RU2481358C2 - Amphiphilic copolymer material - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to an amphiphilic polymer material which has a straight or branched polymer backbone chain and multiple side chains. The amphiphilic polymer material has general formula (I): B-(OR)_x, where B is a straight or branched polymer backbone chain, OR is a hydrophilic side chain bonded to the backbone chain, where x is the number of side chains and ranges from 1 to 5000. The backbone chain contains alternating monomer links of an ethylenically unsaturated aliphatic hydrocarbon monomer containing at least 3 carbon atoms and maleic anhydride. Also disclosed is a method of producing polymer material along with bases, compositions and emulsions of chewing gum which contain amphiphilic polymer materials.

EFFECT: reduced stickiness or adhesion to the surface of compositions which are contained in the polymer material.

26 cl, 3 dwg, 7 tbl, 10 ex

Description

The present invention relates to a new amphiphilic copolymer material, which is a copolymer comprising a main chain of maleic anhydride and ethylenically unsaturated monomer and having many side chains attached to this main chain. This new material reduces the stickiness or adherence to the surface of the compositions in which it is included, in particular chewing gum compositions.

The stickiness of chewing gum creates a big problem for the environment.

After chewing a chewing gum of the usual composition, there remains a water-insoluble portion, commonly called “chewing gum”. The main component of chewing gum is the original base of chewing gum. Although chewing gum can, in principle, be easily disposed of, its inappropriate disposal leads to a number of environmental problems, where the costs associated with removing chewing gum from public places are most noteworthy.

WO 2006/016179 discloses new polymeric materials that have reduced stickiness. It is shown that these new polymeric materials reduce the stickiness of the chewing gum compositions in which they are included. These polymeric materials have a straight or branched carbon-carbon polymer backbone and a plurality of side chains attached to the main chain. These side chains are formed from alkylsilyl polyoxyalkylene or polyoxyalkylene, for example, linked to the main chain via maleic acid / anhydride grafted units.

Maleic anhydride copolymers together with an ethylenically unsaturated monomer are well known in the art and are commercially available. For example, poly (ethylene-black-maleic anhydride) and poly (isobutylene-black-maleic anhydride) can be purchased from the catalog of Sigma-Aldrich.

Poly (ethylene glycol) was crosslinked with the main chain of some polymers poly (monomer-black-maleic anhydride). For example, Eckert et al. Macromolecules (1996), 29, 560-567 describe partial grafting of poly (styrene-cher-maleic anhydride) monomethoxypoli (ethylene glycol). The resulting product was crosslinked to form hydrogel microspheres. EP 0 945 501 describes copolymers of styrene and anhydride grafted with polyethylene glycol. Similarly, Liming et al. in the Chinese Journal of Polymer Science (1995), 13 (3), 264-272, the inoculation of poly (ethylene glycol) monomethyl ether onto the backbone of poly (vinyl methyl ether-cher-maleic anhydride) is reported. US 2006/0057209 describes anhydride-based copolymers and methods for functionalizing these polymers. In one example, poly (styrene-co-maleic anhydride) is reacted with an amino-containing nucleophile, which may be, for example, an amino-functionalized derivative of PEG. The polymers are coated onto the surface in order to modify the hydrophilicity of the surface.

Known methods for producing compositions containing grafted copolymers on an anhydride basis, without the use of a solvent. For example, EP 0 945 473 describes a process which involves mixing an ethylenically unsaturated monomer, an anhydride monomer and either a monofunctional polyglycol having a hydroxyl or amine end group or a polyfunctional polyglycol and a free radical initiator to form a mixture. The mixture is heated to form a mixture of grafted copolymer materials of polyglycol and an ethylenically unsaturated monomer, including a grafted copolymer product, which may be useful as a dirt-repellent agent in detergent preparations.

The method of the present invention differs from the solution described in EP 0945473 in that the method in the latter document results in many different products. The method used in this invention avoids this problem by reacting a preformed polymer backbone with side chain precursors.

It is desirable to obtain new additional polymeric materials that have a reduced stickiness, and the synthesis of which is cheap and effective.

In accordance with a first aspect of the invention, an amphiphilic polymeric material of the general formula (I) is provided:

where B is a straight or branched polymer backbone, which is a copolymer of at least one ethylenically unsaturated aliphatic hydrocarbon monomer containing at least three carbon atoms, and maleic anhydride, and each OR is a hydrophilic side chain attached to the main chain, where x denotes the number of side chains and is in the range from 1 to 5000.

According to a second aspect of the invention, there is provided a method for producing an amphiphilic polymer material according to a first aspect of the invention, wherein the starting copolymer material of at least one ethylenically unsaturated aliphatic hydrocarbon monomer and maleic anhydride is reacted with side chain precursors of the general formula (III), HO-R, to obtain an amphiphilic polymeric material of the general formula (I).

According to a third aspect of the invention, there is provided an amphiphilic polymer material that has a straight or branched polymer backbone and a plurality of hydrophilic side chains attached to the main chain, where the main chain is a terpolymer of maleic anhydride, ethylene and an additional ethylenically unsaturated monomer.

According to a fourth aspect of the invention, there is provided a method for producing an amphiphilic polymeric material, which comprises a straight or branched backbone of a terpolymer, which is within the scope of the third aspect of the invention.

According to a fifth aspect of the invention, there is provided a chewing gum base which comprises an amphiphilic polymer material having a straight or branched polymer backbone and a plurality of hydrophilic side chains attached to the main chain, where the main chain is a copolymer of at least one ethylenically unsaturated monomer and maleic anhydride .

In accordance with a sixth aspect of the invention, there is provided a chewing gum composition comprising an amphiphilic polymer material as defined in the fifth aspect of the invention and one or more than one sweetener or flavoring.

In accordance with a seventh aspect of the invention, there is provided an emulsion comprising an amphiphilic polymeric material as defined in the first and third aspects of the invention.

The main chain of the polymer material according to the invention is flexible and provides more attachment points for side chains than polymers in WO 2006/016179 that do not have maleic anhydride in the main chain. The new polymer material may have a variety of different polymer backbones with varying different chemical functional groups and varying proportions of maleic anhydride. Therefore, it is possible to control the degree of conversion of the side chains more precisely than in polymers according to WO 2006/016179. This makes it possible to better control the physical properties of the new polymer material. The ethylene comonomers in the main chain of the terpolymer increase the chemical stability of the main chain.

By "amphiphilic" the inventors mean that the polymeric material has separate hydrophilic and hydrophobic sites. "Hydrophilic" usually means a site that interacts intramolecularly with water and other polar molecules. "Hydrophobic" usually means a site that interacts predominantly with oils or fats more likely than with an aqueous medium. Typically, side chains and a main chain (where the side chains are hydrophilic and the main chain hydrophobic) provide this compartment. The degree of hydrophobicity of the main chain can be varied by changing the proportion of maleic anhydride in the main chain or the nature of the comonomer. Side chains and the main chain can be ionic or non-ionic.

"Side chain precursors" are side chain starting materials that become side chains in the polymer material. A “starting copolymer material” is a copolymer of maleic anhydride with one or more than one other monomer that interacts with side chain precursors and becomes the main chain in the polymer material. Similarly, the “terpolymer starting material” is a terpolymer of maleic anhydride, ethylene and an additional ethylenically unsaturated monomer, which reacts with side chain precursors to form a backbone in the polymer material. A terpolymer is a copolymer formed by the polymerization of three different monomers. Therefore, the term "terpolymer" is within the scope of the term "copolymer". The inventors use the term "copolymer" in connection with the first aspect of the invention, and the term "terpolymer" in connection with the third aspect of the invention. However, the first aspect of the invention also encompasses terpolymers. It should be understood that there are many chains of copolymer / terpolymer in the starting material. Similarly, in the polymer material there should be many polymer backbones attached to the side chains.

The side chains in the polymer material are usually attached to the polymer backbone via units formed from maleic anhydride.

When talking about maleic anhydride in the main chain, we mean units formed from maleic anhydride, which is present in the copolymer or terpolymer. In the polymer material, the “main chain” includes units formed from maleic anhydride, together with units formed from other monomers polymerized to form the main chain of the polymer material. “Side chains” include the residual structure of the side chain precursors after they have reacted with the starting copolymer or terpolymer material.

When the main chain is a copolymer, the polymeric material of the general formula (I) comprises from 1 to 5000 side chains per main chain, preferably from 1 to 1000, more preferably from 1 to 500 or from 1 to 300, even more preferably from 1 to 150 , from 1 to 100 or from 1 to 50. It is clear that the desired number of side chains that are grafted onto the main chain should depend on the molecular weight of the main chain and on the desired properties of the resulting polymer material. In some embodiments, not all units formed from maleic anhydride in the main chain are attached to the side chains. Each unit formed from maleic anhydride can be attached to either one or two side chains.

When the backbone of the polymer material is terpolymer, a plurality of hydrophilic side chains are attached to this backbone. Typically, from 1 to 5000 side chains are attached to each main chain, preferably from 1 to 1000, from 1 to 500, or from 1 to 300, even more preferably from 1 to 150, from 1 to 100, or from 1 to 50.

The side chains of the amphiphilic polymeric material are usually hydrophilic. In the polymer material of the general formula (I), each side chain is represented by the formula OR. In an amphiphilic polymer material that has a terpolymer backbone, side chains can be linked to the backbone either through a nitrogen atom or through an oxygen atom. Accordingly, the amphiphilic polymeric material may be represented by the general formula (IV)

where B ¹ represents a straight or branched main chain of the polymer, and each YR ¹ represents a hydrophilic side chain attached to the main chain, where Y represents an oxygen atom (O), or NR ⁵ , where R ⁵ represents H or C _{1 -4} alkyl, and x ¹ denotes the number of side chains and is in the range from 1 to 5000.

Y is preferably an oxygen radical, O.

Without being bound by theory, when a material is incorporated into a composition such as a rubber base, the hydrophilic side chains significantly reduce the mobility of the rubber base in the dry state, which makes the discarded chewing gum harder when dried and is easier to remove from the surface. In addition, hydrophilic side chains can enable saliva to act as an elastomer plasticizer during chewing, which makes the gum more easily chewed.

Hydrophilic side chains impart surface-active properties to the polymer material. In a rubber base, a polymer material with hydrophilic side chains becomes surface enriched during chewing, forming a hydrophilic coating that does not bond with hydrophobic surfaces, such as asphalts and slippery stones for the pavement. In the presence of water, the polymer material is easier to remove from the most common surfaces.

The hydrophilic side chains of the polymeric material are preferably formed from poly (ethylene oxide) (PEO), polyvinyl alcohol, poly (styrene sulfonate) sodium, polyglycidyl, proteins / polypeptides, polysaccharide (eg sugars and starches) or polyacrylic acid); most preferably from poly (ethylene oxide). The side chains, prior to joining the main chain, can have terminal hydroxyl groups for the formation of ester bonds with maleic anhydride monomers. Poly (ethylene oxide) binds strongly to simple anionic surfactants, such as those used in hair shampoos and washing fluids, to produce electrolyte. In the presence of such anionic surfactants and water, the polymeric material is repelled by many conventional anionic surfaces, including oxide surfaces, cotton and hair. This mainly makes it possible to remove the rubber base, including new polymers with vaccinations containing a significant percentage of poly (ethylene oxide), washing with soapy water.

Typically, a sufficient number of side chain precursors are added so that their proportion is sufficient to inoculate two side chains on each unit of maleic anhydride. Preferably, a sufficient amount of side chain precursors is reacted to ensure that 1-100% by weight of maleic anhydride units is converted by side chains, even more preferably 2-50%, in most cases 2-30%. However, in some embodiments of the invention, a sufficient number of side chain precursors are added so that 100% of maleic anhydride units in the main chain are derivatized. In another embodiment, a sufficient number of side chain precursors can be added so that two or between one and two side chain precursors interact with each maleic anhydride unit.

In the polymer material, preferably the side chains of OR or OR ¹ preferably have the formula II

where each of Y and Z independently represents an alkylene group having from 2 to 4 carbon atoms, and R ³ represents H or an optionally substituted alkyl group having 1-12 carbon atoms, or another polymer chain linked via an acyl group;

and each of a and b independently represents an integer from 1-200, provided that the sum of a + b has a value in the range of 1-250.

The two monomers YO and ZO can be polymerized to form a block copolymer (for example, by sequentially connecting the monomer to the system) or alternatively they can form a random, random or alternating copolymer. Other forms of implementation may have side chains including a third monomer.

The sum of a + b is preferably in the range of 5-200, more preferably from 20-120.

Typically, in the compound of formula II, both alkylene groups Y and Z are —CH ₂ —CH ₂ . In one form of exercise in group II, group R ³ is H.

In another embodiment, R ^{3 is} alternatively —CH ₃ or another lower alkyl (up to 4 carbon atoms) group.

In a first aspect of the invention, the polymer backbone is a copolymer of at least one ethylenically unsaturated aliphatic hydrocarbon monomer containing at least three carbon atoms and maleic anhydride. The copolymer is usually a bipolymer, that is, it includes two different monomers (maleic anhydride and one ethylenically unsaturated monomer). The hydrocarbon monomer includes only carbon and hydrogen atoms. Most preferably, the ethylenically unsaturated monomer is selected from isobutylene, 1,3-butadiene, isoprene and octadecene. Preferably, the ethylenically unsaturated aliphatic hydrocarbon monomer has 3-5 carbon atoms. Such a polymer material usually has a greater degree of hydrophilicity than a polymer material with a hydrocarbon monomer containing more than 5 carbon atoms in the main chain.

Alternative ethylenically unsaturated monomer includes 7 or more carbon atoms. For example, it can have 8-30 carbon atoms. The increased number of carbon atoms in such polymeric materials gives the main chain a greater degree of hydrophobicity, which makes the material more suitable for certain applications. Typically, the copolymer contains 1-75 wt.% Maleic anhydride, preferably 1-50% or 5-50%, even more preferably 10-50%.

In a third aspect of the invention, the polymer backbone is a terpolymer of maleic anhydride, ethylene and an additional ethylenically unsaturated monomer. An additional ethylenically unsaturated monomer is designated as “additional” to distinguish it from ethylene (also an “ethylenically unsaturated monomer”).

Typically, the additional ethylenically unsaturated monomer is an alkyl acrylate, for example methyl, ethyl, propyl or butyl acrylate.

In another embodiment, the further ethylenically unsaturated monomer is alkenyl acetate, preferably vinyl acetate. Alternatively, it may be vinyl ether.

Particularly preferred terpolymer polymer backbones are copolymers of ethylene, butyl acrylate and maleic anhydride and copolymers of ethylene, vinyl acetate and maleic anhydride.

The copolymer of ethylenically unsaturated monomer and maleic anhydride may be a random, statistical, alternating or block copolymer, for example, block copolymers A-B or A-B-A. In one embodiment, the copolymer is an alternating copolymer. In another embodiment, the copolymer is a random (or random) copolymer. Similarly, the terpolymer C-D-E may be a random polymer or block copolymer (where C is ethylene, D is maleic anhydride and E is an additional ethylenically unsaturated monomer):

.

.

Typically, C is present in the range of 25-95% by weight. D is usually present in the range of 1-50 wt.%. E is usually present in the range of 5-70 wt.%.

The terpolymer starting material described in this invention typically contains 1-50% by weight of units derived from maleic anhydride, more preferably 1-30%, even more preferably 1-15% by weight, of units derived from maleic anhydride.

Before reacting with side chain precursors, the molecular weight of the copolymer / terpolymer starting material is usually in the range of 1000-1000000, more preferably in the range of 2000-100000. Each side chain precursor typically has a molecular weight of 200-100000, more preferably 450-100000, preferably 500-50000, most preferably 1000-10000.

In the method for producing the polymeric material according to the first aspect of the present invention, side chain precursors terminate with hydroxyl groups, HO-R. In the method for producing an amphiphilic polymer material of the general formula (IV) B ¹ - (YR ¹ ) x ^{1, the} starting material of the maleic anhydride terpolymer, ethylene and additional ethylenically unsaturated monomer is reacted with side chain precursors of the general formula (V), H-YR ¹ , to obtain amphiphilic polymeric material of General formula (IV). Thus, in this embodiment, side chain precursors can terminate with either hydroxyl or amino groups. Hydroxyl functional materials are generally widely recognized as being safe for consumption in moderation in the food industry. However, typically side chain precursors terminating in amino groups more readily interact with main chain precursors, which allows the interaction of more side chain precursors with each main chain precursor.

Suitable side chain precursors, which are polyester amines, are commercially available; a number of mono- and difunctionalized amine polymers of ethylene oxide (EO) and propylene oxide (PO) are sold under the trade name Jeffamine by Huntsman. The interaction between amine functionalized polymers with one unit of maleic anhydride, for example, can form any of three different structures:

The structure denoted by C can be formed as a result of intramolecular interaction A, accompanied by the removal of H ₂ O, and is more likely carried out by catalysis (for example, by adding acid). Both mono- and di-, tri-, tetrafunctional amine polymers can be used in the invention, some of which are commercially available from Hunstman. Depending on the reaction conditions, the use of hydrophilic difunctional amine side chain precursors may result in an amphiphilic polymeric material that is crosslinked or elongated. Alternatively, mono- and difunctional side chain precursors can be combined to modify the properties of the resulting polymeric material to the desired properties. The structure and properties of Jeffamine M-1000 and M-2070 are particularly preferred for side chain precursors:

[x = 6; y = 35, where R is a mixture of H for (EO) or CH ₃ for (PO) units].

Jeffamine M-1000 is a monoaminopolyester with an EO: PO ratio of 19: 3 and a molecular weight of about 1000, M-2070 is a monoaminopolyether with an EO: PO ratio of 31:10 and a molecular weight of about 2000. Due to the relatively high proportions of ethylene oxide units in these polymers they are considered as hydrophilic materials. It was found that both M-1000 and M-2070 interact effectively with PIP-gr-MA.

Side chain precursors typically terminate with an alcohol link at one end and an alkyloxy group at the other. MeO-PEO-OH is an example of a preferred side chain precursor. In the method of forming the polymer material, such side chains interact with units formed by maleic anhydride by alcoholysis of the anhydride to produce a carboxylic acid ester and a carboxylic acid.

The interaction of maleic anhydride with alcohol is a reaction of alcoholysis, the result of which is the formation of ether and carboxylic acid. This reaction is also known as esterification. This reaction is relatively quick and does not require a catalyst, although acidic or basic catalysts can be used.

A pure reaction may be presented as shown below. P _x and P _Y are the copolymer / terpolymer residue, and ROH is a representative side chain precursor.

In the method, two side chain precursors represented by ROH can be reacted with the same maleic anhydride monomer to give a compound of general formula

Alternatively, one side chain precursor reacts on the maleic anhydride monomer. This leaves a unit formed from maleic anhydride with a free carboxylic acid group that can be converted to a derivative at a later stage in the process. This group can also be deprotonated to give an ionic backbone in the polymer material.

Side chain precursors need not be directly reacted with units formed from maleic anhydride in the main chain. For example, a preliminary step may be carried out where the linker is reacted with units formed from maleic anhydride. The linker may be, for example, a short chain hydrocarbon functionalized at either end with suitable reaction groups, such as an alcohol capable of reacting with maleic anhydride, and a halide capable of reacting with a base catalyzed reaction with a PEG hydroxyl group. The side chain precursors are then reacted with a linker in a subsequent reaction step. The reaction can be carried out in solution or with one of the reagents, for example PEG, as a solvent.

In the method of the invention, side chain precursors can have hydroxyl groups at each of their ends, and each end interacts with a unit formed from maleic anhydride in different main chains to form a crosslinked polymeric material.

After the interaction of the side chain precursors with the copolymer or terpolymer starting material, any unreacted units formed from maleic anhydride in the main chain can be subjected to ring breaking. This can be done by hydrolysis or using a base. The resulting product may be ionizable. This additional reaction step is particularly useful when a large proportion of maleic anhydride is present in the main chain, for example, in an alternating copolymer.

Since the methods of this invention are suitable for producing new polymeric materials according to the invention, each of the preferred features of the polymeric material discussed above is equally applicable to the polymeric material obtained by this method.

Alternative methods for producing an amphiphilic polymeric material include a process in which side chain precursors are reacted with maleic anhydride monomers, which are then polymerized with ethylenically unsaturated monomers in a subsequent step to form a polymeric material.

The polymer starting material can be obtained from an appropriate chemical supplier, such as Sigma-Aldrich. For example, both firms, Sigma-Aldrich and Kuraray Co. Ltd supply poly (isobutylene-cher-maleic anhydride), Kuraray Co. Ltd, under the trade name ISOBAM.

Regarding poly (maleic anhydride-cher-octadecene), Chevron Philips Chemical Company LLC manufactures a range of materials in the range of their PA18 polyanhydride resins, which are suitable.

Copolymers of poly (ethylene-butyl acrylate-co-maleic anhydride) can be obtained from Arkema and are sold under the trade name Lotader (e.g. grades 2210, 3210, 4210 and 3410). Copolymers in which butyl acrylate is replaced with other alkyl acrylates (including methyl acrylate [grades 3430, 4404 and 4503] and ethyl acrylate [grades 6200, 8200, 3300, TX 8030, 7500, 5500, 4700 and 4720) are also available and are also sold in the Lotader range.

A number of Orevac materials (grades 9309, 9314, 9307 Y, 9318, 9304, 9305) are suitable terpolymers of ethylene, vinyl acetate, and maleic anhydride.

Similarly, suitable side chain precursors such as monomethoxypoly (ethylene glycol) (MPEG) polyvinyl alcohol) and polyacrylic acid) can, for example, be obtained from Sigma-Aldrich.

Side chain precursors are reacted with the copolymer / terpolymer starting material, as described in detail in the Examples. For this reaction, the copolymer / terpolymer starting material and side chain precursors are usually dissolved in a suitable solvent. Often suitable, for example, is a mixture of DMF (dimethylformamide) and toluene. The mixture is then heated, preferably to a reflux temperature (from ~ 110 to 120 ° C.) in an inert atmosphere for about 24 hours. Preferably, an inert atmosphere is provided with an inert gas such as nitrogen or argon. Water can be removed from the reaction mixture using distillation, for example, using azeotropic distillation. This is not necessary when the copolymer / terpolymer starting material and side chain precursors are anhydrous. The resulting polymer material is cooled and then separated from the solvent solution. Precipitation, filtration and drying are typical stages of isolation.

Alternatively, the copolymer / terpolymer starting material and side chain precursors can be reacted in the absence of solvent, for example, the reactions can be carried out by mixing the molten mixture of the copolymer / terpolymer starting material and side chain precursors together at an appropriate temperature (i.e., most preferably at 100-200 ° C ) In another embodiment, the process can be carried out by adding the copolymer / terpolymer starting material and side chain precursors together or individually to the hot extruder; and then carry out the process by reactive extrusion. It is usually preferable to carry out these reactions in an atmosphere of inert gas (for example, nitrogen) or in vacuum to prevent decomposition of the polymers.

The reaction mixture at the end of the reaction usually contains unreacted starting materials, which may include a free side chain precursor and a main chain precursor. Some residual amount of catalyst may be present if used in the reaction. This reaction usually does not form by-products. The amphiphilic polymeric material does not need to be purified from the reaction mixture, since it may be preferable to have free side chain precursors in the final composition. The free side chain precursor can interact with the amphiphilic polymeric material and thereby improve its properties.

Most preferably, the amphiphilic polymeric material is included in the chewing gum composition as defined in the sixth aspect of the present invention. In this aspect, the amphiphilic polymeric material has a straight or branched polymer backbone and a plurality of hydrophilic side chains attached to the main chain. The main chain is a copolymer of at least one ethylenically unsaturated monomer and maleic anhydride. The term copolymer covers both bipolymers and terpolymers. Preferably, the monomer is a hydrocarbon monomer. By the term "ethylenically unsaturated polymerizable hydrocarbon monomer", we mean a polymerizable hydrocarbon containing at least one carbon-carbon double bond that is capable of polymerizing to form a straight-chain or branched hydrocarbon polymer having a carbon-carbon polymer backbone. According to one preferred embodiment, the ethylenically unsaturated polymerizable hydrocarbon monomer contains 4 or 5 carbon atoms and is, for example, isobutylene (2-methylpropene). The ethylenically unsaturated monomer may alternatively be a conjugated diene hydrocarbon monomer, in particular containing 4 or 5 carbon atoms, such as 1,3-butadiene or isoprene. The main chain may be a terpolymer as described in a third aspect of the invention. The ethylenically unsaturated monomer may alternatively be 1-octadecene.

In this aspect of the invention, the ethylenically unsaturated monomer may be aromatic and / or contain atoms other than hydrogen and carbon. Suitable ethylenically unsaturated monomers include styrene and vinyl methyl ether.

Side chains are usually hydrophilic. Side chain precursors that interact with the copolymer / terpolymer starting material can terminate with either hydroxyl or amine groups. A particularly preferred amphiphilic polymeric material has the general formula B ² - (Y ² R ² ) x ² , where B ² is a straight or branched polymer backbone which is a copolymer of at least one ethylenically unsaturated monomer and maleic anhydride or terpolymer as described above, Y ² represents O or NR ⁵ and x ² represents the number of side chains and is in the range from 1 to 1000. R ⁵ represents H or C _1-4 alkyl, and each Y ² R ² represents a hydrophilic side chain .

A typical starting copolymer material contains from 1 to 50 wt.% Maleic anhydride.

Preferably, the polymeric material is as defined in the first or third aspect of the present invention.

Due to their very nature, chewing gum compositions are sticky. Chewing gum compositions typically contain a portion of a water-soluble filler, a water-insoluble chewing gum base, and flavoring agents. The rubber base usually contains a mixture of elastomers, vinyl polymers, elastomeric plasticizers (or solvents), emulsifiers, fillers and softeners (plasticizers). It is known that all elastomers, waxes, elastomeric plasticizers and vinyl polymers contribute to the stickiness of the rubber base.

An amphiphilic polymeric material can be incorporated into a chewing gum base manufactured in accordance with standard technologies known in the art, which are further described in WO 2006/016179. Amphiphilic polymeric material can alternatively be included in the chewing gum composition, regardless of the rubber base. In a preferred embodiment of the invention, the amphiphilic polymeric material is in both the rubber base and the chewing gum composition.

The incorporation of the polymeric material into the rubber base in addition to or instead of part or all of the wax, elastomeric material and / or elastomeric solvent reduces the stickiness of the rubber base and makes it easier to remove chewing gum from the surfaces. The rubber base can thus be advantageously removed by washing with water or in a mild detergent solution. In addition, in contrast to the rubber bases of the prior art, the hardness of the rubber base is changed due to the solvation (plasticization) of the polymer material is more likely than only due to an increase in temperature in the mouth. The ingredients of the rubber base can be varied in accordance with this invention to obtain a variety of rubber bases and compositions to suit a wide range of surfaces and environmental conditions in nature.

Of course, all compounds of the rubber base must be acceptable for human consumption, for example, they must have a food or pharmaceutical category.

Typically, the polymeric material comprises 3-90 wt.% The basis of chewing gum, preferably 3-15 wt.%. The polymer material may act as a substitute for part or all of the rubber-based ingredients that contribute to tack.

The base of the chewing gum may contain from 0 to 6 wt.% Wax. Examples of waxes that may be present in a rubber base include microcrystalline wax, natural wax, petroleum wax, paraffin wax, and mixtures thereof. Waxes typically contribute to the hardening of rubber substrates and to an improvement in shelf life and texture, as well as in controlling the release rate of flavoring agents. It has also been found that waxes soften the base blend and improve elasticity during chewing.

Preferably, the rubber base is substantially wax free, and these properties are provided by the polymeric material.

The elastomeric material provides the desired elasticity and texture properties, as well as a filler. Suitable elastomeric materials include synthetic and natural rubber. More specifically, the elastomeric material is selected from copolymers of butadiene and styrene, polyisobutylene and copolymers of isobutylene and isoprene. It has been found that if the total amount of elastomeric material is too low, the rubber base lacks elasticity, chewing texture and bonding ability, whereas if the content is too high, the rubber base is solid and rubbery. Typical rubber bases contain 10-70 wt.% Elastomeric material. Typically, the polymeric material should comprise at least 1 wt.%, Preferably at least 10 wt.%, More preferably at least 50 wt.% Of the chewing gum base elastomeric material. In some embodiments, the polymeric material completely replaces the chewing gum base elastomeric material.

Elastomeric plasticizers soften the elastomeric material and include methyl glycerol or pentaerythritol esters of resins or modified resins, such as hydrogenated, dimerized or polymerized resins, or mixtures thereof. Examples of elastomeric plasticizers suitable for use in the chewing gum base of the present invention include pentaerythritol ether of partially hydrogenated wood resin, pentaerythritol ether of wood resin, glycerin ether of partially dimerized resin, glyceric ether of polymerized resin, glyceric ether of resin tall oil resin, glyceric ether partially hydrogenated wood resin and partially hydrogenated methyl ester resin; terpene resins, including polyterpene, and polymers of α-pinene or β-pinene and mixtures thereof. Elastomeric plasticizers can be used up to 30 wt.% Rubber base. The preferred range of elastomeric solvent, however, is from 2 to 18 wt.%. Preferably, it is less than 15% by weight. Alternatively, the elastomeric solvent may not be used.

The mass ratio of the elastomer together with the polymer material to the elastomeric plasticizer is preferably in the range (1 to 50): 1, preferably (5 to 25): 1.

The chewing gum base preferably contains a non-toxic vinyl polymer. Such polymers have an affinity for water and include polyvinyl acetate, ethylene / vinyl acetate copolymers and vinyl laurate / vinyl acetate. Preferably, the non-toxic vinyl polymer is polyvinyl acetate. Preferably, the non-toxic vinyl polymer is present in an amount of 15-45% by weight of a gum base. A non-toxic vinyl polymer must have a molecular weight of at least 2000.

The chewing gum base also preferably contains a filler. Fillers are used to modify the texture of the rubber base and help with its processing. Examples of typical fillers include calcium carbonate, talc, amorphous silica and tricalcium phosphate. Preferably, the filler is silica. The particle size of the filler has an effect on the bonding ability, density and technological characteristics of the rubber base during compounding. Smaller filler particles have been shown to reduce the stickiness of the rubber base.

Preferably, the chewing gum base contains a softener. Softeners are used to regulate the binding ability, to modify the texture, and to introduce sharp melting phase transitions during chewing of the product. Softeners provide thorough mixing of the rubber base. Typical examples of emollients are hydrogenated vegetable oils, lanolin, stearic acid, sodium stearate, potassium stearate and glycerin. Softeners are typically used in amounts of from about 15% to about 40% by weight of the gum base, and preferably in amounts of from about 20% to about 35% of the gum base.

A preferred chewing gum base comprises an emulsifier. Emulsifiers contribute to the dispersion of the immiscible ingredients of the chewing gum composition in a single stable system. Suitable examples are lecithin, glycerin, glycerol monooleate, lactic fatty acid esters, lactilated fatty acid esters of glycerol and propylene glycol, mono-, di- and tristearyl acetates, monoglyceride citrate, stearic acid, stearyl monoglyceride-glyceryl glycerol-2-acetyl triethyl citrate and polyethylene glycol. An emulsifier typically comprises from about 2% to about 10%, and preferably from about 4% to about 6%, of a gum base.

The chewing gum composition comprises a chewing gum base and one or more than one sweetener and flavoring. The chewing gum composition may further comprise a biologically active ingredient. Amphiphilic polymeric material regulates the release of the active ingredient from the chewing gum composition.

A biologically active ingredient is any substance that modifies a chemical or physical process in the human or animal body. Preferably, it is a pharmaceutically active ingredient and is selected, for example, from antiplatelet drugs, drugs against erectile dysfunction, NSAIDs, NO donors for angina pectoris, non-opioid analgesics, antibacterial drugs, antacids, diuretics, antiemetics, antihistamines, anti-inflammatory drugs, antidiabetic agents (e.g., insulin), opioids, hormones, and combinations thereof. Preferably, the active ingredient is a stimulant such as caffeine or nicotine. Alternatively, the active ingredient is an analgesic. An additional example of the active ingredient is insulin.

In one embodiment, the biologically active ingredient is a non-steroidal anti-inflammatory drug (NSAID) such as diclofenac, ketoprofen, ibuprofen or aspirin. Alternatively, the active ingredient is paracetamol (which is usually not classified as NSAID).

In another embodiment, the biologically active ingredient is a vitamin, mineral, or other nutritional supplement.

The biologically active ingredient may be an antiemetic, for example, dolasetron. Alternative biologically active ingredient is a medicine against erectile dysfunction, such as sildenafil citrate.

Typically, the chewing gum composition contains 0.01-20 wt.% The active ingredient, more preferably 0.1-5 wt.%. The chewing gum composition may be in the form of a unit dosage form suitable for oral administration. This unit dosage form preferably has a weight in the range of 0.5-4.5 g, for example, about 1 g. Typically, the chewing gum composition contains 1-400 mg of biologically active ingredient, more preferably 1-10 mg, depending on the active ingredient. When the active ingredient, for example, is nicotine, the chewing gum composition typically contains 1-5 mg of nicotine. When the active ingredient is a non-steroidal anti-inflammatory drug, such as ibuprofen, the composition usually contains 10-100 mg of the active ingredient.

As a rule, the chewing gum composition should be chewed up to an hour, although more often up to 30 minutes. Preferably, after 30 minutes of chewing, at least 40%, more preferably at least 45%, most preferably at least 50% of the active ingredient present in the chewing gum composition is released in the mouth. Depending on the nature of the active ingredient and its purpose, the release may take place over a relatively longer or shorter period. For some active ingredients, for example, a slow, sustained release is preferable, as this can reduce the side effects of the active ingredient. This is the case for sildenafil citrate, as described in US 6,592,850. In such cases, it is preferable that no more than 50% of the active ingredient is released after 15 minutes of chewing, and that the release of the active ingredient still continues between 15 and 30 minutes after the termination of chewing.

Alternatively, a faster release may be preferable. For example, smokers using nicotine replacement therapy would prefer faster delivery of nicotine to satisfy their nicotine hunger. In such cases, it is preferred that 25-100% of the active ingredient is released after 10 minutes of chewing. More preferably, 35-65% of the active ingredient is released after 10 minutes of chewing. A quick release chewing gum composition that provides a higher total nicotine release after a reasonable chewing period has the advantage that the consumer needs to buy and chew less chewing gum (i.e., fewer gum or less gum). Alternatively and as an advantage for the manufacturer, a smaller amount of the active ingredient must be added to the chewing gum composition.

The sweetener can be selected from a wide range of substances, including water-soluble artificial sweeteners, water-soluble agents and dipeptide sweeteners, including mixtures thereof. Flavoring agents may be selected from synthetic flavoring lipids and / or oils isolated from plants, leaves, flowers, fruits (etc.) and combinations thereof. Suitable sweeteners and flavoring agents are further described in US 4,518,615.

The chewing gum composition of the present invention may contain additional amphiphilic polymeric material (that is, in addition to the polymeric material that may be present in the chewing gum base) in addition to the chewing gum base, sweetener and flavoring agent. Preferably, this additional polymeric material, if present, is 1-20%, more preferably 3-15% by weight of the chewing gum composition. It may be soluble or insoluble in water.

A method of manufacturing a chewing gum composition typically involves mixing a rubber base with a biologically active ingredient, as well as sweeteners and flavoring agents. Standard methods for preparing chewing gum compositions are described in Formulation and Production of Chewing and Bubble Gum. ISBN: 0-904725-10-3, which include the manufacture of coated chewing gums and liquid cores.

Typically, chewing gum compositions are prepared by mixing the rubber base with sweeteners and flavoring agents in molten form, followed by cooling the mixture.

A suitable device for forming a chewing gum base and composition includes a device capable of mixing the components together at an elevated temperature. The mixture may be heated, but more preferably, the mixer is heated with a jacket around the mixing tank or cavity. In the HAAKE laboratory, the MiniLab Micro Compounder (Thermo Fisher Corporation) can be used to produce both a rubber base and a chewing gum composition. On an industrial scale, a suitable worm (or screw) mixing apparatus, apparatus with Z-shaped blades or double sigmoid blades is particularly suitable.

In the case of a rubber base, the ingredients are usually mixed together by adding them stepwise in the range of 80-120 ° C, usually about 100 ° C. After obtaining the rubber base, the material is extruded from Minilab.

Chewing gum compositions may require heating to a temperature of about 100 ° C (for example, in the range of 80-120 ° C) for uniform mixing of the components. This can be a problem when a biologically active ingredient is present in the chewing gum composition and is thermosensitive, i.e. unstable at such high temperatures. If the active ingredient is thermosensitive, it is preferable to mix the gum base with one or more sweetening and / or flavoring agents and heat to a temperature in the range of 80-120 ° C (preferably 100 ° C). Typically, the mixture is cooled to a temperature in the range of 40-80 ° C, preferably 50-70 ° C. The mixture is then cooled to a temperature at which the active ingredient is stable, and the active ingredient is added to the cooled mixture, optionally together with one or more additional sweetening and flavoring agents, to form a chewing gum composition. The amphiphilic polymeric material, as defined above in the first aspect of the invention, is added either at the stage of molding the rubber base, or at stage (ii) when the chewing gum composition is formed. Polymer material can be added during both of these steps.

After mixing, the chewing gum composition is extruded.

The dosage form of the chewing gum composition can be obtained by extruding the chewing gum and molding the extrudate into the desired shape. The unit dosage form usually has a weight in the range of 0.5-2.5 g, typically about 1 g. The unit dosage form may be in the form of a cylindrical or spherical body or tablet.

Typically, the chewing gum composition contains 5-95 wt.%, Preferably 10-50 wt.%, More preferably 15-45% of the gum base. Additional polymeric material may also be added to obtain a chewing gum composition in such an amount that it is 1-15%, more preferably 3-15% of the chewing gum composition.

The steps for preparing a chewing gum composition can be carried out sequentially in the same apparatus, or can be carried out in different places, in which case cooling and heating steps can be alternated.

Although the useful properties of the new polymeric material are particularly evident with respect to chewing gum bases, it should also be understood that the new polymers will give their useful properties to other compositions that require reduced adhesion or a modified hydrophilic / hydrophobic balance. Since new polymers are considered non-toxic, they can be included in compositions that are used in contact with the human body.

The new polymeric material can be used for personal hygiene, for example, in detergents for the body and / or hair, cosmetics, skin care products and against the sun. The polymeric material can also be used as an emulsifier in food products. One particularly preferred use of the polymeric material is an emulsifier, dispersing agent or adjuvant in cosmetic products, or use as a stabilizer. Alternatively, the polymeric material can be used in the household, such as in detergents, detergents for carpets, fabrics, windows, bathrooms, kitchens, as well as multi-purpose cleaners. Polymeric materials may also be useful as surfactants or cleaning products for personal care or household applications.

It is shown that a new polymer material affects the interaction of water with surfaces. This means that the polymer material can be used to cover fabrics, glass and surfaces of architectural structures. This polymeric material can also be used in a coating composition that prevents glass from fogging.

Coatings from these grafted copolymers can be useful in protecting a number of surfaces, for example, sidewalks, roads, surfaces of architectural structures, such as cement, concrete, glass, metal, brick, stone, granite, ceramic tiles and other brickwork and fabrics.

In an alternative embodiment, the new polymeric material is used as a moisturizing agent, for example, on the surface of contact lenses, or is used as an adjuvant for agricultural sprayers (moisturizing agent for leaves).

In a sixth aspect of the present invention, there is provided an emulsion comprising an amphiphilic material as described above with respect to a chewing gum composition, wherein the amphiphilic material generally acts as an emulsifier. The emulsion may be an oil-in-water or water-in-oil emulsion. The emulsion can be used in cosmetic products or alternatively household products such as paints. Amphiphilic polymeric material can act as a surfactant to stabilize the emulsion.

In this embodiment, it is particularly preferred that, in the process of producing the polymer material, unreacted maleic anhydride in the polymer backbone is subjected to ring opening (eg, by hydrolysis or using a base). In an emulsion, typically the polymeric material comprises from 0.1 to 10 wt.%, Preferably about 1 wt.% Of the oil phase, but it can be varied to modify the stability of the emulsion. In this context, by oil, the inventors mean a relatively hydrophobic liquid that is not miscible with water. The oil may be, for example, silicone oil or toluene. The ratios of water to oil usually vary according to application and may vary between those based primarily on water and mainly on oil. The solubility of the polymer material in water and in oils determines the method for preparing the composition and the structure of the emulsion. Typically, an emulsion stabilized using an oil-soluble emulsifier will result in a water-in-oil emulsion, while an emulsion formed using a water-soluble material will result in an oil-in-water emulsion. As described in detail above, the choice of the main chain of the polymer determines its hydrophilicity and the degree of possible conversion by hydrophilic side chains. Polymeric materials with more hydrophobic backbones (or less hydrophilic side chains) should be prone to stabilize water-in-oil emulsions, while more hydrophilic main chains (or polymeric materials with a large number of side chains) should be prone to stabilize oil-in-oil emulsions. in water.

The value of HLB (hydrophilic-lipophilic balance) of the polymer material can give a good indication of the ability of this material to act as an emulsifier. HLB values are more fully described in Colloid & Surface Chemistry, Duncan J. Shaw , 4 ^th edition, ISBN: 0750611820. Typically, if the polymeric material has an HLB value ranging from 3 to 6, it forms a water-in-oil emulsion, and if the HLB value is in the range from 8 to 15, the polymer material forms an oil-in-water emulsion.

The invention further provides the use of an amphiphilic polymeric material, as described above with respect to a chewing gum composition, as a surfactant for cleaning and washing. Preferably, in this embodiment, the unreacted maleic anhydride in the main chain is subjected to ring opening, as described in detail above, using a base, for example, NaOH. Most preferably, the amphiphilic polymeric material is a sodium or potassium salt.

The invention is now illustrated by the following Examples, which refer to figures 1-3, in which:

1 shows contact angle measurements for various grafted copolymers.

Figure 2 shows the release of cinnamaldehyde from chewing gum.

Figure 3 shows the release of ibuprofen from samples.

Reference Example 1.0 - Polymer backbones

1.1 Copolymers of maleic anhydride

Poly (isobutylene-cher-maleic anhydride):

Two molecular weights (M _n : 6000, 60,000 g / mol, as described by the supplier), both obtained from Sigma-Aldrich.

Poly (maleic anhydride-cher-octadecene):

Molecular weight of 30-50000 g / mol (as stated by the supplier); obtained from Sigma-Aldrich.

1.2 Ethylene Maleic Anhydride Terpolymers

These polymers are random copolymers of ethylene, maleic anhydride and another monomer.

Poly (ethylene-co-butyl acrylate-co-maleic anhydride)

This polymer is a copolymer of ethylene (91 wt.%), N-butyl acrylate (6%) and maleic anhydride (3%). This material was obtained from Sigma-Aldrich (molecular weight information is proprietary and proprietary).

Poly (ethylene-co-vinyl acetate-co-maleic anhydride)

This polymer is a copolymer of ethylene, vinyl acetate and maleic anhydride. The polymer was obtained from Arkema and is commercially available under the trade name Orevac (used brand 9304).

Test Example 2.0 - Side Chain Precursors

In all cases, the graft component of the copolymer was methoxypoly (ethylene glycol) (MPEG), also known as poly (ethylene glycol) methyl ether (PEGME). The material was obtained from two suppliers, Sigma-Aldrich and Clariant (commercially available as Polyglykol M 2000S). In both cases, the polymers were sold as having a molecular weight of 2000, and are believed to have very similar chemical structures and properties. Polymers 1, 3-5, and 7 (Table 1) were synthesized using Aldrich material, others were synthesized using Clariant material.

Reference Example 3.0 - Grafted Copolymers

By “grafted copolymer,” we mean “polymeric material,” and the two terms are used interchangeably.

A number of grafted copolymers were synthesized by grafting MPEG onto the backbones described in Control Examples 1 and 2.

Table 1 Researched polymers. Polymer Sample Number Main circuit Main circuit M _n Grafted component Grafted component M _n The number of MA in the main circuit (wt.%) Target MA (% mol / mol) ⁱⁿ one P (IB-Cher-MA) 6000 MPEG 2000 64 ^a 10 2 P (IB-Cher-MA) 6000 MPEG 2000 64 ^a 28 3 P (IB-Cher-MA) 60,000 MPEG 2000 64 ^a 10 four P (MA-Cher-O) 30-50000 MPEG 2000 28 ^a eleven 5 P (MA-Cher-O) 30-50000 MPEG 2000 28 ^a eleven 6 P (MA-Cher-O) 30-50000 MPEG 2000 28 ^a one hundred 7 P (E-co-BA-co-MA) Unknown MPEG 2000 3 one hundred 8 P (E-co-VA-co-MA) Unknown MPEG 2000 3 ^B fifty 9 P (E-co-VA-co-MA) Unknown MPEG 2000 3 ^B one hundred 10 P (IB-Cher-MA) 6000 JM-1000 ^u 1000 64 ^a one hundred ^a = Polymers are approximately 50% mol / mol MA, the value for wt.% depends on the Fw of the monomer; ^b = The amount of MA in the main chain varies between 1.6-3.2%, the values are calculated using 3.2%; ^c = percentage of available MA aimed at interaction; ^g = Jeffamine M-1000 manufactured by Huntsman

"The amount of MA in the main chain" means the percentage of the molar mass of the main chain, which consists of MA. “Target MA” means the percentage of the total number of moles of MA in the backbone that would be expected to interact with MPEG added to the reaction mixture. In the case of polymers where this value is 100, enough MPEG was added to inoculate the PEG chain on each MA link on the main chain.

As should be obvious from table 1, often not all MA was aimed at interaction. For example, in the case of polymer samples 1-5, only the proportion of maleic anhydride in the alternative backbone of the copolymer interacted. In this regard, there remains a number of rings of maleic anhydride present on the main chains, which themselves can be used by opening the ring (see the section related to emulsification). It can be noted that in some cases, not all maleic anhydride, aimed at interacting with MPEG, can react.

3.1 Synthesis of grafted copolymer

Polymer 1:

Poly (isobutylene-cher-maleic anhydride) (M _n : 6000 g / mol, 40 g) and poly (ethylene glycol) methyl ether (M _n : 2000 g / mol, 50 g) were dissolved in a mixture of DMF (100 ml) and toluene (100 ml) in a reaction flask. The flask was heated at reflux temperature in an atmosphere of gaseous nitrogen for 24 hours, removing any water present from the reaction mixture by azeotropic distillation and collection in a Dean-Stark apparatus. The resulting polymer solution was cooled and precipitated in diethyl ether, the polymer was isolated using filtration, and dried to remove traces of solvent. The grafting of MPEG on the main chain was confirmed using infrared spectroscopy, which used a Bruker spectrophotometer, by observing changes in the region of 1700-1850 cm ^-1 associated with units of maleic anhydride.

The concentration of maleic anhydride (MA) in the main chain was first determined by dissolving the sample in chloroform and measuring the transmittance at 1830 and 1790 cm ^-1 . In the case of a pure solvent, a transmittance of about 83% is usually observed at these points. The presence of MA causes a decrease in the transmittance of infrared radiation at these points, where this decrease is directly proportional to the concentration of MA in the polymer. As the concentration of MA decreases as a result of the grafting process, it is expected that the transmittance increases again. Thus, by comparing the transmittance at these two points before and after the interaction, it is possible to assess whether the grafting process was successful.

Polymer 2:

Polymer 2 was synthesized in the same way as polymer 1, using poly (ethylene glycol) methyl ether (M _n : g / mol, 110 g) as the grafted component of the copolymer. The reactions allowed to proceed for a total of 36 hours. The polymer was characterized in the same way as polymer 1.

Polymer 3:

Polymer 3 was synthesized in the same way as polymer 1, using poly (isobutylene-cher-maleic anhydride) (M _n : 60,000 g / mol, 40 g) as the main chain. The polymer was characterized similarly to polymer 1.

Polymer 4:

Polymer 4 was synthesized in the same way as polymer 1 using poly (maleic anhydride-cher-octadecene) (M _n : 30-50000 g / mol, 50 g) as the main chain and poly (ethylene glycol) methyl ether (M _n : 2000 g / mol, 30 g) as a grafted component. Toluene (200 ml) was used as a solvent for the reaction mixture; in this case, the polymer solution was precipitated in water. The amphiphilic nature of the resulting grafted copolymer led to a low yield (25% of theoretical). The polymer was characterized similarly to polymer 1.

Polymer 5:

Polymer 5 was synthesized in the same way as polymer 4, except that the polymer solution was not precipitated in water; instead, the reaction solvent was removed in vacuo. As a result, the material was isolated at a higher yield than P4, and may be suitable for applications where the excess PEG in the final product is not critical. The polymer was characterized similarly to polymer 1.

Polymer 6:

Polymer 6 was synthesized in the same way as polymer 4 using poly (maleic anhydride-cher-octadecene) (M _n : 30-50000 g / mol, 20 g), poly (ethylene glycol) methyl ether (M _n : 2000 g / mol, 136 g) as a grafted component. Toluene (500 ml) was used as a reaction solvent; the polymer solution was precipitated in hexane. The reactions made it possible to proceed for a total of 36 hours. The polymer was characterized as polymer 1. Excess PEG can be removed from the polymer by dialysis or a similar methodology.

Polymer 7:

Polymer 7 was synthesized in the same way as polymer 1, using poly (ethylene-co-butyl acrylate-co-maleic anhydride) (40 g) as the main chain and poly (ethylene glycol) methyl ether (M _n : 2000 g / mol, 30 g) as a grafted component. A mixture of xylene (100 ml) and toluene (100 ml) was used as a reaction solvent; in this case, the polymer solution was precipitated in ethanol. The polymer was characterized similarly to polymer 1.

Polymer 8:

Polymer 8 was synthesized in the same way as polymer 1, using poly (ethylene-co-vinyl acetate-co-maleic anhydride) (40 g) as the main chain and poly (ethylene glycol) methyl ether (M _n : 2000 g / mol, 13 g) as a grafted component. A mixture of xylene (125 ml) and toluene (125 ml) was used as a reaction solvent; in this case, the polymer solution was precipitated in ethanol. The polymer was characterized similarly to polymer 1.

Polymer 9:

Polymer 9 was synthesized in the same way as polymer 8, using poly (ethylene glycol) methyl ether (M _n : 2000 g / mol, 39 g) as the grafted component. The polymer was thoroughly washed with additional ethanol after filtration to remove PEG from the polymer. The polymer was characterized similarly to polymer 1.

Polymer 10:

Polymer 10 was synthesized in the same way as polymer 1 using (isobutylene-cher-maleic anhydride) (M _n : 6000 g / mol, 20 g) and Jeffamine M-1000 (amine functionalized polyester, M _n : 1000 g / mol, 129 g) as a grafted component. The reactions were allowed to proceed for a total of 24 hours and toluene (200 ml) was used as a solvent. The resulting polymer solution was cooled and precipitated in hexane at 0 ° C. The polymer was characterized similarly to polymer 1.

Example 4: Application Tests

In all cases, with the exception of test 2 (adhesion tests, 4.2), all tests are based on a property that results from the amphiphilicity of the grafted copolymers.

4.1 The use of polymers as emulsifiers / surfactants - Test 1

4.1.1 Purpose

To measure the ability of polymers to act as emulsifiers (demonstrating surface activity) for emulsions of two immiscible liquids. Since the amphiphilic polymeric material acts as a surfactant (surfactant), it must be present at the interfaces between the two phases. Hydrophilic sites (PEGs) and possibly hydrolyzed MA units should be in the aqueous phase or adjacent to the aqueous phase, while the hydrocarbon sections of the polymer backbone should be associated with oil (which is usually not completely miscible with water).

4.1.2 Methodology

Materials

A 2 M NaOH solution: NaOH (8 g, Aldrich, ACS grade) was dissolved in water (100 ml).

Silicone oil: Dow Corning Corporation 200® liquid, viscosity 5 cSt (25 ° C).

Water-in-oil emulsion

It is applicable where the grafted copolymer is soluble in oil (in this case demonstrated with toluene), but has a lower or insignificant solubility in water (this type of dissolution is common for all grafted copolymers described in the examples, to some extent with the exception of 6), which demonstrated here with polymer 9. Without being bound by theory, it is believed that the resulting colloidal mixture of oil and water has oil as a dispersion medium and water as a dispersed phase; and can therefore be described as a water-in-oil emulsion. It is generally accepted that the phase in which the emulsifier (surfactant) is more soluble tends to be a dispersion medium (this generalization is known as Bancroft's rule). Therefore, a water-in-oil emulsion is usually formed when the formation of the emulsion is successful as a result of adding water to the solution of a relatively hydrophobic or water-insoluble surfactant in oil, as in this case. Information about whether oil or water is a dispersion medium in an emulsion can be obtained by specialists in this field of technology in various ways. They are described, for example, in Introduction to Colloid & Surface Chemistry (Duncan J. Shaw, 4 ^th edition, ISBN: 0750611820). One suitable method described is the addition of water and oil (or an oil mixture) to two different aliquots of the emulsion. If the emulsion can be easily mixed with oil (that is, without the formation of a separate layer of oil), the dispersion medium is oil, and the emulsion has a water-in-oil structure; if the emulsion can be mixed with water, the dispersion medium is water, and the emulsion is an oil-in-water emulsion.

Polymer 9 (0.44 g) and toluene (44 g, 50 ml) were weighed into a 100 ml beaker, and the polymer was dissolved by heating the mixture at 80 ° C. in a water bath. Deionized water (50 ml) was heated in a separate glass in the same water bath. Then, both glasses were removed from the water bath, and a paddle mixer controlled by a mixer located on top was placed in the solution. While both solutions were still hot, deionized water was gradually added to the vigorously stirred solution in toluene. Once the addition was complete (~ 2 min), the emulsion was mixed with shearing force using a Silverson laboratory emulsifier for 1 min. Then, stirring was started again with a paddle stirrer and maintained until the emulsion reached room temperature. Then the emulsion sample was placed in a sealed jar with a screw cap and visual monitoring was carried out at certain intervals (1 h, 24 h, 1 week).

One aliquot of the emulsion was mixed with toluene, and one with water. The emulsion was easily mixed with toluene, but not mixed with water, which formed a separate layer. Therefore, the resulting colloidal mixture was considered a water-in-oil emulsion in which the surfactant was 0.5% by weight of the total emulsion.

Oil-in-water emulsion

It is applicable where further modification of the grafted copolymer is actually soluble in water (in this case, demonstrated with toluene), but has lower (as in this case) or insignificant solubility in oil. Without being bound by theory, it is believed that the resulting colloidal mixture of oil and water has water as a dispersion medium and oil as a dispersed phase; and can therefore be described as an oil-in-water emulsion. This structure usually occurs when an emulsion is formed by adding oil to a solution of a relatively hydrophilic surfactant in water.

Polymer 6 (2 g) and deionized water (50 ml) were added to a 100 ml beaker, and the polymer was dissolved by stirring the mixture with a magnetic stirrer. The polymer solution was then mixed with shearing force using a Silverson laboratory emulsifier, while silicone oil (50 ml) was gradually added to it. As soon as the addition was completed (~ 2 min), the emulsion sample was placed in a sealed jar with a screw cap and visual monitoring was carried out at regular intervals (1 h, 24 h, 1 week).

One aliquot of the emulsion was mixed with silicone oil, and one with water. The emulsion was easily mixed with water, but not mixed with silicone oil, which formed a separate layer. Therefore, the resulting colloidal mixture was considered an oil-in-water emulsion in which the surfactant is about 2% by weight of the total emulsion.

Oil-in-water emulsion using open ring grafted copolymers

In these cases, although the copolymers are amphiphilic, they are not sufficiently soluble in water to dissolve at useful concentrations to serve as emulsifiers. Therefore, unreacted maleic anhydride present on the main chains is subjected to ring opening by hydrolysis, most preferably using the aid of a base. The acid or salt groups with an open ring contribute to the dissolution of the grafted copolymer. Without being bound by theory, it is believed that the resulting colloidal mixture of oil and water has water as a dispersion medium and oil as a dispersed phase; and can therefore be described as an oil-in-water emulsion.

Polymer 3 (2 g) and a 2 M NaOH solution (50 ml) were added to a 100 ml beaker, and the polymer was dissolved by stirring the mixture with a magnetic stirrer. Then the polymer solution was mixed with shearing force using a Silverson laboratory emulsifier, while silicone oil (50 ml) was gradually added to it. As soon as the addition was completed (~ 2 min), the emulsion sample was placed in a sealed jar with a screw cap and visual monitoring was carried out at certain intervals (1 h, 24 h, 1 week).

One aliquot of the emulsion was mixed with silicone oil, and one with water. The emulsion was easily mixed with water, but not mixed with silicone oil, which formed a separate layer. Therefore, the resulting colloidal mixture was considered an oil-in-water emulsion in which the surfactant is about 2% by weight of the total emulsion.

4.1.3 Results

Emulsions are prepared in three different ways. The water-in-oil emulsion was stabilized by polymer 9, and the oil-in-water emulsion was stabilized by polymer 6. In the case of polymer 3, the grafted polymer was dissolved by opening the ring of residual maleic anhydride in the polymer backbone using a base. The emulsions turned out to be stable during the weekly period; in the case of polymer emulsion 6 after this period, a small amount of separation was observed, which was immediately easily redispersed by gentle shaking of the mixture manually. The stability of emulsions depends on a number of factors, including the concentration of surfactant (emulsifier), and can, therefore, be changed to some extent by changing its concentration. It can be expected that the use of more emulsifier will increase the duration of the stability of the emulsions. In some cases, the use of another surfactant (for example, an ionic surfactant like sodium dodecyl sulfate, or a nonionic surfactant like alcohol ethoxylate) can be used to increase the stability of emulsions containing these surfactants. It should be obvious that in industrial or consumer applications, emulsions can be enhanced with a number of other ingredients, which may include functional or active ingredients specific to the application, stabilizers, preservatives, pigments and colorants, flavors, thickeners, defoamers, film-forming agents, among other ingredients . The amphiphilic nature of the grafted copolymers leads to their surface activity and activity as emulsifiers. Since the hydrophilicity of the polymeric material can be varied, they have the potential to be used to stabilize emulsions of various oils and water, which can have both oil-in-water and water-in-oil structures.

4.1.4 Conclusions

Grafted copolymers can be used as surfactants for oil and water emulsions. These polymers can be used without modification or in the form of an open ring. Highly grafted PEG grafted copolymers typically have better solubility in water than in oil, and are therefore more likely to be useful as oil-in-water emulsifiers. In contrast, polymers with lower degrees of hydrophilic grafting are more likely to be used as surfactants for water-in-oil emulsions. The solubility of the polymers in water can be increased by opening the ring of residual maleic anhydride in these cases, which makes it possible to use the resulting material as an oil-in-water emulsifier.

Example 4.2.0 Adhesion Tests - Test 2

4.2.1 Purpose

To measure the ability of grafted copolymer films to decrease the ability of a sticky substance (commercial chewing gum) to adhere to a substrate, thereby forming a non-sticky surface.

4.2.2 Methodology

Cooking discs

A series of smooth disks with a diameter of 5 cm and a thickness of 3 mm was created by cutting sticks of nylon, PTFE (polytetrafluoroethylene), brass, and stainless steel to an appropriate size. Then prepared solutions of the tested polymers. Polymer 1 was dissolved in THF (5 wt.% Solution); 3 was dissolved in THF (3.3 wt.% Solution); 6 in THF (2.5 wt.% Solution); polymers 2, 7, 8 and 9 were dissolved in toluene (5 wt.% solutions), and 4 were dissolved in ethyl acetate (2.5 wt.% solution). Then, still warm solutions were carefully applied to the discs using a small brush, covering one of each substrate with each solution. The discs were left to dry for at least 30 minutes, after which they were re-coated. The total number of coatings was adjusted in accordance with the concentration of the solutions, so that, for example, only 4 coatings were applied in the case of 5 wt.% Solutions, eight in the case of 2.5 wt.% Solutions. The discs were left overnight in a fume hood to dry completely.

Test conditions

Pieces of chewing gum (Wrigley's Extra trademark with peppermint flavor) were chewed for 5 minutes, and a freshly chewed piece was applied to each dry disk. Then, a square piece of PTFE film was placed on top of the gum, and a load of 1 liter glass bottle filled with 1 liter of water was placed on top of the square of PTFE.

The samples were left for three nights, after which the goods were removed, and then the PTFE squares (with the gum chewing gum attached) were carefully peeled off using a human hand to calibrate the force with which the gum stuck to the surface of the disks. PTFE was used because it creates a thin inert layer that is easy to remove.

4.2.3 Results

Nine polymers were tested on four surfaces, the adhesion of the gum to the surfaces was evaluated on a scale between 1-5, where one is a test with very low adhesion between the chewing gum of the gum and the surface of the substrate, five is a surface with very high adhesion between the two surfaces (table 2 ) Control experiments were also carried out in which there was no polymer coating in order to determine the effect of the coating with a decrease in adhesion compared to an unprotected surface.

table 2 Chewing gum adhesion test results for polymer films Polymer Nylon PTFE Brass Stainless steel one one 3 2 one 2 one 3 one one 3 one 5 one one four one one 2 one 5 one one 3 one 6 3 5 2 one 7 one 2 one one 8 one one one 3 The control 3 5 four 5

Based on the control, it is clear that high adhesion is usually observed between the four substrates and gum chewing gum. All grafted copolymers are suitable for reducing the adhesion ability of surfaces. In all cases, with the only exception of polymer 7, grafted copolymers created a non-sticky surface on nylon; with the exception of polymers 3 and 7, they created a non-sticky surface or a surface with reduced stickiness on PTFE disks. All grafted copolymers created a non-sticky surface or a surface with reduced stickiness on the surfaces of both metals.

4.2.4 Conclusion

Grafted copolymers are suitable for reducing the stickiness of surfaces. Universally, they reduced the stickiness of metal surfaces, and in almost all cases they reduced the stickiness of gum to polymer substrates.

Example 4.3.0 Contact Angle Measurement - Test 3

4.3.1 Purpose

To measure the ability of grafted copolymers to modify surface properties by using different hydrophilicity of materials to produce either water-repellent surfaces or wettable surfaces.

4.3.2 Methodology

Smooth glass disks with a diameter of 5 cm and a thickness of 3 mm were prepared by cutting glass rods to a suitable size. They were coated using solutions prepared similar to test 2 (4.2.2). The concentration of all solutions was 2.5 wt.%, Polymers 1-3 and 6 were dissolved in THF; 4 was dissolved in ethyl acetate, and 7-9 was dissolved in toluene.

In all cases, still warm solutions were carefully applied to glass disks with a small brush. The discs were left to dry for at least 30 minutes, after which they were re-coated. The total number of coatings was adjusted according to the concentration of the solutions, so that, for example, only four coatings were applied in the case of 5 wt.% Solutions, eight in the case of 2.5 wt.% Solutions. The discs were left overnight in a fume hood to dry completely.

After that, a drop of water was placed on each disk and the contact angle between the water and the substrate was measured using a goniometer of the contact angle to analyze the Kruss drop shape (model No. DSA 10-Mk2).

4.3.3 Results

The contact angle of the water droplet was measured on polymer films and on a control glass without coating every 30 s for 10 min. In some cases, the contact angle of a drop of water decreased so quickly that it was impossible to measure its value over a full ten-minute period. In these cases, an attempt was made to measure the initial contact angles.

Table 3 Initial and final contact angle for various grafted copolymers Contact angle Polymer t = 0 min t = 4 min P3 57.4 55.5 P4 82.8 80.2 P7 77.6 75 P8 83.3 80.7 P9 86.1 82.6 The control 41.6 34.6

The contact angle data is easiest to compare and see in FIG.

It was observed that water creates an angle of contact with glass of about 42 ° after 0 min and 35 ° after 4 min. Figure 1 shows the contact angle of water with disks coated with a number of different polymers. Although some wetting of the surface occurs on the disks, it is seen that the grafted copolymers increase the contact angle of water with the disks, which indicates that they provide some degree of water repulsion from the surface. Polymers 7, 8, and 9 provide the highest degrees of water repulsion, probably due to their high hydrophobicity as materials having a very low PEG content. In general, materials with lower hydrophobicity have a smaller contact angle. Although samples P3 and P4 had a similar PEG content, samples in P4 had long-chain alkyl octadecene groups, which should affect the overall hydrophilic-lipophilic balance (HLB) of the grafted copolymers, and this explains their smaller contact angle than was observed on P3 films. Thus, amphiphilic copolymers are either more hydrophilic or more hydrophobic, and the subsequent behavior of the grafted copolymers can be changed by changing the main chain and the PEG content to the desired. A contact angle of 0 ° was recorded after 2 min on a disk coated with P6 (not shown in FIG. 1). This (without connection with theory) is mainly due to the fact that the water-soluble polymer was dissolved at this stage or adsorbed water. It should be noted that the main chain of P4 and P6 is identical, differing only in the content of PEG (which is five times higher in P6). This suggests that the hydrophilicity of the grafted copolymers can be controlled in such a way as to make them either wetting or water-repellent agents.

4.3.4 Conclusions

The tunable amphiphilic nature of the grafted copolymers means that the interaction of water with the surfaces coated with them can be changed by changing the main chain and the content of amphiphil grafted onto the main chain.

Example 4.4.0 Use of amphiphilic grafted copolymers to mediate the release of a chemical from chewing gum

4.4.1 Objectives

Demonstration that grafted copolymers in chewing gum mediate the release of a chemical (in this case, commercial cinnamaldehyde flavoring).

4.4.2 Methodology

Chemical reagents

All substances, calcium carbonate (CaCO ₃ ), esterified rosin, hydrogenated vegetable oil (HVO, hydrogenated soybean oil), polyisobutylene (PIB molecular weight 51000), poly (vinyl acetate) (PVAc molecular weight 26000), glyceromonostearate (HMS), microcrystalline wax (Microwax mp 82-90 ° C), liquid sorbitol and solid sorbitol, were food grade and obtained from the Gum Base Company. Cinnamaldehyde (98 +%) was obtained from Fisher-Scientific UK.

Chewing gum making

The gum base has a composition as shown in the table below:

Table 4 Recipe for making rubber foundations Stage Ingredient % Songs Mass / g one PIB 13 1,04 PVAc 6 0.48 CaCO ₃ 6 0.48 Esterified rosin 3.6 0.288 2 Esterified rosin 5,4 0.432 CaCO ₃ 9 0.72 3 PVAc 9 0.72 Esterified rosin 9 0.72 CaCO ₃ fifteen 1,2 four Hvo 12 0.96 Gms 6 0.48 X 6 0.48 Total one hundred 8 X is one of the new grafted copolymers, or microcrystalline wax in the case of control S3, HVO = hydrogenated vegetable oil, PVAc = poly (vinyl acetate).

The rubber base materials were mixed on a Haake Minilab microcompounder from Thermo Electron Corporation, which is a small-scale laboratory mixer / extruder. The ingredients were mixed together in four stages, where the rubber was extruded only after the final stage. The rubber base was mixed at 100 ° C.

Chewing gum was mixed in accordance with the table below.

Table 5 Chewing Gum Ingredients Stage Time Ingredient amount one 15 minutes 37.5% Rubber base containing X 3 g 10% Sorbitol Liquid 0.8 g 17% Sorbitol Powder 1.36 g 2 15 minutes 25.5% Sorbitol Powder 2.04 g 6% X 0.48 g 3% Sorbitol Liquid 0.24 g 1% Corrigent Cinnamaldehyde 0.08 ml 30 minutes TOTAL 8 g X represents one of the new grafted copolymers or microcrystalline wax in the case of control S3

The rubber was mixed using the same equipment as for the base, and extruded after the final stage. Rubber was mixed at 60 ° C. In step 1, liquid and powder sorbitol were pre-mixed before adding them to the rubber.

Experimental method

Each preformed gum was weighed before chewing and weight was recorded to allow an estimate of the total amount of drug in each gum.

Used chewing machine 'ERWEKA DRT-1' from the company AB FIA, which works by alternately compressing and twisting the gum between two woven nets. A water jacket with a water temperature set to 37 ° C was used to control the temperature in the chewing cell to the temperature expected by in vivo chewing, and the chewing rate was set to 40 'chewing' per minute. The gap between the jaws was set at 1.6 mm.

40 ml of artificial saliva (consisting of an aqueous solution of various salts, approximately at pH 6 — see below, table 6) was added to the chewing cell, then a plastic net was placed on its bottom. Gum of known mass was placed on the center of the grid, and a second grid was placed on top.

Table 6 Artificial Saliva Composition Ingredients Amount (mmol / L) KH ₂ PO ₄ 2,5 Na ₂ HPO ₄ 2,4 KHCO ₃ fifteen NaCl 10 MgCl ₂ 1,5 CaCl ₂ 1,5 Lemon acid 0.15 Ph adjusted to 6.7 HCl

Methodology for the analysis of the profiles of the release of active ingredients from gum

When chewing always used the parameters shown in table 7, unless otherwise noted.

Table 7 Chewing options Parameter Value Temperature 37 ° C Gap between jaws 1.6 mm Twist angle 20 ° Chewing frequency 40 bpm

At the beginning of each experiment, a cell containing artificial saliva and gum was left for 5 minutes so that the system could balance to 37 ° C. Then chewing gum. Then, a 0.5 ml sample volume was removed from the test cell periodically during the release experiment (5, 10, 15, 20, 25, 30, 40, 50, and 60 minutes).

All samples were then analyzed by HPLC using a typical Perkin Elmer Series 200 HPLC system equipped with an automatic dispenser, pump and digital diode detector. Instrument handling and control data was provided through Totalchrom v 6.2 software.

Gum (pieces of known mass of about 1 g) was placed between two plastic nets and chewed mechanically in artificial saliva. All were analyzed using an HPLC chromatograph. A detailed description of this equipment is given below.

A typical Perkin Elmer HPLC system is data processing and instrument monitoring using Totalchrom v 6.2 software. The system is based on the 200 Series system, equipped with an automatic dispenser, pump and digital diode detector.

In this case, HPLC was used to analyze free cinnamaldehyde in solution, which was released as a result of chewing. The set of conditions for cinnamaldehyde is as follows:

Column: Varian Polaris 5u C18-A 250 × 4.6 mm

Mobile phase: Acetonitrile / 0.05% phosphoric acid (60/40)

Flow rate: 1 ml / min

Detection: UV 250 nm

Injection Volume: 5 μl

Samples in saliva were injected neat after filtering through a 10 mm PTFE Akrodisk syringe filter.

Samples were compared with standards (prepared in artificial saliva) covering a range of 0.02-1.00 mg / ml. The retention time of cinnamaldehyde was determined to be 4.9 min on this equipment, therefore, the peak at a given retention time was used to detect released cinnamaldehyde. Samples were chewed two or three times, and in all cases two consistent release curves were constructed. All samples were dispersed in duplicate on an HPLC apparatus, indicating that the results were highly reproducible.

4.4.3 Results

Gum was made from polymers 1-4 and 6-9 and chewed in artificial saliva. Released cinnamaldehyde was analyzed by HPLC. A control (S3) was also obtained in which the grafted copolymers were replaced by Microwax and analyzed in the same way (FIG. 2).

It was observed that control (S3) gave a fairly stable release of cinnamaldehyde, culminating in approximately 60% release after 60 minutes. Although gum containing two (P8 and P9) grafted copolymers had release profiles similar to Microwax, most had cinnamaldehyde release profiles either with a faster and higher maximum, or with a slower and lower maximum. For example, polymer 8 releases only 40% of cinnamaldehyde in gum after 60 minutes; compared to 50% in the case of control. In contrast, the release of cinnamaldehyde from a gum made using P4 appears to have reached a plateau of approximately 70% cinnamaldehyde up to 30 minutes. The release rate from the gum containing RE was slower, but the maximum release was comparable to or slightly higher.

4.4 Conclusions

By changing the main chain and the degree of grafting (hence hydrophilicity) of amphiphilus, it is possible to change the release profile of chemicals from chewing gum, in this case demonstrated by the example of cinnamaldehyde. The release rate is apparently determined by a number of factors, including the chemical identity of the main chain and the degree of grafting, resulting in a change in interaction with saliva and other gum ingredients. Thus, graft copolymer systems are disclosed with a range of different release rates that are potentially available for inclusion in a chewing gum composition.

4.5.0 Use of amphiphilic grafted copolymers to mediate the release of the active ingredient

4.5.1 Objectives

Demonstrate the use of amphiphilic grafted copolymers for the delivery and release of active ingredients, demonstrated by observing the release of ibuprofen from solid blends of polymers and ibuprofen, that is, those containing ibuprofen. By inclusion, the inventors mean that the active ingredient is physically coated or enclosed by the grafted copolymer.

4.5.2 Methodology

Materials

Ibuprofen (grade 40) was obtained from Albemarle.

Obtaining solid mixtures of polymer and ibuprofen

The powdered graft copolymer and ibuprofen were weighed into a beaker so that ibuprofen was 1% by weight. The two ingredients were pre-mixed with a spatula to give a roughly uniform mixture, and then mixed and extruded using the Haake Minilab microcompound at 60 ° C. In the case of polymer 2, 3.96 g of polymer and ibuprofen (0.04 g) were used; in the case of polymer 3, 2.97 g of polymer and ibuprofen (0.03 g) were used.

Test method

Samples of included ibuprofen (approximately 1 g of a substance of known mass) were placed between two plastic nets and chewed mechanically in artificial saliva. The chewing details of included ibuprofen are identical to those used for chewing gum with cinnamaldehyde (4.4.2), with samples taken after 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 40 minutes, 50 minutes and 60 minutes. After that, they were prepared for HPLC analysis by filtration through a 10 mm PTFE syringe filter Akrodisk. Samples were analyzed using an HPLC chromatograph as described above (4.4.2) using the detailed experimental description below.

Detailed description of ibuprofen HPLC: (Column: Hypersil C18 BDS, 150 × 4.6 mm; mobile phase: acetonitrile / 0.05% aqueous phosphoric acid in a ratio of 60/40; 1 ml / min; UV detector, wavelength - 220 nm).

Samples of included ibuprofen were chewed two or three times and, in all cases, two consistent release curves were constructed. All samples were separated on an HPLC apparatus in duplicate, indicating that the results were highly reproducible.

4.5.3 Results

Two different polymers were used to incorporate ibuprofen, both were chewed, and the release profile was monitored by HPLC (FIG. 3).

Both polymer / ibuprofen mixtures released ibuprofen into the solution during chewing, and similar total amounts of ibuprofen were released into saliva — about 60% of the total maximum, the point at which the release appeared to plateau in the two tested examples. Interestingly, the release of ibuprofen is much faster in the case of polymer 2 than polymer 3. Although both polymers have chemically similar backbones, the amount of MPEG grafted onto the backbone is significantly higher in case 2. A possible explanation, therefore, is that an increase in the hydrophilicity of polymers contributes to the loosening of the included samples, resulting in faster release during chewing / grinding (polymers are solids).

4.5.4 Conclusions

Ibuprofen was included in two samples of grafted copolymers and was released by chewing samples in artificial saliva. Grafted copolymer 2 releases ibuprofen faster than grafted copolymer 3; the first also contains more PEG and is more hydrophilic. It is seen that by regulating the hydrophilicity of amphiphilic grafted copolymers, it is possible to change the rate of release of ibuprofen.

Claims (26)

1. Amphiphilic polymeric material of General formula (I):

where B is a straight or branched polymer backbone, which is a copolymer of at least one ethylenically unsaturated aliphatic hydrocarbon monomer containing at least 3 carbon atoms and maleic anhydride, and each OR is a hydrophilic side chain attached to the main chain, where x denotes the number of side chains and is in the range from 1 to 5000. 2. The amphiphilic polymeric material according to claim 1, wherein the ethylenically unsaturated hydrocarbon monomer is selected from isobutylene, 1,3-butadiene, isoprene, and octadecene. 3. The amphiphilic polymeric material according to claim 1, where the side chains of OR are attached to maleic anhydride in the main chain. 4. The amphiphilic polymeric material according to claim 1, where x is in the range from 1 to 300, preferably from 1 to 150. 5. The amphiphilic polymer material according to claim 1, where each side chain has a molecular weight in the range of 800-10000. 6. The amphiphilic polymeric material according to claim 1, where the main chain has a molecular weight in the range of 1000-10000. 7. The amphiphilic polymeric material according to claim 1, where the R group has the general formula (II)

where each of Y and Z independently represents an alkylene group having from 2 to 4 carbon atoms, and R ³ represents H, an optionally substituted alkyl group having from 1 to 12 carbon atoms;
and each of a and b independently represents an integer from 1 to 200, provided that the sum of a + b has a value in the range from 1 to 250. 8. The amphiphilic polymeric material according to claim 7, where in formula II both alkylene groups Y and Z are —CH ₂ CH ₂ -. 9. The amphiphilic polymeric material according to claim 7, where in formula II, the group R ³ represents H or CH ₃ . 10. The amphiphilic polymeric material according to claim 7, where in formula II, the sum b + c has a value in the range from 20 to 120. 11. Amphiphilic polymer material according to any one of claims 1 to 10, where the main chain contains 1-50 wt.% Maleic anhydride. 12. A method for producing an amphiphilic polymeric material according to any one of claims 1-11, wherein the starting material of a copolymer of at least one ethylenically unsaturated aliphatic hydrocarbon monomer and maleic anhydride is reacted with side chain precursors of the general formula (III), HO-R, to produce an amphiphilic a polymer material of the general formula (I). 13. The method according to item 12, where sections of the maleic anhydride of the main chain interact with the precursors of the side chains to obtain an amphiphilic polymer material of the general formula (I). 14. An amphiphilic polymeric material that has a straight or branched polymer backbone and one or more hydrophilic side chains attached to the main chain, where the main chain is a terpolymer of maleic anhydride, ethylene and an additional ethylenically unsaturated monomer. 15. The amphiphilic polymeric material according to 14, where the additional ethylenically unsaturated monomer is an alkyl acrylate. 16. The amphiphilic polymeric material according to 14, where the additional ethylenically unsaturated monomer is an alkenyl acetate, preferably vinyl acetate. 17. Amphiphilic polymer material according to any one of paragraphs.14-16 of the General formula (IV):

where B ¹ represents a straight or branched main chain of the polymer, and each YR ¹ represents a hydrophilic side chain attached to the main chain, where Y represents O or NR ⁵ , where R ⁵ represents H or C _1-4 alkyl, and x ¹ denotes the number of side chains and is in the range from 1 to 5000, and R ¹ has the same meaning as R defined above. 18. Amphiphilic polymeric material according to 17, where Y represents O. 19. A method for producing an amphiphilic polymer material according to claim 17 or 18, wherein the starting material of terpolymer of maleic anhydride, ethylene and additional ethylenically unsaturated monomer is reacted with side chain precursors of the general formula (V), H-YR ¹ , to obtain an amphiphilic polymer material of the general formula (Iv). 20. A chewing gum base comprising an amphiphilic polymeric material, wherein the polymeric material is as defined in any one of claims 1-11 or 14-18. 21. A chewing gum composition comprising a chewing gum base according to claim 20, and one or more sweeteners or flavoring agents. 22. The chewing gum composition according to item 21, which further comprises a biologically active ingredient. 23. An emulsion containing an amphiphilic polymeric material according to any one of claims 1 to 11 or 14-18. 24. The emulsion according to item 23, which is an emulsion of water-in-oil or oil-in-water. 25. The use of amphiphilic polymeric material, as defined in any one of claims 1 to 11 or 14-18, as an emulsifier. 26. The use of an amphiphilic polymeric material, as defined in any one of claims 1-11 or 14-18, as a surfactant for cleaning or washing purposes.

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