CH633304A5 - Polymer-containing composition, process for the preparation thereof, and use thereof - Google Patents

Description

The present invention relates to a polymer-containing composition which contains a polymer with hydrophilic properties and at least one volatile or volatile active ingredient. The volatile or volatilizable active ingredient present in the polymer-containing composition can be, for example, an aromatic oil and / or an insecticide.

Furthermore, the present invention relates to a process for the preparation of the polymer-containing composition and the use of the polymer-containing composition for the production of moldings,

which release the volatile or volatilizable active ingredients.

With the aid of the polymer-containing compositions according to the invention, a controllable release of the active components into a medium can be achieved, in which they then develop their desired effectiveness. In particular, the present invention relates to the use of synthetic hydroxyl-containing polymers as carrier materials for active ingredient components.

Synthetic hydrophilic polymers are known which contain polymerized hydroxyalkyl esters of vinylically unsaturated carboxylic acids, these polymers being able to absorb water.

It has been suggested that a variety of active ingredient components can be included in such hydrophilic polymers and then released into a medium in which they are desired to exert their exploitable effects. Such systems can be used to introduce the active ingredients into aqueous media which tend to cause the polymer to swell and thereby facilitate the release of the active ingredient. It has also been proposed to make the polymer water soluble. Until now, however, the controlled and determined release of active ingredient components to other media, such as, for example, evaporation into the atmosphere, was practically not feasible according to this method, because the active components which were enclosed inside a polymer body in the absence of added water or solvent could not migrate to the surface to be released there.

It has now been found that a multiplicity of active constituents can be introduced into a synthetic hydrophilic resin and can then be gradually released therefrom, for example by evaporation or volatilization at a rate which can be determined to a substantial extent in advance if an appropriate solubility enhancement agent is also present.

The present invention is defined in the independent claims.

As used herein, the term "solubility enhancer" or "solution enhancer" means a generally organic cationic or nonionic compound with both hydrophilic and lipophilic properties associated with the polymer

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is inert or soluble in it and which is more compatible (e.g. more miscible with, more soluble in or a better solvent for) with the active ingredient or one of its components than the polymer. Typically, the solubility enhancer is a nonionic or cationic surfactant or a hydrotropic compound.

The hydroxyl-containing polymers which can be used in the practice of the present invention are preferably polymers of vinyl-unsaturated carboxylic acid esters which have hydrophilic functions such as, for example, alkoxy or preferably hydroxy groups. Typical monomers are hydroxyethyl acrylate or preferably hydroxyethyl methacrylate and the hydroxypropyl, hydroxybutyl and glycerol esters of acrylic acid or methacrylic acid. Polyoxyalkylated derivatives of the above-mentioned monomers can also be used, such as, for example, polyoxyethylene acrylic acid esters or polyoxypropylene glycerol monomethacrylic acid esters. The number of oxyalkylene groups is usually up to 20, although higher amounts of alkoxylate are also effective and can be preferred for certain specialized forms of use. Glycidyl esters of unsaturated fatty acids can also be used as monomers. Esters of maleic acid and fumaric acid are less preferred.

In addition, the monomer mixture preferably contains mono- or polyunsaturated monomer components which carry 2 or more vinyl functions. For example, the diacrylic acid esters and dimethacrylic acid esters of ethylene glycol or of 1,3-butylene glycol or of 1,6-hexanediol are bifunctional constituents and can be used by the process according to the invention, but they have no free hydrophilic functions and are accordingly less preferred than glycerol or Trimethylolpropane diacrylic acid ester and dimethylacrylic acid ester, which also have two vinyl functions, or hydroxy esters of divinyl carboxylic acid, such as butadiene dicarboxylic acid. Trifunctional groups are, for example, glycerol or trimethylolpropane triacrylic acid esters and preferably pentaerythritol triacrylic acid esters, which is particularly valuable as a crosslinking agent. Polyunsaturated monomers which have more than three vinyl groups, such as, for example, compounds with 4 functional groups, such as, for example, pentaerythritol tetra-acrylic acid ester, can be used if very high strength is to be achieved. Alkoxylated derivatives of hydroxy-containing polyfunctional monomers and glycidyl esters are also suitable.

The polymer can optionally also contain a certain proportion of monomers without hydroxyl functions, such as, for example, ethyl methacrylic acid ester or isobutyl acrylic acid ester. It may also, but less preferably, contain small amounts of other vinylic monomers such as vinyl alcohol, vinyl chloride and styrene. In general, however, such monomers tend to require excessively high temperatures to initiate the polymerization, so that they are no longer suitable for use in the process according to the invention. However, the polymer preferably contains at least 50 mol% of hydroxyl groups or, less preferably, equivalent amounts of hydrophilic functional groups, based on the monomer and particularly preferably at least 90 mol%. In the context of the present description it can be assumed that a hydroxyl group is equivalent to 4 oxyethylene groups or 6 oxypropylene groups with regard to the hydrophilic functionality. The hydrophilic functionality can, to a certain extent, depend on the particular633304

related active ingredient, with less hydrophilic (i.e. less polar) polymers being preferred when more lipophilic (i.e. less polar) active ingredients are present, thereby ensuring greater tolerance.

The level of additional vinylic unsaturation due to the presence of polyunsaturated monomers in the monomer mixture determines the degree of crosslinking of the polymer contemplated by the present invention, and it may vary according to the texture of the polymer and the rate of release of the active agent that is required. to get voted. The more the polymer is cross-linked, the smaller the mobility of the active ingredient, and accordingly the release rate is slower. In contrast, the polymer is softer at low crosslinking and the rate of release for the active ingredient is greater. In general, the polymers produced by the process according to the invention and contained in the composition have up to 20% crosslinking, based on the number of monomer units (i.e. a total of 6 vinyl groups per 5 mol of monomer in the polymerization mixture). The polymers have no crosslinking when a very soft resin is desired. The proportion of crosslinking is preferably in the range up to 10%. Crosslinking is achieved by using polyunsaturated monomers. For example, one bifunctional monomer unit per 4 monofunctional units gives a degree of crosslinking of 20%.

The solubility enhancers are any compounds that have both hydrophilic and lipophilic characteristics. These compounds must be compatible with the polymer in the sense that they have a solubility of at least 5% by weight based on the weight of the polymer therein, and they must be more compatible with the active ingredient or one of its components than with the polymer. The solubility-reducing agents preferably have a molecular weight of less than 1200 and in particular less than 1000.

The solubility facilitating agent can be a surfactant, preferably a non-ionic surfactant such as a polyalkylene oxide, e.g. polyethylene oxide or polypropylene oxide with 2-25 oxyalkylene units or a polyoxyalkylene condensate with a fatty acid alcohol or an alkylphenol or with a glycerol or sorbitol ester or Polyoxylalkylene esters of a fatty acid. Typical examples are polyoxyethylene stearic acid esters, polyoxypropylene sorbitol monolauric acid esters, polyoxyethylene glycerol mono-oleic acid esters and nonylphenoxypolyethoxyethanol. Glycerol and sorbitol fatty acid esters themselves are similarly effective as other commonly used non-ionic surfactants, such as alkylolamines such as monoethanolamine or dipropanolamine. Sometimes it is convenient to use low molecular weights, namely nonionic hydrotropes such as hydroxyethyl acetic ester, methyl hydroxyethyl ketone, methyl hydroxyethyl ether or propanediol. The solubility-promoting agent preferably has at least one hydroxyl group and at least one alkyl group which preferably contains 3 to and with 18, and in particular 3 to and with 10 carbon atoms. The solubility-improving agent can additionally, for example, ether, keto, ester, amide,

Contain amine, aryl and / or cycloaliphatic groups. For most purposes, it is preferred that the solubility enhancer be sufficiently non-volatile so that it does not substantially dissolve out of the polymer

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evaporates or evaporates. However, it has been found that for certain specialized applications it can be advantageous to use solubility-promoting agents which contain volatile substances. It is often convenient to use a mixture of agents that support solubility and in particular mixtures of agents that support solubility that have significantly different HLB values.

The selection of the optimal agents that support solubility depends on the nature of the active ingredient as well as the hydrophilic and other properties of the resin. For example, the solubility enhancing agent can be selected according to its HLB value so that it is compatible with both the active ingredient and the polymer. Accordingly, for highly lipophilic active ingredients, a more lipophilic agent to aid solubility is favorably used, and preferably the polymer is given a more lipophilic character by reducing the proportion of hydroxyl groups or by using a mixture of relatively lipophilic and relatively hydrophilic agents applied to facilitate solubility.

Although nonionic solubility enhancers are highly preferred, it is sometimes possible or even advantageous to use cationic surfactants or hydrotropes at least in part as components of the solubilizer, such as quaternary ammonium salts or imidazolines.

The proportion of the solubility facilitating agent is preferably selected in the range of 4-200% based on the amount of monomers used to make the polymer, depending on the requirements of the system including the relative compatibility of the active agent and the polymer , the amount of active agent to be incorporated, the desired strength of the polymer and the rate of release for the active ingredient. Larger amounts of the solubility enhancer tend to soften the polymer, increase the capacity for the active agent and increase the rate of release and facilitate the production of a clear resin.

The active ingredient can be any volatile or volatilizable substance which is intended to escape from the polymer into the surrounding atmosphere in order to have a desired effect there. The present invention is particularly applicable to flavors, including natural and concentrated oils and synthetic fragrances, and mixtures thereof. Typical examples of odorant compositions which can be used as such or usually as parts of the active ingredient are, for example, derivatives of 2,6-dimethyl-2-alkoxy-octan-7-ol (described in British Patent No. 1414458 des present patent proprietor) Vetivertöl, vetiverol, Vetiveryl-essigsäureester, guaiac wood oil, guaiac essigsäureester, coumarin, musk ketone, lauric aldehyde, benzyl acetate, lemon oil, dimethylbenzylcarbinol, Dimethylbenzylcarbinyl-essigsäureester, Rosenabsolutex tract, jasmine absolute, Ionone, Iso-nonyl acetate, Me-thylphenylacetat , Styrallyl acetate, B-phenylethanol, citronellal, citronellol, hydroxyzitronellal, geranium oil, geraniol, linaloi, nerol, lavender oil, linalyl acetate, patchouli oil, petitgrain oil, bergamot oil, heliotropin, brassylic acid ethylaldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, and zec aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, undecyl aldehyde, and zec aldehyde, , Cinnamon alcohol, clove germ oil, bay oil or laurel oil, nutmeg oil, clove pepper fruit oil or allspice oil, Terpi-neol, ylang oil, benzoic acid benzyl ester, sandalwood oil, oil of a certain type of sage (clary sage oil), salicylic acid amyl ester, ladan resin, methyl ionone, dihydromyrcenol, orange oil, vanillin, ethyl vanillin, frankincense resin or oli-ban oil, amerbello moss, rhodinol musk , Mandarin oil, methyl nonyl acetaldehyde, neroli oil or bitter orange blossom oil, cedrol or cedar camphor, acetylcedrene, oak moss, isovalanon, eugenol, iso-eugenol, cedarwood oil, p-tert.-butyl-cyclohexyl acetate, amyl cinnamon aldehyde and hexylzime. Typically, at least 5 of the above and usually at least 10 of the above and / or other perfume ingredients and compositions are used in the active ingredients provided according to the invention.

Alternatively or in addition, the active ingredient may contain a volatile insecticide and / or a synergistically active insecticide such as pyrethrum or a bacteriostat or a pheromone or an active agent which is volatilized on heating, such as volatilizable fiber softeners of the type which can be volatilized if the resin is heated in a clothes dryer, for example, whereby the fabrics obtained therein are softened.

The level of active ingredient can range from the minimally effective concentration, which depends on the active ingredient used, to the maximum amount that can actually be introduced, depending on how the active agent with the polymer and the species and is compatible with the amount of the solvent-promoting agent. It has been found that up to 200% of certain active constituents, based on the weight of the polymer, can be introduced by the process according to the invention. Other active ingredients can give suitable results when there are levels down to 100 ppm or less. Typically, however, the proportion of the active ingredient is between about 2.5% and 100%, based on the weight of the polymer, and for example 5-50%.

The composition according to the invention optionally contains water. The presence of at least some water is generally desirable as a support for the catalyst system in the preparation of the polymer. However, it has been found that with certain catalysts it is possible to produce essentially anhydrous polymers. The presence of water generally accelerates the volatilization of the active ingredient by entrainment during evaporation or evaporation, and therefore it is often desirable for the water to be available up to the maximum absorption capacity of the system, which in practice is usually about 50% by weight .-% of the polymer. Typically the water content is between about 1 and about 40% by weight of the polymer.

The compositions according to the invention can optionally contain additional constituents which are relatively non-volatile, such as dyes and pigments. The compositions according to the invention usually contain residues of the polymerization catalysts and their decomposition products.

The novel polymers contained in the compositions are produced by the process according to the invention simply by mixing the monomer, the solution-promoting agent and the active constituents with one another and with the water which may be required, and preferably adding a polymerization catalyst. In some cases it is possible to polymerize the mixture without the addition of a catalyst, for example by heating or allowing the mixture to stand for a sufficiently long time, but for most practical purposes it is advisable to add a catalyst4

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give. A major problem that arises here once the volatile active ingredients have been added to the polymer in the polymerization step is that elevated temperatures are usually necessary to allow the polymerization to proceed in an economically acceptable time. Together with the heat released during the exothermic polymerization reaction, this can lead to premature volatilization of active ingredients or to the partial decomposition of heat-sensitive material. A catalyst system is therefore provided which is effective at low temperatures and which, in some preferred cases, works satisfactorily at room temperature or below. The reaction can be catalyzed by free radical swelling, or preferably by oxidizing or reducing agents, and most preferably by mixtures of both, i.e. through redox catalysts. In general, it is preferred to use organic oxidizing agents and in particular organic peroxides such as, for example, benzoyl peroxide, 2,5-dimethyl-2,5-bis (2-ethyl-hexanoyl-peroxy) hexane, hexanoyl peroxide or isobutyl peroctoate. Inorganic peroxide compounds such as potassium or ammonium persulfates can also be used, but are less preferred because inorganic residues are formed in the polymer. However, a particularly preferred oxidizing agent is an inorganic oxidizing agent, namely hydrogen peroxide, which is reduced to water.

The oxidizing agent is preferably used together with a reducing agent such as sodium thiosulfate or, preferably, an organic reducing agent such as ascorbic acid or iso-vitamin C (Araboas-corbic acid, erythorbic acid). The latter two are particularly effective and their use as polymerization catalysts, preferably together with an oxidizing agent, in particular a persulfate or particularly preferably together with hydrogen peroxide, forms an important embodiment of the present invention.

Mixtures of ascorbic acid and hydrogen peroxide initiate the polymerization quickly at room temperature, which prevents the polymer from overheating. The catalysts can be supported by the presence of certain monomer units which react particularly easily and thus act as secondary initiators, such as, for example, pentaerythritol triacrylate. Cocatalysts such as amines or salts of transition metals such as cobalt, iron, nickel and manganese are also valuable.

The proportions of the polymerization catalysts are not critical, but higher proportions result in shorter average chain lengths. For practical purposes, it is usually not suitable to add more than about 5% by weight of catalyst, based on the total weight of the mixture, and preferably about 0.1 to about 2.5% by weight.

The polymerization is preferably carried out under an inert gas atmosphere, for example under carbon dioxide or nitrogen or under airtight cover films, in order to suppress the prevention of the polymerization on the surface by oxygen. The polymerization mixture is preferably kept neutral or slightly acidic with water, and it may be advantageous to add small amounts of a strong mineral acid, especially in cases where ascorbic acid and hydrogen peroxide are used as the catalyst system. For example, a few drops of a strong mineral acid, which does not adversely affect the active ingredient or the polymer, can be added to the polymerization mixture, and usually the suitable acid is hydrochloric acid.

In particular, the present invention provides a high degree of flexibility in the selection of the active ingredient, in the charge density, in the rate of release and in the physical nature and appearance of the composition. This is of particular importance in the case of volatile active constituents which can have a strongly lipophilic to relatively hydrophilic character and which, in particular in the case of flavors, are complex mixtures of compounds whose affinities vary widely in the range mentioned above. The solution-promoting agent increases the compatibility of the active ingredient with the polymer and allows at least a substantial part of the active agent to be present in the composition in the form of a solution. This increases the capacity of the polymer to take up the active ingredient and enables the latter to migrate to the surface of the polymer. In addition, the solution-supporting agent tends to loosen the structure of the polymer and thereby further increase the mobility of the active ingredient therein, thereby obtaining a softer composition. The increased mobility helps to increase the rate at which the active agent is released from the composition.

If a high loading of the polymer with active ingredients is desired without the composition being softened too much, the effect of the solvent on the hardness of the composition can be compensated for by increasing the amount of polyfunctional monomers. A high water content favors the rapid volatilization of the active ingredient due to entrainment, and lower water levels and / or solvent aid levels can be used for lower release rates.

A particular advantage of the present invention is that it becomes possible to obtain effective amounts of the active ingredient, essentially completely dissolved in the polymer, whereby a clear, transparent composition can be obtained, which has a wider range of uses for decorative shapes.

The water content in the composition influences its dimensional stability. If the water content is high, the composition may shrink as the water evaporates. Low water contents result in better form and dimensionally stable compositions.

The present invention is particularly suitable for the production of a large range of perfumed moldings, such as, for example, fragrance balls, air fresheners, artificial flowers and the like. Shaped bodies of this type can alternatively or additionally also be used as fly killers, insect repellants and / or attractants, in each case by using insecticides, insect repellants and / or pheromones as or as part of the active constituents. It is possible to use the polymers to deliver pharmaceutically active volatile components at an adjustable rate.

Alternatively, the polymers can be used to give synthetic imitations of natural materials an improved resemblance to natural substances such as wood, leather, fabrics, leaves, flowers or baits in fishing by applying an authentic flavor to them.

The polymers can be allowed to harden in molds, which can give them a variety of artificial decorative shapes, such as figurative or similar ornamental designs.

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The polymers can be subject to visible changes, for example when indicators are incorporated which change color, for example if the water content drops below a certain value, or biphilic strips can be produced from polymers with different water contents which change their shape as a result of different shrinkage. The former effect is applicable, for example, to indicate the degree of depletion of active ingredient, while the latter effect can be used, for example, to produce flowers whose petals open when left standing.

In some cases, it may be possible to reload the polymer with the active ingredient after it is depleted of release by letting it reabsorb the active ingredient. The rate of release for the active component can also be adjusted by replenishing the water content of the resin.

It is also possible to incorporate moisturizers (such as glycerin) or hygroscopic salts (such as calcium chloride) into the system, thereby reducing the composition in the event that the water content drops below a critical point in a low humidity environment then can absorb moisture from the environment when the relative humidity becomes higher again, thereby providing a renewed aid for the release of the active ingredient. Such a property is particularly valuable in rooms such as bathrooms, for example, which have wide fluctuations in terms of moisture. In addition, in those cases where it is desired that the product exhibit a significant physical change (e.g., shrinkage) that occurs along with the active ingredient release, a low molecular weight solvent that coexists with the active ingredient can be used and the water evaporates or volatilizes during use.

The invention will now be explained in more detail using the following examples:

example 1

Self-adhesive disc

81.4 mg of ascorbic acid were mixed with 12.5 ml of hydroxyethyl methacrylate, 9.8 ml of polyethylene glycol (molecular weight 400) and 1.5 ml of rose oil concentrate. 0.125 g of potassium persulfate was separately dissolved in 6 ml of water, and then the two solutions were quickly mixed together. The liquid was poured into a cylindrical dish to a layer height of 6.35 mm (Vi inches) and placed in a vacuum chamber at a pressure of 177.8 torr. (7 inch Hg) at a temperature of 25 ° C. After 30 minutes the polymerized disc, which contained 5% rose oil, was removed. It was clear, colorless and had a sticky surface.

Example 2

Non-stick disc

40.7 mg of isovitamin C (erythorbic acid) were mixed with 12.5 ml of hydroxypropyl methacrylic acid ester, 9.8 ml of polyethylene glycol (molecular weight 400) and 7.1 ml of rose oil in an ice bath. 62.5 mg of potassium persulfate was separately dissolved in 6 ml of water and cooled in an ice bath. The two solutions were then mixed.

A cylindrical bowl was pre-cooled to 0 ° C and the liquid mixture was poured to a layer thickness of 6.35 mm (QA inch). The plate was then left in an ice bath under a carbon dioxide atmosphere,

and after an hour the polymeric material was removed to give a non-sticky disc containing 20% rose oil.

Example 3

Self-adhesive disc

40.7 mg of d-araboascorbic acid (isovitamin C) were mixed with 9.8 ml of polyethylene glycol (molecular weight 600), 6.2 ml of hydroxyethyl methacrylic acid ester, 6.2 ml of glycidyl methacrylic acid ester and 3.1 ml of the mixed flower aroma oil mixed and chilled in an ice bath. A pre-cooled solution of 62.5 mg potassium persulfate in 6.0 ml water was added and the mixture was poured into pre-cooled cylindrical vessels to a layer thickness of 3.18 mm (1/2 inch). The tubes were placed in an ice bath under a low-oxygen, nitrogen-enriched atmosphere and allowed to cure for 45 minutes. The plates so obtained were clear, sticky and contained 10% of the aromatic oil.

Example 4

Self-adhesive sheet

0.107 g ascorbic acid, 12 ml water, 25 ml hydroxyethyl methacrylic acid ester, 19.6 ml polyethylene glycol (molecular weight 400) and 0.25 ml polymerization initiator, namely 2,5-dimethyl-2,5-bis (2-ethylhexanol peroxy) - hexane were mixed and heated to 50 ° C with stirring until the mixture began to thicken. Then 6.3 ml of spruce oil or pine oil was stirred in, and the mixture was poured into a rectangular mold to a layer thickness of 6.35 mm ('A inch), and the vessel was left in a carbon dioxide atmosphere at room temperature for curing. After one hour, the cured sheet containing 10% pine or pine oil was removed and placed between two pieces of releasable paper.

Example 5

Self-adhesive strip

0.43 g of isovitamin C (erythorbic acid), 100 ml of water, 100 ml of hydroxypropyl methacrylic acid ester, 78.5 ml of polyethylene glycol (molecular weight 400), 10 ml of distilled peppermint oil and 1 ml of ultraviolet catalyst "Trigonal 14" were placed in a rectangular container to a height of 6.35 mm (! A inch), and irradiated with long-wave, ultraviolet light at room temperature in a low-oxygen, nitrogen-enriched atmosphere. After 4 hours, the sheet containing 3.5% flavor was removed, cut into 25.4 mm (1 inch) wide strips and between 2.54 mm wide (1 inch) and 25.4 ix (1 mil) thick Polyethylene strips inserted, and you rolled up on a self-adhesive tape dispenser.

Example 6

The procedure of Example 2 was repeated using 7.1 ml of lemon oil instead of rose oil. The product was a non-sticky disc which was applicable as an insect repellant.

Example 7

Cast molded body in the form of a duck

80 ml of hydroxyethyl methacrylic acid ester, 80 ml of nonylphe-noxy-polyethoxyethanol (HLB value 8.8), 5 ml of ethylene glycol dimethacrylic acid ester and 10 ml of cinnamaldehyde were mixed with 418 mg of ascorbic acid dissolved in 5 ml of water and stirred 320 mg of ammonium persulfate dissolved in 15 ml of water. A drop of brown aqueous paint was added and the mixture was split into a two-part mold for making a plastic

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duck filled. The bottom was closed with an air-impermeable plastic sheet and hardened for 30 minutes. The transparent, colored product contained 5% dissolved flavor.

Example 8

The procedure of Example 2 was repeated by adding 0.25 ml of ethylene glycol dimethacrylic acid ester to the hydroxypropyl methacrylic acid ester monomer. This product showed a stiffer texture and a lower release rate than the product from Example 2 because more crosslinking had been introduced.

Example 9 Colored, glassy shaped body

58.6 g of hydroxypropyl methacrylate, 26.1 g of alkylphenoxy polyethoxyethanol (HLB value 14), 3.4 g of pentaerythritol triacrylate, 10 g of strawberry aroma oil and a drop of an oil-soluble, red dye were mixed with 1.3 g of a warm solution of ascorbic acid in water (50:50) was added, then 0.3 g of 35 percent hydrogen peroxide was added and finally 0.2 g of concentrated hydrochloric acid was added and poured into a 4.763 mm (vie inch) heatable Mold, which contained a shaping metal frame in the form of a strawberry, and the mold was covered with an air-impermeable sheet made of plastic and cured for 5 minutes. The cured product, which contained less than 1% moisture, was a hanging red molded body with a metal frame, which had the appearance and aroma of a strawberry. During use over a period of several months, during which the content of 10% of the aromatic oil slowly evaporated, the product showed no cracking and no detectable shrinkage of the polymer material and no lifting off from the metal frame, as with a product which has a significantly higher water content (about 5%) would occur.

Example 10 Polymer material with display effect 24 ml of hydroxypropyl methacrylate, 7 ml of nonylphenoxy-polyethoxyethanol (HLB value 12.5), 3 ml of pentaerythritol tri-acrylate, 5.8 ml of rose aroma oil, 1 ml of a 14 percent aqueous solution of cobalt chloride Hexahydrate, 13 ml water and 2.5 ml 23 percent aqueous solution of ascorbic acid were quickly mixed in 1.3 ml 3 percent hydrogen peroxide solution and 0.1 ml concentrated hydrogen chloride solution and poured into a petri dish, which was placed in a Chamber with nitrogen atmosphere was introduced. The pink product thus obtained contained 10% flavor and 30% water. When water and aroma were evaporated together for a certain period of time, during which the levels of aroma and water reached the point of exhaustion (at about 5% water content), the pane turned bright blue (due to the drainage of the cobalt salt).

Example 11 Moldings in Cherry Shape

264 ml of hydroxyethyl methacrylate, 168 ml of a polyoxyethylene (10) polyarylphenol, 6 ml of ethylene glycol dimethacrylate and 6 ml of cherry aroma oil were mixed together. To this mixture was added a solution of 1.1 g of isovitamin C (erythorbic acid) in 24 ml of water, and then 0.85 g of ammonium persulfate in 120 ml of water containing a red dye was added, and the mixture was quickly made into spherical glass molds

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(about 40 ml capacity) poured. 25.4 mm (1 inch) long plastic rods (stems) were immersed half-deep in each solution. The molds were placed in an oxygen-free carbon dioxide atmosphere and cured for 30 minutes. The clear, cherry-shaped moldings contained 10% cherry aroma and 22%

Water.

Example 12 Star made of two-layer material 12.5 ml of hydroxyethyl methacrylic acid ester, 9.8 ml of nonyl-phenoxy-polyethoxyethanol (HLB value 13.0), 0.25 ml of pentaerythritol tetraacrylate and 14.8 ml of aromatic oil from the German honeysuckle were mixed with 0.13 g of ascorbic acid dissolved in 2 ml of water, then 0.6 g of ammonium persulfate dissolved in 10.0 ml of water was stirred in and a drop of aqueous green paint was added. A star-shaped mold was half-filled with the mixture and left to cure in the uncovered state for 20 minutes. The following mixture was then poured on: 12.5 ml of hydroxyethyl methacrylate, 9.8 ml of nonylphenoxy-polyethoxyethanol (HLB value 13.0), 0.13 ml of ethylene glycol dimethacrylate, 14.8 ml of oil from the German Honeysuckle, 0.13 g ascorbic acid in 2 ml water, 0.10 g ammonium persulfate in 20 ml water and a drop of watery green color. The mixture was then covered with polyvinylidene chloride and hardened. The resulting two-layer star was removed and the star tips slowly rotated during the time during which the aromatic oil and the water slowly evaporated to varying degrees over a period of several weeks from the two layers. (One side of the star contained 30% aroma oil and 24% water, while the other side contained 25% oil and 37% water.)

Example 13

Shrinking disc

25 ml of hydroxyethyl methacrylate, 9.8 ml of 2-methoxyethanol, 8.4 ml of propylene glycol, 7.6 ml of 2-hydroxyethyl acetic acid ester, 0.25 ml of ethylene glycol dimethacrylate and 19 ml of rose oil aroma were mixed together. A solution of 0.13 g of ascorbic acid in 1 ml of water and then 0.1 g of ammonium persulfate in 2 ml of water were stirred in and the mixture was poured into a dish and covered with an air-impermeable polyvinylidene chloride film for one hour. The disc contained 25% aromatic oil and a total of 42% volatile components of aromatic oil and carrier materials (including water), which evaporated at different speeds. The three organic carrier materials showed lipophilic and hydrophilic functional groups. After all volatile components had completely evaporated, the pane shrank to a third of its original size.

Example 14 Flavoring bath sponge 10 ml hydroxypropyl methacrylate, 5 ml nonylphenoxy polyethoxyethanol (HLB value 8.8), 0.25 ml pentaerythritol triacrylate, 2.4 ml aromatic oil of the German honeysuckle, 5 ml myristilic acid isopropyl ester and 9 ml 23 percent aqueous ascorbic acid was mixed with 0.1 ml 35 percent hydrogen peroxide and 0.5 ml concentrated hydrochloric acid and poured into an 88.9 mm (3 Vi inch) diameter petri dish and covered with an air impermeable layer of polyvinylidene chloride. The disc contained 10% aroma oil and 21% isopropyl myristic acid and was cut into 12.7 x 25.4 mm (Vi x 1 inch) strips which were cut into slots in the center of a household.

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sponge (cellulose or polyurethane foam). When the sponge is used, when it is wet, a pleasant aroma and the skin-caring oil myristic acid isopropyl ester are released.

Example 15

Cast soap dish

57 ml of hydroxypropyl methacrylate, 26 ml of nonylphenoxy polyethoxyethanol (HLB value 12.5), 2.7 ml of pentaerythritol triacrylate and 11 ml of lilac aroma oil were mixed with 4.4 ml of a 23% aqueous solution of ascorbic acid and a drop was stirred aqueous crystal violet solution and 0.48 ml of 35 percent hydrogen peroxide and 5 drops of concentrated hydrochloric acid, which were quickly mixed, and the mixture was poured into a mold for making a soap dish and covered with a polyvinylidene chloride film. The product so obtained, which was obtained after polymerizing and cooling for 10 minutes, was optically clear and hard and showed randomly distributed internal cracks (due to the relatively high degree of crosslinking). The product contained 2.4% water and 11% aromatic oil. If this product was used as a soap dish, the excess water from freshly used soap partially hydrated the dish, and the subsequent re-evaporation of the absorbed moisture removed the lilac aroma faster than the normal rate of evaporation.

Example 16

Moisture sensitive disc

25 ml of hydroxyethyl methacrylate, 20 ml of nonylphenoxy polyoxyethanol (HLB value 12.5), 0.50 ml of ethylene glycol dimethacrylate, 14.2 ml of lavender oil and 1 g of calcium chloride (anhydrous) in 8 ml of water were mixed with 0.13 g Ascorbic acid dissolved in 2 ml of water was mixed, and finally 0.1 g of ammonium persulfate in 2 ml of water and a drop of violet color were added and poured into a heatable mold in the form of a flower and covered with an air-impermeable polyvinylidene film. This sample was sensitive to the relative humidity in its environment. After some of the moisture contained together with the dissolved 20% of the aromatic oil

8th

had distilled off, the product reached a composition in which the product absorbed moisture from the environment above a relative humidity of about 35-40%, and when the ambient humidity decreased, this absorbed moisture evaporated together with the aroma oil, whereby an acceleration of normal aroma oil release occurred. This “moisture pumping” effect was repeated throughout the effective life of the product.

10th

Example 17

Cast molded body in the form of an oak leaf 16 ml of hydroxypropyl methacrylate, 3 ml of octylphenoxy polyethoxyethanol (HLB value 12), 1 ml of pentaerythritol tri-ls acrylate and 2.42 ml of a suitable aromatic oil were mixed with a solution of 300 mg of ascorbic acid in 1 ml of water was mixed, then 1 ml of 3 percent hydrogen peroxide and a drop of an aqueous green paint were added, and finally a drop of concentrated hydrochloric acid was added and the mixture was stirred and poured into a heatable mold in the form of an oak leaf (thickness 6.35 mm ; Va Inch) and covered with an air-impermeable polyvinylidene chloride film and cured. The product was removed from the mold after 5 minutes and it was transparent and stiff and contained 10% aroma and 8% water. It was installed in a stand and used as an air freshener.

30 Example 18

Cast molded body in the form of a chick 65 ml of hydroxyethyl methacrylate, 67 ml of nonylphenoxy polyoxyethanol (HLB value 12.5), 3.1 ml of ethylene glycol dimethacrylate and 37.5 ml of rose aroma oil were mixed with 340 mg of 35 ascorbic acid, which in 2, 6 ml of water was mixed and mixed, and 260 mg of ammonium persulfate dissolved in 12 ml of water was added and poured into a silicone rubber mold in the form of a chick and covered with a 25.4 ji (1 mil) thick Layer of polyvinylidene chloride and 40 cured over 20 minutes. The product so obtained was a firm, transparent chick containing 20% rose aroma oil.

B

Claims (10)

633304 PATENT CLAIMS 1. Polymer-containing composition containing a polymer with hydrophilic properties and at least one volatile or volatilizable active ingredient, characterized in that the polymer with hydrophilic properties is a homopolymer or copolymer of vinyl-unsaturated monomers in which at least some of the monomer components are free Hydroxyl-containing esters are derived from vinylically unsaturated carboxylic acids, and that the composition contains, as a further component, at least one solution-promoting agent which has both hydrophilic and lipophilic properties and which is compatible with the polymer having hydrophilic properties to the extent that the solution-promoting agent has a solubility in it of at least 5 wt .-%, based on the weight of the polymer, and that the solution-promoting agent is better compatible with the active ingredient mentioned or one of its components than with the Polymers. 2. Composition according to claim 1, characterized in that the solution-promoting agent contained therein with both hydrophilic and lipophilic properties is a cationic or non-ionic, organic surface-active agent or a hydrotrope, preferred such agents being a fatty acid, a polyoxyethylene or a polyoxyethylene condensate with a fatty acid alcohol or alkylphenol or with a glycerin or sorbitol ester and wherein this solvent-promoting agent is present in an amount of 4 to 200 wt .-%, based on the polymer contained in the composition. 3. Composition according to claim 1 or 2, characterized in that the volatile or volatile active ingredient contained therein is an aroma and / or an insecticide. 4. Composition according to claim 1 to 3, characterized in that the polymer material has a smaller proportion of monomer units which originate from pentaerythritol triacrylate or from pentaerythritol trimetha-crylate. 5. A process for the preparation of the polymer-containing composition according to claim 1, characterized in that the vinylically unsaturated monomers for the preparation of the homopolymer or copolymer having hydrophilic properties and which contain free hydroxyl-containing esters of vinylically unsaturated carboxylic acids with at least one volatile or volatile active ingredient Component and at least one of both hydrophilic and lipophilic properties-promoting solution mixed, and that this mixture is polymerized in the presence of a polymerization catalyst to the polymer-containing composition. 6. The method according to claim 5, characterized in that the catalyst used contains a peroxide and a reducing agent, wherein the peroxide is preferably hydrogen peroxide. 7. The method according to claim 5 or 6, characterized in that the catalyst contains ascorbic acid or araboascorbic acid (isovitamin C). 8. The method according to claim 5, characterized in that a nonionic organic surfactant or a hydrotrope is used as the solution-promoting agent, the solution-promoting agent in an amount of 4 to 200% by weight, based on the amount of the monomer materials for the preparation of the Polymers. 9. The method according to claim 5, characterized in that the monomer materials used contain a small proportion of pentaerythritol triacrylate or pentaerythritol trimethacrylate. 10. Use of the polymer-containing composition according to claim 1 for the production of moldings which serve to release the volatile or volatile active ingredients.