AU685922B2 - Polymers of unsaturated saccharides and their derivatives and their copolymers having ethylenically unsaturated compounds, and process for preparing them - Google Patents

Description

-2- Polymerisates of unsaturated saccharides end their derivatives, as well as their co-polymers with ethylenically -unsa t urated compounds and processes for their preparation The invention concerns new polymers of unsaturated saccharides and their derivatives which contain a double bond in the ring (endocyclic) or on the ring (exocyclic), as well as co-polymers with ethylenicallyunsaturated compounds. These compounds are preparable and obtainable by radical-initiated polymerisation (homo-, co) of ethylenically-unsaturated monosaccharides, disaccharides, oligosaccharides which contain a double bond in the ring (endocyclic) or on the ring (exocyclic), chemically protected or unprotected, enzymatically or chemically modified unsaturated mono-, di- or oligosaccharides or mixtures of the said compounds or co-polymers of components corresponding to with monomers or monomer mixtures from the following groups: monoethylenically-unsaturated

C

3 to carboxylic acids and their alkali metal, alkaline earth metal or ammonium salts, monoethylenically-unsaturated C1- to C 12 carboxylic acid esters,

I-

acrylic acid or metbacryli acid dialkylaminoalkyl esters with, in all, up to 30 C-atoms in the dialkylaminoalkyl radical which can be present' in N.quaternised or salt form, acrylic acid amides, methacrylic acid amide, N-(dialkyl)-acrylic acid or -methacrylic acid amide, N-vinylimidazoles which can be substituted on the heterocyclic ring by up to three Cl- to

C

12 -alkyl radicals and can be present in Nquaternised form or in salt form, five- to eight -membered N-vinyllactams which can be substituted on the ring by up to three

C

l to C 12 -alkyl radicals, maleic acid anhydride, maleic acid dialkyl esters with, in all, up to 3 C-atoms in the alkyl radical, styrene which can be substituted on the aromatic ring by up to two C1- to C -alkyl radicals, acrylonitrile, metbacrylonitrile, N.vinylpyridines which can be substituted on the heterocyclic ring by ap- Cl- to 012alkyl radicals and can be present in N.

quaternised form or in salt form..

PreTerabigl 25 the mol ratio of f (95 to to Depending upon the nature of the monomers and comonomers used,the polymers according to the invention find use as active material components, industrial uA uC~ Kb adjuvants, such as e.g. thickening agents, dispersing agents, for the increasing of viscosity or in the pharmaceutical, medicinal and cosmetic field.

Furthermore, the new polymers are suitable as components for adhesives and for the reduction of flow resistance. The biocompatibility offers especial advantabes in pastes, salves, joint coverings, contact lenses, adjuven.ts in biotechnology, e.g. chromatography.

Depending upon the desired properties, products can be desired of relatively low molecular weight (less tham about 20,000), average molecular weight (about 20,000 to 100,000), e.g. for the adjustmanet of correspondingly desired viscosities, or high molecular weight (above 100,000), e.g with high viscosity in solution at low concentration.

In addition, such different, specifically produced molecular weights can be desired in the case of use as material components since, as is known, the structureproperty relationships play a great part.

Furthermore, the invention concerns a process for the preparation of these polymers and their characterisation.

The polymer formation with the mentioned saccharide derivatives according to has hitherto not been described. From this field, in the literature only 4 communications are known from which it follows that glucose derivatives with double bond in the ring, p.

so-called D-glucal derivatives, can be co-polymerised with maleic acid anhydride and thereby form oligomers with low molecular weight Koyama, M. Kawata and K. Kurita, Polymerisation of unsaturated sugars, I, Radical Copolymerisation of D-glucal derivatives and maleic anhydride, Polymer Journal, 19 (1987), 687-693.

II, Radical copolymerisation of a furanoid glucal, 3-0-benzyl-l,2-dideoxy-5,6-0-isopropylidene-D-arabinohex-l-enofuranose, ibid. 19 (1987), 695-700i, M.J. Han et al., Synthesis and Biological Activity of poly- ((tri-0-acetyl-D-glucal)-alt-(maleic anhydride) derivatives, Bull. Korean Chem. Soc., 12 (1991) 85-87, and Makromol. Chem., Macromol. Sympos. 33 (1990), 301 509). A biological axtivity of these substances as carrier for anti-tumour active materials is investigated.

It was the task of the present invention to prepare new polymers from unsaturated sugar monomers and to make available to the technology new materials with new properties. These are characterised in that the carbohydrate components impart their specific qualities to them. To these belong hydrophilia or a characteristic balance between hydrophila and hydrophobia, compatability especially with biological systems, and here e.g. especially with the skin, no or low toxicity, biological decomposability etc.

-6- This task is solved by the features of the main claims and promoted by the subsidiary claims.

A series of new, surprising findings could be achieved which, starting from the prior art, were not to be expected.

It is possible to obtain homopolymers from unprotected and protected unsaturated saccharide derivatives.

Sugar derivatives with double bond in various positions in or on the-ring can be (co)polymerised.

It was shown that monomers, which themselves polymerise, can be brought to co-polymerisation with sugar derivatives of the type as co-monomers.

There can be prepared not only low molecular oligomeric products but also high molecular polymers or co-polymers (with molecular weights above 10,000 Dalton), All these (co)polymerisations lead to previously unknown products. Consequently, the invention refers to new polymers from unsaturated saccharides or sachharide derivatives which contain a double bond in the ring (endocyclic) or on the ring (exocyclic), as well as co-polymers with eth3lenically-unsaturated compounds.

These polymers are obtained by polymerisation in substance, in solvents and/or aqueous systems,initiated with radical starters, of ethylenically unsaturated saccharides, chemically protected or unprotected, enzymatically or chemically modified mono-, di-, trisaccharides or -7mixtures of the said compounds with a double bond in the ring (endocyclic) of the following formula I or stereoisomers

OR

0

(I)

OR

1

R

2 0 2 in which R 1 signifies hydrogen, an acetyl, benzoyl, methyl or benzyl group,

R

2 represents hydrogen, an acetyl, benzoyl, methyl, benzyl group or a glucosyl radical and R is hydrogen, an acetyl, benzoyl, methyl or benzyl group, formula II or stereoisomers

(II)

OR

3 1

R

2 0 2 in which R 2 represents hydrogen, an acetyl, benzoyl, methyl, benzyl group or a glucopyl radical,

R

3 is hydrogen, an acetyl, benzoyl, methyl, benzyl group or (R 2 ,R can be a protective group usual in organic chemistry, such as e.g. 4,6-0-benzylidene or 4,6-0-isopropylidene, formula III or stereoisomers OR 3 3 2 in which Ri represents hydrogen, an acetyl, benzyl, beuzoyl, alkyl group with, in all, up to 2 C-atoms in the alkyl radical, R?2 represedtps hydrogen, an acetyl, benzoyl, benzyl, alkyl group with I 3 C-atoms or a glycosyl radical, R 3is hydrogen, an acetyl, benzoyl, benzyl, methyl group, formula IV or stereoisomers OR 3 0 Lo

(IV)

R

2 03 2 in which R?2 signif'ies hydrogen, an acetyl, benzoyl, alkyl, benzyl group or a glucosyl radical, R3 is hydrogen, an acetyl, benzoyl, methyl, benzyl, tosyl group or (R 2 1R 3 can be a protective group usual in organic chemistt'y (such as e.g. 4,6-0-beuzylidene), f'ormula V -9-

COOR

4

O

4 OR OR 1

(V)

OR

2 in which R 1 is hydrogen, an alkyl group or a galacturonic acid radical, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group,

R

3 signifies hydrogen, anacetyl, benzoyl, benzyl, alkyl group,

R

4 represents hydrogen, a methyl or ethyl group, or those with a double bond on the pyranoside ring (exocyclic) of the following formula VI or stereoisomers 0 OR OR (VI) R4 OR 2 in which R 1 can be hydrogen, an acetyl, benzoyl, benzyl group, or alkyl group with 1 3 C-atoms or a fructosyl radical, R 2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R is an acetyl, benzoyl, benzyl, alkyl group,

R

4 represents hydrogen, an acetyl, benzyl, benzoyl, alkyl group, formula VII or stereoisomers OR2(V) R 30

OR

in which R. is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R2 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group,

R

3 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group or a glucosyl radical,

R

4 signifies hydrogen, an aceyl, benzoyl, benzyl or alkyl group, formula VIII or stereoisomers

O

R OR2 (VIII)

RRO

R

1 0 in which R 1 is hydrogen, anacebyl, benzoyl, benzyl, alkyl group,

R

2 is hydrogen, an.acetyl, benzoyl, benzyl, alkyl group,

R

3 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, and the corresponding derivatives on leucrose basis or their stereoisomers, formula IX or stereoisomers -11 OR

(IX)

3

OR

1 in which Rlis hydrogen, an acetyl, benzoyl, benzyl, alkyl group,

R

2 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, Rrepresents hydrogen, an acetyl, benzoyl, benzyl, alkyl group or a glucosyl radical, or those with a double bond on the furanoside ring of the following formula X and their stereoisomers ~67~OR 1 Mx RDO

OR

2 -3 2 in which R. can be hydrogen or an alkyl radical with 1 to 3 C-atoms,

R

2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, Rsignifies hydrogen, anacetyl, benzyl, benzoyl, alkyl group, or (R 2 2R 3 can be a protective group usual in organic chemistry, formula XI R 3 01{ 2 0 RO (XI) OR 2 -12in which R R 2 is hydrogen, an acetyl, benzyl, benzoyl, alkyl group,

R

3 represents hydrogen or a glucosyl radical, such as e.g. in the case of palatinose, formula XII

R

3 0H 2 C 0 RqO X II

OR

2 in which RI, R2, R 3 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group,

R

4 represents a glucosylradical, such as e.g. in the case of saccharose, or co-polymerisation with monomers or monomer mixtures from the group monoethylenically-unsaturated

C

3 to carboxylic acids and 'their alkali metal, alkaline earth metal or ammonium salts, monoethylenically-unsaturated C to C 12 carboxylic acid esters, acrylic acid or methacrylic acid dialkylaminoalkylesters with, in all, up to 30 C-atoms in the dialkylaminoalkyl radical which can be present in N.quaternised form or salt form, acrylic acid amides, methacrylic acid amide, N- (dialkyl)-acrylic acid or methacrylic acid amide N-vinylimidazoles which can be substituted on the heterocyclic ring by up to three C 1 I- up to C 12 alkyl radicals and can be present in Nguaternised form or in salt form, Mi~ five- to eight-membered N-vinyllactams which can be substituted on the ring by up to three C I- to C 12 alkyl radicals, maleic acid anhydride, maleic acid dialkyl esters with, in all, up to 2 C-atoms in the alkyl radical, styrene which can be substituted on the aromatic ring by up to two C 1 I- to C 3-alkyl radicals, acrylonitrile, methacrylonitrile N-vinlylpyridines which can be substituted on the heterocyclic ring by-Rj;4 C I- to C 12 alkyl radicals and can be present in N-quaternised form or in slt f orm, 4i-a the mol ratio of Of- (95 to to h'O~ preferably (75 to 20):(25 to Examples for the formula I are l,5-anhydro-2-deoxyarabinobex-l-enitol (or 1 ,2-dide oxyarabinohex-l-enopyranose), briefly called Iglucal", and its derivatives, such as tri-0-acetyl-D-glucal, t ri-0-benzyl-IJ-glucal, tri-O-benzoyl-D-glucal, tri-0-methyl-D-biucal, tri-Oethyl-D-glucal.

Examples for the formula II are l,2-dideoxyerythrohex-l-enopyranose-3-ulose, 4,6-benzylidene-l,2-dideoxyerythrohex- i-enopyranose-3-ulose and 4,6-0-is opropyl- __j -14idene-l ,2-dideoxyerythrohex-l-enopyranose-3-ulose.

Examples for the formula III are 2,3-dideoxyerythrohex-2-enopyranose (briefly called "pseudoglucal") and its derivatives, such as tri-O-acetylpseudoglucal, tri-0-benzoylpseudoglucal, tri-O-benzylpseudoglucal, 1-ethoxy- and, 1-methoxydiacetyipseudoglucal, I-ethoxyand l-methoxydibenzylpseudoglucal, 1-ethoxy- and 1math oxypseud~glucal, l-hydroxydiacetylpseudoglucal.

Examples for formula IV are 2,3-dideoxyer'ythrohex- 2-enono-l,5-lactone and its derivatives 4,6-O-benzylidene-,4,6-di-0-acetyl-, 4,6-di-O-benzoyl- and 4,6-di- 0-benzyl-2 ,3-dideoxyerythrohex-2-enono-l Examples for the formula V are methyl 4-deoxy-Lthreohex-4-enopyranoside.- uronic acid, methyl (methyl- 4-deoxy-I-threohex-4-enopyranoside).,-uronate, methyl- 2,3-di-O-benzyl (or methyl) -4-deoxi.J.-threohex-4enopyranoside-uronic acid methyl ester and unsaturated digalacturonic acid (O-(4-deoxy-Ii-threohexopyranose-4-enyluronic acid)-(174)-D-galacturonic acid.

Examples for the formula VI bre 1,2,3,4-tetra-0acetyl-6-deoxy-p3-D-xylohex-5-eflopyranose, 1,2,3,4tetra-0-benzoyl-6-p3-D-xylohex-5-enopyranose, 6-deoxymethyl-2,3,4-tri-0-acetyl-6methyl-2,3,4-tri-0benzyl-6-de oxy-D-xylohex-5-enopyranoside, methyl-6deoxy-2 ,3 and Examples for the formula VII are 2,6-anhydro-ldeoxygluco (or galacto)- hept-l-enitolv 3,4,5,7tetra-0-benzyl-, 3,4,57P--tetra-...benzoyl-, 5,4,5,7tetra-0-acetyl- or\4,5,7-tetra-O-trinethyl (or triethyl)-dilyl-2 ,6-a nhydro-l-deoxyglucohept-l-enitol..

Examples for the formula VIII are 5,4,5-tri-Obenzoyl-1-deoxy-2 ,6-anhydro-D-xylosehex-l-enitol, 3,4 ,5-tri-0-acetyl-l-de oxy-2 ,6-anhydro-D-xyl ose hex-lenitol, 1-deoxy-2 ,6-anhydro-D-xylosehex-l-enitoI and the 1,2-unsaturated enol ether of leucrose hexabenzoate (or hexaacetate).

Examples for the formula IX are 2,5,4-tri-O-acetyl (benzovyl, benzyl, methyl)-6-deoxy-D- enolact one.

Examples for the formula X, are pent-4-enofuranoside, methyl-2,3-ibopropylidene-5-deox-yerytbropent-4-enofurenoside, 2,5-anhydro-6-benzyl-1deoxY-3,4-0-isopropylidene--D-ribohex-1-enitoI and 2,5-anhydro-6--(tert.-butylphenylsilyl)-l-deoxY-3,4bis-0-trimethylsilyl-D-ribohex-l-enitol and 5-de oxyjl,2-O-isopropylidenethreopent-4-enofuranose (from JLarabinose).

Examples for the formula XI are ,4 ,6-O-trimethylsilyl-D-arabinohex-1-enitol and the l,2-unsaturated enol ether of palatinose, hexabenzoate (or hexaacetate).

Examples for the formula XII are 6-deoxy.-2,5-0- (from L- -16sorbpse) and the 1,2-unsaturated enol ether of saccharose hexaacetate.

Examples of the co-monomers are: acrylic acid methacrylic acid (MAA), dimethylacrylic acid, ethylacrylic acid, vinylacetic acid, ailylacetic acid and vinyipropionic acid. From this group, one preferably uses acrylic acid, methacrylic acid, their mixtures, as well as the sodium, potassium, calcium or ammonium salts or their mixtures.

In this group are found alkyl, hydoxyalkyl and vinyl esters, such as methacrylate ethylacrylate, n-propylacrylate, n-butylacrylate, methylmethacrylate (MMA), hydroxyethylacrylate hydroxypropylacry late (EPA), hydroxybutylacrylate (EBA), hydroxyethylmethacrylate (EMEA) and vinyl formate, vinyl acetate (VA), vinyl propionate, as well as mixtures thereof.

Wd In this group come into consideration dimethylaminoethyl acrylate, diethylaminoethyl acrylate, methylethylaminoethyl acrylate, di-tert.-butylaminaoethyl Ptrylate, dimethylamino-met~yl (or butyl, hexyl, octyl, stearyl)-acrylate, dimethyl (or diethyl, methylethyl, di-tert.-butyl)-aminoethyl methacrylate, dimethylaminomethyl (or butyl, amyl, hexyl, octyl, stearyl)-methacrylate.

Acrylic acid amide methacrylic acid amide (MAM), Ni-dimethylacrylic acid amide, N-d imethylmethacrylic acid amide -17- Examples of the N-vinylimidazoles are e.g. 1-vinylimidazole, 2-methyl-l-vinylimidazole, 4-methyl-l-viplimidazole, 2,4-dimethyl-l-vinylimidazole or 2-ethyl-1vinylimidazole. For the quarternised N-vinylimidazoles, there can be used usual quaternisation agents of organic chemistry.

(fV As N-vinyllactams, there are suitable, for example, l-vinylpyrrolidone, 1-vinylcaprolactam, 1-vinylpiperidone, 4-methyl-l-vinylpyrrolidone, vinylcaprolantam.

Maleic acid anhydride, maleic acid diethyl ester, maleic acid dimethyl ester.

Styrene, 1-vinyltoluene, 3-vinyltoluene or their mixture.

acrylonitrile, methacrylonitrile.

N-vinylpyridines which are substituted n the heterocyclic ring by so C- to C 12 -alkyl radicals and can be present in N quatermised form or in salt form.

Preparation: For the preparation of the polymers according to the invention, the sugar monomers are polymerised radically initiated with or without co-monomers Because of the properties of the resulting polymers, in some cases it can be interesting, to use two of the compounds mentioned under or two sugar monomers and one monomer of the compounds mentioned under or i I -18one sugar monomer and two monomers The radical polymerisation can be carried out in the presence of or also in the absence of inert or polar solvents, as well as in aqueous systems. The polymerisation in the absence of solvents, briefly called substance or melt polymerisation, is carried out in a vacuum.

Since this technique is not convertable into a large scale, the solution polymerisation in solvents or in water is preferred. In this case, the compounds mentioned under and and the polymer formed are present in dissolved form. Suitable inert solvents are, for example, benzene, toluene, p-xylene and their isomer mixtures, ethylbenzene, tert.-butylbenzene, chlorobenzene, p-dichlorobenzene, aliphatic hydrocarbons, such as bexane, heptane, octane, nomne, dodecane, cyclobexane, as well as mixtures of the said hydrocarbons. Furthermore, there are suitable chlorohydrocarbons, such as chloroform, carbon tetrachloride and dichloromethane. As polar solvents, there are suitable dimethyl sulphoxide, tetrahydrofuran, dioxane, butanone and acetone, as well as mixtures of the said polar solvents.

With polar water-soluble sugar monomers, the polymerisations are preferably carried out in aqueous media.

Tn the case of smaller batches, in which a sure removal of the heat of polymerisation is ensured, the -19reaction participants can be polymerised discontinuously in that the reaction mixture is beated to the polymerisation temperature. As a rule, this temperature lies in the range of 20 to 15000 and especially preferably between 40 to 130 0 0. As soon as the temperature in the case of the polymerisation lies above the bpiling point of the inert solvent or of the monomers and/or the polymerisation is carried out under pressure. In this case, the concentration of the components and amounts to 10 to 90, preferably 20 to 70 mol The polymerisation can be carried out continuously.

For this purpose, there can be used especially the continuous polymerisation at temperatures of 50 to 1500C. Under these polymerisation conditions, one uses catalysts which form radicals, e.g. inorganic and prganic peroxides, persulphates, azo compounds and so-called redox catalysts. As radical-forming initiators, there are preferably suitable all compounds which, at the chosen polymerisation temperature, have a half life time of about 3 hours.

If one first starts the polymerisation at low temperature and leads to the end at higher temperature, it is expedient to work with at least two initiators decomposing at different temperatures, namely, at first to begin with an initiator breaking down at low temperature and then to carry out the main polymerisation to the end with an initiator which breaks down at higher temperature.

Referred to total monomers used in the case of the polymerisation, one uses 0.01 to 20, preferably 0.1 to mol of a polymerisation initiator or of a mixture of several polymerisation initiators.

One can use water-soluble or water-insoluble initiators or mixtures of water-soluble and waterinsoluble initiators. The initiators insoluble in water are then soluble in the organic phase.

For the temperature ranges given in the following, one can, for example, use the initiators stated theref or: Temperature: 4lC to 600C acetylcyclohexanesulphonyl peroxide, diacetyl-, dicyclohexyl-, di- 2-ethylbexyl peroxydicarbonate, tert.butyl-, tert.-amyl perneodecanoate, 2,2'-azo-bis-(tmethoxy-2,4-dimethylvaleronitrile), 2,2'-azo-bis-(2amidinopropane) dihydrochloride, 2,2' -azo-bis-(2-(2imidazolin-2-yl)-propane) dihydrochloride; Temperature: 60 to 80 00 tert.-butyl-, tert.-amyl perpivalate, dioctanoyl-, dilauryl peroxide, 2,2'-azo-bis-(2,4-dimethylvaleronitrile), 2,2'-azo-bis-(isobutyronitrile); Temperature: 80 to 100 0

C

dibenzoyl peroxide, tert.-butylper-2-ethyl hexanoate, tert.-butyl perinaleinate, dimethyl-2,21-azo-bis-isobutyrate, sodium persulphate, potassium persulphate, ammonium persulphate; -21- Temperature: 100 to 120 C bis-(tert.-butylperoxy)-cyclobexane, tert.-butylperoxyisopropyl carbonate, tert.-butyl peracetate, hydrogen peroxide; Temperature: 120 to 14000 2,2-bis-(tert.-butylperoxy)-butane, dicumyl peroxide, di-tert.-amyl peroxide, di-tert.-butyl peroxide; Temperature: 140 0 p-mentbane, pinane, cumol and tert.-butyl hydroperoxide.

If one wishes to reduce the half life times of the stated radical-forming initiators, in addition to the mentioned initiators one also uses salts or complexes of heavy metals, e.g. copper, cobalt, manganese, iron, vanadium, nickel or chromium salts, or organic compounds, e.g. benzoin, dimetbylaniline or ascorbic acid.

The reducing components of redox catalysts can be formed, for example, from compounds such as sodium sulphite, sodium bisulphite, sodium formaldehyde sulphaoylate or hydrazine.

As redox components, one adds 0.01 to 50 mol of the reducing-acting compounds. Heavy metals are used in the range of 0.1 to 100 ppm, preferably of to 10 ppm. It is often of advantage to use a combination of peroxide, reducing agent and heavy metal as redox catalyst. Thus, one can, for example, already so activate tert.-butyl hydroperoxide with the addition of 5 ppm copper III acetylacetonate or cobalt octanoate that one can already polymerise at 100°C.

The solution polymerisation usually takes place in an inert gas atmosphere with exclusion of atmospheric oxygen and moisture. The solvents are freshly distilled and degassed immediately before the polymerisation.

The monomer compounds given under and are very pure, water- and stabiliser-free. As already mentioned, the monomers and are present in dissolved form.

During the polymerisation, care is taken for a good mixing up of the reaction participants.

The preparation of the polymers according to the invention can be carried out in usual polymerisation devices. For this purpose, one uses, for example, agitator vessels or double-walled reactors which are equipped with anchor, paddle, impeller or multi-step impulse countercurrent stirrers.

Preparation processes: The polymers according to the invention can be prepared by polymerisation in substance or solution polymerisation of the components or and in non-polar or polar solvents, whereby the solution polymerisation in water or water-alcohol mixture is especially preferred.

In the case of solution polymerisation in aqueous medium, the unprotected water-soluble sugar monomers and possibly with polar co-monomers and the -23water-soluble initiator are present in dissolved form.

The polymerisation reaction is carried out under the same conditions (temperature, initiator concentration, monomer ratio) as in the case of the polymerisation in solvents.

The polymers according to the invention can also be prepared in alcoholic aqueous solution. In this case, there are present the alcohol portions of 1 to preferably 5 to 20 As alcohol, there are suitable methanol, ethanol, isopropanol, n-propanol, as well as mixtures of the said inert solvents.

Examples If not otherwise indicated, the statements in percent mean mol percent.

Isolation and characterisation of the polymers according to the invention: The chain reactions were stopped by addition of inhibitors, such as e.g. hydroquinone or pyrocatechol. The polymers formed are isolated by precipitating out (in the tenfold parts by volume of the precipitation agent) and filtration. In general, methanol, ether, diethyl ether, hexane or their mixtures were used as precipitation qgent.

The molecular weights of the polymers were determined by gel permeation chromatography.

The composition of the polymers was calculated by elementary analysis or wet analysis.

-24- In different examples, the FT-IR spectra were additionally determined.

Examples with glucal derivatives Example 1 A mixture of 41.6 g tri-0-benzoyl-D-glucal (TBzG) and 10.415 g styrene and 100 ml of solvent (benzene) forms feed 1. Feed 2 was prepared from 0.32 g azo-bis-isobutyronitrile (AIBN) and 10 ml benzene. In a 1 1 polymerisation reactor, which is equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, feed 1 and feed 2 are heated to 600C with stirring. After reaching of the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 25.0 wt.% yield.

The GPC analysis gave a molecular weight of 140,400.

Example 2 Example 1 was repeated with the change that, instead of styrene, one used 7.206 g acrylic acid (AA) and polymerised in dimethyl sulphoxide or dioxane.

One obtained a white solid material with 41 wt.% yield which had a molecular weight of 12,000.

Example 3 Example 2 was repeated with the change that, instead of one used 7.108 g acrylic acid amide (AM) and polymerised in acetone or tetrahydrofuran.

One obtained a white solid material with 35 wt.% yield which had a molecular weight of 6500.

Examples with glucal Example 4 Feed 1 consisted of 14.60 g glucal in 120 ml of water. Feed 2 was prepared from 0.228 g ammonium peroxydisulphate and 10 ml of water. In a 1 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet and dosing devices, feed 1 and 2 were placed and warmed -to 40 0 C. It was then further polymerised at this temperature for 24 hours.

One obtained a while solid material with 36 wt.% yield.

The GPC analysis gave a molecular weight of 3900.

Example Feed 1 consisted of a mixture of 14.6 g glucal, 17.2 g acrylic acid diethyl ester (MDE) in a ratio of 1:1 and 120 ml of water. As feed 2, there served a solution of 0.473 g V 50 (2,2'-azo-bis-(2-amidinopropane)HCl) in 20 ml of water. In a 1 1 vessel, which is equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 500C. After reaching the intended temperature, it was further stirred for 24 or 48 hours at this temperature.

After ending of the reaction, one obtained a white solid material with 25.0 weight yield. The GPC analysis gave a molecular weight of 2300.

-26- Example 6 Feed 1 consisted of a mixture of 14.60 g glucal, 10.01 g methacrylic acid methyl ester (MMA) in a ratio of 1:1 in 120 ml of water. As feed 2, there served a solution of 0.185 g sodium disulphite/0.228 g ammonium peroxydisulphate as redox catalyst in 20 ml of water.

In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 4000. After reaching of the intended temperature, it was further stirred for 24 to 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with wt.% yield. The GPC analysis gave a molecular weight of 4300.

Example 7 Feed 1 consisted of a mixture of 14.6 g glucal, 13.02 g hydroxyethylmethacrylic acid ester (HEMA) in a ratio of 1:1 and 120 ml of water. As feed 2, there served a solution of 0.456 g ammonium peroxydisulphate in 20 ml of water. In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed land feed 2 and heated to 80 0

C.

After reaching the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 70 wt.% yield. The GPC -27analysis gave a molecular weight of 10,000.

Example 8 Feed 1 consisted of a mixture of 14.6 g glucal, 7.206 g acrylic acid (AA) in a ratio of 1:1 and 120 ml of water. As feed 2, there served a solution of 0.185 g sodium disulphite/0.228 g ammonium peroxydisulphate as redox catalyst and 20 ml of water. In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and inlet devices, were place feed 1 and feed 2 and heated to 400C. After reaching the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 17 wt.% yield. The GPC analysis gave a molecular weight of 2300.

Example 9 Feed 1 consisted of a mixture of 14.6 g glucal, 8.61 g methacrylic acid (MAA) in a ratio of 1:1 and 120 ml of water. As feed 2, there served a solution of 0.185 g sodium disulphite/0.228 g ammonium peroxydisulphate as redox catalyst and 20 ml of water.

In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and warmed to 400C. After reaching of the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with -28- 52 Wt.% yield. The GPC analysis gave a molecular weight of 5200.

Example Feed 1 consisted of a mixture of 14.6 g glucal, 8.61 g acrylic acid methyl ester (MA) in a ratio of 1:1 and 120 ml of water. As feed 2, there served a solution of 0.185 g sodium disulphite/0.228 g ammonium peroxydisulphate as redox catalyst and 20 ml of water. In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed land'feed 2 and warmed to 40 0 C. After reaching of the intended temperature, it was further stirred at this temperature for 24 or 48 hours. After ending of the reaction, one obtained a white solid material with 55 wt.% yield.

The GPC analysis gave a molecular weight of 5500.

Example 11 Feed 1 consisted of a mixture of 14.6 g glucal, methacrylic acid amide (MAM) in a ratio of 1:1 and 120 ml of water. Feed 2 was prepared from 0.456 g ammonium peroxydisulphate and 20 ml of water. In a 1 1 glass vessel with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and putlet devices were placed feed 1 and feed 2 and warmed to 6000. After reaching the intended temperature, it was further stirred for 24 hours at this temperature. After ending of the reaction, one obtained a white solid material with 39 wt.% yield. The GPC analysis gave i -I; -29a molecular weight of 4900.

Example 12 Feed 1 consisted of a mixture of 14.6 g glucal, 8.61 g acrylic acid methyl ester (MA) in a ratio of 1:1 and 120 ml of water. As feed 2, there served a solution of 0.112 g H 2 0 2 in 10 g ethanol. In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and warmed to 550C. After reaching of the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 48 wt.% yield. The GPC analysis gave a molecular weight of 3100.

Examples with pseudoglucals Example 13 Feed 1 consisted of 17.6 g 1-ethoxypseudoglucal in 120 ml of water. Feed 2 was prepared from 0.114 g ammonium peroxydisulphate/0.093 g sodium bisulphite and 20 ml of water. In a 1 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet were placed feed 1 and 2 and warmed to 600C. It was then further polymerised for 24 hours at this temperature. One obtained a white solid material with 15 wt.% yield. The GPC analysis gave a molecular weight of 2000.

-M M Example 14 Feed 1 consisted of a mixture of 17.6 g 1-ethoxypseudoglucal, 17.2 g maleic acid diethyl ester (MDE) in a ratio of 1:1 and 120 ml of water. As feed 2, there served a solution of 0.472 g V 50 in 20 ml of water. In a 1 1 vessel, which is equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed a and heated to 50 0 C. After reaching of the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 20 wt.% yield.

The GPO analysis gave a molecular weight of 2200.

Example Feed 1 consisted of a mixture of 17.6 1-ethoxypseudogLucal, 8.609 g methacrylic acid (MAA) in a ratio of 1:1 and 120 ml of water. As feed 2, there served a solution of 0.185 g sodium disulphite/0.228 g ammonium peroxydisulphate as redox catalyst and 20 ml of water.

In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 400C. After reaching of the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with wt.% yield. The GPC analysis gave a molecular weight of 7000.

-31- Example 16 A mixture of 25.4 g 1-ethoxydiacetylpseudoglucal (EDAPG) and"9.806 g maleic acid anhydride (MAh) and 100 ml of solvent (benzene) forms feed 1. Feed 2 was prepared from 0.52 g azo-bis-isobutyronitrile (AIBN) and 10 ml benzene. In a 1 1 polymerisation reactor, which is equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, feed 1 and feed 2 are heated to 6000, with stirring. After reaching of the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 15 wt.% yield.

The GPC analysis gave a molecular weight of 2900.

Example 17 Feed 1 consisted of a mixture of 25.4 g 1-ethoxydiacetylpseudoglucal (EDAPG), 10.415 g styrene (1:1) and 100 ml benzene. Feed 2 was prepared from 0.32 g azo-bis-isobutyronitrile (AIBN) and 10 ml benzene.

In a 1 1 glass flask, which is equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, feed 1 and feed 2 are heated to 600C, with stirring. After reaching of the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 20 wt.% yield. The GPC analysis gave a molecular weight of 12,500.

~L -32- Example 18 Example 16 was repeated with the change that, instead of maleic acid anhydride, one used 11.1 g Nvinylpyrrolidone and polymerised for 24 hours. One obtained a white solid material with 34 wt.% yield.

The GPC analysis gave a molecular weight of 205,000.

Example 19 Example 16 was repeated with the change that, instead of maleic acid anhydride, one used 8.609 g methacrylic acid One obtained a white solid material with 21 it.% yield. Tne GPC analysis gave a molecular weight of 4800.

Examples with "5,6-exo-glucal" Example 33.03 g 1,2,3,4-tetra-0-acetyl-6-deoxy-p-D-xyloare polymerised at 8000 for 24 hours in a vacuum in the presence of 0.242 g benzoyl peroxide.

One obtained a white solid material with 15% yield. The homopolymer had a molecular weight of 1600.

Example 21 Feed 1 consisted of 17.62 g methyl-6-deoxy-a-Din 120 ml of water. Feed 2 was prepared from 0.228 g ammonium peroxydisulphate in 20 ml of water. In a 1 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet and dosing devices, feed 1 and 2 were placed and warmed to 500C. It was then further polymerised at this at this temperature for 24 hours. One obtained a -53white solid material with 21 wt.% yield. The GPC analysis gave a molecular weight of 1900.

Example 22 33.03 g 1,2,3,4-tetra-0-acetyl-6-deoxy-p-D-xylohex-5-enopyran a polymerised at 100 0 C for 24 hours in toluene by 0.146 g di-tert.-butyl peroxide (DTBP) activated with 5 ppm copper acetylacetonate. One obtained a white solid material with 25% yield. The homopolymer had a molecular weight of 1600.

Example 23 Feed 1 consisted of 33.03 g 1,2,3,5-tetra-O-acetylin 100 ml tert.-butylbenzene (TBB). Feed 2 was prepared from 0.146 g (DTBP) and 10 ml TBB. In a 1 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet and dosing devices were placed feed 1 and 2, heated to 120°C and polymerised for 24 hours. Then, at this temperature, the remaining feed 2 was dosed in within minutes and further stirred for 24 hours. One obtained a white solid material with 25 wt.% yield. The GPC analysis gave a molecular weight of 5600.

Example 24 Feed 1 consisted of 30.23 g methyl-2,3,4-tri-0-acetylin 100 ml tert.-butylbenzene (TBB). Feed 2 was prepared from 0.73 g (DTBP) and 100 ml TBB. In a 1 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet and dosing devices were placed feed 1 and 20 ml of feed 2, -34and heated to 1200C and polymerised for 24 hours. Then, at this temperature, of the remaining feed 2, every 3 hours 20 ml were added thereto and further stirred for 24 hours. One obtained a white solid material with 19 wt.% yield. The GPC analysis gave a molecular weight of 3020.

Example Feed 1 consisted of 57.86 g 1,2,5,4-tetra-0-benzoyland 120 ml toluene.

As feed 2, there served a solution of 0.242 g BOP and ml toluene. In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 800C. After reaching of the intended temperature, it was further stirred at this temperature for 24 or 48 hours. After ending of the reaction, one obtained a white solid material with wt.% yield. The GPC analysis gave a molecular weight of 2830.

Example 26 Feed 1 consisted of a mixture of 33.03 g 1,2,3,4tetra-0-acetyl-6-deo-xy-D-xylohex-5-enopyranose, 9,,806 g maleic acid anhydride (MAh) in a raio of 1:1 and 100 ml benzene. As feed 2, there served a solution of 0.52 g AIBN and 20 ml benzene. In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and i 1 heated to 60°C. After reaching of the intended temperature, it was further stirred at this temperature for 24 or 48 hours. After ending of the reaction, one obtained a white solid material with 37 wt.% yield.

The GPC analysis gave a molecular weight of 5200.

Example 27 Feed 1 consisted of a mixture of 33.03 g 1,2,5,4tetra-0-acetyl-6-deoxy--D-xylohex-5-enopyranose, 7.206 g acrylic acid (AA) in a ratio of 1:1 and 100 ml toluene. As feed 2, there served a solution of 0.484 g BOP and 20 ml toluene. In a 1 1 vessel, which was equipped with a stirrer, heater, reflux condenser, .thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 80 0 C, After reaching of the intended temperature, it was further stirred for 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 34 wt.% yield. The GPC analysis gave a molecular weight of 5100.

Example 28 Example 27 was repeated with the change that, instead of acrylic acid, one used 10.42 g styrene (St).

One obtained a white solid material with 28 wt.% yield.

The GPC analysis gave a molecular weight of 3200.

Example 29 Feed 1 consisted of a mixture of 57.86 g 1,2,3,4tetra-0-benzoyl-6-deoxy-0-D-xylohex-5-enopyranose, 9.806 g maleic acid anhydride (MAh) in a ratio of 1:1 -36in 120 ml benzene. As feed 2, there served a solution of 0.29 g DTBP and 20 ml tert.-butylbenzene. In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and fee&2 and heated to 11000. After reaching of the intended temperature, it was further stirred at this temperature for 24 or 48 hours. After ending of the reaction, one obtained a white solid material with 18 wt.% yield.

The GPC analysis gave a molecular weight of 12,200.

Example Feed 1 consisted of a mixture of 57.86 g 1,2,3,4tetra-0-benzoyl-6-deoxy-p-D-xylobex-5-enopyranose, 8.609 g methacrylic acid (MAA) in a ratio of 1:1 and 120 ml toluene. As feed 2, there served a solution of 0.484 g BOP and 20 ml toluene. In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 8000. After reaching of the intended temperature, it was further stirred at this temperature for 24 or 48 hours. After ending of the reaction, one obtained a white solid material with 32 wt.% yield. The GPO analysis gave a molecular weight of 5700.

Example 31 Feed 1 consisted of a mixture of 18.62 g anhydro- 3,4-di-0-benzoyl-5-0-(2,5,4,6-tetra-0-benzoyl-a-Dglucopyranoxyl)-l-deoxy-D-arabinohex-l-enitol OMMMOOMMOMMM01W -37- (briefly called "leucren"), 1.961 g maleic acid anhydride (MAh) in a ratio of 1:1 and 120 ml TBB.

As feed 2, there served a solution of 0.058 g DTBP and 10 ml TBB. In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 130 0

C.

After reaching of the intended temperature, it was further stirred for 64 hours at this temperature.

After ending of the reaction, one obtained a white solid material with 46 wt.% yield. The GPC analysis gave a molecular weight of 27,000.

Example 32 Feed I consisted on 18.60 g methyl-5-deoxy-2,3-0isopropylidene-erythropent-4-enofuranoside (briefly called "ene-ribose") in 100 ml TBB. Feed 2 was prepared from 0.146 g (DTBP) and 10 ml TBB. In a 1 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet and dosing devices, were placed feed 1 and feed 2. The reaction mixture was heated to 11000. After reaching of the intended temperature, it wad further stirred at this temperature for 24 hours. After ending of the reaction, one obtained a white solid material with 35 wt.% yield. The GPC analysis gave a molecular weight of 2100.

Example 33 Feed 1 consisted of a mixture of 18.60 g eneribose, 9.806 g maleic acid anhydride (MAh) in a -38ratio of 1:1 and 100 ml TBB. As feed 2, where served a solution of 0.292 g DTBP and 20 ml TBB. In a 1 1 vessel, which was equipped with stirrer, beater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 11000. After reaching of the intended temperature, it was further stirred at this temperature for 24 hours. After ending of the reaction, one obtained a white solid material with 47 wt.% yield.

The GPC analysis gave a molecular weight of 3700.

Example 34 Example 33 was repeated with the difference that, instead of maleic acid anhydride, 11.1 g N-vinylpyrrolidine was used and polymerised for 6 hours.

One obtained a white solid material with 53wt.% yield.

The GPC analysis gave a molecular weight of 106,500.

Claims (6)

1. Polymers of unsaturated saccharides and their derivatives which contain a double bond in the ring (endocyclic) or on the ring (exocyclic), as well as co-polymers with ethylenically-unsaturated compounds, characterised in that the unsaturated saccharides are ethylenically-unsaturated monosaccharides, disaccharides, oligosaccharides which contain a double bond in the ring (endocyclic) or on the ring (exocyclic), chemically protected or unprotected, enzymatically or chemically modified unsaturated mono-, di- or oligosaccharides or mixtures of the said compounds and the monosaccharides correspond to the following general formulae formula I or stereoisomers OR 3 0 OR 1 1 (I) 2 in which R 1 signifies hydrogen, an acetyl, benzoyl, methyl or benzyl group, R 2 represents hydrogen, an acetyl, benzoyl, methyl, benzyl group or a glucosyl radical and R 3 is hydrogen, an acetyl, benzoyl, methyl or benzyl group, formula II or stereoisomers I- i OR 3 0 R 2 0 2 in which R 2 represents hydrogen, an acetyl, beuzoyl, methyl, benzyl group or a glucosyl radical, R 3 is hydrogen, an acetyl, benzoyl, methyl, benzyl group or (R 2 2,R 3) can be a protective group usual in organic chemistry, such as e.g. 4,6-0-beuzylidene or

4.6-O-isopropylidene, formula III or stereoisomers OR 5 3 0 OR 1 (III) 3 2 in which R 1 represents hydrogen, an acetyl, benzyl, benzoyl, alkyl group with, in all, up to 2 C-atoms in the alkyl radical, R 2 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group with 1 3 C-atoms or a glycosyl radical, R 3is hydrogen, an acetyl, benzoyl, benzyl, methyl group, f'ormula IV or stereoisomers -41- OR, 0 S0 (IV) R 2 0 3 2 in which R 2 signifies hydrogen, an acetyl, benzoyl, alkyl, benzyl group or a glucosyl radical, R 3 is hydrogen, an acetyl, benzoyl, methyl, benzyl, tosyl group or (R2,R 3 can be a protect.ve group usual in organic chemistry.(such as e.g. 4,6-0-benzylidene), formula V COOR4 0 4 OR OR 1 (V) OR 2 in which R L is hydrogen, an alkyl group or galacturonic acid radical, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R 3 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R 4 represent hydrogen, a methyl or ethyl group, or those with a double bond on the pyranoside ring (exocyclic) of the following formula VI or stereoisomers L- -L II -42- O -OR (VI) R4 0 OR 2 in which R1 can be hydrogen, an acetyl, benzoyl, benzyl group or alkyl group with 1 3 C-atoms or a fructosyl radical, R 2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R is an acetyl, benzoyl, benzyl, alkyl group, R 4 represents hydrogen, an acetyl, benzyl, benzoyl, alkyl group, formula VII or stereoisomers OR4 O OR2 (VII) OR in which R 1 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R 2 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R 5 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group or a glucosyl radical, R4 signifies hydrogen, an acetyl, benzoyl, benzyl or alkyl group, I -43- formula VIII or stereoisomers in which RIis hydrogen, anl acetyl, benzoyl, benzyl, alkyl group, R 2 is hydrogen, an acetryl, benzoyl, benzyl, alkyl group, R 3is hydrogen, an acetyl, benzoyl, benzyl, alkyl group and the corresponding derivatives on leucrose basis or their stereoisomers, formula IX or stereoisomers ORu0 (Tx) in which F? 1 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R?2 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, Rrepresents hydrogen, an acetyl, benzoyl, benzyl, alkyl gro 1 ip or a glucosyl radical, or those with a double bond on the furanoside ring of the following formula X and their stereoisolners -44- RO3 OR 2 in which Rcan be hydrogen or en alkyl radical with i to 3 C-atoms, R 2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R 3 signifies hydrogen, an acetyl, benzyl, benzoyl, alkyl group or (R 2 3R 3) can be a protective group usual in organic chemistry, formula XI R 3OH 2 C 0 R 0 (XI) OR 2 in which Rj,R 2 is hydro.gen, an acetyl, benzyl, benzoyl, elkyl group, Rrepresents hydrogen or a glucosyl radical, such as e.g. in the case of pelatinose, formula XII R 3 H 2 C0 R 4 R O 2 in which RI, R 2 R 3 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R represents a glucosyl radical, such as e.g. in the case of saccharose, the ethylenically-unsaturated compounds are selected from the group monoethylenically-unsaturated C to C0O- carboxylic acids and their alkali metal, alkaline earth metal or ammonium salts, monoethyle.n.ically-unsaturated C 3 to C12- carboxylic acid esters, acrylic acid or methacrylic acid dialkylaminoalkyl esters with, in all, up to 30 C-atoms in the dialkyl- aminoalkyl radical which can be present in N- quaternised form or in salt form, acrylic acid amides, methacrylic acid amide, N- (dialkyl)-acrylic acid or methacrylic acid amide, N-vinylimidazoles which are substituted on the heterocyclic ring by up to three C l to C 12 -alkyl radicals and can be present in N.quaternised form or in salt form, five- to eight-membered N-vinyllactams which can be substituted on the ring by up to three Cl- to C 12 -alkyl radicals, maleic acid anhydride, maleic acid dialkyl esters with, in all, up to 2 C-atoms in the alkyl radical, whereby co-polymers with compounds of the formula I are excluded, styrene which can be substituted on the aromatic ring by up to two C1- to C -alkyl radicals, 46 acrylonitrile, methacrylonitrile, N-vinylpyridines which can be substituted on the heterocyclic ring by Ci- to C 12 -alkyl radicals and can be present in N-quaternised form or in salt form. 2. Co-polymers according to claim 1, characterised in that the mol ratio of the saccharides to the ethylenically-unsaturated compounds amounts to 95:5 to 5:95, preferably 70:30 to 30:70. 3. Process for the preparation of polymers and co- polymers according to one of claims 1 to 2, characterised in that the monomers are polymerised by free radical polymerisation. 4. Process according to claim 3, characterised in that the free radical polymerisation is conducted in the presence of an inert, polar solvent. Process according to claim 3, characterised in that the free radical polymerisation is initiated by a "atalyst whic~h form radicals. 20 6. Process according to claim 5, characterised in that the catalyst is selected from inorganic and organic peroxides, persulphates, azo compounds or so-called radox catalysts in an amount of 0.01-20 mol%.

7. Process according to any one of claims 3 to 6, characterised in that the polymerisation is conducted at temperatures of 40-150 0 C, preferably 50-130 0 C.

8. Process according to claim 7, characterised in that the polymerisation is started at a low temperature Swith a radical initiator and ended at a higher temperature with another radical initiator.

9. Use of polymers and co-polymers according to claim 1 to 2, as active material components, industrial adjuvants or as thickening agents for the increasing of viscosity or in the pharmaceutical, medicinal or cosmetic field. Dated this 13th day of October 1997 AL/U VERIN DE ZUCKERINDUSTRIE AND KLAUS BUCHHOLZ \\mELBOI\honeS\Chelley\Keep\BJN\18940.95.doc 13/10/97 47 By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent Attorneys of Australia \NMELBO I\homne$\Chel 1ey\Keep\W1A 189 40.95.doc 13/10/97 1NIXNX1')(NA SKARIW1 103(r001I lIto ial Apltlittti1ri 'Sit PCT/EP 95/00930 A. (:I.ASSlI*ICA\l'l(s, 1 Stllli:(i MA l'rR IPC 6 C08F234/02 According to International Patent CassificPaon (IPC) or to both national classification and IPC B. FIELDS SEARCHED Mimnmum documentation searched (classification system followed by classificaton symbols) IPC 6 CO8F Documentation searched other than rminimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted dunng the international search (name of data base and, where practical, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category Citation of document, with indication, where appropnate, of the relevant passages Relevant to claim No. A POLYMER JOURNAL, 1 vol. 19, no. 6, 1987 page 687-693 KOYAMA ET AL 'Polymerisation of unsaturated sugars I. Radical Copolymerization of D-Glucal Derivatives and Maleic Anhydride' cited in the application A DE-A-36 28 240 (BASF) 5 March 1987 1 Further documents are listed in the continuation of box C. V Patent family members are listed in annex. Speaal categones of ated documents Special ategoes of cted documents'T lar document published after the Intematonal filing date document definin th al stat f th or priority date and not in conflict with the application but documentdefinin the general state of the art which is not cited o understand the pnciple or theory underlng the considered to be of particular relevance invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on pnority claim(s) or involve an inventive step when the document is taken alone which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document refernng to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the intemational filing date but in the art. later than the priority date claimed document member of the same patent family Date of the actual completion of the international search Date of maling of the international search report

28.06.95 June 1995 2 9 Name and mailing address of the ISA Authonzed officer European Patent Office, P.B. 5818 Patentlaan 2 NL 2280 HV Rljswilk Tel. (+31-70) 340-2040, Tx. 31 651 epo Meul emans, R Fax: (+31-70) 340-3016 man Form PCT/ISA/210 (second sheet) (July 1992) i- 111I'A,0 1 IM10A 111,11) ICI PCT/EP 95/00930 Patent documentII Publication Patent family Publication cited in search report I date member(s) date DE-A-3628240 05-03-87 NONE Form PCT/ISA/210 (patent family annex) (July 1992) 111tor alc AWAM1fitl PCT/EP 95~/00930 IPK 6 C08F234/02 Nach der Intcrnationalen Patenthas~ifikation (IPK) oder nach der nationalcn Kharikation und der lI'K Rechcrchiertcr M lndcstprufstoff (Klassifikationsystern und Klas~fikationssymbole) IPK 6 C08F Rcchcrchicrte aber nicht zurn Mindcstprufstoff gehbrendc Veroffentlichungen, soweit diese uiner die rcchcrchierten Gebicte fallen Wahrend der intcmnationalcn Recherche konsultierte ticktronische Datenbank (Namec dcr Datenbank und evil vcrwendec Suchbcgniffe) C. ALS WESENTLICH ANGESEHENE UNTERLAGEN__________ Kategonc* Iezeichnung der Verdffientlichung, sowelt erforderlIch unter Angabc der in Betacht kommenden Tefle Betr. Anspruch Nr. A POLYMER JOURNAL, 1 Bd. 19, Nr. 6, 1987 Seite 687-693 KOYAMA ET AL 'Polymerisation of unsaturated sugars I. Radical Copolymerization of 0-Glucal Derivatives and Maleic Anhydride' in der Anmeldung erw~hnt A DE-A-36 28 240 (BASF) 5.Mdrz 19871 [I Weatere Veroffentlichungen sind der Forisetzunig Yon Feld C zu jJ Siehe Anhanii Patentfarrnie critrichmen K *Besondere Kategonen von angegebcnen Ver6ffentlichungen Sptre Verofferatlichung, dic nach dem interinationalen Anmeldcdatum Verdffentliehung, dic den allgemeinen Stand der Technik definiert, oder dcm Pnionitsdatumn veroffentlicht worden lit und nut dcr aber nicht als besonders bedcutsam anzusehen ist Aneldung nicht kolidicrt, sondern nur zurnVerstrndnis des der E alere Doumet, as jdoe ert a odr nch drn nteaisnain Bfindung zugrundeliegcnden Prnzzps oder der tir zugrundeliegenden ltccs okucnt dasjcdch rstam dernachdemintrnaionlen Theone angegcben ist Aneidedatum verolffcntlicht Worden ist W Vcr~ffentlichung von besonderer Bcdeutung; die beanspruchte ErfindunF 'L Veroffentliehung, die geeignet ist, cinen PrioritAtsanspruch zweiftlhaft Cr- kann acin aulfgrund dieser Ver6ffentlichung rucht als neu oder auf scheinen zu lasn, oder durch die das Vcr6ffenthchungsdatum ciner erfindeniseher TAitext bcnihcnd beirachtet werden andcren im Rccherehenbenicht genannten Veroffentliehung belcgt werden yVer6ffenihbung von besondcrer Bedeutung; die beanspruchte ErindunE soil oder die aus cinem andereni besonderen Grund angegeben ist (wie kann nscht als auf crfindenscher Titigkceit beruhend betrachtet ausgefftlirt) werden, wcnn die Verofentlichung mit: einer oder mehreren anderen Veroffentlichung, die sich auf esne muindliche Offenbaring, Veroffentlichungen dieser Kategolie in Verbitidung gcbracht wird ufld etne Bcnutzung, emne Aussteliung odcr andere Mallnahmnr bezneht diese Verbindung fdr einen Fachxnann nahelsegend Ist Vcr6ffentlichung, die vor dem intemationalen Anmneldedatum, abcr nach Verfffentiehung, die Mitglied derselben Patentfaxnilie ist dem beanspruehten Pnioniidaturn veroffentlicht warden ist Datum des Abschlusscs der inteematonalen Recherche Absendedatum des intemnationalen Rccherehenbenchts 1995 28, 06. Name und Postanschrift der Internattonale Rceherchenbehdrde Bevollixniehtigter Bediensteter Europiisches Patentamt, P.13. 5818 Patentlaan 2 NL 2280 HV Rijswijk Tel. (+31-70) 340-2040, Tx.31 651 elpa ni, M u mn5 Fax (+31-70) 340-3016 Muea s Forenblatt PCT/ISA/21 0 (Blatt 2) (Juli 1992) A ngaho Vu V crolfcnUiOungo, dic Zut $01ben PAWntiAly'llic VIwfcn PCT/EP 95/00930 Im Rccherchenbericht I Datum der IMitg!,cd(or) der I Datumn der angcfuhrtes Patentdokument Vcroffentlhchung I Patcntfamilic I V crofrentlichung OE-A-3628240 05-03-87 KEINE I Formblatt PCr/ISA/210 (Anhang Patentfamilie)(Juli 1992)