CA2185321A1 - Polymers of unsaturated saccharides and their derivatives and their copolymers having ethylenically unsaturated compounds, and process for preparing them - Google Patents
Polymers of unsaturated saccharides and their derivatives and their copolymers having ethylenically unsaturated compounds, and process for preparing themInfo
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- CA2185321A1 CA2185321A1 CA 2185321 CA2185321A CA2185321A1 CA 2185321 A1 CA2185321 A1 CA 2185321A1 CA 2185321 CA2185321 CA 2185321 CA 2185321 A CA2185321 A CA 2185321A CA 2185321 A1 CA2185321 A1 CA 2185321A1
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- Prior art keywords
- acetyl
- benzoyl
- benzyl
- hydrogen
- alkyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F34/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
- C08F34/02—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring in a ring containing oxygen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F24/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
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- Organic Chemistry (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Dermatology (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Saccharide Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention concerns polymers of unsaturated saccharides and their derivatives which contain a double bond in the ring (endo-cyclic) or on the ring (exo-cyclic). It further concerns copolymers having ethylenically unsaturated compounds. The unsaturated saccharides are ethylenically unsaturated monosaccharides, disaccharides or oligosaccharides which contain a double bond in the ring (endo-cyclic) or on the ring (exo-cyclic), chemically protected or unprotected, enzymatically or chemically modified unsaturated mono, di or oligosaccharides or mixtures of said compounds. The ethylenically unsaturated compounds are selected from the group containing: (a) monoethylenically unsaturated C3 - C10 carboxylic acids and their alkali metal, alkaline earth metal or ammonium salts; (b) monoethylenically unsaturated C3 - C12 carboxylic acid esters; (c) acrylic or methacrylic acid dialkylaminoalkyl esters with a total of up to 30 carbon atoms in the dialkylaminoalkyl residue and which may be present in the N-quaternary or salt form; (d) acrylic acid amides, methacrylic acid amide, N-(dialkyl)-acrylic or methacrylic acid amide; (e) N-vinylimidazoles which may be substituted on the heterocyclic ring by up to three C1 - C12 alkyl residues and may be present in the N-quaternary or salt form; (f) five to eight-member N-vinyllactams which may be substituted on the ring by up to three C1 - C12 alkyl residues; (g) maleic acid anhydride, maleic acid dialkyl ester which may be present with a total of up to two carbon atoms in the alkyl residue; (h) styrene which may be substituted on the aromatic ring by up to two C1-C3 alkyl residues; (i) acrylnitrile, methacrylnitrile; and (j) N-vinylpyridines which may be substituted on the heterocyclic ring by up to four C1- C12 alkyl residues and may be present in the N-quaternary or salt form.
Description
2l8~32~
Polgmerisates of unsaturated ssccharides ~nd their derivatives, as well as their co-polymers with ethylenical~y_unsaturated compoun~s and processes f or their preparation ~rhe invention concerns new polymers of unsaturated sacchari~es and their derivatives which contain a double bond in the ring (endocyclic) or on the ring (exocgclic), as well 8S co-polymers with ethylenicallg-unsaturated compounds. ~hese compounds are preparable ~0 and obtai~able by radical-initiated polymerisation ~homo-, co~ oP
(A) ethy~enicallg-unsatursted monosacchsrides, di-saccharides, oligosaccharides which contain a double bond in the ring (endocyclic) or on the ring (exoc;yclic), chemically protected or unprotected, enzgmaticallg or ch~mi c~ I g modified unsaturated mono-, di- or oligossccharides or mixtures of the said compounds (~) or co-polymers o~ components corresponding to (A) with (B~ monomers or mDnomer mixtures from the fo~lowing groups:
(a) monoethylenicallg-unsaturated C3- to C10-carboxylic acids and their a~kali metaL, alkaLine earth metal or ammonium salts, (b) monoethylenically-unsaturated Cl- to C12-carboxylic acid esters, 21~32 ~
--3~
(c) scrylic acia or methacrgL~c acid dialkyLamino-alkyl esters with, in all, up to 30 C-stoms in the dialkDlaminoalk;yl radicsl which can be present in N_quaternised or salt form, (d) acr;ylic acid amides, methacrylic acid amide, N-(dialkyl)-acrylic acid or -m,ethacrylic acid smide, (e) N-yin;rlimidazoles which can be substituted on the heterocgclic ring by up to three Cl- to L0 CL2-alkyl radicsls and can be present in ~-quaternised form or in salt form, (f ) five- to eighi; ~-membered N-vin;~llactams which can be substituted on the ring bg up to three CL- to C~L2-alkyl rsdicals, 1.5 (g) maleic acid anh;~dride, maleic scid dialkyl esters with, in all, up to 3 C-atoms in the alkyl radical (h) st;~rrene which can be substituted on the aromatic ring b~ up to two CL- to C3-allsgl radicals, (i) acrylonitrile, methacr;ylonitrile, (~J ) N_vinylpyridines which can be substituted on the heterocycLic ring by up to Cl- to C~L2-all~yl r~3dicals and can be present in ~_ quaternised form or in salt form, 25 in the mol ratio of (A) :{B) rf (95 to 5): (5 to 95) .
Depending upon the nature of the monomers and co-monomers used,the polymers according to the invention find use- as active material components, industrial 218~32~
ad,~uvsnts, such a3 e.g. thickening ag~nts, dispersing agent3, for the increasing-of viscositg or in the phsrmaceutical, medicinal and cosmetic field.
Furthermore, the new pol~mers are suitat~le as 5 components f or adhesive6 a~d f or the reduction of ~ow resistance ~he biocompatibility offers especial advantages in ?astes, salves, ~ oint coYerings, contact lenses, ad~uven~ts in biotech~ology, e.g. chromato-grsphy .
Dependimg upon the desïred properties, products can be desired of relatively low molecular weight (less tham about 20,000), average molecular weight (about 20,000 to lOOtO00), e.g. for the ad~ustmanet of correspondingl~r desired viscos~ties, or high molecular 15 weight (above 100,000), e.g with high viscosity insolution at low concentration.
In addition, such di~ferent, specifically produced molecular weights can be desired in the case of use as material components since, as is known, the structure-20 property relationships pl ay a great part.
Fur~hermore, the inventio~ concerns a process forthe preparation of these polymers a~d their character-isation .
~ he polymer ~ormation with the mentioned saccharide 25 derivstives according to (A) has hitherto not ~een described. ~rom this field, in the ~iterature only 4 c, ,c~tions are known from whicb it follows that 3 glucose derivatives with double bond in the ring, ~ 218S321 so-called D-~,lucal derivatives, can be co-polymerised with maleic acid anhgd~ide a~d thereby ~orm oligomers with low molecular weight (Y, Koyama, M, Kawata and K. Kurita, Polymerisation of unsaturated sugars, I, 5 Radical Copolymerisation of D-slucal derivatives and maleic anh;srdride, POlymer JOurnal, 19 (L987), 687-693.
II, Radical copolymerisation of a furanoid g~ucal, ~i-O-benzyl 1,2-dideoxy-5,6-0-isoprop;yLidene-D-arabino-hex-l-e~ofuranose, ibid. 19 (~987~, 695-700i, M,J. Han 10 et al., S~nthesis and BiologiCal Activity of polD-( Ctri-O-acetgl-D-glucal) -alt- (maleic anhydride ) d~rivatives, Bull. Eores~ Che~0 Soc,, 12 (1991) 85-87, and ~akromol. Chem, , Macromol. S;~mpos . 3~ (1990), 301 - 309~ ~ A biological axtivity of these substances 15 as carrier for anti-tumour active materials is investigated, It was the task o~ the present invention tD prepare new polymers from unsaturated sugar monomers and to make available to the technolog;~ new materials with 20 new properties. ~hese are characterised in that the carbohydrate components impart their specific qualities to them. 'rO these belong hydrophilia or a character-istic bslance between hydrophila and hydrophobia, ~ompatability especiall~ with biological s;~stems, 25 and here e.g. especial~y with the skin, no or low toxicity, biological decomposability etc, ~, I
21~3211 ~his task is soLved by the features of t~e main claims and promoted by the subsidiary cLaims.
d series o~ new, surprising findings could be achieved which, starting from the prior srt, were not 5 to be expected, - It is possible to obtain homopolymers from unprotectsd ' and protected unsa~urated ssccharide derivatlves.
- Sugar derivatives with doubLe bond in various positions in or on the ring can be (co)polymerised.
10 - It was sho~n that monomers, which themselves poLg-merise, can be brought to co-polgmerisstion with sugar derivatives of the tgpe (A) as co-monomers.
- ~!here csn be prepsred not onlD ~ow molecular oligo-meric products but slso high moleculsr po~gmers or co-pol;ymers (with molecular weights sbove 10,000 ~alt on ), All these (co)poLgmerisations lead to previousLg unknown products. Conseguently, the invention refers to n~w poLymers from unsstursted ssccharides or sacQharide 20 derivstives which contsin a doubLe bond in the ring (endocgclic) or on the ring (exocgclic), as well 85 co-polymers with eth;5~1eiically-unsaturated compounds.
rhese polymers are obtained bg polymerisation in substance, in solvents and/or sgueous systems,initisted 25 with rsdical stsrters, of (A) - ethylenicslly unsaturated sacc harides, c h~m; ~gl 1 y protected or unprotec~ed, enz~msticalLy or chemic-ally modified mono-, di-, trisacchsrides or 2~8532~
` . ~
mixtures c~ the said compounds ~A), with a double bond in the ring (endocgclic) o~ the ~ollowing formuls I or st~reoisomers OR
~0 R20~ 1 (I) 5 in which Rl signi~ies hgdrogen, an acetgl, bQnzogl, ! methgl or benzg~ group, R2 represents hgdrogen, an acetgl, benzog~, me~h;
be~z;yl group or a glucos;s!l radical ~nd R3 is hgdrogen, an acetgl, benzo~l, methgl or benz~rl 10 grouP, ~ormula II or stereoisomers ,OR3 R20k~ (II) i~ wbich R2 represents hgdrogen, an acetyl, benzo;yl, methgl, benzgl group or a glucosgl radical, 15 R3 is hgdrogen, an acetgl, benzo;yl, methgl, benzg~
group or (R2,R3) can be a protectlve group usual in organic chemistrg, such as e,g, 4,6-0-benzglidene or 4,6-O-isopropglidene, formula III or stereoisomers 218~32 . ~
OR~
~0 ~`ORl ( III ) in which R1 represents hydrogen, an acetyl, benzyl, benzoyl, alkgl group with, in all, up to 2 C-atoms in the alkyl rsdical, 5 R2 r~prese~ts hydrogen, an acetyl, benzo;yl, benzyl, alkyl .
group with 1 - 3 C-atoms or a glgcosgl radical, R3 is h;rdrogen, an acst;yl, benzogl, benzyl, meth~rl group, ~ormula IV or stereoisomers ~0 ~ ~O (IV) ~\,J
i~ which R2 signi~i~s hgdrogen, an acetgl, benzoyl, ~lkgl, benzyl group or a glucos;~1 radical, R3 is bgdrogen, an acetgl, benzo;~rl, methyl, benzyl, tosgl group or ~R2,R3) can be a protective group usual in ~5 organic chemistry (such as e.g. ~,6-0-benz;ylidene), :Eormula V
218~3 . ~
g 4 ~ ORl (V) in wbich RL is hgdrogen, an alkyl group or a galsct-uronic acid radical, R2 is hydrogen, an acetgl, benzoyl, benzyl, alkyl group, 5 R3 signifies hydrogen, anacet;yL, benzoyl, be~zyl, alkgl group, R4 represe~ts hydrogen, a methyl or eth;rl group, or those with a double bond on the pyrsnoside ring (exocyclic) of the following formula VI or stereo-10 isomers ~ORl (VI~ ;
in which RJ can be hydrogen, an acetyl, benzoyl, be~zyl grou~, or alkyl grou~ with L - ~ C-atoms or a fructosyl radical, R2 is h;~drogen, an acet;yl, benzoyl, benzyl, ~5 alk;yl group, R~ is au acetyl, benzoyl, benzyl, alk;~1 group, R4 represents hgdrogen, an acetyl, benzyl, be~zoylJ
alkyl grou~, formula VII or stereoisomers ~ i 218~21 ~10--~0' ~ (VII) in which RI is hydrogen, an acetyl, benzoyl, benzy~
slkyl group, R2 r~presents hgdrogen, an acetyl, be~zogl, benzyl, 5 alkyl group, R3 represents hydrogen, an scetyl, benzogl, benz;yl, alkgl group or a gluc05;5r1 radical, R4 ~;~n;~ies hgdroge~, sn acetg~ benzoyl, benzgl or alXyl group, LO f ormula ~III or stereoisomers (VIII~
in which Rl is hydrogen, anæe~gl, benzoyl, benzgl, al~y~ group~
R2 is hDdroge~, an acet;yl, benzoy~, benzgl, al~yl group, 15 R~S is hydrogen, an a cetyl, benzoyl, benz;srl, alkyl group, and the corresponding derivatives on leucrose basis or t~eir stereoisomers, f ormula I~ or stereoisomers 2~532~
~o (~) R30 ORl in which Rl is hydrogen, an a cetyl, benzoDl, benzyl, alkyl group, R2 signifies hDdrogen, an acet;yl, benzoDL, benzDl, 5 alkyl group, R3 represents hydrogen, an acetyl, benzo~l, benzDl, alkyl group or a glucos;yl radical, or those with a double bond on the furanoside ring of the following formula g and their stereoisomers O
~_ OR
in which Rl can be ~ydrogen or an alkyl radical with 1 to 3 C-atoms, R2 is hDdrogen, an acetyl, be~zoyl, benzyl, alkDl group, R3 s;gn;~;P~ hydroge~, anacet~l, benzDl, benzogl, al}~Dl ~5 grou~, I
or (R2,R3) can be a protective group usual in organic chemistry, f ormula ~I
R30~2G o ~R1~ (XI ) ~ 218~2~
in which R, R2 is ~gdrogen, an acet;~l, benzgL, benzogl, alkgl ~roup, R3 represents hgdrogen or a glucosgL radical, such as e g, in the case of ~aLatin~se, 5 f ormula I~II
R40>~ ~XII ) in which RL, R2, R3 signifies hgdrogen, an acetgl, ben~ogl, benzgl, alkgl group, R4 represents ~ glucosg~radical, such as e.g. in the 10 case of saccharose, or co-~ool;srmerisation with (E~) monomers or monomer mixtures from the group (8) monoethglenicallg-unsaturated C3- to C10-carbox;ylic acids anG - their alkali metal, alkaline earth metal or ammonium salts, (b) monoethgle~icsllg-unsaturated C3- to C12-carboxgLic acid esters, (c j acrglic acid or methacrglic acid diaLkylamiLo-alkgl esters with, in alL, up to ~0 C-atoms in the dialkglaminoalk~L radicaL which can be present in ~i_quaternised form or saLt form, (d) acrylic acid amides, methacrglic acid amide, N-(dialkgL)-acrylic acid or methacrglic acid amide -218~321 (e) ~-vin~limidszoles which can be substituted on the heteroc~clic ring by up to t~ree Cl- up to C12-alkgl radicals and C8tl be present in ~l-qusternised form or in salt form, (f ) five- to eight-membered N-vi~gllsctsms which can be substituted on the ring bg up to three Cl- to C~L2-alkgl radicals, (g) maleic acid anh;srdride, maleic acid dialkgl esters with, in al~, up to 2 C-atoms in the alk;yl radical, (h) stDrene which can be substituted on the ~romatic rin~ by up to two Cl- to C3-alk;rl radicals, (i) acrylonitrile J methacrylonitrile (j) N-vinglp;rridines which can be substituted on the heteroc;yclic ring b~ up to Ci to C12-alkgl radicals and can be present i~ I~-quaternised f orm or in ~lt form, in the mol ratio o~ (A): (B) Or (95 to 5): (5 to 95), especially o~ (75 to 20): (25 to 80) .
Exsmples for the formula I are 1,5-anh;ydro-2-deoxg-arabinohex-~-enitol ( or 1 ,2-dide ox;~arabi~oh~-l-eno-pyranose~, brieIlg called glucal", and its derivatives, such as tri-0-acetyl-D-glucal, tri-0-~enz;srl-D-glucal, tri-0-benzo~l-D-glucal) tri-0-methyl-D-glucal, tri-0-eth;yl-D-glucal.
Examp~es :~or the formuls II are 1,2-dideoxger;ythro-hex-l-enopgranose-~-ulose, 4,6-benz~lidene-1,2-dideoxg-er~throhex-l-enop rranose-3-ulose and 4,6-o-isopropgl-.... _ _ _ . .... . .. _ _ _ . _ . . . . _ .. _ . _ _ _ _ .
2~ 8532:~
.
idene-1~2-dideoxyerythrohex-1-enopgranose-3-ulose .
Examples ~or the formula III are 2,3-dideoxy-erythrohe~-2-enopgranose (briefly ca~led "pseudoglucal'1) and its derivatives, such as tri-0-acetylpseudoglucal, tri-0-benzoylpseudoglucal, tri-0-benz;s~lpseudoglucal, l-ethoxg- and l-methoxydiacetylpseudoglucal, l-ethox;y-and L-methoxydibenzylpseudoglucal, l-ethoxy- and 1-methoxgpseudoglucal, l-h;~droxydiacet;ylpseudoglucal.
F~mr~Ps for formula IV are 2,3-dideoxgergthrohex-Z-enono-1,5-lactone and its derivatives 4,6-0-benzyl-idene-J4,6-di-0-acetyl-, 4,6-di-0-benzo;sr~- and 4,6-di-O_benz;s 1-2,~-dideoxyer;ythrohex-2-enono-L,5-lactone.
Examples ~or the ~ormula V are meth;yl 4-deoxy-~-threohex-4-enopyranosid~- uronic acid, meth;yl (methyl-4-deoxy-~-threohex-4-enop;s~ranoside)-uronate, methgl-2,3-di-0-benxyl (or methyl)-4-deoxy-1-threohex-4-enopyranoside-urDnic acid methyl ester and unsatur-~ted digalacturonic acid (0-(4-deoxg-L-threohexo-pgranose-4-engluronic acid)-(1-4)-~-galacturonic acid.
Examples ror the formula VI are ~,2,~,4-tetra-0-acetsrl-6-deoxy-~-D-I~ylohex-5-enopyranose, 1,2,3,4-tetra-0-benzo;y1-6-~-D-x~lohex-5-enopyranose, 6-deox~-~_xylohex-5-enopgranose, methyl-2,3,4-t~i-0-acetyl-6-deox~r-D-xylo~heX-5-enopgranoside, meth;yL-2,~,4-tri-0-benz;s~l-6-deoxy-D-xylohe~-5-enop;srranoside, methgl-6-deoxy-2,3,4-tri-0-methyl-D_xylohex-5-enop~ranoside and m~thyl-6-deoxy-D_xglohex-5-enopyranoside.
~8~321 Examples for the formul2 VII are 2,6-a~hydro-1-deoxggLuco (or galscto)- hept-l-enitol, 3,4,5,7-tetrs-0-benzgl-, 3,4,5,7-te~rs-O_be~Lzogl-, 3,4,5,7-tetra-0-scetyl-- or 4,5,7-tetra-0-trimethyl (or tri-5 ethgL)-siLyl-2,6-anhydro-1-deoxygLucohept-l-enitol.
Examples for the formula VIII are 3,4,5-tri-0-be~zogl-l-deoxg-2 ,6-anhgdro-D-xgiosehQx-l-enitol, 3,4 ,5-tri-0-acetgl-L_deoxy-2,6-a~hydro-D-xglosehex-1-e~itol, l-deoxy-2,6-a~hydro-D_xylosehex-l-enitol a~d 10 the i,2-unsaturated e~ol ether of leucrose hexa-benz on te ( or hexaacetate ), FY~mp~es for the lormuLa Il~ sre 2,3,4-tri-0-acetgl (benz0gl, ben~gl, methyl)-6-deoxg-D-lucono-1,5-e~olsctone .
Examples lor the f ormuls X are methgl-5-deoxyerythro-pent-4-e~ofura~oside, methgl-2,3-isopropglide~e-5-deoxy-eFgthrope~t-4-enofura~oside, 2,5-snhgdro-6-benzgl-1-deoxg-3,4-0-isopropylidene-D-ribohex-l-e~itol and 2, 5-~nhydro-6-0-~tert .-butglphenylsilgl) -1-deoxy-3,4-20 bis-0-trimethyLsilyL-D-ribohex-l-e~ ol ~d 5-deox~-1,2-0-isopropg~idenethreopent-4-e~ofuranose (from I,-arabinose ) .
Examples for the formula ~I sre 2,5-anhydro-1-deoxg-3,4,6-0-trimethylsilyl-D-ar~binohex-l-e~itol 25 and the 1,2-unsaturated enol ether of paLati~ose hexabenzoate (or he2rsacetate).
Ex2mples for the formula ~II are 6-deoxg-2,3-0-i~sopropylide~ethreohex-5-enulofur~ose (from ~-2~8~3~
sorbpse) and the 1,2-unsaturated enol ether of saecharose hexaaeetate.
Examples of the eo-monomers (B) are:
(a) aer~lic acid (A), methacrglie aeid (MAA), dimethgl-5 serglic acid, ethglaerglie aeid, vinglaeetie aeid, allyl-aeetie acid and vinglpropionie aeid. From this grouP, one pre~erably uses serylie aeid, methaerylie aeid, their mixtures, as well as the sodium, potassium, calcium or ammonium sslts or their mixtures .
10 (b) In this group are ~ound e.g. alkgl, bgdoxgalkgl and vinyl esters, sueh as methaer;ylate (MA), ethglaerglate, n-propglaerylate, n-butglaerglate, methylmethacr;ylate ~qMA), hgdroxgethylaerg~ate (E~A), hgdroxgpropglscrglate (HPA), hydroxgbutglaerglate (~IBA), hgdroxgethglmeth-15 aerglate (EEMA) and vingl ~ormate, vi~yl aeetate (VA),vingl propionate, 8S well as mixtures thereo~, (e)~ In this group come i~to consideration e.g.: dimethgl-aminoethgl acrglate, diethylaminoethyl aerylate, methgl-e~hglaminoeth;srl aerglate, di-tert.-butglaminoethgl 20 ~3~rglate, dimethglamino-methgl (or butyl, hexy}, oetgl, steargl)-acrglate, dimethgl (or diethgl, methglethgl, di-tert -butgl~-aminoethgl methaerglate, dimethglamino-methgl (or butyl, amgl, hexgl, oetylr stearyl)-meth-aerglate 25 (d) Acrglic acid amide (AM), methacryLic acid amide ~MAM), ~i-dimethglacrglic acid amide, ~-dimethglmethacrglie aeid amide .
(e) Exsmples of th2 N-vinglimidazoles are e.g. l-vingl-imidazole, 2-methgl-~-vinglimidazole, 4-methgl-1-vin~
imidazole, 2,4-dimethgl-1-vinylimidazole or 2-ethgl-1-vinglimidazoLe. For the quarternised N-vinglimidszoles, 5 there can be used usual quaternisation agents of organic chemistrg .
(f) As ~-vinDllactams, there are suitable, for ~cample, l-vinglpgrrolidone, I-vinglcsprolactam, ~-vinglpiper-idone, 4-methgl-1-vinglpgrrolidone, ~,5-dimethyl-1-10 vinglcsprolactam.
(g~ Maleic acid anhydride, maleic acid diethgl ester, maleic acid dimethyl ester.
(h) Stgrene, l-vinyltcluene, 3-vingltoluene or their mixture.
(i) acrgLonitrile, methscrglonitrile.
-vinglpyridines which are substituted on the hetero-cyclic ring by up to Cl- to C12-all~gl radicals and can be presen in ~I quatermised f orm or in salt f orm .
Preparati on:
For the ~reparation of the polgmers according to the invention, the sugar monomers (A) sre polymerised radically initiated with or without co-monomers (B).
Because of the properties of the resulting polgmers, in some cases it can be interesting, - to use t~o of ~ he compounds mantioned under (A) or - two sugar monomers and one monomer of the compounds mentioned under (B) or -218~321 - one sugsr monomer (A) a~d two monomers (B).
I'he radical polymerisation can be carriea out in the presence of or also in the absence of i~ert or polar solvents, as well as in aqueous s~stems. ~he 5 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 sca~e, the solution polymerisation in solvents lO Or in water is preferred. In this case, the compounds mentioned under (A) and (B) and the polymer f ormed are present in dissolved f orm. Suitable i~ert solvents are, ~or example, benzene, toluene, o-, m-, p-xylene and their i30mer mixtures, eth;ylbenzene, tert.-butyl-15 benzene, chlorobenzene, o-, m-, p-dichlorobenzene, aliphatic hydrocarbons, such as hexane, heptane, octane, nonane, dodecane, cyclohexane, as well as mixtures of the said hydrocarbons. ~urthermore, there are suitable chlorohydrocarbons, such 89 ch~oroform, carbon tetra-20 chlori~e and dichloromethane. As polar solvents, thereare suitable dimethyl sulphoxide, tetrahydrofuran, dioxane, butanone and acetone, as well as mixtures of the said polar solvents.
With polar water-soluble sugar monomers, the 25 polymerisations are preferably carried out in aqueous media .
I~ the case of smaller batches, in which a sure removal of the heat of pol;pmerisation is ensured, the _ 218~32~
reactio~ participants can be polymerised discontinuously i~ that the reaction mixture is heated to the polgmer-isation temperature. As a rule, this temperature lies in the range of 20 to 150C and especiallg preferabl;sr 5 between 40 to 130C. As soo~ 8S the temperature i~ the case of the polymerisation lies above the bpiling point of the inert solvent or of the m~nomers (A) a~d/or (B), the polgmerisstion is carried out under pressure. In this case, the conce~tration of the cDmponents (A) and 10 (B) amounts to 10 to 90, preferably 20 to 70 mol %.
I~he polymerisation can be carried out continuously.
l?or this purpose, there can be used especisllg the continuous polgmerisation at temperatures of 50 to 130C Under these polymerisation conditions, o~e uses 15 catalgsts which f orm radicals, e .g. i~or~anic and prgs~ic peroxides, persulphates, a~o compounds and so-called redox catalysts. As radical-forming initiators, there are preferably suitable all compounds which, at the chosen polymerisation temperature, hsve 20 a ha~f life time of about 3 hours.
If one first starts the polymerisatio~ at 10W
temperature and leads to the end at higher temperature, it is expedient to work with at least two initiators decomposing at different temperatures, namel;sr, at 25 first to begin with an initiator breaking down at low temperature and then to carr;~ out the main poly-merisation to the end with an initiator which breaks down at higher temperature 2~ 8~32 ~
Referred to total monomers used in the case of the po~ymerisation, one usies 0.01 to 20, preferably 0.1 to 10 mol % o~ a polymerisstion initiator or OI a mixture of several polgmeri3ation initiators One can use water-soluble or water~insoluble initiators or mixtures o~ water-soluble and water-insoluble initiators. The initiators insoluble in water are then soluble in the organic phsse.
For the temperature ranges given in the f ollowing, one can, for e2~ample, use the initi2tors stated there~or:
Temperature: 40 to 60C
acet;srlcyclohexanesulphon;~l peroxide, diacet;srl-, dicyclohe~c~l-, di-2-ethylhexyl perox;ydicarbonate, tert.-but~l-, tert.-amyl perneodecanoate, 2,2'-azo-bis-(4-methoxg-2,4-dimethylvaleronitrile), 2,2'-azo-bis-(2-amidinopropane) dihydrocbloride, 2,2'-azo-bis-(2-(2-imidazolin-2-yl)-propane) dihgdrochloride;
~emperature: 60 to 80C
tert.-butyl-, tert.-am~l perpivalate, dioctanoyl-, dilaur;yl peroxide, 2,2'-azo-bis-(2,4-dimeth;~valero-nitrile), 2,2'-azo-bis-(isobutyronitrile);
~emperature: 80 to 100C
dibenzoyl peroxide, tert.-butylper-2-eth;srl hexanoate, tert.-butyl permaleinate, dimethyl-2,2'-azo-bis-iso-but;yrai~e, sodium persulphate, potassium persulphate, ammonium persulphate;
21~5321 -2~--!romperature: 100 t o 120&
bis-(tert -butylperoxg)-cyclohexane, tert.-butyl-peroxgisopropgl csrbo~ate, tert.-butyl peracetat2, hgdrogen peroxide;
5 ~emperature: 120 to 140C
2,2-bis-(tert.-butglperoxg)-butane, dicumgl peroxide, di-tert.-smyl peroxide, di-tert.-butgl peroxide;
~empersture: ~ 140C
p-menthane, pinane, cumol snd tert.-butyl hydro-~0 peroxide.
If one wishes to reduce the half life times o~the stated radical-forming initiators, in addition tD
the mentioned ini~iators one also uses sslts or complexes of hesvg metals, e.,g. copper, cobalt, ~5 m~n~nf ~e, iro~, vsnsdium, nickel or chromium sslts, or organic compounds, e.g. benzoi~, dimethylaniline or sscorbic scid.
~ he reducing components of redox cstalysts can be formed, for exsmple, from compounds such 8S sodium 20 sulphite, sodium bisulphite, sodium formaldehyde sul~hacglate or hydrazine.
As- redox components, one adds 0 01 to 50 mol % of the reduci~g-acting compounds. ~eavg metals are used in the ra~ge of 0.1 to ~00 ppm, preferablg of 0.5 25 to 10 ppm. It is often of advantage to use a c ombination of peroxide, reducing agent and heavy metal as redox catalgst. I'hus, one csn, for example, alreadg so activate tert.-butyl hydroperoxide with 21~53~1 the ~ddition of 5 ppm copper III acetDlacetonate or cobalt Octanoate that one can alresdy polymerise at 100C, ~he solution polymerisation usuallg takes place in an inert gQS atmosphere with exclusion of atmospheric oxygen and moisture. The solvents are freshl~ distilled and degassed immediately be~ore the polymerisation.
The monomer compounds given under (A) and (13~ are verg pure, water- and stabiliser-free~ As alreadg mentioned, the monomers (A) and (B) 8re pregent in dissolved form, During the pol;ymerisation, care is taken f or a good mixing up of the reaction participaLts.
~he preparation of the polgmers according to the invention can be carried out in usual polDmerisation devices. Eor this purpose, one uses, for example, agitator vessels or double-walled reactors which are equipped witb anchor, paddle, impeller or multi-step impulse countercurrent stirrers.
Pr~paration processes:
The polgmers according to the invention can be prepared bg polgmerisation in substance or solution polgmerisation of the components (A) or (A) and (B) in non-polar or polar solvents~ wherebg 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 (A) and possibly with polar co-monomers (B) and the 21~321 water-soluble initiator are present in di6solved form.
The polymerisstion reaction i8 carried out under the same conditions (temperature, initiator concentratiOn, monomer ratio) as in the case of the polgmerisation 5 in solvents~
The polgmers according to the invention can also be prepared in alcoholic agueous solution. In this case, there are present the alcohol portions of 1 to 50, preferably 5 to 20 wt.g~. As alcohol, there are 10 suitQble methanol, ethanol, isopropanol, n-propsnol, as well as mixtures of the said inert solvents.
E~amples If not otherwise indicated, the stRtements in percent mesn mol percent.
15 Isolation ~nd characterisation of the pol;ymers according to the invention:
The chain reactions were stopped by addition of inhibitors, such as e.g. hgdroquinone or pDro-catechol. I~he po~ymers formed are isolated ~9 20 precipitating out (in the ten~old parts b;st volume of the precipitation asent) and filtration. In general, methanol, ether, diethgl ether, hexane or their mixtures were used as precipitation agent.
The molecular weighbs of the polgmers were 25 determined bg geL perme~tion chromatographg.
The composition of the polymers was calcuLated bD
elementarg anal~sis or wet analgsis.
218~321 In different examples, the F~-IR spectra were additionally determined.
~amples with ~lucal derivatives E~ample I
A mixture (1:1) of 4L.6 g tri-O-~enzo~l-D-glucal (~BzG) and 10.415 g st;srrene snd 100 ml of so~vent (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 10 equipped with stirrer, heater, reflu~ condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, feed 1 and feed 2 are heated to 60C
with stirring After reaching of the intended temper-ature, it was further stirre~ for 24 or 48 hours at 15 this temperature. After ending of the resction, one obtained a white solid material with 25.0 wt.g6 ;yield, ~he GPC analgsis gave a molecular weig~t of 140,400.
13sample 2 Exsmple 1 was repeated with the change that, 20 instead of styrene, one used 7,206 g acr~lic acid (AA) and polymeri3ed in dimeth;~l sulphoxide or dioxane, One obtained a white' solid material with 41 wt.%
~ield which had a molecular weight of 12,000.
E~cample 3 Example 2 was repeated with the change that, instead of (AA), one used 7.108 g acrylic acid amide (AM) and pol;ymerised in acetone or tetrah~drofuran.
21~3~i O~e o~tained a white solid material with 35 wt gield which had a molecular weight of 6500.
Examples with glucal Example 4 Feed l cOnsisted o~ L4 60 g glucal ia 120 ml of water Feed 2 wa~ prepared from o.æ8 g smmonium perox;ydisulphate and 10 ml of water. I~ 8 1 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet aQd outlet and dosing devices, feed l 10 and 2 were placed and warmed -to 40C. It was then further polymerised at this temperature f or 24 bours .
One obtained a while solid material with ~6 wt.76 ;yield.
~he GPC ansl~sis gave 8 molecular weight of 3900.
Example 5 Feed 1 consisted of a mixture of 14.6 g glucal, 17.2 g acrylic acid dieth~l ester (~DE~ iu a rati~ of 1:1 and 120 ml of waterO A~ feed 2, there served solution of 0.47~ g V50 (2,2'-azo-~is-(2-amidi~o-propane)~I~l) in 20 ml of w~ter, In a 1 1 vessel, which 20 is equipped with stirrer, he~ter, reflux condenser, thermometer, dosing devices, nitroge~ inlet and outlet devices, were p~aced feed ~ and feed 2 and heated to 50~C. After reaching tbe intended temperature, it was further stirred for 24 or 48 hours at this temperature.
25 After ending of the reaction, one obtained a white solid materia~ witb 25.0 weight % ~ield. ~he C-PC
snalysi~ ~aYe a molecuLar weight of 23CO.
2 ~ 8~32 . --Example 6 Feed L consisted of a mixture of 14.60 g glucal, 10.01 g methacrylic acid methyl ester (MMA) in a ratio o~ l:L in 120 ml of water. As feed 2, there served a 5 solution of 0.185 g sodium disulphite/0,228 g ammonium peroxgdisulphate as redox catalyst in 20 ml of water.
In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometor, dosing devices, nitrogen inlet and outlet devices, were plsced feed 1 10 and feed 2 snd heated to 40C, 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 50 wt ~% yield . ~rhe GPC analysis gave a molecular 15 weight of 4~00, Example 7 Feed 1 consisted of a mixture of 14 .6 g glucal, 13.02 g hydroxgethylmethacrylic acid ester (~I~A) in a ratio of l:L and 120 ml of water, A feed 2, there 20 served a solution of 0,456 g ammonium peroxydisulphate in 20 ml of water. In a L 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, ~ere placed feed-land fe~d 2 and heated to 80C.
25 After reachin~ the intended temperature, it was further~ stirred for 24 or 48 hours at this temper-ature. After ending of the reaction, one obtained a white solid material with 70 wt.% yield. ~he ~PC
I
2 1 ~32 ~
analysis gsve a molecular weight of L0,000, E~rample 8 Feed 1 co~sisted OI a mixture of 14.6 g glucaL, 7.206 g àcrglic acid (AA) in a ratio of 1:1 and 120 mL
5 of water. As feed 2, there served a solution of 0.185 g sodium disulphite/0.228 g ammonium perox~disu~phate as redox catalgst and 20 ml of water. In a 1 1 vessel, which W8S eguipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet 0 and inlet devices, were place feed 1 a~d feed 2 and heated to 40C, After resching the intended temperature, it was further stirred f or 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 17 wt.q6 gield. ~he GPC
15 snal;~sis gave a molecu~ar weight of 2300, E~c2mple 9 Feed 1 cOnsisted of a mixture of 14.6 g glucal, 8.61 g methacrylic acid (MAA) in a ratio of L:l and 120 ml of water. As feed 2, there served a solution of 20 0.185 g sodium disulphite/0,2Z8 g ammonium peroxg-disulphate as redox catalyst and 20 ml of water.
In a 1 1 vesseL, which w~s equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 25 and feed 2 and ~.rarmed to 40C After reaching of the intended temperature, it was further stirred f or 24 or 48 hours at this temperature. 4fter ending of the reaction, one obtained a white aolid material with 21~32i 52 ~t.~6 yield. ~he GPC analysis gave a molecular weight of 5200, Example 10 l~eed L consisted of a mixture of 14.6 g glucal, 5 8.61 g scrylic acid methyl ester (I~A) in a ratio of L:l and 120 ml of water. As feed 2, there served a solution of 0~185 g sodium disulphite/0.228 g ammonium peroxy-disulphate as redox catalgst and 20 ml nf water. In a 1 1 vessQ1, which was equipped with stirrer, heater, 10 reflux cnndenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed L and~feed 2 and warmed to 40C, After reaching of the intended temperature, it wsg further stirred at this temperature for 24 or 48 hours. After ending of the reaction, one 15 Obtained a white soLid material with ~5 wt.% yield.
~he GPC analysis gave a molecular weight of 3~00, E~ample 11 ~ eed 1 consisted of a mixture of 14.6 g glucal, methacrylic acid amide (~AM) in a ratio of 1:1 and 20 12C ml of water, Feed 2 was prepared from 0.456 g a~monium peroxydisulphate and 20 ml of water. In a 1 1 glass vessel with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen i~et snd nutlet devices were placed feed 1 and feed 2 and warmed to 25 60C. After reaching the intended temperature, it was further stirred f or 24 hours at this temperature . After ending Of the reaction, one obtained a white solid material with 39 wt,% yield. ~he GPC analysis gave 218~32~
a molecuLar weight of 490C.
Example 12 -Feed I Gonsisted of a mixture of 14.6 g glucal, 8,6L g acrylic acid methyl ester (I'~A) in a ratio of 1:1 5 and 120 ml of water. As feed Z, there served a solution of 0,112 g lI202 in 10 g ethanol. In 8 1 1 vessel, which W8S equipped with stirrer, heater, reflux condenser, thermo~eter, dosing devices, nitrogen inlet snd outlet devices, were pLaced feed 1 and feed 2 and warmed to LO 55C. After reaching of the intended temperature, it was further stirred f or 24 or 48 hours at this temper-ature, After ending of the reaction, One obtsined a white solid material with 48 wt.g~ yield. ~he GPC
analysis gave a molecular weight of 3100.
15 Examples with ~seudo~lucsls Example L~
Feed 1 consisted of 17,6 g l-ethoxypseudoglucal in 12G ml of; water. Feed 2 was prepared from 0,114 g ammonium peroxydisulphate/0,093 g sodium bisulphite 20 and 20 mL of water. In a L 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet w~re placed feed 1 and 2 and waro~ed to 60C. It was then further polymerised f or 24 hours at this temper-ature. One obtained a white soLid material with 15 wt.s6 25 yield. he GPC anaLysis gave a mo~ecular weight of 2000.
218~32~
-~o-- I
Exampla 14 Feed I consisted of a m~xture of 17.6 g l-ethoxy-pseudoglucal, 17,2 g maleic acid diethyl ester (MDE) in a ratio of 1:1 and 120 ml of water. As feed 2, there 5 served a solution of 0.472 5 V50 in 20 ml of wster. In a 1 1 vessel, which is equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet snd outlet deviceg, were placed feed 1 and feed a and heated to 50C. After resching of the intended 10 tempersture, it wss further stirred for 24 or 48 hours at this tempera~ure. After ending of the resction, one obtained a white solid materisl with 20 wt.% yield.
~he GPC snalysis gave 8 moleculsr weight of 2200.
Example ~5 Feed 1 consisted of a mixture of 17.6 1-ethoxy-pseudo~Lucsl, 8.609 g methacrylic acid (P~AA) in 8 rstio of l:l s~d 120 ml of ~ster. As feed 2, there served 8 solutio~ of 0,185 g sodium disulphite/0.228 g smmonium perox;s~disulphste as redox cstalyst and 20 ml of wster.
20 In 8 1 1 vessel, which wss equipped with stirrer, heatQr, reflux condenser, thermometer, dosing devices, ~itrogen i~let and outlet devices, were placed feed 1 snd feed 2 and heated to 40C. After reaching of the intended temperature, it was further stirred for 24 or 25 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 55 wt.% ~ield. The GPC analysis gave a molecular weight of 7000, 218~321 ., E~cample 16 A mixturQ (~:1) o~ 25~4 g l-ethoxgdiacet~lpseudo-glucal (EI)A~G) a~d~9.806 g maleic acid anh~dride (~lAh) and 100 m~ of solvent (benzene) forms feed 1. Feed 2 5 w2s prepared rrOm 0,~2 g azo-bis-isobut;~ronitrile (AIBN) and 10 mI benzene. In a 1 1 polymerisation reactor, which is equippea with stirrer, heater, reflu~
cOndenser, thermometer, dosi~g devices, nitrogen inlet a~d outlet devices, feed 1 a~d feed 2 are heated to 10 60C, 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, o~e obtained a white solid material with 15 wt.% yield.
~he GPC allals~sis gave a molecular weight of 2900.
15 Exsmple 17 Feed 1 consisted of 8 mixture of 25.4 g l-ethoxg-diacetylpseudoglucal (EDAPG), 10,415 g st;rrene (1:1) and 100 ml benzene. Feed 2 was prepared ~rom 0.~2 g azo-bis-isobut;~ronitrile (AIBN) and 10 ml benzene.
20 In a 1 1 glas6 flaak, which is equipped wit~ stirrer, heater, ref~ux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, ~e~d 1 and ~eed 2 are heated to 60C, with stirring. A~ter reaching of the i~tended temperature, it was further stirred f or 25 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material wit~} 20 wt.X ;srield, ~he GPC analsrsis gave a molecu~ar weight of 12,~oO.
21 8~32 ~
Example 18 Example L6 w8s repeated with the chan~e that, instead of maleic acid anhgdride, one used ~1.1 g N-vinglpgrrolidone and polymerised f or 24 hours . One 5 obtai~ed a white soLid material with 34 wt.~ gieLd.
l~he GPC s~algsis gsve a molecular weight of 205, 000.
Example 19 E~cample L6 was repeated with the change that, instead of maleic acid a~hgdride, one used 8.609 g 10 methacrglic acid (MA) . Oue obtairLed a white solid ~aterial with 21 ~t.% gield. ~he GPC a~algsis gave a molecular weight of 4800.
E~ramples with "5,6-e~o-glucal"
E~amp~e 20 L5 33-3 g 172,3,4-tetra-O-acetgl-6-deoxy-~-D-xglo-hex-5-e~op;~ranose are polgmerised at 80C f or 24 hours in a vacuum in the presence of 0.242 g benzoDl peroxide.
One obtai~ed a white solid materia~ with 15g6 gield ~he homopolymer had a molecular weight of 1600.
20 Example 2L
Feed 1 consisted of 17.62 g methgl-6-deoxg-cL-D-xylohex-5-enopyranoside in 120 ml of water. Feed 2 was prepared from 0.228 g ammonium peroxyd~sulphate in 20 mL of water. In a 1 1 glass vessel ~qith stirrer, 25 heater, reflux condenser, nitrogen ir~let ard outlet and dosing devices, feed 1 and 2 were placed and warmed to 50C. It was then further poJ,g~erised at this at this temperature f or 24 hours . One o~tained a ~, 218S321 white solid materiaL with 21 wt.g6 yield, ~he GPC analysis gave a molecular weight o~ 1~00.
Erample 22 33.03 g L,2,3,4-tetra-0-acetgl-6-deoxy-~-D_xylo-5 hex-5-enopyranose are polymerised at 100C ~or 24 hour3 in toluene by 0,146 g di-tert.-butyl peroxide (DTBP) activated with 5 ppm copper acetylacetonate . One obtained a white solid msterial with 23X yield. ~he homopolymer had a monecular weight of 1600.
10 Esample 23 Feed 1 consisted of 33.03 ~ 1,2,3,5-tetra-0-acetyl-6-d~oxy-~-D-xylohex-5-enopyranose in 100 mL tert.-butyl-benze~e (TBB). Feed 2 was prepgred from 0,146 g (DTBP) and 10 ml TBB, In a 1 1 g~2ss vessel with stirrer, 15 heater, reflux condenser, nitroge~ inlet and outlet and dosing devices were placed feed L and 2, heated to 120C and polymerised f or 24 hours . Then, at this temperature, the remaining feed 2 was dosed in within 30 minutes and further stirred f or 24 hours, One obtained 20 a white solid material with 25 wt.76 yield. The GPC
analysis gave a molecular weight of 3600.
Example 24 Feed 1 consisted of 30.23 g methyl-2,3,4-tri-0-acetyl-6-deoxy-ll-D-x;ylohex-5-enopyranosQ in 100 ml tert,-butyl-25 benzene (TB~). Feed 2 was prepared from 0.73 g (DTBP)and 100 ml TBB. In a 1 1 gIass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet and dosing devices were placed feed 1 and 20 m~ of feed 2, 218~32:~
_34_ and heat2d to 120C and polymerised for 24 hours ~hen, at this temperature, of the remaining fe~d 2, every ~5 hours 20 ml were added thereto and further stirred for 24 hours. One obtained a white solid material with 5 19 wt .96 ;yield . ~he GPC snalysis gave a moleculsr weight of ~i020.
Example 25 Feed 1 consisted of 57.86 g 1,2,~5,4-tetra-0-benzoyl-6-deoxy-~-D-xylohex-5-enopyranose and 120 ml toluene.
10 As feed 2, there served a solution of 0.242 g BOP and 20 ml toluene, In a ~ 1 vessel, which was eguipped with 3tirrer, heater, reflux condenser, t~ermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 ~nd feed 2 and heated to 80C, After reaching of 15 the inte~ded 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 15 wt.s~ yield. ~he GPC analysis ~ave a molecular weight of 28~0.
20 Example 26 Feed 1 Gonsisted of a mixture of 3~.03 g 1,2,3,4-tetra-O-acetyl-6-deox;sr-~-D-xylohex-5-enopyranose, 9.806 g ma~Qic acid anhydride (~h) in a raio of 1:1 a~d 100 ml benze~e, ~s feed 2, there served a solution 25 of 0.32 g AIBi~ 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
218~321 heated to 60C. A~ter reaching of the intended temper-ature, it was further stirrea at this temperature f or 24 or 48 hours. After e~ding of the reaction, one obtained a white soLid material with 37 wt.~6 gield.
5 I!he (;PC analgsis gave a moLacular weight of 5200, Example 27 Feed 1 consisted of a mixture of 33 03 g 1,2,3,4-tetra-O-acetgl-6-deoxg-~-D-xglohex-5-enopgra~ose, 70206 g acrglic acid (AA) in a rstio of L:l and 100 m~
lO toluene. As feed 2, there served a solution of 0.484 g BOP and 20 ml toluene. In a L 1 vessel, which was eguipped with a stirrer, heater, reflux co~denser, ;thermometer, dogi~g devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 15 80C. After reaching of the intended temperature, it W88 further stirred f or 24 or 48 hours at this temper-atureO After ending of the reaction, one obtained a white solid material with 34 wt.~ yield ~he GPC analgsis gave a molecular weight of 5100.
20 Example 28 Example 27 was repeated with the chang2 that7 instead of acrglic acid, one used 10.42 g stgrene (~t) .
One obtained a white solid material with 28 wt.76 ;gield4 ~he GPC analysis gave a molecular weight of 3ZCO.
25 Example 29 Feed 1 consisted of a mixture of 57.86 g L,2,3,4-tetra-O-benzogL-6-deoxy-~-D-xglohex-5-e~o~granose, 9.806 g maleic acid a~hgdride (~Ah) in 2 ratio of 1:1 21 8~321 in 120 ml benzene, As fesd 2, thers served a solution of 0.29 g D~BP and 20 ml tert.-butylbenzene. In 8 1 1 vessel, which W2S equipped with stirrer, heater, reflu condenser, thermometer, dosing devices, nitrogen inlet 5 snd outlet devices, were plsced fsed 1 and ~ee~2 and hested to 110C_ After reaching of the intended temper-~ture, it was further stirred st this tempersture for 24 or 48 hours. After ending of the reaction, one obtained a white solid msterial with 18 wt.g6 ~ield.
10 ~he GPC analgsis gave a molecular weight of 12,200.
E~csmple 30 Fsea 1 consisted of a mixture of 57.86 g 1,2,3,4-tetra-O-benzoDl-6-deoxD-,~-l)-x;ylohex-5-enop;yranose, 8.609 g methacrDlic acid (M~gA) in a ratio of 1:1 and ~5 120 m~ toluene. As feed 2, there ssrved a solution of 0,484 g BOP and 20 ml toluene. In a 1 1 vsssel, which was equipped with stirrer, hester, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 snd hested to 20 80C. After reaching of the intended temperature, it was further stirred at this temperature for 24 or 48 hours. After ending o~ the reaction, one obtained a white solid material with 32 wt.g6 ;rield ~he G~C
anal~sis gsve a molecular weight of 5700.
25 Example 31 Feed 1 consisted o~ a mixture of 18.62 g anh;srdro-~,4-di-0-benzo~1-5-0-(2,3,4,6-tetra-0-benzo;sl-G-D-glucopDranox;~ l-deoxg-D-arabinohex-l-enitol ~ - 218~32~ ~
~37-(briefly cslled "leucren'~), 1.961 g maleic scid anhgdride (r~:h) in a ratio of 1:~ and 120 ml ~BB.
As feed 2, there served a so~ution of 0.058 g D~BP
and 10 ml ~BB. In a 1 1 vessel, which W8S equipped 5 with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed I and reed 2 snd hested to 130C.
After resching of the intended tempersture, it was ~urther ~tirred for 64 hours at this temperature.
10 After ending of the reaction, one obtained a white solid material with 46 wt.% yield ~he GPC analysis gsve 8 molecular weight of 27,000.
Example 32 Feed ~ consisted on 18.60 g meth;srl-5-deoxy-2,3-0-15 isopropylidene-erythropent-4-enofuranoside (briefly called "ene-ribose") in 100 ml ~BB. Feed 2 wss prepared from 0,146 g (D~BP) snd 10 ml ~BB. In a 1 1 glass vessel with stirre-r, heater, re~lux conae~ser, nitrogen inlet and outlet and dosing devices, were 20 placed feed 1 and feed 2. ~he reaction mixture was heated to llO~C. After reaching of the intended tempersture, it was further stirred at this temperature for 24 hours. ~fter ending of the reaction, one obtaine~
8 white solid msterial with 35 wt.gS yield. ~he GPC
25 analysis gave a molecular weight of 2100.
Example 33 Feed I consisted of a mixture of 18.60 g ene-ribose, 9.806 g maleic acid anhydride (MAh) in a 218~321 ra~ ~ of l:~ and lOO ml ~BB~ As feed 2, where served a soLution of 0.292 g D~BP and 20 ml l!BB. In a 1 1 vesseL, which was equipped with stirrer, heatar, reflux condenser, thermoneter, dosin~ devices, 5 nitrogen inlet and out~et de~ices, were placed feed 1 snd feed 2 and hested to 110C. After reaching of the intenaed tenperature, it was further stirred at this temper2ture for 24 hours. After ending o~ the reaction, one obtained 8 white solid material with 47 wt.% ;srield.
10 ~he GPC anal;ysis gave a molecula~ weight of 3700.
E~ample 34 Exam~la 33 wss repeatad with the difference that, instead of maIeic acid anhydride, 11.1 g ~-vingl-pyrrolidine was used and polymerised f or 6 hour~ .
15 One obtained a white solid material with 53wt.~ ~ield.
Th~ GPO aual~ gave a mol~o~lar ~igbt Df' lOb,~O~.
Polgmerisates of unsaturated ssccharides ~nd their derivatives, as well as their co-polymers with ethylenical~y_unsaturated compoun~s and processes f or their preparation ~rhe invention concerns new polymers of unsaturated sacchari~es and their derivatives which contain a double bond in the ring (endocyclic) or on the ring (exocgclic), as well 8S co-polymers with ethylenicallg-unsaturated compounds. ~hese compounds are preparable ~0 and obtai~able by radical-initiated polymerisation ~homo-, co~ oP
(A) ethy~enicallg-unsatursted monosacchsrides, di-saccharides, oligosaccharides which contain a double bond in the ring (endocyclic) or on the ring (exoc;yclic), chemically protected or unprotected, enzgmaticallg or ch~mi c~ I g modified unsaturated mono-, di- or oligossccharides or mixtures of the said compounds (~) or co-polymers o~ components corresponding to (A) with (B~ monomers or mDnomer mixtures from the fo~lowing groups:
(a) monoethylenicallg-unsaturated C3- to C10-carboxylic acids and their a~kali metaL, alkaLine earth metal or ammonium salts, (b) monoethylenically-unsaturated Cl- to C12-carboxylic acid esters, 21~32 ~
--3~
(c) scrylic acia or methacrgL~c acid dialkyLamino-alkyl esters with, in all, up to 30 C-stoms in the dialkDlaminoalk;yl radicsl which can be present in N_quaternised or salt form, (d) acr;ylic acid amides, methacrylic acid amide, N-(dialkyl)-acrylic acid or -m,ethacrylic acid smide, (e) N-yin;rlimidazoles which can be substituted on the heterocgclic ring by up to three Cl- to L0 CL2-alkyl radicsls and can be present in ~-quaternised form or in salt form, (f ) five- to eighi; ~-membered N-vin;~llactams which can be substituted on the ring bg up to three CL- to C~L2-alkyl rsdicals, 1.5 (g) maleic acid anh;~dride, maleic scid dialkyl esters with, in all, up to 3 C-atoms in the alkyl radical (h) st;~rrene which can be substituted on the aromatic ring b~ up to two CL- to C3-allsgl radicals, (i) acrylonitrile, methacr;ylonitrile, (~J ) N_vinylpyridines which can be substituted on the heterocycLic ring by up to Cl- to C~L2-all~yl r~3dicals and can be present in ~_ quaternised form or in salt form, 25 in the mol ratio of (A) :{B) rf (95 to 5): (5 to 95) .
Depending upon the nature of the monomers and co-monomers used,the polymers according to the invention find use- as active material components, industrial 218~32~
ad,~uvsnts, such a3 e.g. thickening ag~nts, dispersing agent3, for the increasing-of viscositg or in the phsrmaceutical, medicinal and cosmetic field.
Furthermore, the new pol~mers are suitat~le as 5 components f or adhesive6 a~d f or the reduction of ~ow resistance ~he biocompatibility offers especial advantages in ?astes, salves, ~ oint coYerings, contact lenses, ad~uven~ts in biotech~ology, e.g. chromato-grsphy .
Dependimg upon the desïred properties, products can be desired of relatively low molecular weight (less tham about 20,000), average molecular weight (about 20,000 to lOOtO00), e.g. for the ad~ustmanet of correspondingl~r desired viscos~ties, or high molecular 15 weight (above 100,000), e.g with high viscosity insolution at low concentration.
In addition, such di~ferent, specifically produced molecular weights can be desired in the case of use as material components since, as is known, the structure-20 property relationships pl ay a great part.
Fur~hermore, the inventio~ concerns a process forthe preparation of these polymers a~d their character-isation .
~ he polymer ~ormation with the mentioned saccharide 25 derivstives according to (A) has hitherto not ~een described. ~rom this field, in the ~iterature only 4 c, ,c~tions are known from whicb it follows that 3 glucose derivatives with double bond in the ring, ~ 218S321 so-called D-~,lucal derivatives, can be co-polymerised with maleic acid anhgd~ide a~d thereby ~orm oligomers with low molecular weight (Y, Koyama, M, Kawata and K. Kurita, Polymerisation of unsaturated sugars, I, 5 Radical Copolymerisation of D-slucal derivatives and maleic anh;srdride, POlymer JOurnal, 19 (L987), 687-693.
II, Radical copolymerisation of a furanoid g~ucal, ~i-O-benzyl 1,2-dideoxy-5,6-0-isoprop;yLidene-D-arabino-hex-l-e~ofuranose, ibid. 19 (~987~, 695-700i, M,J. Han 10 et al., S~nthesis and BiologiCal Activity of polD-( Ctri-O-acetgl-D-glucal) -alt- (maleic anhydride ) d~rivatives, Bull. Eores~ Che~0 Soc,, 12 (1991) 85-87, and ~akromol. Chem, , Macromol. S;~mpos . 3~ (1990), 301 - 309~ ~ A biological axtivity of these substances 15 as carrier for anti-tumour active materials is investigated, It was the task o~ the present invention tD prepare new polymers from unsaturated sugar monomers and to make available to the technolog;~ new materials with 20 new properties. ~hese are characterised in that the carbohydrate components impart their specific qualities to them. 'rO these belong hydrophilia or a character-istic bslance between hydrophila and hydrophobia, ~ompatability especiall~ with biological s;~stems, 25 and here e.g. especial~y with the skin, no or low toxicity, biological decomposability etc, ~, I
21~3211 ~his task is soLved by the features of t~e main claims and promoted by the subsidiary cLaims.
d series o~ new, surprising findings could be achieved which, starting from the prior srt, were not 5 to be expected, - It is possible to obtain homopolymers from unprotectsd ' and protected unsa~urated ssccharide derivatlves.
- Sugar derivatives with doubLe bond in various positions in or on the ring can be (co)polymerised.
10 - It was sho~n that monomers, which themselves poLg-merise, can be brought to co-polgmerisstion with sugar derivatives of the tgpe (A) as co-monomers.
- ~!here csn be prepsred not onlD ~ow molecular oligo-meric products but slso high moleculsr po~gmers or co-pol;ymers (with molecular weights sbove 10,000 ~alt on ), All these (co)poLgmerisations lead to previousLg unknown products. Conseguently, the invention refers to n~w poLymers from unsstursted ssccharides or sacQharide 20 derivstives which contsin a doubLe bond in the ring (endocgclic) or on the ring (exocgclic), as well 85 co-polymers with eth;5~1eiically-unsaturated compounds.
rhese polymers are obtained bg polymerisation in substance, in solvents and/or sgueous systems,initisted 25 with rsdical stsrters, of (A) - ethylenicslly unsaturated sacc harides, c h~m; ~gl 1 y protected or unprotec~ed, enz~msticalLy or chemic-ally modified mono-, di-, trisacchsrides or 2~8532~
` . ~
mixtures c~ the said compounds ~A), with a double bond in the ring (endocgclic) o~ the ~ollowing formuls I or st~reoisomers OR
~0 R20~ 1 (I) 5 in which Rl signi~ies hgdrogen, an acetgl, bQnzogl, ! methgl or benzg~ group, R2 represents hgdrogen, an acetgl, benzog~, me~h;
be~z;yl group or a glucos;s!l radical ~nd R3 is hgdrogen, an acetgl, benzo~l, methgl or benz~rl 10 grouP, ~ormula II or stereoisomers ,OR3 R20k~ (II) i~ wbich R2 represents hgdrogen, an acetyl, benzo;yl, methgl, benzgl group or a glucosgl radical, 15 R3 is hgdrogen, an acetgl, benzo;yl, methgl, benzg~
group or (R2,R3) can be a protectlve group usual in organic chemistrg, such as e,g, 4,6-0-benzglidene or 4,6-O-isopropglidene, formula III or stereoisomers 218~32 . ~
OR~
~0 ~`ORl ( III ) in which R1 represents hydrogen, an acetyl, benzyl, benzoyl, alkgl group with, in all, up to 2 C-atoms in the alkyl rsdical, 5 R2 r~prese~ts hydrogen, an acetyl, benzo;yl, benzyl, alkyl .
group with 1 - 3 C-atoms or a glgcosgl radical, R3 is h;rdrogen, an acst;yl, benzogl, benzyl, meth~rl group, ~ormula IV or stereoisomers ~0 ~ ~O (IV) ~\,J
i~ which R2 signi~i~s hgdrogen, an acetgl, benzoyl, ~lkgl, benzyl group or a glucos;~1 radical, R3 is bgdrogen, an acetgl, benzo;~rl, methyl, benzyl, tosgl group or ~R2,R3) can be a protective group usual in ~5 organic chemistry (such as e.g. ~,6-0-benz;ylidene), :Eormula V
218~3 . ~
g 4 ~ ORl (V) in wbich RL is hgdrogen, an alkyl group or a galsct-uronic acid radical, R2 is hydrogen, an acetgl, benzoyl, benzyl, alkyl group, 5 R3 signifies hydrogen, anacet;yL, benzoyl, be~zyl, alkgl group, R4 represe~ts hydrogen, a methyl or eth;rl group, or those with a double bond on the pyrsnoside ring (exocyclic) of the following formula VI or stereo-10 isomers ~ORl (VI~ ;
in which RJ can be hydrogen, an acetyl, benzoyl, be~zyl grou~, or alkyl grou~ with L - ~ C-atoms or a fructosyl radical, R2 is h;~drogen, an acet;yl, benzoyl, benzyl, ~5 alk;yl group, R~ is au acetyl, benzoyl, benzyl, alk;~1 group, R4 represents hgdrogen, an acetyl, benzyl, be~zoylJ
alkyl grou~, formula VII or stereoisomers ~ i 218~21 ~10--~0' ~ (VII) in which RI is hydrogen, an acetyl, benzoyl, benzy~
slkyl group, R2 r~presents hgdrogen, an acetyl, be~zogl, benzyl, 5 alkyl group, R3 represents hydrogen, an scetyl, benzogl, benz;yl, alkgl group or a gluc05;5r1 radical, R4 ~;~n;~ies hgdroge~, sn acetg~ benzoyl, benzgl or alXyl group, LO f ormula ~III or stereoisomers (VIII~
in which Rl is hydrogen, anæe~gl, benzoyl, benzgl, al~y~ group~
R2 is hDdroge~, an acet;yl, benzoy~, benzgl, al~yl group, 15 R~S is hydrogen, an a cetyl, benzoyl, benz;srl, alkyl group, and the corresponding derivatives on leucrose basis or t~eir stereoisomers, f ormula I~ or stereoisomers 2~532~
~o (~) R30 ORl in which Rl is hydrogen, an a cetyl, benzoDl, benzyl, alkyl group, R2 signifies hDdrogen, an acet;yl, benzoDL, benzDl, 5 alkyl group, R3 represents hydrogen, an acetyl, benzo~l, benzDl, alkyl group or a glucos;yl radical, or those with a double bond on the furanoside ring of the following formula g and their stereoisomers O
~_ OR
in which Rl can be ~ydrogen or an alkyl radical with 1 to 3 C-atoms, R2 is hDdrogen, an acetyl, be~zoyl, benzyl, alkDl group, R3 s;gn;~;P~ hydroge~, anacet~l, benzDl, benzogl, al}~Dl ~5 grou~, I
or (R2,R3) can be a protective group usual in organic chemistry, f ormula ~I
R30~2G o ~R1~ (XI ) ~ 218~2~
in which R, R2 is ~gdrogen, an acet;~l, benzgL, benzogl, alkgl ~roup, R3 represents hgdrogen or a glucosgL radical, such as e g, in the case of ~aLatin~se, 5 f ormula I~II
R40>~ ~XII ) in which RL, R2, R3 signifies hgdrogen, an acetgl, ben~ogl, benzgl, alkgl group, R4 represents ~ glucosg~radical, such as e.g. in the 10 case of saccharose, or co-~ool;srmerisation with (E~) monomers or monomer mixtures from the group (8) monoethglenicallg-unsaturated C3- to C10-carbox;ylic acids anG - their alkali metal, alkaline earth metal or ammonium salts, (b) monoethgle~icsllg-unsaturated C3- to C12-carboxgLic acid esters, (c j acrglic acid or methacrglic acid diaLkylamiLo-alkgl esters with, in alL, up to ~0 C-atoms in the dialkglaminoalk~L radicaL which can be present in ~i_quaternised form or saLt form, (d) acrylic acid amides, methacrglic acid amide, N-(dialkgL)-acrylic acid or methacrglic acid amide -218~321 (e) ~-vin~limidszoles which can be substituted on the heteroc~clic ring by up to t~ree Cl- up to C12-alkgl radicals and C8tl be present in ~l-qusternised form or in salt form, (f ) five- to eight-membered N-vi~gllsctsms which can be substituted on the ring bg up to three Cl- to C~L2-alkgl radicals, (g) maleic acid anh;srdride, maleic acid dialkgl esters with, in al~, up to 2 C-atoms in the alk;yl radical, (h) stDrene which can be substituted on the ~romatic rin~ by up to two Cl- to C3-alk;rl radicals, (i) acrylonitrile J methacrylonitrile (j) N-vinglp;rridines which can be substituted on the heteroc;yclic ring b~ up to Ci to C12-alkgl radicals and can be present i~ I~-quaternised f orm or in ~lt form, in the mol ratio o~ (A): (B) Or (95 to 5): (5 to 95), especially o~ (75 to 20): (25 to 80) .
Exsmples for the formula I are 1,5-anh;ydro-2-deoxg-arabinohex-~-enitol ( or 1 ,2-dide ox;~arabi~oh~-l-eno-pyranose~, brieIlg called glucal", and its derivatives, such as tri-0-acetyl-D-glucal, tri-0-~enz;srl-D-glucal, tri-0-benzo~l-D-glucal) tri-0-methyl-D-glucal, tri-0-eth;yl-D-glucal.
Examp~es :~or the formuls II are 1,2-dideoxger;ythro-hex-l-enopgranose-~-ulose, 4,6-benz~lidene-1,2-dideoxg-er~throhex-l-enop rranose-3-ulose and 4,6-o-isopropgl-.... _ _ _ . .... . .. _ _ _ . _ . . . . _ .. _ . _ _ _ _ .
2~ 8532:~
.
idene-1~2-dideoxyerythrohex-1-enopgranose-3-ulose .
Examples ~or the formula III are 2,3-dideoxy-erythrohe~-2-enopgranose (briefly ca~led "pseudoglucal'1) and its derivatives, such as tri-0-acetylpseudoglucal, tri-0-benzoylpseudoglucal, tri-0-benz;s~lpseudoglucal, l-ethoxg- and l-methoxydiacetylpseudoglucal, l-ethox;y-and L-methoxydibenzylpseudoglucal, l-ethoxy- and 1-methoxgpseudoglucal, l-h;~droxydiacet;ylpseudoglucal.
F~mr~Ps for formula IV are 2,3-dideoxgergthrohex-Z-enono-1,5-lactone and its derivatives 4,6-0-benzyl-idene-J4,6-di-0-acetyl-, 4,6-di-0-benzo;sr~- and 4,6-di-O_benz;s 1-2,~-dideoxyer;ythrohex-2-enono-L,5-lactone.
Examples ~or the ~ormula V are meth;yl 4-deoxy-~-threohex-4-enopyranosid~- uronic acid, meth;yl (methyl-4-deoxy-~-threohex-4-enop;s~ranoside)-uronate, methgl-2,3-di-0-benxyl (or methyl)-4-deoxy-1-threohex-4-enopyranoside-urDnic acid methyl ester and unsatur-~ted digalacturonic acid (0-(4-deoxg-L-threohexo-pgranose-4-engluronic acid)-(1-4)-~-galacturonic acid.
Examples ror the formula VI are ~,2,~,4-tetra-0-acetsrl-6-deoxy-~-D-I~ylohex-5-enopyranose, 1,2,3,4-tetra-0-benzo;y1-6-~-D-x~lohex-5-enopyranose, 6-deox~-~_xylohex-5-enopgranose, methyl-2,3,4-t~i-0-acetyl-6-deox~r-D-xylo~heX-5-enopgranoside, meth;yL-2,~,4-tri-0-benz;s~l-6-deoxy-D-xylohe~-5-enop;srranoside, methgl-6-deoxy-2,3,4-tri-0-methyl-D_xylohex-5-enop~ranoside and m~thyl-6-deoxy-D_xglohex-5-enopyranoside.
~8~321 Examples for the formul2 VII are 2,6-a~hydro-1-deoxggLuco (or galscto)- hept-l-enitol, 3,4,5,7-tetrs-0-benzgl-, 3,4,5,7-te~rs-O_be~Lzogl-, 3,4,5,7-tetra-0-scetyl-- or 4,5,7-tetra-0-trimethyl (or tri-5 ethgL)-siLyl-2,6-anhydro-1-deoxygLucohept-l-enitol.
Examples for the formula VIII are 3,4,5-tri-0-be~zogl-l-deoxg-2 ,6-anhgdro-D-xgiosehQx-l-enitol, 3,4 ,5-tri-0-acetgl-L_deoxy-2,6-a~hydro-D-xglosehex-1-e~itol, l-deoxy-2,6-a~hydro-D_xylosehex-l-enitol a~d 10 the i,2-unsaturated e~ol ether of leucrose hexa-benz on te ( or hexaacetate ), FY~mp~es for the lormuLa Il~ sre 2,3,4-tri-0-acetgl (benz0gl, ben~gl, methyl)-6-deoxg-D-lucono-1,5-e~olsctone .
Examples lor the f ormuls X are methgl-5-deoxyerythro-pent-4-e~ofura~oside, methgl-2,3-isopropglide~e-5-deoxy-eFgthrope~t-4-enofura~oside, 2,5-snhgdro-6-benzgl-1-deoxg-3,4-0-isopropylidene-D-ribohex-l-e~itol and 2, 5-~nhydro-6-0-~tert .-butglphenylsilgl) -1-deoxy-3,4-20 bis-0-trimethyLsilyL-D-ribohex-l-e~ ol ~d 5-deox~-1,2-0-isopropg~idenethreopent-4-e~ofuranose (from I,-arabinose ) .
Examples for the formula ~I sre 2,5-anhydro-1-deoxg-3,4,6-0-trimethylsilyl-D-ar~binohex-l-e~itol 25 and the 1,2-unsaturated enol ether of paLati~ose hexabenzoate (or he2rsacetate).
Ex2mples for the formula ~II are 6-deoxg-2,3-0-i~sopropylide~ethreohex-5-enulofur~ose (from ~-2~8~3~
sorbpse) and the 1,2-unsaturated enol ether of saecharose hexaaeetate.
Examples of the eo-monomers (B) are:
(a) aer~lic acid (A), methacrglie aeid (MAA), dimethgl-5 serglic acid, ethglaerglie aeid, vinglaeetie aeid, allyl-aeetie acid and vinglpropionie aeid. From this grouP, one pre~erably uses serylie aeid, methaerylie aeid, their mixtures, as well as the sodium, potassium, calcium or ammonium sslts or their mixtures .
10 (b) In this group are ~ound e.g. alkgl, bgdoxgalkgl and vinyl esters, sueh as methaer;ylate (MA), ethglaerglate, n-propglaerylate, n-butglaerglate, methylmethacr;ylate ~qMA), hgdroxgethylaerg~ate (E~A), hgdroxgpropglscrglate (HPA), hydroxgbutglaerglate (~IBA), hgdroxgethglmeth-15 aerglate (EEMA) and vingl ~ormate, vi~yl aeetate (VA),vingl propionate, 8S well as mixtures thereo~, (e)~ In this group come i~to consideration e.g.: dimethgl-aminoethgl acrglate, diethylaminoethyl aerylate, methgl-e~hglaminoeth;srl aerglate, di-tert.-butglaminoethgl 20 ~3~rglate, dimethglamino-methgl (or butyl, hexy}, oetgl, steargl)-acrglate, dimethgl (or diethgl, methglethgl, di-tert -butgl~-aminoethgl methaerglate, dimethglamino-methgl (or butyl, amgl, hexgl, oetylr stearyl)-meth-aerglate 25 (d) Acrglic acid amide (AM), methacryLic acid amide ~MAM), ~i-dimethglacrglic acid amide, ~-dimethglmethacrglie aeid amide .
(e) Exsmples of th2 N-vinglimidazoles are e.g. l-vingl-imidazole, 2-methgl-~-vinglimidazole, 4-methgl-1-vin~
imidazole, 2,4-dimethgl-1-vinylimidazole or 2-ethgl-1-vinglimidazoLe. For the quarternised N-vinglimidszoles, 5 there can be used usual quaternisation agents of organic chemistrg .
(f) As ~-vinDllactams, there are suitable, for ~cample, l-vinglpgrrolidone, I-vinglcsprolactam, ~-vinglpiper-idone, 4-methgl-1-vinglpgrrolidone, ~,5-dimethyl-1-10 vinglcsprolactam.
(g~ Maleic acid anhydride, maleic acid diethgl ester, maleic acid dimethyl ester.
(h) Stgrene, l-vinyltcluene, 3-vingltoluene or their mixture.
(i) acrgLonitrile, methscrglonitrile.
-vinglpyridines which are substituted on the hetero-cyclic ring by up to Cl- to C12-all~gl radicals and can be presen in ~I quatermised f orm or in salt f orm .
Preparati on:
For the ~reparation of the polgmers according to the invention, the sugar monomers (A) sre polymerised radically initiated with or without co-monomers (B).
Because of the properties of the resulting polgmers, in some cases it can be interesting, - to use t~o of ~ he compounds mantioned under (A) or - two sugar monomers and one monomer of the compounds mentioned under (B) or -218~321 - one sugsr monomer (A) a~d two monomers (B).
I'he radical polymerisation can be carriea out in the presence of or also in the absence of i~ert or polar solvents, as well as in aqueous s~stems. ~he 5 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 sca~e, the solution polymerisation in solvents lO Or in water is preferred. In this case, the compounds mentioned under (A) and (B) and the polymer f ormed are present in dissolved f orm. Suitable i~ert solvents are, ~or example, benzene, toluene, o-, m-, p-xylene and their i30mer mixtures, eth;ylbenzene, tert.-butyl-15 benzene, chlorobenzene, o-, m-, p-dichlorobenzene, aliphatic hydrocarbons, such as hexane, heptane, octane, nonane, dodecane, cyclohexane, as well as mixtures of the said hydrocarbons. ~urthermore, there are suitable chlorohydrocarbons, such 89 ch~oroform, carbon tetra-20 chlori~e and dichloromethane. As polar solvents, thereare suitable dimethyl sulphoxide, tetrahydrofuran, dioxane, butanone and acetone, as well as mixtures of the said polar solvents.
With polar water-soluble sugar monomers, the 25 polymerisations are preferably carried out in aqueous media .
I~ the case of smaller batches, in which a sure removal of the heat of pol;pmerisation is ensured, the _ 218~32~
reactio~ participants can be polymerised discontinuously i~ that the reaction mixture is heated to the polgmer-isation temperature. As a rule, this temperature lies in the range of 20 to 150C and especiallg preferabl;sr 5 between 40 to 130C. As soo~ 8S the temperature i~ the case of the polymerisation lies above the bpiling point of the inert solvent or of the m~nomers (A) a~d/or (B), the polgmerisstion is carried out under pressure. In this case, the conce~tration of the cDmponents (A) and 10 (B) amounts to 10 to 90, preferably 20 to 70 mol %.
I~he polymerisation can be carried out continuously.
l?or this purpose, there can be used especisllg the continuous polgmerisation at temperatures of 50 to 130C Under these polymerisation conditions, o~e uses 15 catalgsts which f orm radicals, e .g. i~or~anic and prgs~ic peroxides, persulphates, a~o compounds and so-called redox catalysts. As radical-forming initiators, there are preferably suitable all compounds which, at the chosen polymerisation temperature, hsve 20 a ha~f life time of about 3 hours.
If one first starts the polymerisatio~ at 10W
temperature and leads to the end at higher temperature, it is expedient to work with at least two initiators decomposing at different temperatures, namel;sr, at 25 first to begin with an initiator breaking down at low temperature and then to carr;~ out the main poly-merisation to the end with an initiator which breaks down at higher temperature 2~ 8~32 ~
Referred to total monomers used in the case of the po~ymerisation, one usies 0.01 to 20, preferably 0.1 to 10 mol % o~ a polymerisstion initiator or OI a mixture of several polgmeri3ation initiators One can use water-soluble or water~insoluble initiators or mixtures o~ water-soluble and water-insoluble initiators. The initiators insoluble in water are then soluble in the organic phsse.
For the temperature ranges given in the f ollowing, one can, for e2~ample, use the initi2tors stated there~or:
Temperature: 40 to 60C
acet;srlcyclohexanesulphon;~l peroxide, diacet;srl-, dicyclohe~c~l-, di-2-ethylhexyl perox;ydicarbonate, tert.-but~l-, tert.-amyl perneodecanoate, 2,2'-azo-bis-(4-methoxg-2,4-dimethylvaleronitrile), 2,2'-azo-bis-(2-amidinopropane) dihydrocbloride, 2,2'-azo-bis-(2-(2-imidazolin-2-yl)-propane) dihgdrochloride;
~emperature: 60 to 80C
tert.-butyl-, tert.-am~l perpivalate, dioctanoyl-, dilaur;yl peroxide, 2,2'-azo-bis-(2,4-dimeth;~valero-nitrile), 2,2'-azo-bis-(isobutyronitrile);
~emperature: 80 to 100C
dibenzoyl peroxide, tert.-butylper-2-eth;srl hexanoate, tert.-butyl permaleinate, dimethyl-2,2'-azo-bis-iso-but;yrai~e, sodium persulphate, potassium persulphate, ammonium persulphate;
21~5321 -2~--!romperature: 100 t o 120&
bis-(tert -butylperoxg)-cyclohexane, tert.-butyl-peroxgisopropgl csrbo~ate, tert.-butyl peracetat2, hgdrogen peroxide;
5 ~emperature: 120 to 140C
2,2-bis-(tert.-butglperoxg)-butane, dicumgl peroxide, di-tert.-smyl peroxide, di-tert.-butgl peroxide;
~empersture: ~ 140C
p-menthane, pinane, cumol snd tert.-butyl hydro-~0 peroxide.
If one wishes to reduce the half life times o~the stated radical-forming initiators, in addition tD
the mentioned ini~iators one also uses sslts or complexes of hesvg metals, e.,g. copper, cobalt, ~5 m~n~nf ~e, iro~, vsnsdium, nickel or chromium sslts, or organic compounds, e.g. benzoi~, dimethylaniline or sscorbic scid.
~ he reducing components of redox cstalysts can be formed, for exsmple, from compounds such 8S sodium 20 sulphite, sodium bisulphite, sodium formaldehyde sul~hacglate or hydrazine.
As- redox components, one adds 0 01 to 50 mol % of the reduci~g-acting compounds. ~eavg metals are used in the ra~ge of 0.1 to ~00 ppm, preferablg of 0.5 25 to 10 ppm. It is often of advantage to use a c ombination of peroxide, reducing agent and heavy metal as redox catalgst. I'hus, one csn, for example, alreadg so activate tert.-butyl hydroperoxide with 21~53~1 the ~ddition of 5 ppm copper III acetDlacetonate or cobalt Octanoate that one can alresdy polymerise at 100C, ~he solution polymerisation usuallg takes place in an inert gQS atmosphere with exclusion of atmospheric oxygen and moisture. The solvents are freshl~ distilled and degassed immediately be~ore the polymerisation.
The monomer compounds given under (A) and (13~ are verg pure, water- and stabiliser-free~ As alreadg mentioned, the monomers (A) and (B) 8re pregent in dissolved form, During the pol;ymerisation, care is taken f or a good mixing up of the reaction participaLts.
~he preparation of the polgmers according to the invention can be carried out in usual polDmerisation devices. Eor this purpose, one uses, for example, agitator vessels or double-walled reactors which are equipped witb anchor, paddle, impeller or multi-step impulse countercurrent stirrers.
Pr~paration processes:
The polgmers according to the invention can be prepared bg polgmerisation in substance or solution polgmerisation of the components (A) or (A) and (B) in non-polar or polar solvents~ wherebg 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 (A) and possibly with polar co-monomers (B) and the 21~321 water-soluble initiator are present in di6solved form.
The polymerisstion reaction i8 carried out under the same conditions (temperature, initiator concentratiOn, monomer ratio) as in the case of the polgmerisation 5 in solvents~
The polgmers according to the invention can also be prepared in alcoholic agueous solution. In this case, there are present the alcohol portions of 1 to 50, preferably 5 to 20 wt.g~. As alcohol, there are 10 suitQble methanol, ethanol, isopropanol, n-propsnol, as well as mixtures of the said inert solvents.
E~amples If not otherwise indicated, the stRtements in percent mesn mol percent.
15 Isolation ~nd characterisation of the pol;ymers according to the invention:
The chain reactions were stopped by addition of inhibitors, such as e.g. hgdroquinone or pDro-catechol. I~he po~ymers formed are isolated ~9 20 precipitating out (in the ten~old parts b;st volume of the precipitation asent) and filtration. In general, methanol, ether, diethgl ether, hexane or their mixtures were used as precipitation agent.
The molecular weighbs of the polgmers were 25 determined bg geL perme~tion chromatographg.
The composition of the polymers was calcuLated bD
elementarg anal~sis or wet analgsis.
218~321 In different examples, the F~-IR spectra were additionally determined.
~amples with ~lucal derivatives E~ample I
A mixture (1:1) of 4L.6 g tri-O-~enzo~l-D-glucal (~BzG) and 10.415 g st;srrene snd 100 ml of so~vent (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 10 equipped with stirrer, heater, reflu~ condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, feed 1 and feed 2 are heated to 60C
with stirring After reaching of the intended temper-ature, it was further stirre~ for 24 or 48 hours at 15 this temperature. After ending of the resction, one obtained a white solid material with 25.0 wt.g6 ;yield, ~he GPC analgsis gave a molecular weig~t of 140,400.
13sample 2 Exsmple 1 was repeated with the change that, 20 instead of styrene, one used 7,206 g acr~lic acid (AA) and polymeri3ed in dimeth;~l sulphoxide or dioxane, One obtained a white' solid material with 41 wt.%
~ield which had a molecular weight of 12,000.
E~cample 3 Example 2 was repeated with the change that, instead of (AA), one used 7.108 g acrylic acid amide (AM) and pol;ymerised in acetone or tetrah~drofuran.
21~3~i O~e o~tained a white solid material with 35 wt gield which had a molecular weight of 6500.
Examples with glucal Example 4 Feed l cOnsisted o~ L4 60 g glucal ia 120 ml of water Feed 2 wa~ prepared from o.æ8 g smmonium perox;ydisulphate and 10 ml of water. I~ 8 1 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet aQd outlet and dosing devices, feed l 10 and 2 were placed and warmed -to 40C. It was then further polymerised at this temperature f or 24 bours .
One obtained a while solid material with ~6 wt.76 ;yield.
~he GPC ansl~sis gave 8 molecular weight of 3900.
Example 5 Feed 1 consisted of a mixture of 14.6 g glucal, 17.2 g acrylic acid dieth~l ester (~DE~ iu a rati~ of 1:1 and 120 ml of waterO A~ feed 2, there served solution of 0.47~ g V50 (2,2'-azo-~is-(2-amidi~o-propane)~I~l) in 20 ml of w~ter, In a 1 1 vessel, which 20 is equipped with stirrer, he~ter, reflux condenser, thermometer, dosing devices, nitroge~ inlet and outlet devices, were p~aced feed ~ and feed 2 and heated to 50~C. After reaching tbe intended temperature, it was further stirred for 24 or 48 hours at this temperature.
25 After ending of the reaction, one obtained a white solid materia~ witb 25.0 weight % ~ield. ~he C-PC
snalysi~ ~aYe a molecuLar weight of 23CO.
2 ~ 8~32 . --Example 6 Feed L consisted of a mixture of 14.60 g glucal, 10.01 g methacrylic acid methyl ester (MMA) in a ratio o~ l:L in 120 ml of water. As feed 2, there served a 5 solution of 0.185 g sodium disulphite/0,228 g ammonium peroxgdisulphate as redox catalyst in 20 ml of water.
In a 1 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometor, dosing devices, nitrogen inlet and outlet devices, were plsced feed 1 10 and feed 2 snd heated to 40C, 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 50 wt ~% yield . ~rhe GPC analysis gave a molecular 15 weight of 4~00, Example 7 Feed 1 consisted of a mixture of 14 .6 g glucal, 13.02 g hydroxgethylmethacrylic acid ester (~I~A) in a ratio of l:L and 120 ml of water, A feed 2, there 20 served a solution of 0,456 g ammonium peroxydisulphate in 20 ml of water. In a L 1 vessel, which was equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, ~ere placed feed-land fe~d 2 and heated to 80C.
25 After reachin~ the intended temperature, it was further~ stirred for 24 or 48 hours at this temper-ature. After ending of the reaction, one obtained a white solid material with 70 wt.% yield. ~he ~PC
I
2 1 ~32 ~
analysis gsve a molecular weight of L0,000, E~rample 8 Feed 1 co~sisted OI a mixture of 14.6 g glucaL, 7.206 g àcrglic acid (AA) in a ratio of 1:1 and 120 mL
5 of water. As feed 2, there served a solution of 0.185 g sodium disulphite/0.228 g ammonium perox~disu~phate as redox catalgst and 20 ml of water. In a 1 1 vessel, which W8S eguipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet 0 and inlet devices, were place feed 1 a~d feed 2 and heated to 40C, After resching the intended temperature, it was further stirred f or 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 17 wt.q6 gield. ~he GPC
15 snal;~sis gave a molecu~ar weight of 2300, E~c2mple 9 Feed 1 cOnsisted of a mixture of 14.6 g glucal, 8.61 g methacrylic acid (MAA) in a ratio of L:l and 120 ml of water. As feed 2, there served a solution of 20 0.185 g sodium disulphite/0,2Z8 g ammonium peroxg-disulphate as redox catalyst and 20 ml of water.
In a 1 1 vesseL, which w~s equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 25 and feed 2 and ~.rarmed to 40C After reaching of the intended temperature, it was further stirred f or 24 or 48 hours at this temperature. 4fter ending of the reaction, one obtained a white aolid material with 21~32i 52 ~t.~6 yield. ~he GPC analysis gave a molecular weight of 5200, Example 10 l~eed L consisted of a mixture of 14.6 g glucal, 5 8.61 g scrylic acid methyl ester (I~A) in a ratio of L:l and 120 ml of water. As feed 2, there served a solution of 0~185 g sodium disulphite/0.228 g ammonium peroxy-disulphate as redox catalgst and 20 ml nf water. In a 1 1 vessQ1, which was equipped with stirrer, heater, 10 reflux cnndenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed L and~feed 2 and warmed to 40C, After reaching of the intended temperature, it wsg further stirred at this temperature for 24 or 48 hours. After ending of the reaction, one 15 Obtained a white soLid material with ~5 wt.% yield.
~he GPC analysis gave a molecular weight of 3~00, E~ample 11 ~ eed 1 consisted of a mixture of 14.6 g glucal, methacrylic acid amide (~AM) in a ratio of 1:1 and 20 12C ml of water, Feed 2 was prepared from 0.456 g a~monium peroxydisulphate and 20 ml of water. In a 1 1 glass vessel with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen i~et snd nutlet devices were placed feed 1 and feed 2 and warmed to 25 60C. After reaching the intended temperature, it was further stirred f or 24 hours at this temperature . After ending Of the reaction, one obtained a white solid material with 39 wt,% yield. ~he GPC analysis gave 218~32~
a molecuLar weight of 490C.
Example 12 -Feed I Gonsisted of a mixture of 14.6 g glucal, 8,6L g acrylic acid methyl ester (I'~A) in a ratio of 1:1 5 and 120 ml of water. As feed Z, there served a solution of 0,112 g lI202 in 10 g ethanol. In 8 1 1 vessel, which W8S equipped with stirrer, heater, reflux condenser, thermo~eter, dosing devices, nitrogen inlet snd outlet devices, were pLaced feed 1 and feed 2 and warmed to LO 55C. After reaching of the intended temperature, it was further stirred f or 24 or 48 hours at this temper-ature, After ending of the reaction, One obtsined a white solid material with 48 wt.g~ yield. ~he GPC
analysis gave a molecular weight of 3100.
15 Examples with ~seudo~lucsls Example L~
Feed 1 consisted of 17,6 g l-ethoxypseudoglucal in 12G ml of; water. Feed 2 was prepared from 0,114 g ammonium peroxydisulphate/0,093 g sodium bisulphite 20 and 20 mL of water. In a L 1 glass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet w~re placed feed 1 and 2 and waro~ed to 60C. It was then further polymerised f or 24 hours at this temper-ature. One obtained a white soLid material with 15 wt.s6 25 yield. he GPC anaLysis gave a mo~ecular weight of 2000.
218~32~
-~o-- I
Exampla 14 Feed I consisted of a m~xture of 17.6 g l-ethoxy-pseudoglucal, 17,2 g maleic acid diethyl ester (MDE) in a ratio of 1:1 and 120 ml of water. As feed 2, there 5 served a solution of 0.472 5 V50 in 20 ml of wster. In a 1 1 vessel, which is equipped with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet snd outlet deviceg, were placed feed 1 and feed a and heated to 50C. After resching of the intended 10 tempersture, it wss further stirred for 24 or 48 hours at this tempera~ure. After ending of the resction, one obtained a white solid materisl with 20 wt.% yield.
~he GPC snalysis gave 8 moleculsr weight of 2200.
Example ~5 Feed 1 consisted of a mixture of 17.6 1-ethoxy-pseudo~Lucsl, 8.609 g methacrylic acid (P~AA) in 8 rstio of l:l s~d 120 ml of ~ster. As feed 2, there served 8 solutio~ of 0,185 g sodium disulphite/0.228 g smmonium perox;s~disulphste as redox cstalyst and 20 ml of wster.
20 In 8 1 1 vessel, which wss equipped with stirrer, heatQr, reflux condenser, thermometer, dosing devices, ~itrogen i~let and outlet devices, were placed feed 1 snd feed 2 and heated to 40C. After reaching of the intended temperature, it was further stirred for 24 or 25 48 hours at this temperature. After ending of the reaction, one obtained a white solid material with 55 wt.% ~ield. The GPC analysis gave a molecular weight of 7000, 218~321 ., E~cample 16 A mixturQ (~:1) o~ 25~4 g l-ethoxgdiacet~lpseudo-glucal (EI)A~G) a~d~9.806 g maleic acid anh~dride (~lAh) and 100 m~ of solvent (benzene) forms feed 1. Feed 2 5 w2s prepared rrOm 0,~2 g azo-bis-isobut;~ronitrile (AIBN) and 10 mI benzene. In a 1 1 polymerisation reactor, which is equippea with stirrer, heater, reflu~
cOndenser, thermometer, dosi~g devices, nitrogen inlet a~d outlet devices, feed 1 a~d feed 2 are heated to 10 60C, 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, o~e obtained a white solid material with 15 wt.% yield.
~he GPC allals~sis gave a molecular weight of 2900.
15 Exsmple 17 Feed 1 consisted of 8 mixture of 25.4 g l-ethoxg-diacetylpseudoglucal (EDAPG), 10,415 g st;rrene (1:1) and 100 ml benzene. Feed 2 was prepared ~rom 0.~2 g azo-bis-isobut;~ronitrile (AIBN) and 10 ml benzene.
20 In a 1 1 glas6 flaak, which is equipped wit~ stirrer, heater, ref~ux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, ~e~d 1 and ~eed 2 are heated to 60C, with stirring. A~ter reaching of the i~tended temperature, it was further stirred f or 25 24 or 48 hours at this temperature. After ending of the reaction, one obtained a white solid material wit~} 20 wt.X ;srield, ~he GPC analsrsis gave a molecu~ar weight of 12,~oO.
21 8~32 ~
Example 18 Example L6 w8s repeated with the chan~e that, instead of maleic acid anhgdride, one used ~1.1 g N-vinglpgrrolidone and polymerised f or 24 hours . One 5 obtai~ed a white soLid material with 34 wt.~ gieLd.
l~he GPC s~algsis gsve a molecular weight of 205, 000.
Example 19 E~cample L6 was repeated with the change that, instead of maleic acid a~hgdride, one used 8.609 g 10 methacrglic acid (MA) . Oue obtairLed a white solid ~aterial with 21 ~t.% gield. ~he GPC a~algsis gave a molecular weight of 4800.
E~ramples with "5,6-e~o-glucal"
E~amp~e 20 L5 33-3 g 172,3,4-tetra-O-acetgl-6-deoxy-~-D-xglo-hex-5-e~op;~ranose are polgmerised at 80C f or 24 hours in a vacuum in the presence of 0.242 g benzoDl peroxide.
One obtai~ed a white solid materia~ with 15g6 gield ~he homopolymer had a molecular weight of 1600.
20 Example 2L
Feed 1 consisted of 17.62 g methgl-6-deoxg-cL-D-xylohex-5-enopyranoside in 120 ml of water. Feed 2 was prepared from 0.228 g ammonium peroxyd~sulphate in 20 mL of water. In a 1 1 glass vessel ~qith stirrer, 25 heater, reflux condenser, nitrogen ir~let ard outlet and dosing devices, feed 1 and 2 were placed and warmed to 50C. It was then further poJ,g~erised at this at this temperature f or 24 hours . One o~tained a ~, 218S321 white solid materiaL with 21 wt.g6 yield, ~he GPC analysis gave a molecular weight o~ 1~00.
Erample 22 33.03 g L,2,3,4-tetra-0-acetgl-6-deoxy-~-D_xylo-5 hex-5-enopyranose are polymerised at 100C ~or 24 hour3 in toluene by 0,146 g di-tert.-butyl peroxide (DTBP) activated with 5 ppm copper acetylacetonate . One obtained a white solid msterial with 23X yield. ~he homopolymer had a monecular weight of 1600.
10 Esample 23 Feed 1 consisted of 33.03 ~ 1,2,3,5-tetra-0-acetyl-6-d~oxy-~-D-xylohex-5-enopyranose in 100 mL tert.-butyl-benze~e (TBB). Feed 2 was prepgred from 0,146 g (DTBP) and 10 ml TBB, In a 1 1 g~2ss vessel with stirrer, 15 heater, reflux condenser, nitroge~ inlet and outlet and dosing devices were placed feed L and 2, heated to 120C and polymerised f or 24 hours . Then, at this temperature, the remaining feed 2 was dosed in within 30 minutes and further stirred f or 24 hours, One obtained 20 a white solid material with 25 wt.76 yield. The GPC
analysis gave a molecular weight of 3600.
Example 24 Feed 1 consisted of 30.23 g methyl-2,3,4-tri-0-acetyl-6-deoxy-ll-D-x;ylohex-5-enopyranosQ in 100 ml tert,-butyl-25 benzene (TB~). Feed 2 was prepared from 0.73 g (DTBP)and 100 ml TBB. In a 1 1 gIass vessel with stirrer, heater, reflux condenser, nitrogen inlet and outlet and dosing devices were placed feed 1 and 20 m~ of feed 2, 218~32:~
_34_ and heat2d to 120C and polymerised for 24 hours ~hen, at this temperature, of the remaining fe~d 2, every ~5 hours 20 ml were added thereto and further stirred for 24 hours. One obtained a white solid material with 5 19 wt .96 ;yield . ~he GPC snalysis gave a moleculsr weight of ~i020.
Example 25 Feed 1 consisted of 57.86 g 1,2,~5,4-tetra-0-benzoyl-6-deoxy-~-D-xylohex-5-enopyranose and 120 ml toluene.
10 As feed 2, there served a solution of 0.242 g BOP and 20 ml toluene, In a ~ 1 vessel, which was eguipped with 3tirrer, heater, reflux condenser, t~ermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 ~nd feed 2 and heated to 80C, After reaching of 15 the inte~ded 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 15 wt.s~ yield. ~he GPC analysis ~ave a molecular weight of 28~0.
20 Example 26 Feed 1 Gonsisted of a mixture of 3~.03 g 1,2,3,4-tetra-O-acetyl-6-deox;sr-~-D-xylohex-5-enopyranose, 9.806 g ma~Qic acid anhydride (~h) in a raio of 1:1 a~d 100 ml benze~e, ~s feed 2, there served a solution 25 of 0.32 g AIBi~ 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
218~321 heated to 60C. A~ter reaching of the intended temper-ature, it was further stirrea at this temperature f or 24 or 48 hours. After e~ding of the reaction, one obtained a white soLid material with 37 wt.~6 gield.
5 I!he (;PC analgsis gave a moLacular weight of 5200, Example 27 Feed 1 consisted of a mixture of 33 03 g 1,2,3,4-tetra-O-acetgl-6-deoxg-~-D-xglohex-5-enopgra~ose, 70206 g acrglic acid (AA) in a rstio of L:l and 100 m~
lO toluene. As feed 2, there served a solution of 0.484 g BOP and 20 ml toluene. In a L 1 vessel, which was eguipped with a stirrer, heater, reflux co~denser, ;thermometer, dogi~g devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 and heated to 15 80C. After reaching of the intended temperature, it W88 further stirred f or 24 or 48 hours at this temper-atureO After ending of the reaction, one obtained a white solid material with 34 wt.~ yield ~he GPC analgsis gave a molecular weight of 5100.
20 Example 28 Example 27 was repeated with the chang2 that7 instead of acrglic acid, one used 10.42 g stgrene (~t) .
One obtained a white solid material with 28 wt.76 ;gield4 ~he GPC analysis gave a molecular weight of 3ZCO.
25 Example 29 Feed 1 consisted of a mixture of 57.86 g L,2,3,4-tetra-O-benzogL-6-deoxy-~-D-xglohex-5-e~o~granose, 9.806 g maleic acid a~hgdride (~Ah) in 2 ratio of 1:1 21 8~321 in 120 ml benzene, As fesd 2, thers served a solution of 0.29 g D~BP and 20 ml tert.-butylbenzene. In 8 1 1 vessel, which W2S equipped with stirrer, heater, reflu condenser, thermometer, dosing devices, nitrogen inlet 5 snd outlet devices, were plsced fsed 1 and ~ee~2 and hested to 110C_ After reaching of the intended temper-~ture, it was further stirred st this tempersture for 24 or 48 hours. After ending of the reaction, one obtained a white solid msterial with 18 wt.g6 ~ield.
10 ~he GPC analgsis gave a molecular weight of 12,200.
E~csmple 30 Fsea 1 consisted of a mixture of 57.86 g 1,2,3,4-tetra-O-benzoDl-6-deoxD-,~-l)-x;ylohex-5-enop;yranose, 8.609 g methacrDlic acid (M~gA) in a ratio of 1:1 and ~5 120 m~ toluene. As feed 2, there ssrved a solution of 0,484 g BOP and 20 ml toluene. In a 1 1 vsssel, which was equipped with stirrer, hester, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed 1 and feed 2 snd hested to 20 80C. After reaching of the intended temperature, it was further stirred at this temperature for 24 or 48 hours. After ending o~ the reaction, one obtained a white solid material with 32 wt.g6 ;rield ~he G~C
anal~sis gsve a molecular weight of 5700.
25 Example 31 Feed 1 consisted o~ a mixture of 18.62 g anh;srdro-~,4-di-0-benzo~1-5-0-(2,3,4,6-tetra-0-benzo;sl-G-D-glucopDranox;~ l-deoxg-D-arabinohex-l-enitol ~ - 218~32~ ~
~37-(briefly cslled "leucren'~), 1.961 g maleic scid anhgdride (r~:h) in a ratio of 1:~ and 120 ml ~BB.
As feed 2, there served a so~ution of 0.058 g D~BP
and 10 ml ~BB. In a 1 1 vessel, which W8S equipped 5 with stirrer, heater, reflux condenser, thermometer, dosing devices, nitrogen inlet and outlet devices, were placed feed I and reed 2 snd hested to 130C.
After resching of the intended tempersture, it was ~urther ~tirred for 64 hours at this temperature.
10 After ending of the reaction, one obtained a white solid material with 46 wt.% yield ~he GPC analysis gsve 8 molecular weight of 27,000.
Example 32 Feed ~ consisted on 18.60 g meth;srl-5-deoxy-2,3-0-15 isopropylidene-erythropent-4-enofuranoside (briefly called "ene-ribose") in 100 ml ~BB. Feed 2 wss prepared from 0,146 g (D~BP) snd 10 ml ~BB. In a 1 1 glass vessel with stirre-r, heater, re~lux conae~ser, nitrogen inlet and outlet and dosing devices, were 20 placed feed 1 and feed 2. ~he reaction mixture was heated to llO~C. After reaching of the intended tempersture, it was further stirred at this temperature for 24 hours. ~fter ending of the reaction, one obtaine~
8 white solid msterial with 35 wt.gS yield. ~he GPC
25 analysis gave a molecular weight of 2100.
Example 33 Feed I consisted of a mixture of 18.60 g ene-ribose, 9.806 g maleic acid anhydride (MAh) in a 218~321 ra~ ~ of l:~ and lOO ml ~BB~ As feed 2, where served a soLution of 0.292 g D~BP and 20 ml l!BB. In a 1 1 vesseL, which was equipped with stirrer, heatar, reflux condenser, thermoneter, dosin~ devices, 5 nitrogen inlet and out~et de~ices, were placed feed 1 snd feed 2 and hested to 110C. After reaching of the intenaed tenperature, it was further stirred at this temper2ture for 24 hours. After ending o~ the reaction, one obtained 8 white solid material with 47 wt.% ;srield.
10 ~he GPC anal;ysis gave a molecula~ weight of 3700.
E~ample 34 Exam~la 33 wss repeatad with the difference that, instead of maIeic acid anhydride, 11.1 g ~-vingl-pyrrolidine was used and polymerised f or 6 hour~ .
15 One obtained a white solid material with 53wt.~ ~ield.
Th~ GPO aual~ gave a mol~o~lar ~igbt Df' lOb,~O~.
Claims (7)
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 (I) in which R1 signifies hydrogen, an acetyl, benzoyl, methyl or benzyl group, R2 represents hydrogen, an acetyl, benzoyl, methyl, benzyl group or a glucosyl radical and R3 is hydrogen, an acetyl, benzoyl, methyl or benzyl group, formula II or stereoisomers (II) in which R2 represents hydrogen, an acetyl, benzoyl, methyl, benzyl group or a glucosyl radical, R3 is hydrogen, an acetyl, benzoyl, methyl, benzyl group or (R2,R3) 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 (III) in which R1 represents hydrogen, an acetyl, benzyl, benzoyl, alkyl group with, in all, up to 2 C-atoms in the alkyl radical, R2 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group with 1 - 3 C-atoms or a glycosyl radical, R3 is hydrogen, an acetyl, benzoyl, benzyl, methyl group, formula IV or stereoisomers (IV) in which R2 signifies hydrogen, an acetyl, benzoyl, alkyl, benzyl group or a glucosyl radical, R3 is hydrogen, an acetyl, benzoyl, methyl, benzyl, tosyl group or (R2,R3) can be a protective group usual in organic chemistry (such as e.g. 4,6-0-benzylidene), formula V
(V) in which R1 is hydrogen, an alkyl group or galacturonic acid radical, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R4 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 (VI) in which R1 can be hydrogen, an acetyl, benzoyl, benzyl group or alkyl group with 1 - 3 C-atoms or a fructosyl radical, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 is an acetyl, benzoyl, benzyl, alkyl group, R4 represents hydrogen, an acetyl, benzyl, benzoyl, alkyl group, formula VII or stereoisomers (VII) in which R1 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R2 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group or a glucosyl radical, R4 signifies hydrogen, an acetyl, benzoyl, benzyl or alkyl group, formula VIII or stereoisomers (VIII) in which R1 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group and the corresponding derivatives on leucrose basis or their stereoisomers, formula IX or stereoisomers in which R1 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R2 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 represents 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 (X) in which R1 can be hydrogen or an alkyl radical with 1 to 3 C-atoms, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 signifies hydrogen, an acetyl, benzyl, benzoyl, alkyl group or (R2,R3) can be a protective group usual in organic chemistry, formula XI
(XI) in which R1, R2 is hydrogen, an acetyl, benzyl, benzoyl, alkyl group, R3; represents hydrogen or a glucosyl radical, such as e.g. in the case of palatinose, formula XII
(XII) in which R1, R2, R3 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R4 represents a glucosyl radical, such as e.g. in the case of saccharose, the ethylenically-unsaturated compounds are selected from the group (a) monoethylenically-unsaturated C3- to C10-carboxylic acids and their alkali metal, alkaline earth metal or ammonium salts, (b) moroethylenically-unsaturated C3- to C12-carboxylic acid esters, (c) 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, (d) acrylic acid smides, methacrylic acid amide, N-(dialkyl)-acrylic acid or methacrylic acid amide, (e) N-vinylimidazoles which are substituted on the heterocyclic ring by up to three C1- to C12- alkyl radicals and can be present in N-quaternised form or in salt form, (f) five- to eight-membered N-vinyllactams which can be substituted on the ring by up to three C1- to C12-alkyl radicals, (g) 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, (h) styrene which can be substituted on the aromatic ring by up to two C1- to C3-alkyl radicals, (i) acrylonitrile, methacrylonitrile, (j) N-vinylpyridines which can be substituted on the heterocyclic ring by up to C1- to C12- alkyl radicals and can be present in N-quaternised form or in salt form.
(V) in which R1 is hydrogen, an alkyl group or galacturonic acid radical, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R4 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 (VI) in which R1 can be hydrogen, an acetyl, benzoyl, benzyl group or alkyl group with 1 - 3 C-atoms or a fructosyl radical, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 is an acetyl, benzoyl, benzyl, alkyl group, R4 represents hydrogen, an acetyl, benzyl, benzoyl, alkyl group, formula VII or stereoisomers (VII) in which R1 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R2 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl group or a glucosyl radical, R4 signifies hydrogen, an acetyl, benzoyl, benzyl or alkyl group, formula VIII or stereoisomers (VIII) in which R1 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group and the corresponding derivatives on leucrose basis or their stereoisomers, formula IX or stereoisomers in which R1 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R2 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 represents 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 (X) in which R1 can be hydrogen or an alkyl radical with 1 to 3 C-atoms, R2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R3 signifies hydrogen, an acetyl, benzyl, benzoyl, alkyl group or (R2,R3) can be a protective group usual in organic chemistry, formula XI
(XI) in which R1, R2 is hydrogen, an acetyl, benzyl, benzoyl, alkyl group, R3; represents hydrogen or a glucosyl radical, such as e.g. in the case of palatinose, formula XII
(XII) in which R1, R2, R3 signifies hydrogen, an acetyl, benzoyl, benzyl, alkyl group, R4 represents a glucosyl radical, such as e.g. in the case of saccharose, the ethylenically-unsaturated compounds are selected from the group (a) monoethylenically-unsaturated C3- to C10-carboxylic acids and their alkali metal, alkaline earth metal or ammonium salts, (b) moroethylenically-unsaturated C3- to C12-carboxylic acid esters, (c) 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, (d) acrylic acid smides, methacrylic acid amide, N-(dialkyl)-acrylic acid or methacrylic acid amide, (e) N-vinylimidazoles which are substituted on the heterocyclic ring by up to three C1- to C12- alkyl radicals and can be present in N-quaternised form or in salt form, (f) five- to eight-membered N-vinyllactams which can be substituted on the ring by up to three C1- to C12-alkyl radicals, (g) 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, (h) styrene which can be substituted on the aromatic ring by up to two C1- to C3-alkyl radicals, (i) acrylonitrile, methacrylonitrile, (j) N-vinylpyridines which can be substituted on the heterocyclic ring by up to C1- to C12- 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 ethylenic-ally-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, character-ised that that the monomers are polymerised radically in the presence of or also in the absence of inert or polar solvents as well as in aqueous systems.
4. Process according to claim 3, characterised in that one uses catalysts which form radicals, e.g. adds thereto inorganic and organic peroxides, persulphates, azo compounds or so-called radox catalysts in an amount of 0.01 - 20 mol %.
5. Process according to claim 3 or 4, characterised in that one works at temperatures of 40 - 150°C, preferably 50 - 130°C.
6. Process according to one of claims 3 to 5, character-ised in that the polymerisation is started at low temperature with a radical initiator and ended at higher temperature with another radical initiator.
7. 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19944408391 DE4408391A1 (en) | 1994-03-12 | 1994-03-12 | Polymers of unsaturated saccharides and their derivatives and their copolymers with ethylenically unsaturated compounds and processes for their preparation |
| DEP4408391.2 | 1994-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2185321A1 true CA2185321A1 (en) | 1995-09-21 |
Family
ID=6512603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2185321 Abandoned CA2185321A1 (en) | 1994-03-12 | 1995-03-13 | Polymers of unsaturated saccharides and their derivatives and their copolymers having ethylenically unsaturated compounds, and process for preparing them |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0750646A1 (en) |
| JP (1) | JPH09512841A (en) |
| AU (1) | AU685922B2 (en) |
| CA (1) | CA2185321A1 (en) |
| DE (1) | DE4408391A1 (en) |
| WO (1) | WO1995025135A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19727362A1 (en) * | 1997-06-27 | 1999-01-07 | Klaus Prof Dr Buchholz | Polymers from unsaturated saccharide acids and their derivatives as well as their copolymers with ethylenically unsaturated compounds and processes for their preparation |
| DE19919785A1 (en) | 1999-04-30 | 2000-12-07 | Wella Ag | Hair treatment agent with polymers of unsaturated saccharides, unsaturated saccharic acids or their derivatives |
| DE19945236A1 (en) * | 1999-09-21 | 2001-03-29 | Wella Ag | Carbohydrate latices, process for their preparation and their use |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3628240A1 (en) * | 1985-09-02 | 1987-03-05 | Basf Ag | Allyl ethers of galactopyranose, process for their preparation and polymerisation and use of the polymers |
-
1994
- 1994-03-12 DE DE19944408391 patent/DE4408391A1/en not_active Withdrawn
-
1995
- 1995-03-13 JP JP7523833A patent/JPH09512841A/en active Pending
- 1995-03-13 AU AU18940/95A patent/AU685922B2/en not_active Expired - Fee Related
- 1995-03-13 CA CA 2185321 patent/CA2185321A1/en not_active Abandoned
- 1995-03-13 WO PCT/EP1995/000930 patent/WO1995025135A1/en not_active Application Discontinuation
- 1995-03-13 EP EP95911328A patent/EP0750646A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE4408391A1 (en) | 1995-09-14 |
| AU685922B2 (en) | 1998-01-29 |
| AU1894095A (en) | 1995-10-03 |
| JPH09512841A (en) | 1997-12-22 |
| EP0750646A1 (en) | 1997-01-02 |
| WO1995025135A1 (en) | 1995-09-21 |
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