Rime, Francois (Delemont, CH)
2. A process according to claim 1 wherein the natural or synthetic clay is a phyllosilicate.
3. A process according to claim 1 wherein the natural or synthetic clay is selected from the group consisting of smectite, montmorillonite, saponite, beidellite, mica, sauconite, ledikite, montronite, hectorite, stevensite, vermiculite, kaolinite, hallosite and combinations thereof.
4. A process according to claim 1 wherein the structural element
5. A process according to claim 1 wherein the structural element
6. A process according to claim 1, wherein in step a3) [in] represents the polymerization initiator fragment of a polymerization initiator of formula (III) capable of initiating polymerization of monomers or oligomers which polymerization initiator is selected from the group consisting of C1-C8-alkyl halides, C6-C15-aralkylhalides, C2-C8-haloalkyl esters, arene sulfonyl chlorides, haloalkanenitriles, α-haloacrylates and halolactones, and p and q represent one.
7. A process according to claim 6 wherein in step a3) the oxidizable transition metal in the transition metal complex salt is present as a transition metal complex ion in the lower oxidation state of a redox system.
8. A process according to claim 1, wherein the nonionic polymer block B is essentially composed of repeating units of ethylenically unsaturated monomers selected from the group consisting of styrenes, acrylic and C1-C4alkylacrylic acid C1-C24alkyl esters, acrylic and C1-C4alkylacrylic acid-C8C11aryl-C1-C4alkyl esters, acrylic and C1-C4alkylacrylic acid-C8-C11aryloxy-C1-C4alkyl esters, acrylic and C1-C4alkylacrylic acid-hydroxy-C2-C6alkyl esters, acrylic and C1-C4alkylacrylic acid-polyhydroxy-C3-C8alkyl esters, acrylic and C1-C4alkylacrylic acid-(C1-C4alkyl)3silyloxy-C2-C4alkyl esters; acrylic and C1-C4alkylacrylic acid-(C1-C4alkyl)3silyl-C1-C4alkyl esters, acrylic and C1-C4alkylacrylic acid-heterocyclyl-C2-C4alkyl esters; acrylic and C1-C4alkylacrylic acid esters having poly-C2-C4alkylene-glycolester groups, wherein the ester groups may be substituted with C1-C24alkoxy groups, acrylic and methacrylic acid amides, acrylic and C1-C4alkylacrylic acid-(C1-C4alkyl)1-2amide, acrylonitrile, esters of maleic acid or fumaric acid, maleinimide and N-substituted maleinimides.
9. A process according to claim 8, wherein the nonionic polymer block B is essentially composed of repeating units of ethylenically unsaturated monomers selected from the group consisting of styrenes, acrylic and methacrylic acid-C1-C24alkyl esters, acrylic and methacrylic acid-hydroxy-C2-C6alkyl esters, acrylic and methacrylic acid-dihydroxy-C3-C4alkyl esters and acrylic and methacrylic acid esters having poly-C2-C4alkyleneglycolester groups, wherein the ester groups may be substituted with C1-C24alkoxy groups.
10. A process according to claim 1, wherein the cationic polymer block A is essentially composed of repeating units of ethylenically unsaturated monomers represented by the cationic part of a salt formed by quaternisation of an amino monomer selected from the group consisting of amino substituted styrene, (C1-C4alkyl)1-2amino substituted styrene, N-mono-(C1-C4alkyl)1-2amino-C2-C4alkyl(meth)acrylamide and N,N-di-(C1-C4alkyl)1-2amino-(C2-C4)alkyl(meth)acrylamide, vinylpyridine or C1-C4alkyl substituted vinylpyridine, vinylimidazole and C1-C4alkyl substituted vinylimidazole and a compound of the formula
CH2═C(—R1)—C(═O)—R2 (V), wherein R1 represents hydrogen or C1-C4alkyl; and R2 represents amino substituted C2-C18alkoxy selected from the group consisting of amino-C2-C18alkoxy, C1-C4alkylamino-C2-C18alkoxy, di-C1-C4alkylamino-C2-C18alkoxy, hydroxy-C2-C4alkylamino-C2-C16alkoxy and C1-C4alkyl-(hydroxy-C2-C4alkyl)amino-C2-C18alkoxy.
11. A process according to claim 10, wherein R1 represents hydrogen or methyl; and R2 represents amino substituted C2-C18alkoxy selected from the group consisting of amino-C2-C4alkoxy, C1-C4alkylamino-C2-C4alkoxy, di-C1-C4alkylamino-C2-C4alkoxy, hydroxy-C2-C4alkylamino-C2-C18alkoxy and C1-C4alkyl-hydroxy-C2-C4alkyl)amino-C2-C4alkoxy.
12. A process according to claim 10, wherein the cationic part of a salt formed from a compound of the formula () is represented by an ester group of the formula (C)
13. A process according to claim 10, wherein the cationic polymer block A is essentially composed of repeating units of an ethylenically unsaturated monomer represented by the cationic part of an acid addition salt or the salt formed by quaternisation of 4-aminostyrene, 4-dimethylaminostyrene, aminoalkyl(meth)acrylate selected from the group consisting of 2-dimethylaminoethyl acrylate (DMAEA), 2-dimethylaminoethyl methacrylate (DMAEMA), 2-diethylaminoethyl acrylate (DEAEA), 2-diethylaminoethyl methacrylate (DEAEMA), 2-t-butylaminoethyl acrylate (t-BAEA), 2-t-butylaminoethyl methacrylate (t-BAEMA) and 3-dimethylaminopropylmethacrylamide, 4-vinylpyridine, 2-vinylpyridine or 1-vinylimidazole.
14. A process according to claim 1 wherein the block or comb copolymer is added to the natural or synthetic clay in an amount of from 1% to 1000% by weight, based on the w,ieight of the clay.
15. A process according to claim 1 wherein the polydispersity of block A and B is between 1 end 2.
16. A process according to claim 1 wherein the polydispersity of the blockcopolymer A-B is between 1 and 2.
17. A process according to claim 1 wherein the number of repeating units of the nonionic block B is from 4-1000.
18. A process according to claim 1 wherein the number of repeating units of the cationic block A is from 1-100.
19. A block or comb copolymer, clay nanocomposite dispersion obtainable by a process according to claim 1.
20. Use of a block copolymer having one ammonium cationic block A, and at least one neutral block B or a comb copolymer having an ammonium ion containing cationic backbone A and neutral oligomefic/polymeric chains B attached thereto, wherein the block copolymer and the comb copolymer is obtained by controlled free radical polymerization according to claim 1 for the preparation of nanocomposite dispersions of natural or synthetic clay.
The instant invention relates to a process for manufacturing nanoparticles by intercalating and/or exfoliating natural or synthetic clays using block or comb copolymers having one cationic block and at least one non polar block, which are prepared by controlled free radical polymerization (CFRP). The invention also relates to improved nanocomposite compositions containing nanoparticles produced by this process and to the use of these nanocomposite compositions as, for example, in coatings, sealants, caulks, adhesives and as plastic additives.
One way of improving polymer properties is by adding a natural or synthetic clay material to polymers to form composite materials. However, incorporating clays into polymers may got provide a desirable improvement in the physical properties, particularly mechanical and optical properties of the polymer may be adversely affected.
Nanonocomposite compositions containing finely dispersed natural or synthetic clay with at least partially intercalated and/or exfoliated layers and mixtures of ethylenically unsaturated monomers and/or polymers therefrom have therefore attracted much interest in the last years. These materials combine the desired effects of dispersed clay by avoiding the negative influence on, for example, the mechanical or optical properties.
Such compositions, methods for making them and their use in polymers and coatings are for example described in WO 02/24759. Polymerization processes are described using montmorillonite clay, acrylate monomers and for example ammonium persulfate as radical initiator. This conventional polymerization process leads to polymers with broad molecular weight distributions and a high polydispersity index (PD).
Another approach is, for example described by Yang et al. in Mat. Res. Soc. Symp. Proc. Vol. 703, 2002, pages 547-552. Di- or triblock copolymers are prepared containing dimethyl-aminoethyl methacrylate as monomer in one block and, for example, methacrylic acid as monomer in the other block. From these copolymers cationic blocks are obtained by protonating the aminoblock in the copolymer. The protonated blockcopolymers are then used for intercalating montmorillonite. The D-spading between the layers is typically between 1.5 and 2 nm. There is nothing disclosed, as to how the preparation of the block copolymers is carried out, in particular, the polydispersity index M W /M n of the individual blocks and of the total block copolymer is not known.
The instant invention provides improved nanoparticles of natural and synthetic clay, having in general higher D-spacings. The nanoparticles are prepared by intercalating and/or exfoliating natural or synthetic clays using block or comb copolymers having one cationic block and at least one non polar block, which copolymers are prepared by controlled free radical polymerization (CFRP).
Controlled free radical polymerization per se is known and can be carried out by using for example atom transfer radical polymerization (ATRP) as described in WO 96/30421. WO 96/30421 discloses a controlled or “living” polymerization process of ethylenically unsaturated monomers such as styrene or (meth)acrylates by employing the ATRP method. According to this method initiators are employed which generate a radical atom such as .Cl, in the presence of a redox system of transition metals of different oxidation states, e.g. Cu(I) and Cu(II), providing “living” or controlled radical polymerization.
Another further suitable polymerization process is disclosed in U.S. Pat. No. 4,581,429. U.S. Pat. No. 4,581,429 discloses a free radical polymerization process by controlled or “living” growth of polymer chains which produces defined oligomeric homopolymers and copolymers, including block and graft copolymers. Disclosed is the use of initiators of the partial formula R′R″N—O—X. In the polymerization process the free radical species R′R″N—O. and .X are generated. .X is a free radical group, e.g. a tert.-butyl or cyanoisopropyl radical, capable of polymerizing monomer units containing ethylene groups.
A variation of the above process s disclosed in U.S. Pat. No. 5,322,912 wherein the combined use of a free radical initiator and a stable free radical agent of the basic structure R′R″N—O. for the synthesis of homopolymers and block copolymers is described.
All three processes are useful for the preparation of blocker comb copolymers wherein the block copolymers have a narrow molecular weight distribution and hence a low polydispersity index.
Surprisingly it has been found, that clay nanoparticles prepared from block- or comb copolymers obtained by CFRP are not only intercalated but in many cases exfoliated and therefore dispersions containing these nanoparticles are much more storage stable. In most cases there is no agglomeration or aggregation even after long storage periods. The nanocomposite compositions of the instant invention can be optically almost transparent, indicating the fine distribution, on the nanometer scale, of the clay.
One aspect of the invention is a process for preparing a block- or comb polymer, clay nanocomposite dispersion comprising
-
- mixing an aqueous dispersion of a natural or synthetic clay having an exchangeable cation; with
- a block copolymer having a cationic block A wherein the cation is based on at least one nitrogen atom, and a nonionic block B, both blocks having a polydispersity between 1 and 3, or
- a comb copolymer having a cationic backbone A wherein the cation is based on a nitrogen atom and nonionic oligomeric/polymeric chains B attached thereto, the cationic backbone A having a polydispersity between 1 and 3 and the nonionic side chains having a polydispersity of 1.0-1.8;
- wherein the block copolymer is obtained
- a1) by polymerizing in a first step an ethylenically unsaturated monomer in the presence of at least one nitroxylether having the structural element
- a1) by polymerizing in a first step an ethylenically unsaturated monomer in the presence of at least one nitroxylether having the structural element
- wherein X represents a group having at least one carbon atom and is such that the free radical X. derived from X is capable of initiating polymerization and adding in a second step to the resulting macromer, which has attached a labile bound
- group, a further ethylenically unsaturated monomer different from that in step 1,
- with the proviso that at least one monomer in the first or second step contains a cation centered on a nitrogen atom or a nitrogen atom from which a cation can be formed; or
- a2) by polymerzing in a first step an ethylenically unsaturated monomer in the presence of at least one stable free nitroxyl radical
- and a free radical initiator and adding in a second step to the resulting macromer, which has attached a labile bound
- group, a further ethylenically unsaturated monomer different from that in step 1;
- with the proviso that at least one monomer in the first or second stop contains a cation centered on a nitrogen atom or a nitrogen atom from which a cation can be formed; or
- a3) by polymerzing in a first step an ethylenically unsaturated monomer in the presence of a compound of formula (III)
- and a catalytically effective amount of an oxidizable transition metal complex catalyst, wherein
- p represents a number greater than zero and defines the number of initiator fragments;
- q represents a number greater than zero;
- [In] represents a radically transferable atom or group capable of initiating polymerization and
- [Hal] represents a leaving group; and adding in a second step to the resulting macromer a further ethylenically unsaturated monomer different from that in step one;
- with the proviso that at least one monomer in the first or second step contains a cation centered on a nitrogen atom or a nitrogen atom from which a cation can be formed;
- wherein the comb copolymer is obtained
- by polymerizing in a first step an ethylenically unsaturated monomer in the presence of a compound of formula (III)
- by polymerizing in a first step an ethylenically unsaturated monomer in the presence of a compound of formula (III)
- and a catalytically effective amount of an oxidizable transition metal complex catalyst, wherein the symbols have the meanings as defined above;
- exchanging the group [HAL] attached to the polymer with a group having an ethylenically unsaturated bond and subjecting the resulting macromer together with a second monomer, which contains a nitrogen based cation or a nitrogen atom from which a cation can be formed, to radical polymerization;
- forming the nitrogen based cation if necessary and exchanging the cation in the natural or synthetic clay, with the nitrogen based cationic block or comb copolymer and intercalating and/or exfoliating the clay at least partially.
If the clay material is a synthetic one, it may be produced by gas-phase or sol-gel processes, for example Optigel® from Süd Chemie.
Natural clay minerals are typically comprised of hydrated aluminum silicates that are fine-grained and have a platy habit. The crystalline structure of a typical clay mineral is a multi-layered structure comprised of combinations of layers of SiO 4 tetrahedra that are joined to layers of AlO(OH) 2 octahedra. A so called “gallery” is formed which describes the defined interlayer spaces of the layered clay minerals. Depending of the clay mineral the gallery may contain water and/or other constituents such as potassium, sodium or calcium cations. Clay minerals vary, based upon the combination of their constituent layers and cations. Isomorphic substitution of the cations of clay mineral, such as Al 3+ or Fe 3+ substituting for the Si 4+ ions in the tetrahedral network, or Al 3+ , Mg 2+ or Fe 2+ substituting for other cations in the octahedral network, typically occurs and may impart a net negative charge on the clay structure. Natural occurring elements within the gallery of the clay, such as water molecules or sodium or potassium cations, are attracted to the surface of the clay layers due to this net charge.
Nanocomposites are compositions in which at least one of its constituents has one or more dimensions, such as length, width or thickness in the nanometer size range. The term nanocomposite, as used herein, denotes the state of matter wherein intercalated and at least partially exfoliated clay layers are surrounded by a polymer matrix.
The term “intercalated nanocomposite”, as used herein describes a nanocomposite that contains a regular insertion between the clay layers.
The term “exfoliated nanocomposite” as used herein describes a nanocomposite wherein the a few nm thick layers of clay with polymer molecules attached to K are dispersed in the matrix (oligomer/polymer) forming a composite structure on the nano/micro scale.
The clay minerals are items of commerce and are for example supplied by Süd-Chemie Inc., Germany or Nanocore, USA.
The natural or synthetic clay is for example a phyllosilicate.
In particular the natural clay is selected from the group consisting of smectite, montmorillonite, saponite, beidellite, mica, sauconite, ledikite, montronite, hectorite, stevensite, vermiculite, kaolinite, hallosite and combinations thereof.
Special preference is given to montmorillonite.
As already mentioned it is indispensable that the block copolymers are prepared by controlled free radical polymerization (CFRP). There are essentially three suitable routes:
a1) polymerization in the presence of alkoxyamine initiator/regulator compounds;
a2) polymerization in the presence of a stable nitroxyl free radical and a radical initiator (source of free radicals) and
a3) polymerization under atom transfer radical polymerization (ATRP) conditions. All three routes are known and widely described.
For example the structural element
may be part of a cyclic ring system or substituted to form a acyclic structure.
Suitable nitroxylethers and nitroxyl radicals are principally known from U.S. Pat. No. 4,581,429 or EP-A-621 878. Particularly useful are the open chain compounds described in WO O8/13392, WO 99/03894 and WO 00/07981, the piperidine derivatives described in WO 99/67298 and GB 2335190 or the heterocyclic compounds described in GB 2342649 and WO 96/24620. Further suitable nitroxylethers and nitroxyl radicals are described in WO 02/4805 and in WO 021100831.
Stable free radicals having a structural element
are for example disclosed in EP-A-621 878.
Examples, such as
are for example given in WO 96/24620.
Preferably the structural element
is a structural element of formula (I)
G 1 , G 2 , G 3 , G 4 are independently C 1 -C 6 alkyl or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 together form a C 5 -C 12 cycloalkyl group;
G 5 , G 6 independently are H, C 1 -C 18 alkyl, phenyl, naphthyl or a group COOC 1 -C 18 alkyl.
In particular the structural element of formula (I) is of formula A, B or O,
wherein
m is t,
R is hydrogen, C 1 -C 18 alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
p is 1;
R 101 is C 1 -C 12 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 18 alkanoyl, C 3 -C 5 alkenoyl or benzoyl;
R 102 is C 1 -C 18 alkyl, C 5 -C 7 cycloalkyl, C 2 -C 8 alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula —CH 2 CH(OH)-Z or of the formula —CO-Z or —CONH-Z wherein Z is hydrogen, methyl or phenyl;
G 6 is hydrogen and G 5 is hydrogen or C 1 -C 4 alkyl,
G 1 and G 3 are methyl and G 2 and G 4 are ethyl or propyl or G 1 and G 2 are methyl and G 3 and G 4 are ethyl or propyl; and
X is selected from the group consisting of
—CH 2 -phenyl, CH 3 CH-phenyl, (CH 3 ) 2 C-phenyl, (C 6 -C 9 cycloalkyl) 2 CCN, (CH 3 ) 2 CCN,
—CH 2 CH═CH 2 , CH 3 CH—CH=CH 2 (C 1 -C 4 alkyl)CR 20 —C(O)— phenyl, (C 1 -C 4 )alkyl-CR 20 —C(O)—(C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl-CR 20 —C(O)—(C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl-CR 20 —C(O—N-di(C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl-CR 20 —C(O)—NH(C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl-CR 20 -C(O)—NH 2 , wherein
R 20 is hydrogen or (C 1 -C 4 )alkyl.
The above compounds and their preparation are described in GB 2335190 and GB 2 361 235.
Another preferred group of nitroxylethers of step al) are those of formula (Ic), (Id), (Ie), (If) i (Ig) or (Ih)
wherein R 201 , R 202 , R R 203 and R 204 independently of each other are C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 3 -C 18 alkinyl, C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 3 -C 18 alkinyl which are substituted by OH, halogen or a group —O—C(O)—R 205 , C 2 -C 18 alkyl which is interrupted by at least one O atom and/or NR 205 group, C 3 -C 12 cycloalkyl or C 5 -C 10 aryl or R 201 and R 202 and/or R 203 and R 204 together with the linking carbon atom from a C 3 -C 12 cycloalkyl radical;
R 205 , R 206 and R 207 independently are hydrogen, C 1 -C 18 alkyl or C 6 -C 10 aryl;
R 203 is hydrogen, OH, C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 3 -C 18 alkinyl, C 1 -C 18 alkyl, C 3 -C 18 alkenyl, C 3 -C 18 alkinyl which are substituted by one or more OH, halogen or a group —O—C(O)—R 205 , C 2 -C 18 alkyl which is interrupted by at least one O atom and/or NR 206 group, C 3 -C 12 cycloalkyl or C 6 -C 10 aryl, C 7 -C 8 phenylalkyl, C 6 -C 10 heteroaryl, —C(O)—C 1 -C 18 alkyl, —O—C 1 -C 18 alkyl or —COOC 1 -C 18 alkyl;
R 209 , R 210 , R 211 and R 212 are independently hydrogen, phenyl or C 1 -C 18 alkyl; and
X is selected from the group consisting of —CH 2 -phenyl, CH 3 CH-phenyl, (CH 3 ) 2 C-phenyl, (C 5 -C 6 cycloalkyl) 2 CCN, (CH 3 ) 2 CNN,
—CH 2 CH═CH 2 , CH 3 CH—CH═CH 2 (C 1 -C 4 alkyl)CR 20 -C(O)-phenyl, (C 1 -C 4 )alkyl-CR 20 —C(O)—(C 1 -C 4 )alkoxy, (C 1 -C 4 )alkyl-CR 20 —C(O)—(C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl-CR 20 —C(O)—N-di(C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl-CR 20 —C(O)—NH(C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl-CR 20 —C(O)—NH 2 , wherein
R 20 is hydrogen or (C 1 -C 4 )alkyl.
More preferably in formula (Ic), (Id), (Ie), (f), (Ig), and (Ih) at least two of R 201 , R 202 , R 203 and R 204 are ethyl, propyl or butyl and the remaining are methyl; or
R 201 and R 202 or R 203 and R 204 together with the linking carbon atom from a C 5 -C 6 cycloalkyl radical and one of the remaining substituents is ethyl, propyl or butyl.
Most preferably X is CH 3 CH-phenyl.
The above compounds and their preparation is described in GB 2342649.
Further suitable compounds are the 4-imino compounds of formula (II)
G 11 , G 12 , G 13 and G 14 are independently C 1 -C 4 alkyl or G 11 and G 12 together and G 13 and G 14 together, or G 11 and G 12 together or G 13 and G 14 together are pentamethylene;
G 15 and G 16 are each independently of the other hydrogen or C 1 -C 4 alkyl;
X is as defined above;
It is 1, 2, 3, or 4
Y is O, NR 302 or when n is 1 and R 301 represents alkyl or aryl Y is additionally a direct bond;
R 302 is H, C 1 -C 18 alkyl or phenyl;
if k is 1
R 301 is H, straight or branched C 1 -C 18 alkyl, C 3 -C 18 alkenyl or C 3 -C 18 alkinyl, which may be unsubstituted or substituted, by one or more OH, C 1 -C 8 alkoxy, carboxy, C 1 -C 8 alkoxycarbonyl;
C 6 -C 12 cycloalkyl or C 5 -C 12 cycloalkenyl;
phenyl, C 7 -C 9 phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C 1 -C 8 alkyl, halogen, OH, C 1 -C 8 alkoxy, carboxy, C 1 -C 8 alkoxycarbonyl;
—C(O)C—C 1 -C 18 alkyl, or an acyl moiety of a c,unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
—SO 3 − Q + , —PO(OR 2 ) 2 , —P(O)(OR 2 ) 2 —SO 2 —R 2 , —CO—NH—R 2 , —CONH 2 , COOR 2 , or Si(Me) 3 , wherein Q + is H + , ammonium or an alkali metal cation;
if k is 2
R 301 is C 1 -C 18 alkylene, C 3 -C 18 alkenylene or C 3 -C 18 alkinylene, which may be unsubstituted or substituted, by one or more OH, C 1 -C 8 alkoxy, carboxy, C 1 -C 8 alkoxycarbonyl;
or xylylene; or
R 301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if k is 3,
R 301 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and
if k is 4, R 301 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
Preferably G 15 is hydrogen and G 16 is hydrogen or C 1 -C 4 alkyl, in particular methyl, and G 11 and G 13 are methyl and G 12 and G 14 are ethyl or propyl or G 11 and G 12 are methyl and G 13 and G 14 are ethyl or propyl.
The 4 imino compounds of formula V can be prepared for example according to E. G. Rozantsev, A. V. Chudinov, V. D. Sholle. :lzv. Aked. Nauk. SSSR, Ber. Khim. (9), 2114 (1980), starting from the corresponding 4-oxonitroxide in a condensation reaction with hydroxylamine and subsequent reaction of the OH group. The compounds are described WO 021100831.
When the polymerization process is carried out according to route a2) the structural element
is for example a structural element of formula (I′)
G 1 , G 2 , G 3 , G 4 are independently C 1 -C 6 alkyl or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 together form a C 5 -C 12 cycloalkyl group;
G 5 , G 6 independently are H, C 1 -C 18 alkyl, phenyl, naphthyl or a group COOC 1 -C 18 alkyl.
Preference is given to compounds wherein the structural element of formula (I′) is of formula A′, B′ or O′,
wherein
m is 1,
R is hydrogen, C 1 -C 18 alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
p is 1;
R 101 is C 1 -C 12 alkyl, C 6 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 18 alkanoyl, C 3 -C 6 alkenoyl or benzoyl;
R 102 is C 1 -C 18 alkyl, C 5 -C 7 cycloalkyl, C 2 -C 8 alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula —CH 2 CH(OH)-Z or of the formula —CO-Z or —CONH-Z wherein Z is hydrogen, methyl or phenyl;
G 6 is hydrogen and G 5 is hydrogen or C 1 -C 6 alkyl,
G 1 and G 3 are methyl and G 2 and G 4 are ethyl or propyl or G 1 and G 2 are methyl and G 3 and G 4 are ethyl or propyl.
Also suitable are the compounds wherein the structural element
is of formula (II′)
G 11 , G 12 , G 13 and G 14 are independently C 1 -C 4 alkyl or G 11 and G 12 together and G 13 and G 14 together, or G 11 and G 12 together or G 13 and G 14 together are pentamethylene;
G 15 and G 16 are each independently of the other hydrogen or C 1 -C 4 alkyl;
k is 1, 2, 3, or 4
Y is 0, NR 302 or when n is 1 and R 301 represents alkyl or aryl Y is additionally a direct bond;
R3m is H, C 1 -C 18 alkyl or phenyl;
if k is 1
R 301 is H, straight or branched C 1 -C 18 alkyl, C 3 -C 18 alkenyl or C 3 -C 18 alkinyl, which may be unsubstituted or substituted, by one or more OH, C 1 -C 8 alkoxy, carboxy, C 1 -C 18 alkoxycarbonyl;
C 5 -C 12 cycloalkyl or C 5 -C 12 cycloalkenyl;
phenyl, C 7 -C 9 phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C 1 -C 8 alkyl, halogen, OH, C 1 -C 8 alkoxy, carboxy, C 1 -C 8 alkoxycarbonyl;
—C(O)—C 1 -C 33 alkyl, or an acyl moiety of a α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
—SO 3 − Q + , —PO(O − Q + ) 2 , —P(O)(OR 2 ) 2 , —SO 2 —R 2 , —CO—NH—R 2 , —CONH 2 , COOR 2 , or Si(Me) 3 , wherein Q + is H + , ammonium or an alkali metal cation;
if k is 2
R 301 is C 1 -C 18 alkylene, C 3 -C 18 alkenylene or C 3 -C 18 alkenylene, which may be unsubstituted or substituted, by one or more OH, C 1 -C 8 alkoxy, carboxy, C 1 -C 8 alkoxycarbonyl;
or xylylene; or
R 301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if k is 3,
R 301 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and
if k is 4, R 301 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
The alkyl radicals in the various substituents may be linear or branched. Examples of alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl oder n-4-octadecenyl.
Preferred is alkenyl with 3 bis 12, particularly preferred with 3 to 6 carbon atoms.
Alkenyl with 3 to 18 is a linear or branched radical as for example propinyl
2-butinyl, 3-butinyl, n-2-octinyl, oder n-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularly preferred with 3 to 6 carbon atoms.
Examples for hydroxy substituted alkyl are hydroxy propyl, hydroxy butyl or hydroxy hexyl.
Examples for halogen substituted alkyl are dichloropropyl, monobromobutyl or trichlorohexyl.
C 2 -C 18 alkyl interrupted by at least one O atom is for example —CH 2 —CH 2 —O—CH 2 —CH 3 , —CH 2 —CH 2 —O—CH 3 — or —CH 2 —CH 2 —O—CH 2 —CH 2 CH 2 —O—CH 2 —CH 3 —. It is preferably derived from polyethylene glycol. A general description is —(CH 2 ) 3 —O) b —H/CH 3 , wherein a is a number from 1 to 6 and b is a number from 2 to 10.
C 2 -C 18 alkyl interrupted by at least one NR 6 group may be generally described as —((CH 2 ) a —NR 5 ) b —H/CH 3 , wherein a, b and R 5 are as defined above.
C 3 -C 12 cycloalkyl is typically, cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl or trimethylcyclohexyl.
C 6 -C 10 aryl is for example phenyl or naphthyl, but also comprised are C 1 -C 4 alkyl substituted: phenyl, C 1 -C 4 alkoxy substituted phenyl, hydroxy, halogen or nit substituted phenyl. Examples for alkyl substituted phenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene or isopropylbenzene. Halogen substituted phenyl is for example dichlorobenzene or bromotoluene.
Alkoxy substituents are typically methoxy, ethoxy, propoxy or butoxy and their corresponding isomers.
C 7 -C 8 phenylalkyl is benzyl, phenylethyl or phenylpropyl.
C 5 -C 10 heteroaryl is for example pyrrol, pyrazol, imidazol, 2, 4, dimethylpyrrol, 1-methylpyrrol, thiophene, furane, furfural, indol, cumarone, oxazol, thiazol, isoxazol, isothiazol, triazol, pyridine, α-picoline, pyridazine, pyrazine or pyrimidine.
If R is a monovalent radical of a carboxylic add, it is, for example, an acetyl, propionyl, butyryl, valeroyl, caproyl, stearoyl, lauroyl, acryloyl, methacryloyl, benzoyl, cinnamoyl or β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
C 1 -C 18 alkanoyl is for example, formyl, propionyl, butyryl, octanoyl, dodecanoyl but preferably acetyl and C 3 -C 5 alkenoyl is in particular acryloyl. in general the polymerization processes using nitroxylethers a1) or nitroxyl radicals together with a free radical initiator a2) are preferred. In particular polymerization process a1) is very suitable.
Particularly suitable nitroxylethers and nitroxyl radicals are those of formulae
The free radical initiator of component a2) is preferably a bis-azo compound, a peroxide, perester or a hydroperoxide.
Specific preferred radical sources are 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methyl-butyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvale-ronitrile, 1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrue, dimethyl-2,2′-azbisisobutyrate, 2-(carbamoylazo)isobutyronitrile, 2,2′-azobis(2,4,4-timethylpentane), 2,2′-azobis(2-methylpropane), 2,2-azobis(N,N′-dimethylenelsobutyramidine), free base or hydrochloride, 2,2′-azobis(2-amidinopropane), free base or hydrochloride, 2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propio namide} or 2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyet hyl]propionamide; acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl pemeodecanoate, t-butyl pemeodecanoate, t-butyl perpivalate, t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl)peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butyl permaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2 bis(t-butylperoxy)propane, dicumyl peroxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxy isopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane, di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.
A suitable component a3) contains a compound of formula (III),
with a radically transferable atom or group .Hal as is described in WO 96/30421 and WO 98/01480. A preferred radically transferable atom or group .Hal is .Cl or .Br, which is cleaved as a radical from the initiator molecule.
Preferably [In] represents the polymerization initiator fragment of a polymerization initiator of formula (III),
capable of initiating polymerization of monomers or oligomers which polymerization initiator is selected from the group consisting of C 1 -C 8 -alkyl halides, C 8 -C 15 -aralkylhalides, C 2 -C 8 α-haloalkyl esters, arene sulfonyl chlorides, haloalkane-nitriles, α-haloacrylates and halolactones, and
p and q represent one.
The polymerization process in the presence of a compound of formula (III) is known as ATRP (Atom Transfer Radical Polymerization) and WO 96/30421 discloses a controlled or “living” polymerization process of ethylenically unsaturated monomers such as styrene or (meth)acrylates by employing the ATRP method. According to this method initiators are employed which generate a radical atom such as .Cl, in the presence of a redox system of transition metals of different oxidation states, e.g. Cu(I) and Cu(II), providing “living” or controlled radical polymerization.
Specific initiators are selected from the group consisting of α,α′-dichloro- or α,α′-dibromoxylene, p-toluenesulfonylchloride (PTS), hexakis-(α-chloro- or α-bromomethyl)-benzene, 2-chloro- or 2-bromopropionic acid, 2-chloro- or 2-bromolsobutyric acid, 1-phenethyl chloride or bromide, methyl or ethyl 2-chloro- or 2-bromopropionate, ethyl-2-bromo- or ethyl-2-chloroisobutyrate, chloro- or bromoacetonitrile, 2-chloro- or 2-bromopropionitrile, α-bromo-benz-acetonitrile and α-bromo-γ-butyrolactone (=2-bromo-dihydro-2(3H)furanone).
The transition metal in the oxidizable transition metal complex catalyst salt used in the process of the invention is present as an oxidizable complex ion in the lower oxidation state of a redox system. Preferred examples of such redox systems are selected from the group consisting of Group V(B), VI(B), VII(B), VIII, IB and IIB elements, such as Cu + /Cu 2+ , Cu 0 /Cu + , Fe 0 /Fe 2+ , Fe 2+ /Fe 3+ , Ru 2+ /Ru 3+ , Ru 3+ /Ru 4+ , Os 2+ /Os 3+ , V n+ /V (n+1)+ , Cr 2+ /Cr 3+ , Co + /Co 2+ , Co 2+ /Co 3+ , Ni 0 /Ni + , Ni + /Ni 2+ , Ni 2+ /Ni 3+ , Mn 0 /Mn 2+ , Mn 2+ /Mn 3+ , Mn 3+ /Mn 4+ or Zn + /Zn 2+ .
The ionic charges are counterbalanced by anionic ligands commonly known in complex chemistry of transition metals, such hydride ions (H − ) or anions derived from inorganic or organic acids, examples being halides, e.g. F − , Cl − , Br − or I − , fluoro complexes of the type BF 4 − ; PF 6 − , SbF 6 − or AsF 6 − , anions of oxygen acids, alcoholates or acetylides or anions of cyclopentadiene.
Anions of oxygen acids are, for example, sulfate, phosphate, perchlorate, perbromate, penodate, antimonate, arsenate, nitrate, carbonate, the anion of a C 1 -C 8 carboxylic acid, such as formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate), unsubstituted or C 1 .C 4 alkyl-, C 1 -C 4 alkoxy- or halo-, especially fluoro-, chloro- or bromo-substituted phenylsulfonate or benzylsulfonate, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate, phosphonates, for example methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphonate or benzylphosphonate, carboxylates derived from a C 1 -C 8 carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, and also C 1 -C 12 -alcoholates, such as straight chain or branched C 1 -C 12 alcoholates, e.g. methanolate or ethanolate.
Anionic ligands and neutral may also be present up to the preferred coordination number of the complex cation, especially four, five or six. Additional negative charges are counterbalanced by cations, especially monovalent cations such as Na + , K + , NH 4 + or (C 1 -C 4 alkyl) 4 N + .
Suitable neutral ligands are inorganic or organic neutral ligands commonly known in complex chemistry of transition metals. They coordinate to the metal ion through a σ-, π-, μ-, η-type bonding or any combinations thereof up to the preferred coordination number of the complex cation. Suitable inorganic ligands are selected from the group consisting of aquo (H 2 O), amino, nitrogen, carbon monoxide and nitrosyl. Suitable organic ligands are selected from the group consisting of phosphines, e.g. (C 6 H 5 ) 3 P, (i-C 3 H 7 ) 3 P, (C 5 H 9 ) 3 P or (C 5 H 11 ) 3 P, di-, tri-, tetra- and hydroxyamines, such as ethylenediamine, ethylenediaminetetraacetate (EDTA), N,N-Dimethyl-N′,N′-bis(2-dimethylaminoethyl)ethylenediam ine (Me 6 TREN), catechol, N,N′-dimethyl-1,2benzenediamine, 2-methylamino)phenol, 3-(methylamino)-2-butanol or N,N′-bis(1,1-dimethylethyl)-1,2-ethanediamine, N,N,N′,N″,N″-pentamethyldiethyltriamine (PMD-ETA), C 1 -C 8 -glycols or glycerides, e.g. ethylene or propylene glycol or derivatives thereof, e.g. di-, tri- or tetraglyme, and monodentate or bidentate heterocyclic e − donor ligands.
Heterocyclic e − donor ligands are derived, for example, from unsubstituted or substituted heteroarenes from the group consisting of furan, thiophene, pyrrole, pyridine, bis-pyridine, picolylimine, g-pyran, g-thiopyran, phenanthroline, pyrimidine, bis-pyrimidine, pyrazine; indole, coumarone, thioniaphthene; carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole, isothiazole, quinoline, bis-quinoline, isoquinoline, bis-isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine, bis-imidazole and bis-oxazole.
The oxidizable transition metal complex catalyst can be formed in a separate preliminary reaction step from its ligands or is preferably formed in-situ from its transition metal salt, e.g. Cu(I)Cl, which is then converted to the complex compound by addition of compounds corresponding to the ligands present in the complex catalyst, e.g. by addition of ethylenediamine, EDTA, Me 8 TREN or PMDETA.
Preferred is a composition, wherein in the step a3) the oxidizable transition metal in the transition metal complex salt is present as a transition metal complex ion in the lower oxidation state of a redox system.
More preferred is a composition, wherein the transition metal complex ion is a Cu(I) complex ion in the Cu(I)/Cu(II) system.
Routs a3) is carried out when comb copolymers are prepared. The preparation of comb copolymers by the ATRP method is for example described in WO 01/51534.
The elimination of the transfer group —Y. e. g. halogen, wit a polymerizable chain terminating group —X is advantageously performed in such a way that the polymerisate is dissolved in a solvent and the monomeric compound corresponding to —X is added in the presence of a non-nucleophilic base, such as diazabicycloundecene (DBU) or similar bases, at elevated temperatures. The reaction, which is a conventional esterification reaction, takes place under conditions of a regular esterification reaction within a temperature range, for example from room temperature to 100° C.
Preferably the nitroxylether of step a1) or the nitroxyl radical of step a2) is present in an amount of from 0.001 mol-% to 20 mol-%, more preferably of from 0.002 mol-% to 10 mol-% and most preferably of from 0.005 mol-% to 5 mol-% based on the monomer or monomer mixture.
Preferably the free radical initiator is present in an amount of 0.001 mol-% to 20 mol-%; based on the monomer or monomer miture.
The molar ratio of free radical initiator to stable free nitroxyl radical is preferably from 20:1 to 1:2, more preferably from 10:1 to 1:2.
Scission of the O—X bond of the nitroxylether may be effected by ultrasonic treatment, radiation with actinic light or heating.
The scission of the O—X bond is preferably effected by heating and takes place at a temperature of between 50° C. and 180° C., more preferably from 90° C. to 150° C.
The initiator of formula (III),
and the oxidizable transition metal are for example present in an amount of 1:10 to 1:100, relative to the monomer. The total amount of oxidizable transition metal to initiator of formula (III) is for e)ample from 0.05:1 to 2:1, in particular from 0.2:1 to 0.5:1.
The polymerization reaction is carried out with preference under atmospheric pressure. In the block or comb copolymer the nonionic polymer block B is composed of non-ionic repeating units of ethylenically unsaturated monomers suitable for the method of controlled or living polymerisation. These monomers are characterised by the presence of at least one group >C═C< Representative monomers are selected from the group consisting of styrenes, acrylic and C 1 - 4 alkylacrylic acid-C 1 -C 24 alkyl esters, acrylic and C 1 -C 4 alkylacrylic acid-C 6 -C 11 aryl-C 1 -C 4 alkyl esters, acrylic and C 1 -C 4 alkylacrylic acid-C 6 -C 11 aryloxy-C 1 -C 4 alkyl esters, acrylic and C 1 -C 4 alkylacrylic acid-hydroxy-C 2 -C 8 alkyl esters, acrylic and C 1 -C 4 alkylacrylic acid-polyhydroxy-C 3 -C 6 alkyl esters, acrylic and C 1 -C 4 alkylacrylic acid-(C 1 -C 4 alkyl) 3 silyl-oxy-C 2 -C 4 alkyl esters; acrylic and C 1 -C 4 alkylacrylic acid-(C 1 -C 4 alkyl) 3 silyl-C 1 -C 4 alkyl esters, acrylic and C 1 -C 4 alkylacrylic acid-heterocyclic-C 2 -C 4 alkyl esters; acrylic and C 1 -C 4 alkylacrylic add esters having poly-C 2 -C 4 alkyleneglycolester groups, wherein the ester groups may be substituted with C 1 -C 24 alkoxy groups, acrylic and methacrylic acid amides, acrylic and C 1 -C 4 alkylacrylic -acid-(C 1 -C 4 alkyl) 1-2 amide, acrylonitrile, esters of maleic acid or fumaric acid, maleinimide and N-substituted maleinimides.
In a preferred embodiment of the invention the nonionic polymer block B is essentially composed of repeating units of ethylenically unsaturated monomers selected from the group consisting of styrenes, acrylic and methacrylic acid-C 1 -C 24 alkyl esters, acrylic and meth-acrylic acid-hydroxy-C 2 -C 6 alkyl esters, acrylic and methacrylic acid-dihydroxy-C 3 -C 4 alkyl esters and acrylic and methacrylic acid esters having poly-C 4 -C 4 alkyleneglycolester groups, wherein the ester groups may be substituted with C 1 -C 24 alkoxy groups.
Suitable styrenes may be substituted at the phenyl group by one to three additional substituants selected from the group consisting of hydroxy, C 1 -C 4 alkoxy, e.g. methoxy or ethoxy, halogen, e.g. chloro, and C 1 -C 4 alkyl, e.g. methyl or methyl.
Suitable acrylic acid or methacrylic add-C 1 -C 24 alkyl esters are acrylic acid or methacrylic acid esters esterified by methyl, ethyl, n-butyl, isobutyl, tert-butyl, neopentyl, 2-ethylhexyl, isobornyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Representative acrylic and C 1 -C 4 alkylacrylic acid-C 8 -C 11 aryl-C 1 -C 4 alkyl esters are acrylic acid or methacrylic acid esters esterified by benzyl, 2-phenylethyl, 1- or 2-naphthylmethyl or 2-(1- or 2-naphthyl)-ethyl. The phenyl or naphthyl groups may be additionally substituted with one to three additional substituents selected from the group consisting of hydroxy, C 1 -C 4 alkoxy, e.g. methoxy or ethoxy, halogen, e.g. chloro, and C 1 -C 4 alkyl, e.g. methyl or methyl.
Representative acrylic and C 1 -C 4 alkylacrylic acid C 8 -C 11 aryloxy-C 1 -C 4 alkyl esters are acrylic acid or methacrylic acid esters esterified by phenoxyethyl or benzyloxyethyl.
Representative acrylic acid and C 1 -C 4 alkylacrylic acid-hydroxy-C 2 -C 4 alkyl esters are acrylic acid- or methacrylic acid-2-hydroxyethylesters (HEA, HEMA) or acrylic acid- or methacrylic acid-2-hydroxypropylester (HPA, HPMA).
Representative acrylic and C 1 -C 4 alkylacrylic acid-polyhydroxy-C 3 -C 6 alkyl esters are acrylic acid- or methacrylic acid esterified by ethylene glycol or glycerol.
Representative acrylic acid- and C 1 -C 4 alkylacrylic acid-silyloxy-C 2 -C 4 alkyl ester are acrylic acid- or methacrylic acid-2-trimethylsilyloxyethylesters (TMS-HEA, TMS-HEMA).
Representative acrylic acid- or C 1 -C 4 alkylacrylic acid-(C 1 -C 4 alkyl) 3 silyl-C 2 -C 4 alkyl esters are acrylic acid- or methacrylic acid-2-trimethylsilylethylesters or acrylic acid- or methacrylic acid-3-trimethylsilyl-n-propylesters.
Representative acrylic and C 1 -C 4 alkylacrylic acid esters having poly-C 2 -C 4 alkyleneglycolester groups, wherein the ester groups may be substituted with C 1 -C 24 alkoxy groups, are illustrated by the formula given below:
wherein
n represents a numeral from one to 100;
R 1 and R 2 independently of one another represent hydrogen or methyl; and
R 3 represents C 1 -C 24 alkyl, e.g. methyl, ethyl, n- or isopropyl, n-, iso-, or tert-butyl, n- or neo-pentyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, or represents aryl-C 1 -C 24 alkyl, e.g. benzyl or phenyl-n-nonyl, as well as C 1 -C 24 alkylaryl or C 1 -C 24 alkylaryl-C 1 -C 24 alkyl.
Representative acrylic acid- and C 1 -C 4 alkylacrylic acid-heterocyclyl-C 2 -C 4 alkyl esters are acrylic acid- or methacrylic acid-2-(N-morpholinyl, 2-pyridyl, 1-imidazolyl, 2-oxo-1-pyrrolidinyl, 4-methylpiperidin-1-yl or 2oxoimidazolidin-1-yl)-ethyl esters.
Representative C 1 -C 4 alkylacrylic acid esters having poly-C 2 -C 4 alkyleneglycolester groups, wherein the ester groups may be substituted with C 1 -C 24 alkoxy groups are acrylic acid- or methacrylic acid esters of ethoxylated decanol, ethoxylated lauryl alcohol or ethoxylated stearyl alcohol, wherein the degree of ethoxylation, as expressed by the index n in the formula above, is typically in the range from 5 to 30.
Representative acrylic and C 1 -C 4 alkylacrylic acid-C 1 -C 4 allyl) 1-2 amide are acrylic acid- or methacrylic acid N-methyl, N,N-dimethyl, N-ethyl or N,N-diethyl amide.
Representative esters of maleic acid or fumaric acid are the C 1 -C 24 alkyl esters, e.g. the methyl, ethyl, n-butyl, isobutyl, tert-butyl, neopentyl, 2-ethylhexyl, isobornyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl esters, the C 8 -C 11 aryl, e.g. phenyl or naphthyl, esters or the C 6 -C 11 aryl-C 1 -C 4 alkyl esters, e. g. benzyl or 2-phenethyl esters. The phenyl or naphthyl groups may be additionally substituted with one to three additional substituents selected from the group consisting of hydroxy, C 1 -C 4 alkoxy, e.g. methoxy or ethoxy, halogen, e.g. chloro, and C 1 -C 4 alkyl, e.g. methyl or methyl.
Representative N-substituted maleinimides are the N—C 1 -C 4 alkyl, e.g. N-methyl or N-ethyl, or N-aryl, e.g. N-phenyl substituted maleinimides.
In the comb or block copolymer the polymer block A additionally contains repeating units of ethylenically unsaturated monomers substituted with cationic groups. A suitable cationic polymer block A is essentially composed of repeating units of ethylenically unsaturated monomers represented by the cationic part of a salt formed by quaternisation of an amino monomer selected from the group consisting of amino substituted styrene, (C 1 -C 4 alkyl) 1-2 amino substituted styrene, N-mono-(C 1 -C 4 alkyl) 1-2 amino-C 2 -C 4 alkyl(meth)acrylamide and N,N-di-(C 1 -C 4 alkyl) 1-2 amino-C 2 -C 4 alkyl(meth)acrylamide, vinylpyridine or C 1 -C 4 alkyl substituted vinylpyridine, vinylimidazole and C 1 -C 4 alkyl substituted vinylimidazole and a compound of the formula
CH 2 ═C(—R 1 )—C(═O)—Re (V),
-
- wherein
- R 1 represents hydrogen or C 1 -C 4 alkyl; and
- R 2 represents amino substituted C 2 -C 18 alkoxy selected from the group consisting of amino-C 2 -C 18 alkoxy, C 1 -C 4 alkylamino-C 2 -C 18 alkoxy, di-C 1 -C 4 alkylamino-C 2 -C 18 alkoxy, hydroxy-C 2 -C 4 alkylamino-C 2 -C 18 alkoxy and C 1 -C 4 alkyl-(hydroxy-C 2 -C 4 alkyl)-amino-C 2 -C 18 alkoxy.
In a particularly preferred embodiment of the invention the repeating unit of an ethylenically unsaturated monomer substituted with an cationic group is represented by the cationic part of a salt formed from a compound of the formula (V), wherein
R 1 represents hydrogen or methyl; and
R 2 represents amino substituted C 2 -C 10 alkoxy selected from the group consisting of amino-C 2 -C 4 alkoxy, C 1 -C 4 alkylamino-C 2 C 4 alkoxy, di-C 1 -C 4 alkylamino-C 2 -C 4 alkoxy, hydroxy-C 2 C 4 -alkylamino-C 2 -C 18 alkoxy and C 1 -C 4 alkyl-(hydroxy-C 2 -C 4 alkyl)amino-C 2 -C 4 alkoxy.
In an alternative embodiment the repeating unit of an ethylenically unsaturated monomer is the acid addition salt or the salt formed by quaternisation of an amino monomer selected from the group consisting of amino substituted styrene, (C 1 -C 4 alkyl) 1-2 amino substituted styrene N-mono-(C 1 -C 4 alkyl) 1-2 aminoC 2 -C 4 alkyl(meth)acrylamide and N,N-di-(C 1 -C 4 alkyl) 1-2 amino-C 2 -C 4 alkyl(meth)acrylamide, vinylpyridine or C 1 -C 4 alkyl substituted vinylpyridine, vinylimidazole and C 1 -C 4 alkyl substituted vinylimidazole.
Representative styrenes are substituted at the phenyl group with one or two amino groups or one or two (C 1 -C 4 alkyl) 1-2 amino groups, particularly one amino group in 4-position. Additional substituents are selected from the group consisting of hydroxy, C 1 -C 4 alkoxy, e.g. methoxy or ethoxy, halogen, e.g. chloro, or C 1 -C 4 alkyl, e.g. methyl or ethyl.
Representative N-mono-(C 1 -C 4 alkyl) 1-2 amino-C 2 -C 4 alkyl(meth)acrylamide, and N,N-di-(C 1 -C 4 alkyl) 1-2 amino-C 4 alkyl(meth)acrylamide are 2N-tert-butylamino- or 2-N,N-dimethyl-aminoethylacrylamide or 2-N-tertbutylamino- or 2-N,N-dimethylaminopropylmethacrylamide. In another preferred embodiment of the invention the repeating unit of an ethylenically unsaturated monomer substituted with an ionic group present in one of the polymer blocks A and B is the acid addition salt or the salt formed by quaternisation of an amino monomer selected from the group consisting of amino substituted styrene, (C 1 -C 4 alkyl) 1-2 amino substituted styrene, and N,N-di-(C 1 -C 4 alkyl) 2 amino-C 2 -C 4 alkyl(meth)acrylamide.
For example the cationic part of a salt according to formula (V) is represented by an ester group of the formula (C)
-
- wherein
- one of R a , R b and R c represents 2-hydroxyethyl and the other ones represent hydrogen, methyl or ethyl; or
R a , R b and R c independently of one another represent hydrogen or a substituent selected from the group consisting of C 1 -C 4 alkyl, aryl-C 1 -C 4 alkyl and (C 1 -C 4 alkyl) 1-3 aryl.
In an especially preferred embodiment of the invention the repeating unit of an ethylenically unsaturated monomer substituted with an ionic group is represented by the cationic part of an acid addition salt or the salt formed by quaternisation of 4-aminostyrene, 4-dimethylaminostyrene and an aminoalkyl (meth)acrylates selected from the group consisting of 2-dimethylaminoethyl acrylate (DMAEA), 2-dimethylaminoethyl methacrylate (DMAEMA), 2-diethylaminoethyl acrylate (DEAEA), 2-diethylaminoethyl methacrylate (DEAEMA), 2-t-butylamino-ethyl acrylate (tBAEA), 2-t-butylaminoethyl methacrylate (t-BAEMA) and 3-dimethylamino-propylmethacrylamide, 4-vinylpyridine, 2-vinylpyridine or 1-vinylimidazole.
For example the number of repeating units of the nonionic block B is from 4-1000.
For instance the number of repeating units of the cationic block A is from 1-100.
In a specific embodiment of the invention the non-ionic block B is composed of butylacrylate (BA) and the ionic block A is composed of 2-dimethylaminoethyl acrylate (DMAEA) or 2-dimethylaminoethyl methacrylate (DMAEMA). In order to get a maximized exploitation the length of the total blocks is for example more than 30 units. However in some cases also lower length may provide a sufficient intercalation and exfoliation.
Typical blockpolymers are for example Poly (BA) 16 -block-(DMAEA) 4,5 or Poly (BA) 68 -block-DMAEA) 19 .
The counterion present in the salt forming component free amino group or a primary, secondary or tertiary amino group may be the anion of a carboxylic acid, phosphonic acid, sulfonic acid, mineralic acid or complex acid. Examples of the anions of mineral acids are F − , Cl − , Br − or I − . Examples for the anions of complex acids are ClO 4 − , SbF 8 − or PtF 6 − .
In a specific embodiment of the invention the counterion of the salt forming component is selected from the group consisting of mono-, bi- or tricyclic sulphonic, carboxylic or phosphonic acids and aliphatic sulphonic, carboxylic or phosphonic acids substituted with mono-, bi- or tricyclic groups alkyl halides substituted with mono-, bi- or tricyclic groups, and C 1 -C 4 alkyl esters of mono-, bi- or tricyclic sulphonic acids.
The mono-, bi-, or tricyclic groups present in the sulphonic, carboxylic and phosphonic acids or the mono-, bi-, or tricyclic substituants of the aliphatic sulphonic, carboxylic or phosphonic acids and alkyl halides are selected from the group consisting of saturated or unsaturated mono-, bi-, or tricyclosliphatic, heteromonocycloaliphatic or heterobicycloaliphatic, carbomonocyclic or carbobicyclic aromatic, partially saturated carbobicyclic aromatic, heteromonocyclic or heterobicyclic aromatic and partially saturated heterobicyclic aromatic groups.
Representative salt forming components which are selected from the group consisting of mono-, bi-, or tricyclic sulphonic, carboxylic and phosphonic acids or represent salt forming components which are selected from the group of aliphatic sulphonic, carboxylic or phosphonic acids substituted with monocyclic, bicyclic or tricyclic groups are illustrated by the list given below:
A preferred group of substituted mono-, bi-, or tricyclic sulphonic, carboxylic and phosphonic acids is represented by the general formula:
wherein
X represents carboxy, sulpho or P(═O)(OH) 2 ; and
R 1 , R 2 or R 3 independently of one another represent hydrogen or a substituent selected from the group consisting of functional groups or derivatised functional groups selected from the group consisting of amino, C 1 -C 4 alkylamino, C 1 -C 4 -dialkylamino, hydroxy, oxo, thio, —NO 2 , carboxy, carbamoyl, sulpho, sulphamoyl, ammonia, amidino, cyano, formylamino, formamido and halogen; or
R 1 , R 2 or R 3 independently of one another represent saturated or unsaturated aliphatic, cycloaliphatic or heterocycloaliphatic groups, carbocyclic or heterocyclic aryl groups, condensed carbocyclic, heterocyclic or carbocyclic-heterocyclic groups, which may additionally be combined with one of these groups or which may additionally be substituted with one of the functional groups or derivatised functional groups mentioned above.
The substituent groups may additionally be interrupted with one or more bivalent groups selected from the group consisting of —O—, —S—, —C(═O)—O—, —O—C(═O)—, —C(═O)—N(C 1 -C 4 alkyl)-, —N(C 1 -C 4 alkyl)-C(═O)—, —S(═O)—, —S(═O) 2 —, —S(═O)—O—, —S(═O) 2 —O—, —O—S(═O)—, —O—S(═O) 2 —, —S(═O)—N(C 1 -C 4 allyl)-, —S(═O) 2 —N(C 1 -C 4 alkyl)-, —(C 1 -C 4 alkyl)N—S(═O)—, —(C 1 -C 4 alkyl)N—S(═O) 2 —, —P(═O)—, —P(═O)—O—, —O—P(═O)— and —O—P(═O)—O—.
Two substituents from the group R 1 and R 2 may also represent bhalent, bridge-types C 2 -C 0 alkylen-, C 4 -C 6 alkyldiyliden- or C 4 -C 8 alkenyldiyliden groups which are connected with one of the above-mentioned cyclic or bicyclic groups.
Specific salt forming components, which are selected from the group consisting of mono- or bicyclic sulphonic acids, are illustrated by their structural formulae given below.
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| 3-nitro-benzene sulphonic acid |
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| 4-chlorobenzene sulphonic acid |
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| 4-dodecylbenzone sulphonic acid |
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| sulphanilic acid |
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| 3-sulphobenzoic acid |
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| 4-succinimidobenzene sulphonic acid |
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| pyridine-3-sulphonic acid |
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| 4-sulphophtalic acid |
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| 4-hydroxy-3-nitrobenzene sulphonic acid |
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| 2,5-dihydroxybenzene sulphonic acid |
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| benzene-1,3-disulphonic acid |
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| 4-acetylsulphonic acid |
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| 4-phthalimidobenzene sulphonic acid |
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| 7-amino-1-naphtol-3-sulphonic acid |
Further specific salt forming components, which are selected from the group consisting of mono- or bicyclic sulphonic acids are illustrated by their structural formulae given below:
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| (+−)camphor-10-sulphonic acid |
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| 2-naphthylamine-1-sulphonic acid acid isomers |
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| naphthalene-2-sulphonic acid |
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| naphthalene-1-sulphonic acid |
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| naphthalene1,5-disulphonic acid and isomers |
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| naphthalene-trisulphonic acid, isomer mixture e.g. |
| naphthalene 1,3,6-trisulphonic acid |
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| 2-naphthylamine-6,8-disulphonic acid and isomers |
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| 8-hydroxyquinoline sulphonic acid |
Specific salt forming components, which are selected from the group consisting of mono- or bicyclic carboxylic acids are illustrated by their structural formulae given below:
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| phthalic acid |
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| isophthalic acid |
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| 4-nitrobenzoic acid and isomers |
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| 3,5-dinitrobenzoic acid and isomers |
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| 2-chlorobenzoic acid and isomers |
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| 2,4-dichlorobenzoic acid and isomers |
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| 4-phenylbenzoic acid |
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| trimellitic acid anhydride |
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| 5-nitro-isophthalic acid |
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| benzoic acid-4-sulphamide |
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| 1-naphthylacetic acid |
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| 3-hydroxynaphthoic acid |
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| N-(4-carboxyphenyl)phthalimide |
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| 1-naphthoic acid |
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| phthaloyl glycine |
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| nicotinic acid |
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| 2,4-dichlorophenoxyacetic acid |
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| quinolinic acid |
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| 3-phthalimidoproplonic acid |
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| 4-methyl-2-phthalimidovaleric acid |
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| 2-phthalimidobutyric acid |
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| 2-phthalimidoglutaric acid |
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| 2,4,6-trichlorophenoxyacetic acid |
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| 4(2,4-dichorophenoxy)-butyric acid |
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| 3,4,5-trimethoxybenzoic acid |
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| nicotinic acid N-oxide |
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| 3-pyridinepropionic acid |
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| pyridine-2,5-dicarboxylic acid |
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| 2-phthalimidopropionic acid |
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| 2-phthalimidoisovaleric acid |
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| phthalimidosuccinic acid |
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| 2-phthalimidobenzoic acid |
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| 2(2,4-dichlorophenoxy)-propionic acid |
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| 3(2,4-dichlorobenzoyl)-propionic acid |
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| 3(2,4-dichlorobenzoyl)-butyric acid |
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| 3(4,5-dichlorophthalimido)-benzoic acid |
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| 3-tetrachlorophthalimidobenzoic acid |
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| theophyline-7-acetic acid |
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| histidine |
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| 2,4-dichlorophenylacrylic acid |
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| 2-tetrachlorophthalimidobenzoic acid |
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| tetrachlorophthaloylglycine |
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| tryptophane |
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| tyrosine |
Further specific salt forming components, which are selected from the group consisting of mono- or bicyclic carboxylic acids and phosphonic acids are illustrated by their structural formulae given below:
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| 2(2-carboxyphenylthiomethyl)succinic acid |
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| 2(5-chlorobenzothiazol-2-ylthio)succinic acid |
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| 2-benzothiazol-2-ylthiosuccinic acid |
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| 2-benzothiazol-2-ylthiomethylglutaric acid |
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| 2-benzimidazol-2-ylthiosuccinic acid |
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