis von estern der polyisobutenbernsteinsäure - Google Patents

Hydrogele auf basis von estern der polyisobutenbernsteinsäure Download PDF

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EP2663627B1
EP2663627B1 EP12700637.7A EP12700637A EP2663627B1 EP 2663627 B1 EP2663627 B1 EP 2663627B1 EP 12700637 A EP12700637 A EP 12700637A EP 2663627 B1 EP2663627 B1 EP 2663627B1
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Prior art keywords
poly
weight
hydrogel
alcohol
range
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EP12700637.7A
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German (de)
English (en)
French (fr)
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EP2663627A1 (de
Inventor
Hannah Maria KÖNIG
Sophia Ebert
Roland Ettl
Ouidad Benlahmar
Marc-Steffen Schiedel
Brigitte Giesen
Petra Plantikow
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Henkel AG and Co KGaA
BASF SE
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Henkel AG and Co KGaA
BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the present invention relates to the use of esters of polyisobutene succinic acid for the preparation of hydrogels and the use of such hydrogels for cleaning and care products for the home (so-called homecare products), for cosmetics and for medical products.
  • Hydrogels ie water-containing gels based on crosslinked, water-swellable but at the same time water-insoluble polymers, are of interest for a wide variety of applications.
  • they are used as biomaterials in the pharmaceutical or medical field, for example for contact lenses, wound closure materials, soft implants, for coating surfaces, for example of biomedical objects such as implants or contact lenses, for the production of biosensors (see Rompp Chemie-Lexikon, 10th edition, Georg Thieme Verlag 1997, p 1835th and cited literature).
  • hydrogels loaded with perfume or surfactants are used in fragrance dispensers or as cleansers.
  • hydrous pastes for fragrance delivery for the sanitary sector which in addition to water and perfumes contain a block copolymer having oligo- or polyethylene oxide, oligo- or polypropylene oxide, or oligo- or polybutylene oxide groups.
  • polyoxyethylene-polyoxypropylene endblock and triblock copolymers adhere well to ceramic surfaces and are not rinsed as a whole under the action of water, but slowly and completely dissolve only after or with frequent repeated exposure to water.
  • a disadvantage proves that such pastes tend to dehydrate at less frequent exposure to water or at longer intervals between repeated actions of water and then can no longer be completely removed. Also, these dried out pastes look unattractive.
  • Another disadvantage of these pastes is their low dimensional stability, causing them to run down the Keramikwandung and form unsightly "noses”.
  • the present invention has for its object to provide new gelling agents for hydrogels. These gelling agents should form hydrogels that have at least one are dimensionally stable over a longer period of time and also have no or no significant surfactant properties. In addition, biocompatibility is desirable.
  • WO 02/02674 describes block copolymers, in particular triblock and higher multiblock copolymers obtainable by reacting silane-terminated polyisobutene with allyl-terminated polyalkylene glycol ethers.
  • the block copolymers are swellable with water. Their production is comparatively complicated.
  • the properties of the hydrogels prepared therefrom, in particular their mechanical properties, are unsatisfactory.
  • the DE 10125158 describes inter alia esters of polyisobutene-succinic acid with an alcohol selected from poly-C 2 -C 4 -alkylene glycols and their use as emulsifier for water-in-oil emulsions.
  • the WO 2007/014915 describes aqueous polymer dispersions of polyolefins using polyisobutenes functionalized with hydrophilic groups, such as esters of polyisobutene succinic acid with an alcohol selected from poly-C 2 -C 4 -alkylene glycols, as emulsifiers.
  • esters of polyisobutene succinic acid with an alcohol selected from poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ethers form stable hydrogels with water, ie as gelling agents Act.
  • the invention thus relates to the use of esters of polyisobutene-succinic acid with an alcohol selected from poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ethers for the preparation of hydrogels or as gelling agents for hydrogels, especially in hydrogels, which can be used in household cleaning and care products (homecare products), cosmetics and medical products.
  • the invention also relates to hydrogels, in particular hydrogels for cleaning and care products for the household, for cosmetics and for medical products, the hydrogels in addition to water at least one ester of polyisobutene with a poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ethers containing selected alcohol.
  • the invention also relates to the use of such esters for the preparation of hydrogels and to a process for preparing the hydrogels comprising reacting at least one ester of polyisobutene succinic acid with one of poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono -C 1 -C 22 -alkyl ethers incorporated alcohol in an aqueous liquid, or mixed with the aqueous liquid.
  • the hydrogels of the invention are stable, d. H. they are dimensionally stable over a wide temperature range of for example 0 to 90 ° C, in particular 0 to 70 ° C and are not prone to segregation even under mechanical stress.
  • the gel formers contained therein, d. H. the esters of polyisobutene succinic acid described here also show no surfactant properties, ie. H. at a concentration of 1 g / l they do not lower the surface tension of the water below 45 mN / m, determined by the ring method according to DIN 53914: 1980-03 at 25 ° C. Due to the gelling agents used, the hydrogels are also biocompatible, i. H. they have no or no appreciable adverse effect on living or living material such as cell material or tissue.
  • the hydrogels according to the invention have a good adhesion to polar surfaces, in particular inorganic surfaces such as glass or ceramic, and are not rinsed off immediately upon exposure to water, but rather dissolve without leaving any residue after prolonged and frequently repeated exposure to water. They can also be formulated with fragrances or other substances that promote the cleaning or disinfection of sanitary ceramics, without disadvantages. Furthermore, these hydrogels tend to dry only to a small extent. In addition, the hydrogels are dimensionally stable and are therefore suitable for the production of moldings, for. B. in fragrance dispensers.
  • the hydrogels according to the invention can be formulated in a simple manner with perfumes or other additives for cleaning agents, such as, for example, surfactants, dyes, preservatives, disinfectants, complexing agents, thickeners, humectants, disintegrants, foam stabilizers or lime or urine stone-dissolving substances, and are particularly suitable for the use in the sanitary area. They adhere well to ceramic surfaces and are not rinsed off as a whole under the action of water, but dissolve slowly and completely only after frequently repeated exposure to water.
  • cleaning agents such as, for example, surfactants, dyes, preservatives, disinfectants, complexing agents, thickeners, humectants, disintegrants, foam stabilizers or lime or urine stone-dissolving substances, and are particularly suitable for the use in the sanitary area. They adhere well to ceramic surfaces and are not rinsed off as a whole under the action of water, but dissolve slowly and completely only after frequently repeated exposure to water.
  • a hydrogel former is understood as meaning a polymer which, when exposed to water and the associated swelling, is at least in a certain temperature range, eg. B. in the range of 5 to 40 ° C, water-stable hydrogels forms.
  • a stable hydrogel is understood to mean a hydrogel which, under mechanical load and / or prolonged storage, at least in a certain temperature range, eg. B. in the range of 5 to 40 ° C, not significantly separated, d. H. in which no significant deposition of an aqueous serum occurs under these conditions.
  • the ester of polyisobutene succinic acid binds the water to form a 3-dimensional polymeric network
  • the polyalkylene groups of the ester presumably bonding the water and good adhesion to the polymer polar surfaces
  • the non-polar polyisobutenyl radicals due to hydrophobic interactions and association to a physical, d. H. non-covalent, crosslinking of the polymer chains and thus lead to the formation of a three-dimensional, dimensionally stable polymer network.
  • polyisobutene succinic acid oligomeric or polymeric macromolecules having an oligomer residue or polymer residue which is derived from isobutene and the radicals derived from succinic acid at one of its termini 1 or 2, ie radicals of the formula BS -CH (COOH) CH 2 COOH (BS) and correspondingly 2 or 4 carboxyl groups, as well as mixtures thereof.
  • Polyisobutene succinic acids can therefore be described by the following formulas IIa and IIb: PIB-CH (COOH) CH 2 COOH (IIa) PIB '- [CH (COOH) CH 2 COOH] 2 (IIb) where PIB in formula IIa stands for a monovalent, polyisobutene-derived oligomer residue or polymer residue and PIB 'in formula IIb represent a bivalent, polyisobutene-derived oligomer residue or polymer residue.
  • esters of polyisobutenesuccinic acid used according to the invention at least one of the carboxyl groups in the form of the ester is present with a poly-C 2 -C 4 -alkylene glycol or a poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ether.
  • esters can be described by the general formulas Ia and Ib: wherein PIB and PIB 'have the meanings given above for formulas IIa and IIb, R and R' are independently hydrogen or Pag and Pag is one of a poly-C 2 -C 4 alkylene glycol or a poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 alkyl ether derived radical.
  • R is in particular hydrogen.
  • Poly-C 2 -C 4 -alkylene glycols are understood as meaning linear or branched oligomers or polymers which are composed essentially of repeating units of the formula -AO- (also referred to below as alkylene oxide repeating units) in which A is C 2 -C 4 -alkanediyl and having hydroxyl groups at their termini.
  • Poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ethers are understood as meaning linear or branched oligomers or polymers which are composed essentially of repeating units of the formula -AO-, where A is C 2 -C 4 -alkanediyl which have an oxygen-bonded C 1 -C 22 -alkyl group at one of their ends and which have hydroxyl groups at the other terminus or the other termini.
  • the repeat units of the formula -AO- may be identical or different. If the poly-C 2 -C 4 -alkylene glycols or poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ethers have different repeat units of the formula -AO-, these may be random, alternating or in several, for. B. 2, 3 or 4 blocks.
  • the poly-C 2 -C 4 -alkylene glycols or poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ethers have different repeating units of the formula -AO-, which are randomly arranged.
  • C 2 -C 4 -alkanediyl in this context denotes a saturated divalent hydrocarbon radical having 2 to 4 C atoms, such as 1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,4-butanediyl, 1, 2-butanediyl, 1,3-butanediyl, 2,3-butanediyl or 1-methyl-1,2-propanediyl.
  • C 1 -C 22 -alkyl in this context represents a saturated, acyclic monovalent hydrocarbon radical having 1 to 22 C atoms, in particular having 1 to 8 C atoms or 1 to 4 C atoms, such as methyl, ethyl, n-propyl, Isopropyl, 1-butyl, 2-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl , n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, myristyl, pentadecyl, palmityl (
  • Isobutene-derived polymer radicals in the following also polyisobutenyl radicals, are understood to mean organic radicals which are derived from linear or branched oligomers or polymers of isobutene and which contain up to 20% by weight, preferably not more than 10% by weight, of isobutene various C 2 -C 12 -olefins, such as 1-butene, 2-butene, 2-methyl-1-butene, 2-methylpentene-1, 2-methylhexene-1, 2-ethyl-pentene-1, 2-ethylhexene-1, 2-propylhepten-1, polymerized may contain.
  • radicals can be in the case of monovalent radicals PIB, for example by the following formulas or in the case of divalent radicals PIB 'be described for example by the following formulas wherein the value p + 2 corresponds to the degree of polymerization and indicates the number of isobutene units in the polyisobutene radical and * means the attachment to the succinic acid (ester) radical.
  • a part of the isobutene units - CH 2 C (CH 3 ) 2 - usually not more than 20 wt .-%, preferably not more than 10 wt .-%, of which different from C 2 -C 12- olefins derived C 2 -C 12 alkane-1,2-diyl be replaced.
  • the degree of polymerization p + 2 is typically in the range of 5 to 100, in particular in the range of 8 to 80 and especially in the range of 15 to 65.
  • esters of polyisobutenesuccinic acid which, based on the total weight of the ester, consist of at least 50% by weight, in particular at least 70% by weight, of esters of the formula Ia.
  • the esters of polyisobutenesuccinic acid, based on the total weight of the ester preferably contain less than 30% by weight, in particular less than 20% by weight, of esters of the formula Ib.
  • the esters of polyisobutene succinic acid may contain unmodified polyisobutene due to the preparation. Unless stated otherwise, this is not attributed to the esters here and below.
  • the proportion of the polyisobutene may be up to 50% by weight, but preferably not more than 40% by weight or not more than 30% by weight, based on the total amount of ester + polyisobutene.
  • esters of polyisobutene succinic acid whose polyisobutene residue of the ester has a number-average molecular weight in the range from 500 to 5000 daltons, in particular in the range from 800 to 3600.
  • polyisobutene radicals of the polyisobutene succinic esters have a narrow molecular weight distribution.
  • the polydispersity is then preferably at most 1.4, more preferably at most 1.3, in particular at most 1.2.
  • esters of polyisobutene-succinic acid which are selected from the group consisting of poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ethers or
  • the alcohol (s) have a number average molecular weight in the range from 500 to 15,000 daltons, in particular in the range from 800 to 10,000 daltons and especially in the range from 1,200 to 5,000 daltons.
  • the alcohol esterified with the polyisobutene succinic acid is unbranched, ie, under linear poly-C 2 -C 4 -alkylene glycols and linear poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 20 alkyl ethers is selected.
  • Unbranched, ie linear poly-C 2 -C 4 -alkylene glycols and linear poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 20 -alkyl ethers can be described by the following formula (III):
  • A is C 2 -C 4 alkanediyl as defined above which may be the same or different and which is preferably selected from 1,2-ethanediyl and 1,2-propanediyl.
  • R ' is hydrogen or C 1 -C 22 -alkyl, in particular hydrogen or C 1 -C 10 -alkyl and especially hydrogen or C 1 -C 4 -alkyl, for.
  • n indicates the average number of repeating units [AO] (number average) and is typically in the range of 10 to 350, in particular in the range of 15 to 200.
  • the radical Pag in the formulas Ia and Ib is preferably a radical of the formula wherein A, R and n have the meanings given above and * denotes the linkage to the oxygen atom of the polyisobutene succinic acid radical.
  • the repeating units of the formula -AO- may be identical or different. If the formulas III or in the formulas for Pag have different repeating units of the formula -AO-, these may be used statistically or in several, for. B. 2, 3 or 4 blocks. In a particular embodiment of the invention, the formulas III or in the formulas for Pag have different repeating units of the formula -AO-, which are randomly arranged.
  • the alcohol which is esterified with the polyisobutene succinic acid to at least 50 mol%, and in particular at least 70 mol%, based on the total number of alkylene oxide repeating units in the alcohol, from repeat units of the formula [CH 2 CH 2 O] is constructed.
  • the proportion of repeating units of the formula [CH 2 CH 2 O] is at least 50 mol%, and in particular at least 70 mol%, based on the total number of repeating units AO.
  • all or almost all repeating units are AO of the poly-C 2 -C 4 -alkylene glycol or of the poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 20 -alkyl ether, or all or almost all of them
  • the repeating units [CH 2 CH 2 O] and [A'-O] different from one another are not block-like but randomly distributed or arranged alternately.
  • the alcohol constituent and the polyisobutene succinic acid on which the ester is based are selected such that the ester has, on average, a weight ratio of polyisobutene radical to alcohol radical in the range from 10: 1 to 1:30, preferably in the range from 1, 5: 1 to 1:20 and in particular in the range of 1: 1 to 1:10.
  • esters of polyisobutene succinic acid used according to the invention can be prepared in a manner known per se by reacting polyisobutene succinic acid or an ester-forming derivative of polyisobutene succinic acid with a poly-C 2 -C 4 -alkylene glycol or poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ether or Mixtures thereof under esterification conditions. Methods for this are generally known, for. B. from the above-cited DE 10125158 and WO 2007/014915 ,
  • Suitable ester-forming derivatives of polyisobutene succinic acid are the acid halides and the C 1 -C 4 alkyl esters of polyisobutene succinic acid and in particular polyisobutene succinic anhydride.
  • esters of polyisobutene succinic acid which is obtainable by reacting polyisobutene succinic anhydride with one selected from poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 2 -C 20 -alkyl ethers, are used Alcohol, especially an alcohol of formula III, or a mixture of these alcohols.
  • Polyisobutene succinic anhydride is understood here and below as meaning the internal anhydrides of polyisobutene succinic acid, ie substances in which the two carboxyl groups of the succinic acid residue form a 1-oxolane-2,5-dione-2-yl radical.
  • Such polyisobutene succinic anhydrides can be described in particular by the following formulas wherein PIB and PIB 'have the meanings given previously for formulas Ia, Ib, IIa and IIb.
  • the polyisobutene succinic anhydride used to prepare the ester, based on the total weight of the anhydride contains at least 50% by weight, in particular at least 70% by weight, of the anhydride of the formula IVa.
  • the polyisobutene succinic anhydride used to prepare the ester, based on the total weight of the anhydride contains less than 30% by weight, in particular less than 20% by weight, of anhydride of the formula IVb.
  • the polyisobutene succinic anhydride may contain polyisobutene due to the production process.
  • the proportion of the polyisobutene may be up to 50% by weight, but preferably not more than 40% by weight or not more than 30% by weight, based on the total amount of polyisobutene succinic anhydride + polyisobutene.
  • the relative proportion of compounds of the formula IVa and IVb in the polyisobutene succinic anhydride used for preparing the ester corresponds to the saponification number of the polyisobutene succinic anhydride, determined in analogy to DIN 53401.
  • the polyisobutene succinic anhydride has a saponification number VZ in the range of 40 to 140 mg KOH / g and in particular in the range of 70 to 100 mg KOH / g, determined according to DIN 53401, has.
  • polyisobutene succinic anhydrides used for the reaction are known, for. B. from the DE 2702604 A1 . US 5883196 . US 5420207 and EP 629638 as well as the publication of M. Tessier et al., Eur. Polym. J, 20, 1984, pp. 269-280 and Mach., Et al., Lubrication Science 12-2, 1999, pp. 175-185 ,
  • Polyisobutene succinic anhydrides which are obtainable by reacting olefinically unsaturated polyisobutenes with maleic anhydride are preferred. Particularly preferred are products obtained by reacting highly reactive polyisobutenes with maleic anhydride. Highly reactive polyisobutenes are understood as meaning polyisobutenes having at least 50 mol%, frequently at least 60 mol% and in particular at least 80 mol%, based on the total number of polyisobutene macromolecules, terminally arranged double bonds.
  • Preferred highly reactive polyisobutenes have predominantly vinylidene double bonds.
  • Highly reactive polyisobutenes are commercially available, for. As the glissopal brands of BASF SE, such. Glissopal® 1000 and Glissopal® 1300, Glissopal® 2300.
  • poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 2 -C 20 -alkyl ethers used for the reaction are likewise known from the prior art and are commercially available, for example under the trade names Pluriol ®, z.
  • Pluronic® PE 3100, Pluronic® PE 3500, Pluronic® PE 4300, Pluronic® PE 6100, Pluronic® PE 6120, Pluronic® PE 6200, Pluronic® PE 6400, Pluronic® PE 6800, Pluronic ® PE 7400, Pluronic® PE 8100, Pluronic® PE 9200, Pluronic® PE 9400, Pluronic® PE 10100, Pluronic® PE 10300, Pluronic® PE 10400 and Pluronic® PE 10500, or can be prepared in analogy to standard methods by base-catalyzed homo- or copolymerization of C 2 -C 4 alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2-methyl-1,2-propylene oxide ( isobutylene oxide) ,
  • reaction of the polyisobutene succinic anhydride with the alcohol selected from poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 2 -C 20 -alkyl ethers can be carried out in a manner known per se in analogy to those described in DE 10125158 and WO 2007/014915 described procedures done.
  • the polyisobutene succinic anhydride with the alcohol selected from poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 2 -C 20 -alkyl ethers in a molar ratio of 2: 1 to 1 is generally employed. 2, in particular 1.5: 1 to 1: 1.5 and especially 1.05: 1 to 1: 1.2, in each case based on the anhydride groups in the polyisobutene succinic anhydride.
  • reaction can be carried out in solution or in bulk.
  • suitable solvents are aromatic hydrocarbons, e.g. As benzene, toluene, xylenes, mesitylene, naphthalene, tert-butylbenzene and mixtures thereof, (cyclo) aliphatic hydrocarbons, eg.
  • halogenated hydrocarbons such as dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1-dichloroethene, 1,2-dichloroethene, Chlorobenzene, dichlorobenzene, chlorotoluene and mixtures thereof, and mixtures of the aforementioned aromatic and (cyclo) aliphatic hydrocarbons and mixtures of the aforementioned hydrocarbons with halogenated hydrocarbons.
  • the reaction can be carried out in the presence of a catalyst or in the absence of catalysts. In general, the reaction takes place at temperatures in the range of 60 to 250 ° C, often in the range of 80 to 200 ° C and in particular in the range of 100 to 180 ° C.
  • Suitable catalysts are especially basic compounds such as alkali metal and alkaline earth metal oxides, hydroxides, carbonates and bicarbonates and tertiary organic amines, eg. B.
  • trialkylamines such as triethylamine, tripropylamine, methyldiisopropylamine, tributylamine, dimethyl-tert-butylamine, and cyclic alkylamines such as N-methylmorpholine, N-methylpiperidine, N-methylpyrrolidine, and triethylenediamine.
  • the catalyst is used in amounts of 0.1 to 20 mol%, based on the anhydride groups in the polyisobutene succinic anhydride.
  • esters of polyisobutene succinic acid with an alcohol selected from poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 1 -C 22 -alkyl ethers form stable hydrogels with water, ie they can be used as a gelling agent.
  • the present invention also hydrogels, in addition to water (hereinafter also referred to component B) at least -alkylene an ester of polyisobutene with a from poly-C 2 -C 4 and the poly-C 2 -C 4 alkylene glycol mono-C 1 relates to C 22 alkyl ethers containing selected alcohol in an amount sufficient to form a hydrogel as described above.
  • component A required to form the hydrogel naturally depends on the other constituents of the hydrogel and on the exact constitution of component A and can be determined in a simple manner by the skilled worker by means of routine experiments. Regardless of the other additives, a stable hydrogel is obtained when the weight ratio of component A to component B, i. H. Water, in the range of 4: 1 to 1: 6, often in the range of 3: 1 to 1: 4 and in particular in the range of 2: 1 to 1: 3.
  • component B i. H. Water
  • the component A generally constitutes from 15 to 80% by weight, frequently from 20 to 75% by weight, and in particular from 25 to 65% by weight, based on the total weight of the hydrogel.
  • the total amount of components A and B is generally at least 70% by weight and in particular at least 80% by weight of the hydrogel.
  • the hydrogel according to the invention may comprise one or more further constituents which are different from components A and B, which depend on the desired application. These components are also referred to below as component C.
  • component C are fragrances and customary additives contained in cleaning agents, such as, for example, surfactants, dyes, preservatives, disinfectants, complexing agents, thickeners, humectants, disintegrants, foam stabilizers and lime or urine stone-dissolving substances and mixtures of the abovementioned substances.
  • cleaning agents such as, for example, surfactants, dyes, preservatives, disinfectants, complexing agents, thickeners, humectants, disintegrants, foam stabilizers and lime or urine stone-dissolving substances and mixtures of the abovementioned substances.
  • an embodiment of the invention relates to a hydrogel which, in addition to component A and water (component B), contains at least one further constituent as component C, which is preferably comprised of perfumes, surfactants, dyes, preservatives, disinfectants, complexing agents, thickeners, humectants, disintegrants, Foam stabilizers and lime or urine-solubilizing substances and mixtures thereof is selected.
  • component C which is preferably comprised of perfumes, surfactants, dyes, preservatives, disinfectants, complexing agents, thickeners, humectants, disintegrants, Foam stabilizers and lime or urine-solubilizing substances and mixtures thereof is selected.
  • the proportion of component C will generally not exceed 30% by weight, often 25% by weight and especially 20% by weight, based on the total weight of the hydrogel, and is typically in the range of 0.1 if desired to 30% by weight and in particular in the range of 1 to 20 wt .-%.
  • the type of component C depends in a conventional manner according to the desired application.
  • the hydrogel contains at least one perfume.
  • Suitable fragrances contained in the hydrogels according to the invention may include synthetic fragrances, semi-synthetic fragrance blends and natural perfume oils.
  • synthetic fragrances are the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • the natural fragrances include in particular those perfume oils that are accessible from vegetable sources. Preference is given to using mixtures of different fragrances which together produce an attractive fragrance.
  • the hydrogel according to the invention comprises at least one surfactant.
  • Suitable surfactants are typically selected from anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof.
  • the hydrogels of the invention preferably contain surfactants in amounts of 0.01 to 30 wt .-%, based on the total weight of the hydrogel.
  • the hydrogels according to the invention may furthermore contain one or more antimicrobial active substances, which as a rule can also act as preservatives.
  • the hydrogels of the invention may further contain lime or urine-solubilizing substances. These include in particular water-soluble builders and their mixtures with acids.
  • the hydrogels of the invention may also contain one or more conventional thickening agents.
  • conventional thickening agents for this purpose, in principle, all viscosity regulators used in detergents and cleaners in the prior art come into consideration.
  • the hydrogel does not contain a conventional thickener.
  • the hydrogels according to the invention are largely dimensionally stable even at relatively high shear stresses, ie their deformability at 30 ° C. and a shear stress of 10 2 Pa is typically less than 5% and in particular less than 1%, determined at 30 ° C. with a shear stress-controlled rotational viscometer with conical Plate geometry and a shear stress range of 10 2 to 10 4 Pa.
  • the yield point as the limit of the elastic deformation range is at 30 ° C usually at a shear stress of at least 10 3 Pa, z. In the range of 10 3 to 10 6 Pa.
  • the hydrogels of the invention typically have a viscosity in the range of 10 5 to 10 10 Pa ⁇ s, often in the range of 10 5 to 10 8 Pa ⁇ s, determined at 30 ° C. with a shear stress-controlled rotational viscometer with cone-plate geometry in the shear stress range of 102 to 10 4 Pa.
  • the hydrogels according to the invention have a good adhesion to polar surfaces, in particular inorganic surfaces such as glass or ceramic, and are not rinsed off immediately upon exposure to water, but rather dissolve without leaving any residue after prolonged and frequently repeated exposure to water. They can also be formulated with fragrances or other substances that promote the cleaning or disinfection of sanitary ceramics, without disadvantages.
  • the invention therefore also relates to the use of a hydrogel as described herein for homecare products, in particular for the preparation of fragrance-releasing compositions, for.
  • perfumes dispensing pastes or for the production of cleaning and care compositions for the sanitary sector especially for pastes for application in toilets and bidets, as in WO 99/66021 .
  • the hydrogels according to the invention can be prepared in a simple manner by reacting at least one ester of polyisobutenesuccinic acid with an alcohol selected from poly-C 2 -C 4 -alkylene glycols and poly-C 2 -C 4 -alkylene glycol mono-C 2 -C 20 -alkyl ethers, as described herein, optionally incorporated with a part or all of the components of component C in an aqueous liquid, which, if desired, in addition to water may already contain a part or the total amount of the components of component C.
  • the incorporation can be carried out by simply mixing water or an aqueous liquid which, in addition to water, contains a part or the total amount of the constituents of component C which may be desired.
  • a solution of component A which optionally contains part or all of the constituents of component C which may be desired, into water or an aqueous liquid and then remove the solvent.
  • the incorporation of the component A and optionally further constituents in water or the aqueous liquid is usually carried out at temperatures in the range of 10 to 100 ° C.
  • the use of mixing devices may be beneficial, but is not usually required.
  • the saponification number VZ was determined analogously to DIN 53401: 1998-06
  • the acid number SZ was determined by titration of the polyisobutene succinic acid ester in a mixture of toluene and ethanol.
  • the SZ indicates the number of mg of potassium hydroxide consumed to neutralize 1 g of the sample.
  • the surface tension OFS was measured by the ring method in analogy to DIN 53914: 1980-03.
  • the OFS is defined as the force in the surface per unit length and has the dimension mN / m (10 -3 Newton / meter).
  • sample 11 The maximum water absorbency of sample 11 was tested both with deionized water (deionized water) and with non-deionized water (Jayco's solution) both at room temperature and at 4 ° C.
  • sample 11 For this purpose, about 3 g of sample were placed in a Petri dish and melted at 80 ° C in a heating oven. After the sample had cooled back to room temperature, either deionized water or Jayco solution was added, setting a sample to water ratio of 1: 9. Subsequently, the swelling behavior of sample 11 was determined gravimetrically.
  • the Jayco solution contained the following salt concentrations: 2 g / L potassium chloride, 2 g / L sodium sulfate, 0.85 g / L ammonium dihydrogen phosphate, 0.15 g / L di-ammonium hydrogen phosphate, 0.5 g / l magnesium chloride hexahydrate, 0.25 g / l calcium chloride dihydrate.
  • Table 2 The maximum water absorption capacity of the polyisobutene succinic acid ester from Preparation Example 11 is shown in Table 2 below: Table 2: Water absorbency of Preparation Example 11 Solvent temperature [° C] VE water Jayco solution 22 4 22 4 Water absorption [% by weight] 2) 81 110 130 103 2) average, based on the initial weight of the copolymer used.
  • Example 21 In analogy to the general preparation instructions, the gel of Example 21 was prepared from the polyisobutene succinic ester of Preparation Example 11 prepared by dilution with water / surfactant. The hydrogel was then viscometrically assayed. The results for Example 21 are shown in Figures 4 and 6.
  • Table 3 example Polyisobutene succinate 3) Water [% by weight] 4) Surfactant [% by weight] 4) SZ [mgKOH / g] 1 2 80 0 7.5 2 3 60 0 9.5 3 4 66.6 0 5.0 4 5 66.6 0 3.6 5 6 66.6 0 8.8 6 7 40 0 7 7 50 0 8th 7 60 0 9 7 70 0 10 8th 40 0 11 8th 50 0 12 8th 60 0 13 8th 70 0 14 8th 14 6 15 8th 24 6 16 8th 34 6 17 8th 44 6 18 10 36 0 19 10 34 6 20 11 14 6 21 11 44 6 22 11 54 6 23 12 44 6 24 13 50 0 25 6 30 10 5) 3) Number of the production example 4) based on the hydrogel 5) Mixture of 9 parts by weight of the nonionic surfactant with 1 part by weight of a conventional perfume oil

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EP12700637.7A 2011-01-11 2012-01-10 Hydrogele auf basis von estern der polyisobutenbernsteinsäure Not-in-force EP2663627B1 (de)

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DE102011004771A1 (de) 2011-02-25 2012-08-30 Henkel Ag & Co. Kgaa WC-Gel
DE102012215615A1 (de) 2012-04-04 2013-10-10 Henkel Ag & Co. Kgaa Streifenförmiges WC-Reinigungsprodukt
US20140274847A1 (en) * 2013-03-15 2014-09-18 Cytec Industries Inc. Corrosion inhibitors and methods of using same
CN107614264B (zh) 2014-12-05 2020-02-04 佛罗里达大学研究基金会有限公司 使用相变材料作为支撑体的3d打印
WO2016130953A1 (en) 2015-02-13 2016-08-18 University Of Florida Research Foundation, Inc. High speed 3d printing system for wound and tissue replacement
US11390835B2 (en) 2015-05-08 2022-07-19 University Of Florida Research Foundation, Inc. Growth media for three-dimensional cell culture
US11027483B2 (en) 2015-09-03 2021-06-08 University Of Florida Research Foundation, Inc. Valve incorporating temporary phase change material
WO2017096263A1 (en) 2015-12-04 2017-06-08 University Of Florida Research Foundation, Incorporated Crosslinkable or functionalizable polymers for 3d printing of soft materials
US11124644B2 (en) 2016-09-01 2021-09-21 University Of Florida Research Foundation, Inc. Organic microgel system for 3D printing of silicone structures
US10877693B2 (en) 2018-06-29 2020-12-29 Intel Corporation Architecture for dynamic transformation of memory configuration

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2702604C2 (de) 1977-01-22 1984-08-30 Basf Ag, 6700 Ludwigshafen Polyisobutene
DE4319672A1 (de) 1993-06-14 1994-12-15 Basf Ag Verfahren zur Herstellung von Polyisobutylbernsteinsäureanhydriden
DE4319671A1 (de) 1993-06-14 1994-12-15 Basf Ag Verfahren zur Herstellung von Polyisobutylbernsteinsäureanhydriden
DE19519042A1 (de) 1995-05-24 1996-11-28 Basf Ag Herstellung von Polyalkenylbernsteinsäure-Derivaten und ihre Verwendung als Kraft- und Schmierstoffadditive
KR19990077187A (ko) * 1996-02-23 1999-10-25 데이비드 엠 모이어 소독 조성물
DE19826293A1 (de) 1998-06-12 2000-03-23 Buck Chemie Gmbh Sanitärmittel
US6555619B1 (en) 2000-06-29 2003-04-29 The University Of Akron Physically crosslinked amphiphilic networks, methods of preparation, and uses thereof
DE10048887A1 (de) 2000-09-29 2002-04-18 Buck Chemie Gmbh Haftendes Sanitärreinigungs- und Beduftungsmittel
DE10125158A1 (de) 2001-05-22 2002-12-05 Basf Ag Nieder-und hochmolekulare Emulgatoren, insbesondere auf Bassis von Polyisobutylen, sowie deren Mischungen
DE10159984A1 (de) 2001-12-06 2003-06-26 Buck Chemie Gmbh Haftende Paste zur Duftstoffabgabe, insbesondere für den Sanitärbereich
EP1913078A1 (de) 2005-08-04 2008-04-23 Basf Se Wässrige dispersionen und ihre verwendung
CN101233187A (zh) * 2005-08-04 2008-07-30 巴斯福股份公司 水分散体及其用途

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* Cited by examiner, † Cited by third party
Title
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CA2822487A1 (en) 2012-07-19
JP2014504665A (ja) 2014-02-24
MX2013008046A (es) 2013-08-29
CN103347993A (zh) 2013-10-09
RU2587157C2 (ru) 2016-06-20
WO2012095404A1 (de) 2012-07-19
RU2013137337A (ru) 2015-02-20
JP6050250B2 (ja) 2016-12-21
KR20140001980A (ko) 2014-01-07
BR112013017101A2 (pt) 2019-01-15
CN103347993B (zh) 2016-10-19

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