PROCESS FOR THE PREPARATION OF POLYMERS CONTAINING TERMINAL GROUPS N? OFIELD OF THE INVENTION The present invention relates to a process for the preparation of polymers containing N-0 terminal groups and to compositions comprising polymers obtained by this process.
BACKGROUND OF THE INVENTION The present invention relates to the preparation of polymers characterized by a low polydispersity range, preferably a polydispersity range which is less than 3, and a better efficiency of the monomer to polymer conversion. In particular, this invention relates to a process of initial polymerization by free radicals, stable, by the method ATRP (Radical Polymerization by Transfer of Atoms), which produces homopolymers, random copolymers, block copolymers, multiblock copolymers, grafted copolymers and the like having a low polydispersity range and predetermined molecular weights. The polymers or copolymers prepared by a conventional free radical polymerization reaction inherently have broad molecular weight distributions and a polydispersity range which is generally greater than 3. This is explained by the fact that the average life of most of the Free radical initiators is relatively long, fluctuating from several minutes to hours. The reactions of the polymer chains are initiated at different points in time, which allows the primers to generate growing chains of various lengths in any period of time during the polymerization process. In addition, the propagating chains can react with each other in free-radical side relationships known as combination and disproportionation. Both are irreversible chain termination reaction steps. The formation of chains of various lengths ends at different points in time during the reaction, resulting in polymers of very different chain lengths, ie from very small to extremely long and wide polydispersity ranges. When a homogeneous molecular weight distribution is desirable in a free radical polymerization process, the growth of the polymer chains c must be initiated simultaneously to avoid termination at different points in time. Therefore, any conventional free radical polymerization process is characterized by significant disadvantages, such as difficulties in preventing or controlling the molecular weight distribution of the obtained polymer and the polydispersity range. In addition, free radical polymerization processes are difficult to control. Most polymerization reactions are strongly exothermic, making it almost impossible to efficiently remove the heat from the highly viscous polymer reaction mixture. The problems of conventional free radical polymerization reactions of the types mentioned above can also result in undesirable formation of gel polymers of broad molecular weight distribution. They are difficult to manipulate in subsequent work steps, such as separation, purification, filtration and drying. There is an urgent need for suitable agents that are useful to overcome these disadvantages and that provide efficient control of polymerizations initiated by free radicals. This will result in the preparation of polymers "of defined chemical and physical properties, such as viscosity, hardness, gel content, clarity, high gloss, durability and the like." Therefore, efficient control of the reaction parameters in the Free radical polymerization processes are highly desirable.Among the various proposed methods some can be defined by the term "living polymerization." This method points to a chain growth defined by the efficient reduction of chain-terminating side reactions. Such polymerization would provide close control of molecular weight and molecular weight distribution (MWD)., 581, 429 discloses a free radical polymerization process which controls the controlled or "living" growth of polymer chains to produce oligomeric homopolymers and copolymers, including block and graft copolymers. One process modality is the use of initiators of the partial formula R'R "N-0-X In the polymerization process the free radical species R'R" N-0"and" X. X is a group of free radical, for example, a tert-butyl or cyanoisopropyl radical, capable of polymerizing monomeric units containing ethylene groups. The monomer units A are replaced by initiator fragments R'R "N-0 * and» X and polymerize structures of the type: R 'R "N-0-An-X. The specific R 'R "N-0-X initiators mentioned are derived from cyclic structures, such as 2,2,6,6-tetramethylpiperidine, or open-chain molecules, such as di-tert-butylamine. / 30421 describes a controlled or "living" polymerization process of ethylenically unsaturated polymers such as styrene or (meth) acrylates using 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, for example Cu (I) and Cu (II), which provide controlled "living" radical polymerization. A general disadvantage of this prior art method is seen in the fact that the polymer chains prepared by the ATRP contain halogen as the terminal fragment, which has been transferred from the polymerization initiator. The halogen content is generally undesirable in polymers. Halogen, especially chlorine and bromine, is subjected to removal as a hydrogen halide depending on the temperature, especially above 150 ° C. The double bond thus formed is subjected to a reaction with atmospheric oxygen, which decreases the antioxidative resistance of the polymer. In addition, the hydrogen halide released from the polymer reacts with other functional groups present in the polymer, such as ester groups present in acrylates. Depending on the type of polymer, the chlorine is also removed in the form of a radical which can initiate undesirable chain reactions in the polymer structure.
The removal of the halogen from the polymer structure, especially in the terminal position of the polymer chain, is the problem with which the present invention is particularly related. It is desirable to replace the halogen with suitable substituents. M. Sawamoto and M. Kamigai to, J. Macromol. Sci. (J.M.S.) - Puré Appl. Chem. A 34 (10, pp. 1803-1814 (1997) describe the ATRP of methyl acrylate with the initiator dichloroacetophenone and a catalyst system consisting of RuCl2 (PPh3) 3 and the cocatalyst Al (0- * iPr) 3. They report that the polymerization reaction is terminated with the addition of large amounts of TEMPO (= 2,2,6,6, TEtraMethylPiperidyl-1-Oxide) or galvinoxyl, there are no reported products that have been isolated and no properties have been described. it has surprisingly found that a terminal halogen in polymerized, especially prepared by ATRP is effectively replaced by the free radical species R'R "N-0", which may have an open or cyclic chain structure.
BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a process for the preparation of a polymer of the formula wherein: In represents a polymerization initiating fragment of a polymerization initiator capable of initiating the polymerization of monomers or oligomers containing groups ethylene; p represents a number greater than zero and defines the number of initiator fragments; A represents an oligopolymer or polymer fragment consisting of repeated units of polymerizable monomers or oligopolymers containing ethylene groups; x represents a number greater than one and defines the number of repeated units in A; B represents a monomer, oligopolymer or polymer fragment copolymerized with A; and represents zero or a 'number greater than zero and defines the number of repeating units of monomer, oligopolymer or polymer in B; q represents a number greater than zero;one of Ri and R2 represents C? -C alkyl and the other represents C? -C4 alkyl or C? -C alkyl substituted by C? -C alkoxycarbon or C? -C4 alkoxy; or Ri and R2 together with the adjacent carbon atom represent both C3-C cycloalkyl; R3 and R are as defined as Ri and R2; Ra represents C? ~C alkyl, cyano, C?-C 4 alkoxycarbonyl, C? ~C alkanoyloxy, C alca-C alca alkanoyloxy;C? -C4-C? -C alkyl, carbamoyl, mono- or di-alkylcarbamoyl of C? -C4 / mono- or di-2-hydroxyethylcarbamoyl, amidino, 2-imidazolyl, l-hydroxy-2-hydroxymethyl-2 -propylcarbamoyl, or 1,1-dihydroxymethyl-2-hydroxycarbamoyl; YRb is how Ra was defined; or a and Rb together represent a divalent group and form an aliphatic or aromatic heterocyclic group of 5,6,7 or 8 members, which may contain 1-3 additional heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur; with the proviso that the compounds of formula I where Ri, R2, R3 and R represent methyl and Ra and Rb represent1, 3-propylene are excluded; which comprises polymerizing by radical transfer polymerization (ATRP) an aliphatic monomer or oligomer containing ethylene groups in the presence of a polymerization initiator of the formula:In -x (ll). p where p and q are as defined above, In represents a radically transferable atom or group capable of initiating the polymerization of monomers or oligopolymers containing ethylene groups and -X represents a leaving group; and replace -X in a polymer of formula(in U- -B., -X (III), P qwhere In, X, A, B, x, y, and p and q are as defined above, with a compound with N-O of formulawhere Ri - R4 and Ra and R. they are as defined above, in the presence of a catalytically effective amount of an oxidizable transition metal complex catalyst. The polymers according to the present invention are useful for many applications, including a variety of specific technical applications, such as block copolymers used as compatibilizers for polymer blends, or dispersants for coating systems. The polymers or copolymers are characterized by a homogeneous molecular weight distribution and a low halogen content. They are especially useful as oligomers or polymers in the coating technology, for the preparation of thermoplastic films, organic pigment resins and dye developing ink resins, liquids or additives for inks for electrographic imaging processes. In a polymer (I) the group In represents the initiator fragment of the polymerization of a polymerization initiator (II); which is capable of initiating the polymerization of fragments A and B and proceeds subsequently by a reaction mechanism known under the term ATRP. A suitable polymerization initiator contains an atom or group "X transferable by free radicals and is described in WO 96/30421 and WO 98/01480. An atom or group * X which is transferable by preferred free radicals is * C1 or * Br, which is cleaved as a radical of the initiator molecule and subsequently placed again after the polymerization as a leaving group with a compound N-O (IV ). The index p is 1 if a group »X (q = 1) is present in the polymerization initiator (II).
The polymerization initiator may also contain more than one group »X. In this case it can be 2 or 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION A preferred embodiment of the invention relates to polymers, where p represents the number one; q represents a number between one to three; and In, A, B, x, and Ri - Rio are as defined above. A preferred polymerization initiator (II) is selected from the group consisting of alkyl halides ofCi-Ca, alkyl halides of C6-C? 5, haloalkyl esters ofC2-C8, aren sulfonyl chlorides, haloalcannitriles, a-haloacrylates and halolactones. The specific initiators are selected from the group consisting of α-dichloro-a, α-dibromoxylene, p-toluenesulfonyl chloride (PTS), hexacis (α-chloro- or α-bromomethyl) -benzene, 2- chloro- or 2-bromopropionic, 2-chloro- or 2-bromoisobutyric acid, 1-phenethyl chloride or bromide, 2-chloro- or 2-bromopropionate methyl or ethyl, ethyl-2-bromo- or ethyl-2-chloroisobutyrate , chloro- or bromoacetonitrile, 2-chloro- or 2-bromopropionitrile, a-bromo-benzacetonitrile and a-bromo-β-butyrolactone (= 2-bromo-dihydro-2 (3H) -furanone).
The term polymer comprises oligopolymers, cooligopolymers, polymers or copolymers, such as block, block, stellate, gradient, random, slate, hyperbranched and dendritic copolymers, as well as grafted or copolymers. An oligopolymer A contains at least two repeating units of polymerizable aliphatic monomers containing ethylene groups. The aliphatic monomers or oligomers may be water soluble or water insoluble and may contain one or more olefinic double bonds. The monomers may be low molecular mass (monomeric) or high molecular mass (oligomeric). Examples of monomers containing an olefinic double bond are styrenes, which can be substituted in the phenyl group by additional substituents selected from the group consisting of hydroxy, C? -C alkoxy, halogen, for example chlorine, and C? -C4 alkyl, for example methyl, acrolein, acrylonitrile, salts of (C? -C) alkyl ammonium of acrylic or alkylacrylic acid of C? -C, salts of (C? -C4 alkyl) 3NH of acrylic or alkylacrylic acid of C? -C4, alkyl ethers of C? -C esters of acrylic or alkylacrylic acid of C? -C4, hydroxyC2-C4 alkyl esters of acrylic or alkylacrylic acid of C? -C, di-alkylamino of C? -C4-C2-C4 alkyl esters of acrylic acid or C? -C alkyl acrylic, acrylic or C? -C4 alkyl acrylamides, acrylic substituted with N, -di-C? -C4 alkyl or C? -C4 alkyl acrylamides, and anhydrides of acrylic or alkylacrylic acid C? ~ C. Specific examples of such monomers are styrene, 4-hydroxystyrene, α-methylstyrene, p-methylstyrene, 4-chlorostyrene, methyl, ethyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, isobornyl, glycidyl,2-hydroxyethyl or 2-dimethylaminoethylacrylate or the corresponding methacrylates, acrylic or methacrylic acid amide, N, N-dimethyl or -diethyl amide of acrylic or methacrylic acid. Silicone acrylates are also advantageous. x represents a number greater than one and defines the number of repeated units in A. The lowest number is two.
A preferred range of x is 2 to 1000. The aforementioned aliphatic monomers may also be present in the polymer as B-comonomers, or as an oligopolymer or polymer fragmentsB copolymerized with A. and represents zero or a number greater than zero and defines the number of repeating units of monomer, oligopolymer or polymer in B. A preferred range of y is from 0 to 1000. A preferred group of aliphatic monomers is selected from group consisting of styrene, acrolein, acrylonitrile, Ci-Cis alkyl esters of Cx-C4 acrylic or alkylacrylic acid, C2-C hydroxyalkyl esters of C? ~ C acrylic or alkylacrylic acid, C? C4-C2-C4 alkyl esters of acrylic or alkylacrylic acid of C2-C, acrylic or alkylacrylamides of C? ~ C4 and anhydrides of acrylic or alkylacrylic acid of C? ~ C. A particularly preferred group of aliphatic monomers is selected from the group consisting of styrene, Ct.-C4 alkyl esters of C? ~ C acrylic or alkylacrylic acid, C2-C4 hydroxy-alkyl esters of acrylic or alkylacrylic acid of C? ~ C4, di-C2-C4 alkylamino of C2-C4 alkyl esters of C? ~ C acrylic or alkylacrylic acid, and C? -C acrylic or alkyl acrylamides for example, styrene, methyl, ethyl, n-butyl , isobutyl, ter. -butyl, 2-ethylhexyl, isobornyl, glycidyl, 2-hydroxyethyl or 2-dimethylaminoethyl (meth) acrylate, or (meth) acrylic acid amide. Examples of monomers containing two or more double bonds are the diacrylates of ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or bisphenol A, 4,4'-bis (2-acryloyloxyethoxy) -diphenylpropane, trimethylolpropane tetraacrylate triacrylate. or vinyl acetate. A polymerizable aliphatic monomer containing ethylene groups is characterized by a relatively high molecular mass of about 500 to 3000. Suitable examples are acrylated epoxy resins or acrylated polyesters. Unsaturated oligomers of this type can also be referred to as prepolymers. In a polymer (I) one of Ri and R 2 represents C 1 -C 7 alkyl, and the other represents C 1 -C 4 alkyl or C 1 -C 4 alkyl substituted by C 1 -C 4 alkoxycarbon or C 1 -C 6 alkoxy; or Ri and R2 together with the adjacent carbon atom represent both C3-C7 cycloalkyl; R3 and R4 are as defined Ri and R2; Ra represents C 1 -C 4 alkyl, cyano, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkanoyloxy, C 1 -C 4 alkanoyloxy C 1 -C 4 alkyl, carbamoyl, mono- or di-alkylcarbamoyl of C 1 - C4, mono- or di-2-hydroxyethylcarbamoyl, amidino, 2-imidazolyl, l-hydroxy-2-hydroxymethyl-2-propylcarbamoyl, or 1, 1-dihydroxymethyl-2-hydroxycarbamoyl; and Rb is how Ra was defined; or Ra and Rb together represent a divalent group and form an aliphatic or aromatic heterocyclic group of 5, 6, 7 or 8 members, which may contain 1-3 additional heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, for example a piperidine, piperazine, morpholine or imidazolidine group. The heterocyclic group can also be condensed with a phenyl group. If Ra and R together represent a divalent group, Ri and R2 and R3 and R4 together may also represent oxygen (exos substitution) or R5 and R6 or R7 and Rs together or R5 and R6 and R7 and Rs together represent oxygen. In a polymer (I) the substituents Ri, R2 and Ra and R3, R4 and Rb in a group of the partial formulatogether with the adjacent carbon atom on the nitrogen atom preferably represent groups of the partial formulasCH, H, C CH, CH, H3C CH, H3C CH, CH30 CH,H3C H3C H3C H3C CH, CH CH, CN CN H3C CN CH, CNCH, CH, HN CH3 N CH3 H3C I "C? NHC (CH2? H) 3 C? NHCCH3 (CH,? H), H2N CH, N H CH,A preferred embodiment of the invention is -H, related to the preparation of polymers (I), wherein one ofRi and R2 represents methyl and the other represents methyl or ethyl and one of R3 and R4 represents methyl and the other represents methyl or ethyl and Ra and Rb together represent a group of formulawhereR5, R6, R7 and Rs independently of each other represent hydrogen, methyl or ethyl; Yone of R9 and Rio independently of each other represents hydrogen or substituents or R9 and Rio both represent substituents.
A particularly preferred embodiment of the present invention relates to a process for the preparation of a polymer of formulawhere :In represents a polymerization initiating fragment of a polymerization initiator (II) capable of initiating the polymerization of monomers or oligopolymers containing ethylene groups;p represents a number greater than zero and defines a number of initiating fragments;A represents an oligopolymer or polymer fragment consisting of repeated units of polymerizable monomers or oligopolymers containing ethylene groups;x represents a number greater than one and defines the number of repeated units in A;B represents a monomer, oligopolymer or polymer fragment copolymerized with A;and represents zero or a number greater than zero and defines the number of repeating units of monomer, oligopolymer or polymer in B;q represents a number greater than zero;Ri /? F R3 and R represent C? -C4 alkyl;Rs, Re, R and Rs represent hydrogen; Yone of Rg and Rio independently represent hydrogen or substituents or R9 and Rio both represent substituents,which comprises polymerizing by radical transfer polymerization (ATRP) an aliphatic monomer or oligomer containing ethylene groups in the presence of a polymerization initiator (II) having a radically transferable atom or group capable of initiating the polymerization of monomers or oligopolymers containing ethylene groups and replacing the leaving group -X in a polymerized (III) with a compound N - > Or formulawhere Ri-Rio are as defined above, in the presence of a catalytically effective amount of an oxidizable transition metal complex catalyst. Another preferred embodiment of the invention relates to the preparation of a polymer of formula:where In, A, B, x, y, and Ri - Rio are as defined above.
In polymers (IA) and (IB) the terminal group containing N - > 0 cyclic, represents a group of the partial formulawhere Rx-Rs are as defined above and position 4 is substituted by one or two substituents. Preferred groups B0 containing substituents at position 4 are represented by partial formulasYwhereRi-Rß are as defined above; m represents a number from one to four;n represents one, two or three;if m represents one, Ra represents hydrogen, Ci-Cis alkyl which is not interrupted or interrupted by one or more oxygen atoms, 2-cyanoethyl, benzoyl-glycidyl, or represents 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, of a α, β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 atoms carbon, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic portion by 1 to 3 -COOZ groups, in which Z represents H, C 1 -C 2 alkyl, C 3 -C 2 alkenyl, cycloalkyl C5-C7, phenyl or benzyl; or Ra represents a monovalent radical of a carbamic acid or acid containing phosphorus or a monovalent silyl radical; orif m represents 2,Ra represents C2-C2 alkylene, C4-C12 alkenylene, xylylene, or represents a divalent radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms, of an aliphatic or aromatic dicarboxylic acid having from 8 to 14 or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having from 8 to 14 carbon atoms, wherein each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic portion by one or two groups -COOZ; or Ra is a divalent radical of an acid containing phosphorus or a divalent silyl radical; orif m represents 3,Ra represents a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic portion by -COOZ, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or is a silyl radical trivalent; orif m represents 4,Ra represents a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid;if n represents one,Rb represents C? -C? 2 alkyl, C5-C7 cycloalkyl, C7-C8 aralkyl, C2-C? Alkanoyl, C3-C5 alkenoyl or benzoyl;Rc represents Ci-Cis alkyl, C5-C7 cycloalkyl, C2-Cs alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, glycidyl or represents a group of the formulas -CH2CH (OH) -Z, -CO -Z- or -CONH-Z wherein Z represents hydrogen, methyl or phenyl, or Rb and Rc together represent the cyclic acyl radical of an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid;if n represents two,Rb is as defined above; YRc represents C2-C2 alkylene, C6-C2 arylene, xylylene, a group -CH2CH (OH) CH2-0-B-0-CH2CH (OH) CH2-, where B represents C2-C alkylene 0, C6-C5 arylene or C6-C6 cycloalkylene; or, provided that Rb is not alkanoyl, alkenoyl or benzoyl, Rc represents a divalent acyl radical of a carboxylic acid or aliphatic, cycloaliphatic or aromatic dicarbamic acid, or represents the group -CO-; orRc represents a group of the partial formulawhere Ti and T2 independently represent hydrogen, Ci-Cis alkyl, or Ti and T2 together represent C4-C6 alkylene or 3-oxapentamethylene; or if n represents 3, Rc represents 2,4,6-triazinyl.
A highly preferred group B0 containing substituents at position 4 is selected from the group consisting of partial formulas Bi and B2, wherem represents 1;Ra represents hydrogen, C? -C? -alkyl which is not interrupted or interrupted by one or more oxygen atoms, 2-cyanoethyl, benzoyl, glycidyl, or represents a monovalent radical of an aliphatic carboxylic acid having from 2 to 12 carbon atoms, of a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, of a α, β-unsaturated carboxylic acid of 3 to 5 carbon atoms or of an aromatic carboxylic acid having from 7 to 15 carbon atoms carbon;m represents 2; Ra represents a divalent radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms;'n represents 1;R b represents C 1 -C 2 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; and Rc represents C? -C? 8 alkyl, C5-C7 cycloalkyl, C2-Ce alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, glycidyl, or represents a group of the formula -CH2CH (OH) -Z, -CO-Z or -CONH-Z, where Z is hydrogen, methyl or phenyl.
Another highly preferred group Bo which contains substituents at the 4-position is selected from the group consisting of the partial formulas Bi and B2, wherem represents 1;Ra represents hydrogen, C? -C18 alkyl,2-cyanoethyl, benzoyl, glycidyl, or a monovalent radical of an aliphatic carboxylic acid having from 2 to 12 carbon atoms;m represents 2;Ra represents a divalent radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms;n represents 1;R b represents C 1 -C 12 alkyl, C 7 -C 8 aralkyl, C 2 -C 8 alkanoyl, C 3 -C 8 alkenoyl or benzoyl; YRc represents C? -C? 8 alkyl, glycidyl or a group of the formula -CH2CH (OH) -Z or -CO-Z, where Z is hydrogen, methyl or phenyl.
Another particularly preferred embodiment relates to the group Bo, where one of Rg and Rio represents hydrogen and the other alkanoylamino of C? ~ C.
An especially preferred embodiment of the present invention relates to a process for the preparation of a polymer (IA), whereinIn represents a polymerization initiating fragment of a polymerization initiator capable of initiating the polymerization of monomers or oligopolymers containing ethylene groups and polymerization initiator which is selected from the group consisting of Ci-Cg alkyl halides, aralkyl halides of C6-C? 5, haloalkyl esters of C2-Cs, aren sulfonyl chlorides, haloalcanitriles, a-haloacrylates and halolactones;p represents one;q represents a number from one to three;A and B represent oligopolymer or polymer fragments containing repeated units of polymerizable monomers selected from the group consisting of styrene, acrolein, acrylonitrile, C? -C alkyl alkylacryl esters of C? -C4, hydroxy alkyl of C? -C acrylic or alkylacrylic esters of C2-C4, di-alkylamino of C? -C -di-alkylamino of C? -C4 esters of acrylic or alkylacrylic acid of C? -C4 or acrylic or alkylacrylamide of C? ~ C4 and anhydrides of acrylic acid or C 1 -C 4 alkyl acrylic acid;x and y represent numbers greater than one;Ri, R2, R and R4 represent methyl;R5, R6, R and R8 represent hydrogen;the cyclic N- »0 fragment in formula IA represents structural modalities selected from the group consisting of partial formulas Bx and B2, wherem represents 1;Ra represents hydrogen, C? -C? 8 alkyl which is uninterrupted or interrupted by one or more oxygen atoms, 2-cyanoethyl, benzoyl, glycidyl, or represents a monovalent radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid of 7 to 15 carbon atoms, or an unsaturated carboxylic acid a, b having from 3 to 5 carbon atoms of an aromatic carboxylic acid having from 7 to 15 carbon atoms;m represents 2;Ra represents a divalent radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms;n represents 1; R b represents C 1 -C 2 alkyl, C 5 -C 7 cycloalkyl, C 7 Ca aralkyl, C 2 -C 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; and R c represents C? -C? 8 alkyl, C5-C7 cycloalkyl, C2-C8 alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, glycidyl, or represents a group of the formula -CH2CH (OH) -Z, -CO-Z or -CONH-Z where Z is hydrogen, methyl or phenyl.
A more preferred embodiment of the present invention relates to a process for the preparation of the polymer (IA), whereIn represents a polymerization initiator fragment of a polymerization initiator capable of initiating the polymerization of monomers or oligopolymers containing ethylene groups and polymerization initiator which is selected from the group consisting of C? -Cs alkyl halides, Cd-Cx aralkylhalides, haloalkyl esters of C2-Cs, aren sulfonyl chlorides, haloalkanitriles, a-haloacrylates and halolactones;p and q represents one;A and B represent oligopolymer or polymer fragments containing repeated units of polymerizable monomers selected from the group consisting of styrene, C? -C alkyl C? -C esters of C? -C alkylacrylic acid, C? -C4 hydroxy alkyl esters of acrylic or alkylacrylic acid of C? -C4, di-alkylamino of C? -C4-alkyl of C? -C4-esters of acrylic acid or alkyl acrylic of C2-C4, and acrylic or alkyl acrylamides of C? -C;x and y represent numbers greater than one;Ri R2, R3 and R4 represent methyl;R5, Re, R7 and R8 represent hydrogen;The fragment of N- > 0 cyclic of formula IA represents structural modalities selected from the group consisting of partial formulas Bx and B2, wherem represents 1; Ra represents hydrogen, C?-C18 alkyl, 2-cyanoethyl, benzoyl, glycidyl, a monovalent radical of a carboxylic acid, aliphatic, having from 2 to 12 carbon atoms;m represents 2;Ra represents a divalent radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms;n represents 1;Rb represents C? -C? 2 alkyl, C7-C8 aralkyl, C2-C? Alkanoyl, C3-Cs alkenoyl or benzoyl; YRc represents C? -C? A, glycidyl alkyl, or a group of the formula -CH2CH (OH) -Z or -CO-Z, where Z is hydrogen, methyl or phenyl.
The (co) polymers (I) obtained by the process of the present invention typically have a low polydispersity. Preferably, the polydispersity is from 1.01 to 2.2, more preferably from 1.01 to 1.9 and more preferably from 1.01 to 1.5.
In the context of the description of the present invention, the term alkyl comprises methyl, ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. An example of an alkyl substituted by aryl is benzyl. Examples of alkoxy are methoxy, ethoxy and the isomers of propoxy and butoxy. Examples of alkenyl are vinyl and allyl. An example of alkylene is ethylene, n-propylene or 1,2-propylene.
Some examples of cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, dimethylcyclopentyl and methylcyclohexyl.
Examples of substituted cycloalkyl are cyclopentyl and cyclohexyl substituted with methyl, dimethyl, trimethyl, methoxy, dimethoxy, trimethoxy, trifluoromethyl, bis-trifluoromethyl and tris-trifluoromethyl. The aryl examples are phenyl and naphthyl. Examples of aryloxy are phenoxy and naphthyloxy. Examples of substituted aryl are phenyl substituted by methyl, dimethyl, trimethyl, methoxy, dimethoxy, trimethoxy, trifluoromethyl, bis-trifluoromethyl or tris-trifluoromethyl. An example of aralkyl is benzyl. Examples of substituted aralkyl are benzyl substituted by methyl, dimethyl, trimethyl, methoxy, dimethoxy, trimethoxy, trifluoromethyl, bis-trifluoromethyl or tris-trifluoromethyl.
Some examples of an aliphatic carboxylic acid are acetic, propionic or butyric acid. An example of a cycloaliphatic carboxylic acid is cyclohexane acid. An example of an aromatic carboxylic acid is benzoic acid. An example of an acid that contains phosphorus is methylphosphonic acid. An example of an aliphatic dicarboxylic acid is malonyl, maleoyl or succinyl. An example of an aromatic dicarboxylic acid is phthaloyl.
The term heterocycloalkyl embraces one or two and heteroaryl of one to four heteroatoms, with heteroatoms being selected from the group consisting of nitrogen, sulfur and oxygen. Some examples of heterocycloalkyl are tetrahydrofuryl, pyrrolidinyl, piperazinyl and tetrahydrothienyl. Some examples of heteroaryl are furyl, thienyl, pyrrolyl, pyridyl and pyrimidinyl.
An example of a monovalent radical silyl is trimethylsilyl.
The process can be carried out in the presence of water or an organic solvent or mixtures thereof. Additional co-solvents or surfactants, such as glycols or ammonium salts of fatty acids, can be added to the reaction mixture. The amount of solvent should be kept as low as possible. The reaction mixture may contain the monomers or oligomers mentioned above in an amount of 1.0 to 99.9% by weight, preferably 5.0 to 99.9% by weight, and especially preferably 50.0 to 9 * 9.9% by weight, in based on the monomers present in the polymerized.
If organic solvents are used, suitable solvents or solvent mixtures are typically pure alkanes (hexane, heptane, octane, isooctane), hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethylene glycol) , ethylene glycol monomethyl ether), esters (ethyl acetate, propyl acetate, butyl or hexyl) and ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran), or mixtures thereof.
If water is used as a solvent, the reaction mixture can be supplemented with a water-miscible or hydrophilic cosolvent. The reaction mixture will then remain in a single homogenous phase through the conversion of the monomer. Any water-soluble or water-miscible cosolvent may be used, as long as the aqueous solvent medium is effective to provide a solvent system that prevents the precipitation or phase separation of the reactants or polymer products until the polymerization is completely complete. Exemplary cosolvents useful in the process can be selected from the group consisting of aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkyl pyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids and salts thereof, esters, organosulfides, sulfoxides, sulfones, alcohol derivatives, derivatives of hydroxyethers such as butyl carbitol or cellosolve, amino alcohols, ketones, and the like, as well as derivatives and mixtures thereof. Specific examples include methanol, ethanol, propanol, dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dipropylene glycol, tetrahydrofuran, and other water-soluble or water miscible materials, and mixtures thereof. When mixtures of water and water-soluble organic solvents or water-miscible solvents are selected for the process, the weight ratio of water to cosolvent is typically in the range of about 100: 0 to about 10:90.
When mixtures of monomers or monomer / oligomer mixtures are used, the mole percent calculation is based on the average molecular weight of the mixture.
The hydrophilic monomers, polymers and copolymers of the present invention can be separated from each other or from the polymerization reaction mixture for example, by distillation, precipitation, extraction, changing the pH of the reaction media or by other conventional separation techniques either known.
The polymerization temperature may range from about 50 ° C to about 180 ° C, preferably from about 80 ° C to about150 ° C. At temperatures greater than about 180 ° C, the controlled conversion of the monomers to the polymers may decrease, and undesirable byproducts such as thermally initiated polymers are formed or decomposition of the components may occur.
The transition metal in the salt of the oxidizable transition metal complex catalyst 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 of the elements, such as Cu + / Cu2 +, Cu ° / Cu +, Fe ° / Fe2 +, Fe2 + / Fe3 +, Cr2 + / Cr3 +, Co + / Co2 +, Co2 + / Co3 +, Ni ° / Ni \ Ni + / Ni2 +, Ni2 + / Ni3 +, Mn ° / n2 +, Mn2 + / n3 +, Mn3 + / Mn4 + or Zn + / Zn2 + .
The ionic charges are counteracted by anionic ligands commonly known in the chemistry of complexes or transition metals, such as hydride ions (H) or anions derived from inorganic or organic acids, examples being halides, for example F ~, Cl ", Br "or I", fluorine complexes of type BF4", PF? , SbF6 * or AsF6", anions of oxygenated acids, alcoholates or acetylides or cyclopentadiene anions.
Oxygenated acid anions are, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C? -C8 carboxylic acid, such as formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example methylsulphonate, ethylsulphonate, propylsulphonate, butylsulphonate, trifluoromethylsulphonate (triflate), phenylsulphonate or benzylsulphonate not substituted or substituted by C? _4 alkyl, alkoxy of C? -C4 or halo, especially fluorine, chlorine or bromine, for example tosylate, mesylate, brosylate, p-methoxy or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2, 6-triisopropylsulfonate, phosphonates, for example methylphosphonate, ethylphosphonate, propylphosphonate , butylphosphonate, phenylphosphonate, p-methylphenylphosphonate or benzylphosphonate, carboxylates derived from a carboxylic acid of Cx-Cs, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate , mono-, di- or trichloro- or -fluoroacetate, and also C 1 -C 2 -alcoholates such as straight or branched chain C 1 -C 2 alkoxides, for example methanolate or ethanolate.
Anionic and neutral ligands may also be present up to the preferred coordination number of the complex cation, especially four, five or six. Additional negative charges are counteracted by cations, especially monovalent cations such as Na +, K +, NH4 + or (C? -C4 alkyl) 4N +.
Suitable neutral ligands are neutral inorganic or organic ligands commonly known in the chemistry of transition complexes or metals. They coordinate with the metal ion through a bond of type s, p, μ,? or any combinations thereof up to the preferred coordination number of the complex cation. Suitable inorganic ligands are selected from the group consisting of water (H20), amino, nitrogen, carbon monoxide and nitrosyl. Suitable organic ligands are selected from the group consisting of phosphines, for example (C6H5) 3P, (i-C3H7) 3P, (C5H9) 3P or (C6Hn) 3P, di, tri, tetra- and hydroxyamines, such as ethylenediamine, ethylenediaminetetraacetate (EDTA), N, N-Dimethyl-N ',' -bis (2-dimethylaminoethyl) -ethylenediamine (MeßTREN), catechol, N, N'-dimethyl-1,2-benzenediamine, 2- (methylamino) phenol, 3- (methylamino) -2-butanol or N, N'-bis (1,1-dimethylethyl) -1,2-ethanediamine, N, N, N ', N ", N" -pentamethyldiethyltriamine(PMDETA), glycols or C? -C8 glycerides, for example ethylene or propylene glycol or derivatives thereof, for example di, tri- or tetraglima, and donor ligands of monodentate or bidentate heterocyclics.
The heterocyclic donor donor ligands are derived, for example, from unsubstituted or substituted heteroarenes from the group consisting of furan, thiophene, pyrrole, pyridine, bis-pyridine, picolilimine,? -piran,? -thiopyran, phenanthroline, pyrimidine, bis -pyrimidine, pyrazine, indole, coumarona, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole, isothiazole, quinoline, bis-quinoline, isoquinoline, bis-isoquinoline, acridine, chromene , phenazine, fenoxacin, 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 itself from its transition metal salt, for example Cu (I) Cl, the which is then converted to the complex compound by the addition of the compounds corresponding to the ligands present in the complex catalyst, for example by the addition of ethylenediamine, EDTA, Me6TREN or PMDETA.
After completing the polymerization step process, the polymers obtained can be isolated or the compound N-O (IV) is added in itself. The isolation step of the present process can be carried out by known methods, for example by distillation and filtration of the unreacted monomer. After completing the substitution of the polymerized compound with N- > 0 (IV), the catalyst salt is filtered, followed by evaporation of the solvent or by precipitation of the polymer with N? -0 (I) in a suitable liquid phase, filtration of the precipitated polymer and washing and drying.
The elimination of the leaving group -X and the substitution of the polymerized with the N - > 0 (IV) is advantageously carried out in such a way that the polymerized is dissolved in a solvent and the compound with N-X) (IV) is added. The reaction takes place within a temperature range from room temperature to the boiling temperature of the reaction mixture, preferably from room temperature to 100 ° C. The transition metal in the complex catalyst salt of the oxidizable transition metal is converted from its lower oxidation state in the aforementioned redox systems to its higher oxidation state. In a preferred embodiment of the process a catalyst salt of Cu (I) complex is converted to the oxidation state of the corresponding Cu (II).
Because the polymerization and derivatization of the present with the compound with O (IV) by ATRP is a "living" polymerization, it can start and end at virtually any time. The different advantages of the process of this type allowing flexible polymerization reactions are described by K. Ma tyjaszewski in ACS Syrnp '. Ser. Vol. ~ 685 (1998), pg. 2-30. Thus, one embodiment of this invention, once the first monomer is consumed in the initial polymerization step, a second monomer can then be added to form a second block on the growing polymer chain in a second polymerization step. Therefore, it is possible to carry out further polymerizations with the same or different monomers to prepare multi-block copolymers. In addition, since this is a radical polymerization, the blocks can be prepared essentially in any order. One is not necessarily restricted to preparing block copolymers where the sequential polymerization steps must flow from the less stabilized intermediate polymer to the more stabilized intermediate polymer, such as in the case of polymerization. In this way, it is possible to prepare a multiblock copolymer in which a block of polyacrylonitrile or poly (meth) acrylate is first prepared, then a block of styrene is attached to it, and so on. In addition, a linking group is not required to join the different blocks of the block copolymer herein. One can simply add monomers successively to form successive blocks.
The polymers or copolymers can be further processed and used in most cases without any additional purification step. This is an important advantage when trying to scale at an industrial level. Another embodiment of the present invention are the polymers, copolymers or oligomers obtainable by the process described above.
Another embodiment of the present invention is a polymer composition which comprisesa) a polymer, copolymer and oligomers obtainable by the aforementioned process;and b) a polymer or oligomer of formulaAx-By (V) whereA represents an oligopolymer or polymer fragment consisting of repeating units of monomers or oligopolymers containing ethylene groups;x represents a number greater than one and defines the number of repeated units in A;B represents a monomer, oligopolymer or polymer fragment copolymerized with A; y y represents zero or a number greater than zero and defines the number of repeated units of monomer, oligopolymer or polymer in B.
The polymers obtained by the process of the present invention and the aforementioned compositions may contain in addition to the aforementioned components conventional additives such as antioxidants or light stabilizers may be added in small amounts, such as UV absorbers, for example those of the hydroxyphenylbenzotriazole type, hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s-triazine. These compounds can be added individually or in mixtures, with or without sterically hindered amines (HALS).
The composition may contain the aforementioned polymer or oligomeric components in an amount of 0.01 to 99% by weight, preferably 0.1 to 95% by weight, particularly preferably 1 to 90% by weight, and especially preferably from 5 to 80% by weight, based on the monomers present in the composition.
The polymers obtained by the process of the present invention and the compositions mentioned above are useful as adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubricants, rheology modifiers, thickeners, crosslinkers, paper treatment compositions, water treatment compositions, electronic materials, paints, coatings, ink materials, imaging materials, superabsorbents, cosmetics, hair products, preservatives, biocides, or modifiers for asphalt, leather, textiles, ceramics and wood.
The compounds with N-O of formula IV are known. They are commercially available or can be prepared according to the methods described in US Specification 5, 204, 473 or 4, 581, 429 and the references cited therein.
The following examples illustrate the invention:Example 1 a) Substitution of terminal bromine in high molecular weight poly-n-butylacrylate (1) with N- * > 0 terminal:1 is a polymer prepared by the ATRP method from methyl-2-bromopropionate (initiator), n-butylacrylate (monomer) and Cu (I) Br / N, N, N ', N ", N" - pentamethyl-diethylenetriamine (PMDETA = catalyst and ligand). Its preparation is described in Example 1 c)..0 g (1.48 mmol of polymer with terminal bromine) of 1, 0.315 g (1.48 mmol) of 2, 0.212 g (1.48 mmol) of CuBr and 10 ml of ethyl acetate solvent were added to a 100 ml round-bottomed flask equipped with a magnetic stirrer. The flask was then sealed with a rubber stopper. The air was removed from the flask by shaking, evacuating and rinsing with nitrogen three times. 0.256 g (310 μl, 1.48 mmol) of PMDETA was added through the rubber seal with a syringe. The solution was then heated at 80 ° C for two hours in an oil bath. The color of the reaction mixture changes from orange to brown and then greenish. After cooling to room temperature the insoluble greenish Cu complex catalyst particles were filtered. By the addition of 3 g of neutral aluminum oxide (ALOX for chromatography, Merck) and filtration, the complex catalyst is completely removed. After drying on the rotary evaporator at 60 ° C and then on the vacuum pump, a colorless polymer was obtained in an almost quantitative yield.
Elemental analysis: Br: < 0.3%, N: 0.36% (0.41% calculated for 100% halogen exchange); GPC (TF): Mn: 5980, Mw: 7010, PDI: 1.17.b) In a analogous reaction a) dioxane solvent was used. The process was carried out for 3 hours at 100 ° C. The drying is at 100 ° C.
Elemental analysis: Br: < 0.3%, N: 0.39% (0.41% calculated for 100% halogen exchange); GPC (TF): Mn: 5950, Mw: 6990, PDI: 1.17.
Both reactions a) and b) demonstrate that more than 75% of the terminal halogen has been substituted with the N->. 0 terminal. The data for the nitrogen of the elemental analysis reveal that the degree of substitution is really greater than88%.c) Preparation of poly-n-butylacrylate (1) with terminal Br-groups by the ATRP method without the addition of solvent ([M]: [I]: [CuBr]: [L] = 50: 1: 0.2: 0.2 ).89.8 g (100 1, 0.7 mol) of n-butylacrylate (Fluka, purum) and 0.40 g (2.8 mmol) of CuBr (Fluka, purified by treatment with acetic acid) were added to a 500 ml round bottom flask equipped with a stirrer. magnetic. The air was removed from the flask by shaking, evacuating and rinsing with nitrogen three times. 0.485 g (0.58 ml, 2.8 mmol) of PMDETA was added through the rubber seal with a syringe. After the addition of 2.34 g (1.56 ml, 14 mmol) of methyl-2-bromo-propionate (initiator) and heating to 80 ° C in the oil bath, the exothermic polymerization reaction began. The temperature rises within 30 minutes to 91 ° C. The quantity produced is determined by 1H-NMR analysis in CDC13 (56%, 30 min, 8%, 1 h, 90%, 2 h). After cooling to room temperature 150 ml of ethyl acetate and 30 g of neutral aluminum oxide (ALOX for chromatography, Merck) were added. The polymer is obtained after stirring for 1 hour at room temperature, filtering and drying in the rotary evaporator at 80 ° C and drying in the vacuum pump.
- Yield: 84 g (93%); Elemental analysis: Br: < 1.18%, Cu: < 10 ppm (X-ray fluorescence); GPC (TF): Mn: 5640 (5920 calculated), Mw: 6790, PDI: 1.20.
Example 2 a) Substitution of terminal bromine in low molecular weight poly-n-butylacrylate (1) with N- * 0 terminal.
The substitution was carried out analogously to Example 1 a).
Table 1Equivalent Temp.; M Analysis Degree [%] of Degree [%] ofs of NO »time PDI elementa substitution substitution 1 (analysis (analysisBr; N [%] of Br > by UV of aggregates NOT »)1. 14 ¡0 ° C 1430 < 0.3; > 94! > 90%0. 5 h l.lí 1.75 '99%1. 00 80 ° C 1410 0.84; 83%0. 5 h 1.17 1.40 (79% *)1. 14 60 ° C 1410 < 0.3; > 94%2. 0 h l.lf 1.66 (94% *)0. 50 60 ° C 1350 2.61; 54%2. 0 h 1.19 0.74 42% * '1. 00 60 ° C 1430 0.42; 91%2. 0 h 1.17 1.47 (83% *)*) calculated from the elemental analysis of N (content of N after the complete substitution: 1.77%).b) Preparation of low molecular weight poly-n-butylacrylate (1) with terminal Br groups by ATRP with the addition of solvent ([M]: [I]: [CuBr]: [L] '= 10: 1: 0.2 : 0.2).160.2 g (1.25 mol) of n-butylacrylate (Fluka, purum), 3.58 g (25 mmol) of CuBr (Fluka, purified by treatment with acetic acid) and 152 ml of dioxane were added.
(Fluka, puriss.) To a 500 ml spherical flask equipped with a magnetic stirrer. The air was removed from the flask by shaking, evacuating and rinsing with nitrogen three times. 4.33 g (25 mmol) of PMDETA were added through the rubber seal with a syringe. After the addition of 20.87 g (0.125 mol) of methyl-2-bromo-propionate (initiator) and heating to 70 ° C in the oil bath the exothermic polymerization reaction was started. The temperature rises slowly to 90 - 100 ° C. The reaction mixture is briefly cooled in an ice bath to maintain the temperature between 90 and 95 ° C. The reaction ends after about 30 minutes, which is determined by 1 H-NMR analysis on CDC13 (> 98 ° C). After cooling to room temperature, 100 ml dioxane and 150 g neutral aluminum oxide (ALOX for chromatography, Merck) were added. The polymer is obtained as a colorless, viscous liquid, after stirring for 30 min. at room temperature, filtration, drying in the rotary evaporator at 60 ° C and drying in the vacuum pump.
Yield: 143 g (79%); Elemental analysis: Br: 4.85%; GPC (TF): Mn: 1280 (1282 calculated), Mw: 1540, PDI: 1.20.
Example 3Substitution of 2 atoms of terminal bromine poly-n-butyl acrylate of low molecular weight (1) with two N- * > 0 interlaced terminals.
The substitution is carried out in a manner analogous to that in (a), the preparation of low molecular weight poly-n-butylacrylate (1) is carried out analogously to Example 2 b).
Table 2 Temp Equivalents; Mn; Analysis Grade [%] of elementary N0 # time PDI substitution of Br; N [%] Aggregates (analysis of Br-)1. 14 60 ° C 2090 0.49; 90%0. 5 h 1.26 0.67 (75 * 1value calculated according to the analysis of NExample 4a) Substitution of terminal chlorine in low molecular weight poly-n-butylacrylate (4) with N- »0 terminal:+ CuCI ". 0 g (3.55 mmol of terminal Cl) of 4.982 g (3.55 mmol) of 5 and 0.351 g (3.55 mmol) of CuCl were mixed under nitrogen with 5.0 ml of dioxane in a three-neck spherical flask equipped with a magnetic stirrer. . The air was removed from the flask by shaking, evacuating and rinsing with nitrogen three times. The mixture was heated in the oil bath at 50 ° C. When 0.615 g (3.55 mmol) of PMDETA is added, the color of the reaction mixture changes from orange to green. After cooling to room temperature the reaction mixture is filtered and 10 ml of dioxane and 2 x 5 g of neutral aluminum oxide (ALOX for chromatography, Merck) are added. After filtration, the polymer 6 is obtained after drying for 1.5 h in the rotary evaporator at 60 ° C.
Yield: 5.41 g (92%Elementary analysis:C H N Cl65 701 9. 131 OT 0. 00165. 60 9,072 0.812 0.30 'i) calculated; 2) found;The degree of substitution of > 84% was calculated from the Cl analysis; GPC (TF, PS-Standard): Mn: 1700 (calculated 17330); PDI: 1.83.b) Preparation of poly-n-butylacrylate (1) with terminal Cl groups with the addition of solvent ([M]: [I]: [CuBr]: [L] = 10: 1: 0.2: 0.2).160.2 g (1.25 mmol) of n-butylacrylate (Fluka, purum) and 2.47 g (25 mmol) of CuCl (Fluka, purified by treatment with acetic acid) were added to a 750 ml round bottom flask equipped with a magnetic stirrer. 152 ml of dioxane were added and the air was removed from the flask by shaking, evacuating and rinsing with nitrogen three times. 4.33 g (25 mmol) of PMDETA were added through the rubber seal with a syringe. After the addition of 15.32 g (125 mmol) of methyl-2-chloropropionate (initiator) and heating to 80 ° C in the oil bath, the exothermic polymerization reaction was started. The temperature rises within minutes to 100DC. After 30 min. the amount produced is determined by 2H-NMR analysis in CDC13 (100%). 100 ml of dioxane and 150 g of neutral aluminum oxide (ALOX for chromatography, Merck) were added. The polymer was obtained after stirring for 30 min. at room temperature, filtration and drying in the rotary evaporator at 80 ° C and drying in the vacuum pump.
Yield: 155.6 g (89%); Elemental Analysis: Cl: < 1.92%, N: 0%; GPC (TF): Mn: 1490 (1400 calculated), Mw: 1490, PDI: 1.87.
Example 54 7 8 a) 5.0 g (2.7 mmol Cl-terminal) of 4. 0.54 g (2.7 mmol) of 7 and 0.267 g (2.7 mmol) of CuCl under nitrogen were mixed with 5.0 ml of dioxane in a three-neck spherical flask. Equipped with a magnetic stirrer. The air was removed from the flask by shaking, evacuating and rinsing with nitrogen three times. The flask was then sealed with a rubber stopper and 0.467 g (2.7 mMol) of PMDETA was added through the rubber seal with a syringe. The mixture was heated in the oil bath at 90 ° C, while the color of the reaction mixture changed from orange on brown to green. After cooling to room temperature the insoluble green copper complexes are filtered. After the addition of 10 ml of dioxane and 5 g of neutral aluminum oxide (ALOX for chromatography, Merck) and another filtration the catalyst residues are removed. After drying at 60 ° C on the rotary evaporator, the colorless polymer 8 is obtained.
Yield: 4.27 g (81th Elemental Analysis:N Cl0. 811 O.OO10. 86 0.18 'i) calculated; 'foundA degree of substitution of > 90% from the Cl analysis; GPC (TF, PS-Standard): Mn: 1760 (1700 calculated); POI: 1.72; Mw: 3030b) In a manner analogous to Example 5 a) a polymer was obtained, but the compound with N - * »0 is replaced withYield: 4.27 g (81%)Elementary analysis:N ClÓXl 0.00 1.25 i i0. 54 '0.41 1.671) calculated; found A degree of substitution of > 80% from the Cl analysis; GPC (TF ,, _ PS-Standard): Mn: 1760 (1630 calculated); POI: 1.72; Mw: 3040Example 611 a) 5.0 g (3.3 mmol of polymer with terminal bromine) of 1.75 g (3.3 mmol) of 10 and 0.47 g (3.3 mmol) of CuBr and 5 ml of ethyl acetate solvent were added to a flask of 50 mi equipped with a magnetic stirrer. The flask was then sealed with a rubber stopper. The air was removed from the flask by shaking, evacuating and rinsing with nitrogen three times. 0.55 g (3.3 mmol) of PMDETA was added through the rubber seal with a syringe. The solution was then heated at 90 ° C for three hours in an oil bath. The color of the reaction mixture changes from orange to brown and then greenish. After cooling to room temperature the insoluble greenish Cu complex catalyst particles were filtered. By the addition of 10 ml of dioxane, 3 g of neutral aluminum oxide (ALOX for chromatography, Merck) and filtration, the complex catalyst was completely removed. After drying on a rotary evaporator at 60 ° C and then on the vacuum pump a colorless polymer was obtained. The halogen exchange is greater than 93%. Elemental analysis: Br: 1.34% (0% calculated), N: 1.60% (1.72% calculated for 100% halogen exchange); GPC (TF): Mn: 1410 (1390 calculated), Mw: 1690, PDI: 1.20.b) In a manner analogous to Example 5 a) a polymer was obtained, but the compound with N- > 0 is replaced withYield: 4.83 g (84%);Elementary analysis:N Br 1.60x 1.49 i1. 71 '1.60i) calculated; ^ foundA degree of substitution of > 94% from the analysis of N; GPC (TF, PS-Standard): Mn: 1360 (1380 calculated); PDI: 1.19; Mw: 1620