Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
  • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-propylene copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
  • C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-propylene-diene terpolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
  • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

• the present invention relates to a process for the preparation of grafted polymers wherein in a first step A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a compound containing a NO-ether to above the melting point of the polymer, mixing and reacting the components at said temperature; and in a second step B) the grafted polymer of step A) is heated in the presence of an ethylenically unsaturated monomer or oligomer to a temperature at which cleavage of the nitroxyl-polymer bond occurs.
• Further subjects of the present invention are grafted polymers prepared by said process, the intermediate polymeric radical initiator, the use of the polymeric radical initiator and the use of NO-ethers for grafting polymers.
• An important chemical modification is the free radical grafting of reactive monomers, which involves reaction of a polymer with a vinyl-group containing monomer or mixture of monomers capable of forming grafts onto the polymer backbone. If the grafts are long, the modified polymer becomes a true graft copolymer, of which the properties will be very different from those of the original polymer substrate. When the grafts are short with less than , for example five moieties, most of the physical and or mechanical properties of the modified polymer substrate will be retained.
• free radical-grafting reactions are usually performed in the presence of a free radical source such as a peroxide and a reactive monomer, such as for example acrylic acid.
• a free radical source such as a peroxide and a reactive monomer, such as for example acrylic acid.
• free radical sources such as peroxides may cause undesired properties and lead to problems during processing (gel formation, crosslinking, molecular weight reduction) or during use.
• the long term stability is reduced and/or the polymer cannot anymore be used in outdoor applications or in applications at elevated temperatures.
• US-A-4 581 429 to Solomon et al issued April 8, 1986 discloses a free radical polymerization process which controls the growth of polymer chains to produce short chain or oligome ⁇ c homopolymers and copolymers, including block and graft copolymers
• the process employs an initiator having the formula (in part) R'R"N-0-X, where X is a free radical species capable of polymerizing unsaturated monomers
• the polymerization processes and resin products of the present invention are useful in many applications, including a variety of specialty applications, such as for the preparation of grafted block copolymers which are useful as compatibilizing agents for polymer blends or dispersing agents for coating systems.
• One subject of the present invention is a process for the preparation of a grafted polymer wherein in a first step
• X is selected such, that cleavage of the O-X bond occurs and a radical X» is formed at about the melting temperature of the polymer, and in a second step
• step B) the grafted polymer of step A) is heated in the presence of an ethylenically unsaturated monomer or oligomer to a temperature at which cleavage of the nitroxyl-polymer bond occurs and polymerization of the ethylenically unsaturated monomer or oligomer is initiated at the polymer radical, maintaining said temperature for further polymerization and afterwards cooling down the mixture to a temperature below 60° C.
• reaction mixture after step A) may also be cooled down to a temperature below 60° C before further reaction of step B) is performed
• a free radical source is additionally present
• reaction mixture after step A) may also be cooled down to a temperature below 60° C before further reaction of step B) is performed
• the free radical source is a bis-azo compound, a peroxide or a hydroperoxide
• Specific preferred radical sources are 2,2 -azobisisobutyronitnle, 2,2'-azob ⁇ s(2-methyl- butyronit ⁇ le), 2,2'-azob ⁇ s(2,4-d ⁇ methylvaleron ⁇ tr ⁇ le), 2,2'-azob ⁇ s(4-methoxy-2,4-d ⁇ methylvalero- nitrile), 1 , 1 '-azob ⁇ s(1 -cyclohexanecarbon ⁇ tr ⁇ le), 2,2'-azob ⁇ s( ⁇ sobutyram ⁇ de) dihydrate, 2- phenylazo-2,4-d ⁇ methyl-4-methoxyvaleron ⁇ tr ⁇ le, d ⁇ methyl-2,2'-azob ⁇ s ⁇ sobutyrate, 2- (carbamoylazo) ⁇ sobutyron ⁇ tr ⁇ le, 2,2'-azob ⁇ s(2,4,4-t ⁇ methyl
• Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut- 1-ene, poiy-4-methylpent-1 -ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be cross nked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE)
• Polyolefins i.e the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods.
• a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table.
• These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or s-coordinated.
• These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, t ⁇ tan ⁇ um(lll) chloride, alumina or silicon oxide.
• These catalysts may be soluble or insoluble in the polymerisation medium.
• the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, lla and/or Ilia of the Periodic Table.
• the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
• These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (- Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
• Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1 -ene copolymers, propylene/isobutylene copolymers, ethylene/but-1 -ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (l
• Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives for example styrene/butadiene, styrene/acrylonit ⁇ le, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acryloni- t ⁇ le/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpo- lymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/iso- prene/styrene,
• Graft copolymers of styrene or a-methylstyrene for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonit ⁇ le copolymers; styrene and acrylonitrile (or methacrylonit ⁇ le) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and
• Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brommated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlo ⁇ nated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydnn homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chlonde/vinylidene chloride, vinyl chlonde ⁇ inyl acetate or viny dene chloride/vinyl acetate copolymers.
• halogen-containing vinyl compounds for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride,
• Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitnles, impact-modified with butyl acrylate.
• Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/ butadiene copolymers, acrylonit le/alkyl acrylate copolymers, acrylonit ⁇ le/alkoxyalkyl acrylate or acrylonit ⁇ le/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers
• Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer, polyacetals modified with thermoplastic poiyurethanes, acrylates or MBS
• Polyamides and copolyamides derived from diammes and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 1 1 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid, polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-tr ⁇ methylhexamethylene terephthalamide or poly-m- phenylene isophthalamide, and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, lonomers or chemically bonded or grafted elastomers, or with polyethers, e g with polyethylene glycol, polypropylene glycol or polytetram
• Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-d ⁇ methylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
• Blends of the aforementioned polymers for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
• polyblends for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, P
• Preferred polymers are polyethylene, polypropylene, polystyrene, styrene block-copolymers, polybutadiene or polyisoprene, EPDM (ethylene-propylene diene monomer) or EPR (ethylene- propylene rubber).
• polyethylene More preferred are polyethylene, polypropylene, polybutadiene, SBS and EPDM (ethylene- propylene diene monomer).
• n is 0 or 1
• R 102 . R 103 are each independently of one another hydrogen, halogen, N0 2 , cyano, -CONR 105 R 10 6 , -(R 109 )COOR, 0 4, -C(O)-R 107 , -OR 108 , -SRio ⁇ , -NHR 108 , -N(R,o ⁇ ) 2 , carbamoyl, d ⁇ (C, C ⁇ 8 alkyl)carbamoyl, unsubstituted C -C 18 alkyl C -C, 8 alkenyl C 2 -C 18 alkynyl, C 7 -C 9 phenylalkyl, C 3 -C 12 cycloalkyl or C 3 -
• R 104 is hydrogen, C,-C 18 alky! phenyl an alkali metal cation or a tetraalkylammonium cation;
• R 105 and R 106 are hydrogen CrC, c alkyl, C 2 -C 18 alkyl which is substituted by at least one hydroxy group or, taken together, form a C ,-C 12 alkylene bridge or a C 2 -C 12 -alkylene bridge interrupted by at least one O or/and NR 108 atom
• R 107 is hydrogen, C,-C 18 alkyl or phenyl
• R 108 is hydrogen, C r C 18 alkyl or d-C 18 alkyl which is substituted by at least one hydroxy group;
• R 10 g is C,-C 12 alkylen or a direct bond
• R 110 is C 4 -C 18 alkyl bound via a tertiary C-atom to the nitrogen atom, Cg-dphenylalkyl, C 3 -
• N0 2 halogen, ammo, hydroxy, cyano, carboxy, d-C 4 alkoxy, d-C 4 alkylth ⁇ o, C 1 -C 4 alkylam ⁇ no or d ⁇ (C ⁇ -C alkyl)am ⁇ no; or phenyl, naphthyl, which are unsubstituted or substituted by C,-C 4 alkyl, C,-C 4 alkoxy, d-
• R 1 is C r C 18 alkyl, C 7 -C 9 phenylalkyl, C 3 -C 12 cycloalkyl or C 3 -C 12 cycloalkyl containing at least one nitrogen or oxygen atom, or
• R 110 and R are together form a C 2 -C 12 alkylene bridge, a C 3 -d 2 alkylen-on bridge or a C 2 -
• C 12 alkylene bridge which is interrupted by at least one O or N atom, which bridges are unsubstituted or substituted with d-C 18 alkyl, hydroxy(d-C 4 )alkyl, phenyl, C 7 -C 9 phenylalkyl,
• N0 2 halogen, ammo, hydroxy, cyano, carboxy, d-C 4 alkoxy, d-C 4 alkylth ⁇ o, C C 4 alkylam ⁇ no or d ⁇ (C C 4 alkyl)am ⁇ no,
• Rn2 is hydrogen, -(R 109 )COOR 10 4, cyano, -OR 108 , -SR 108 , -NHR 108 , -N(R 108 )2, -NH-C(O)-R 108 , unsubstituted d-C 18 alkyl, C 2 -C 18 alkenyl, C -C 18 alkynyl, C 7 -C 9 phenylalkyl, C 3 -C 12 cycloalkyl or C 3 -
• R 111 and R 112 together with the linking carbon atom form a C 3 -C 12 cycloalkyl radical.
• nitroxyl-ether is of formula XXa, XXb or XXc
• Q is O or NR 220 , wherein R 22 o is hydrogen or d-C 18 alkyl,
• R 201 is tertiary C 4 -C 18 alkyl or phenyl, which are unsubstituted or substituted by halogen, OH,
• R 2 ⁇ is hydrogen, a alkali metal atom or d-Ciealkyl and R 222 is d-C 18 alkyl, or R 231 is C 5 -C ⁇ cycloalkyl, C, C 12 cycloalkyl which is interrupted by at least one O or N atom, a polycyclic alkyl radical or a polycyclic alkyl radical which is interrupted by at least one O or N atom
• R 202 and R 233 are independently d-C ⁇ alkyl, benzyl, C D -C, 2 cycloalkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR 22 ' or C(0)-R 22 2 or together with the carbon atom form a C 5 -C 12 cycloalkyl ring,
• R 204 and R 212 are OH, O(alkal ⁇ -metal) C,-C 18 alkoxy, benzyloxy, NR223R224, wherein R 223 and R 22 are independently from each other hydrogen, C ⁇ -C 18 alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR 221 or C(0)-R 22 2, if Y, ⁇ s CH 2 ,
• R 20 4 is OH, C,-C 18 alkoxy, benzyloxy, 0-C(0)-(d-C 18 )alkyl or R 223 R 22 4,
• R212 are a group C(0)R 225 , wherein R 225 is OH, d-daalkoxy benzyloxy, NR 223 R 22 , wherein R 223 and R 224 are independently from each other hydrogen C C, p alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR 2 -t or C(0)-R 222 ,
• R205, R206, R207 and R 208 are independently of each other C, C, 8 alkyl, C 5 -C 12 cycloalykyl or phenyl; or
• R209 and R 2 ⁇ o are independently of each other hydrogen formyl C 2 -C 18 alkylcar bonyl, benzoyl,
• C ⁇ -C 18 alkyl C 5 -C 12 cycloalkyl, C 5 -C 12 cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen OH, COOR 221 or
• R211 is formyl, C 2 -C 18 alkylcarbonyl, benzoyl, C r C 18 alkyl d-C .cycloalkyl, C 5 -C 12 cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR 22 , or C(0)-R 222
• Still another preferred nitroxyl-ether contains a structural element of formula (XXX)
• G 1 t G 2 , G 3 , G are independently C r C 6 alkyl or G, and G or G 3 and G 4 , or G, 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 C 18 alkyl, phenyl, naphthyl or a group COOC ⁇ -C, 8 alkyl.
• G 1 f G 2 , G 3 and G 4 are independently alkyl of 1 to 4 carbon atoms, or G, and G 2 together and
• G 3 and G 4 together, or G , and G 2 together or G 3 and G 4 together are pentamethylene;
• G 5 and G 6 are independently hydrogen or C C 4 alkyl
• R if m is 1 , is hydrogen, C ,-C, 8 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 ⁇ , ⁇ -unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 -COOZ 12 groups, in which Z 12 ⁇ s H, C C 2 oalkyl, C 3 -
• R is a monovalent radical of a carbamic acid or phosphorus-containing acid or a monovalent silyl radical
• R if m is 2, is C 2 -C 12 alkylene, C 4 -C 12 alkenylene, xylylene, a divalent radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having
• each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZ 12 groups; or
• R is a divalent radical of a phosphorus-containing acid or a divalent silyl radical
• R if m is 3, is a t ⁇ valent radical of an aliphatic, cycloaliphatic or aromatic tricarboxyhc acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by
• R if m is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; p is 1 , 2 or 3,
• R is C 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; when p is 1 ,
• R 2 is d-dsalkyl, 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; or when p is 2,
• R 2 is C 2 -C 12 alkylene, C 6 -C 12 -arylene, xylylene, a -CH 2 CH(OH)CH 2 -0-B-0-CH 2 CH(OH)CH 2 - group, wherein B is C 2 -C 10 alkylene, C 6 -C 15 arylene or C 6 -C 12 cycloalkylene; or, provided that R, is not alkanoyl, alkenoyl or benzoyl, R 2 can also be a divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or can be the group -CO-; or R, and R 2 together when p is 1 can be the cyclic acyl radical of an aliphatic or aromatic 1 ,2- or 1 ,3- dicarboxylic acid; or
• R 2 is a group
• T 7 and T 8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T 7 and T 8 together are alkylene of 4 to 6 carbon atoms or 3-oxapentamethylene; when p is 3,
• R 2 is 2,4,6-tr ⁇ az ⁇ nyl
• R 3 is C 2 -C 8 alkylene or hydroxyalkylene or C 4 -C 22 acyloxyalkylene; or
• R 3 is (-CH 2 ) 2 C(CH 2 -) 2 ;
• R 4 is hydrogen, C,-C 12 alkyl, C 3 -C 5 alkenyl, C 7 -C 9 aralkyl, C 5 -C 7 cycloalkyl, C 2 -C 4 hydroxyalkyl, C 2 -
• R 4 is C 2 -C 12 alkylene, C 6 -C 12 -arylene, a group -CH 2 CH(OH)CH 2 -0-D-0-CH 2 CH(OH)CH 2 - wherein D is C 2 -C 10 alkylene, C 6 -C 15 arylene or C 6 -C 12 cycloalkylene, or a group -
• R 5 is hydrogen, d-C 12 alkyl, allyl, benzyl, glycidyl or C 2 -C 6 alkoxyalkyl;
• Q is -N(R 7 )- or -0-;
• E is d-C 3 alkylene, the group -CH 2 CH(R 8 )-0- wherein R 8 is hydrogen, methyl or phenyl, the group -(CH 2 ) 3 -NH- or a direct bond;
• R 7 is CrC 18 alkyl, C 5 -C 7 -ycloalkyl, C 7 -C 12 araikyl, cyanoethyl, C 6 -C, 0 aryl, the group -CH 2 CH(R 8 )-
• G is C 2 -C 6 alkylene or C 6 -C 12 arylene and R is as defined above; or R 7 is a group -E-CO-NH-CH 2 -OR 6 ; R 6 is hydrogen or C,-C ⁇ 8 alkyl;
• Formula (F) denotes a recurring structural unit of a oligomer where T is ethylene or 1 ,2- propylene, or is a repeating structural unit derived from an ⁇ -olefm copolymer with an alkyl acrylate or methacrylate; k is 2 to 100; and R 10 is hydrogen, C,-C 12 alkyl or d-C 12 alkoxy;
• T 2 has the same meaning as R ;
• T 3 and T 4 are independently alkylene of 2 to 12 carbon atoms, or T 4 is a group
• T 5 is C 2 -C 22 alkylene, C 5 -C 7 cycloalkylene, CrC alkylenedi(C 5 -C 7 cycloalkylene), phenylene or phenylenedi(d-C 4 alkylene);
• a, b and c are independently 2 or 3, and d is 0 or 1 ; e is 3 or 4;
• E, and E 2 being different, are each oxo or imino;
• E 3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, said phenyl or said naphthyl substituted by chlorine or by alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or said phenylalkyl substituted by alkyl of 1 to 4 carbon atoms;
• E 4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms; or
• E 3 and E 4 together are polymethylene of 4 to 17 carbon atoms, or said polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms;
• E 6 is an aliphatic or aromatic or aromatic tetravalent radical.
• Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert- butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-t ⁇ decyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
• the alkyl groups may be linear or branched.
• C 3 -C 18 alkyl which is interrupted by one or more oxygen atoms is preferably derived from ethylene oxide or propylene oxide.
• C 3 -C 18 alkyl interrupted by at least one O atom is for example -CH 2 -CH 2 -0-CH 2 -CH 3 , -CH 2 -CH 2 - 0-CH 3 or -CH 2 -CH 2 -0-CH 2 -CH 2 -CH 2 -0-CH 2 -CH 3 . It is preferably derived from polyethlene glycol. A general description is -((CH 2 ) a -0) b -H/CH 3 , wherein a is a number from 1 to 6 and b is a number from 2 to 10.
• C 3 -C 12 alkenyl is linear or branched and for example propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, dodecenyl including their isomers.
• C 3 -C 8 alkynyl is preferably propargyl
• C 5 -C ⁇ 2 cycloalkyl is typically, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl.
• Cycloalkyl which is interrupted by at least one O or N atom is for example 2-tetrahydropyran-yl, tetrahydrofurane-yl, 1 ,4 dioxan-yl, pyrrolidin-yl, tetrahydrothiophen-yl, pyrazolidin-yl, imidazolidin-yl, butyrolactone-yl, caprolactame-yl
• alkali metal examples are lithium, sodium or potassium.
• Alkyl substituted by-OH is typically 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl.
• d-C 18 alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.
• d-C ⁇ 8 Alkyl substituted by C r C 8 alkoxy, preferably by C,-C 4 alkoxy, in particular by methoxy or ethoxy, is typically 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3- butoxypropyl, 3-octoxypropyl and 4-methoxybutyl.
• d-C 18 Alkyl substituted by d ⁇ (C,-C 4 alkyl)am ⁇ no is preferably e g.
• C,-C 18 Alkyl substituted by d-C 4 alkylam ⁇ no is preferably e.g methylammo, ethylamino, 2- methylammoethyl, 2-ethylam ⁇ noethyl, 3-methylam ⁇ nopropyl, 3-ethylam ⁇ nopropyl, 3-butylam ⁇ no- propyl and 4-ethylam ⁇ nobutyl.
• d-C 4 Alkylth ⁇ o is typically thiomethyl, thioethyl, thiopropyl, thioisopropyl, thiobutyl and thioisobutyl.
• C 2 -Ci 8 alkylcarbonyl is for example acetyl, propionyl, butyryl, pentylcarbonyl, hexylcarbonyl or dodecylcarbonyl.
• C 7 -C 9 phenylalkyl or C 7 -C 8 aralkyl is for example benzyl, phenylethyl, phenylpropyl, ⁇ , ⁇ - dimethylbenzyl or ⁇ -methylbenzyl.
• C 2 -C 12 alkylene bridges preferably of C 2 -C 6 alkylene bridges, are ethylene, propylene, butylene, pentylene, hexylene.
• C 2 -C 12 alkylene bridges interrupted by at least one N or O atom are, for example, -CH 2 -0-CH 2 -CH 2 , -CH 2 -0-CH 2 -CH 2 -CH 2 , -CH 2 -0-CH 2 -CH 2 -CH 2 -, -CH 2 -0-CH 2 -CH 2 -0-CH2-, -CH 2 -NH-CH 2 -CH 2 , -CH 2 -NH-CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -NH-CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -NH-CH 2 -CH 2 -NH-CH2- or -CH 2 -NH-CH 2 -CH 2 -0-CH2-.
• C 4 -C 12 cycloalkanone-yl examples are cyclopentanone-yl, cyclohexanone-yl or cycloheptanone-yl
• Phenyl substituted by 1 , 2 or 3 d-C 4 alkyl or d-C 4 alkoxy is typically methylphenyl, dimethyl- phenyl, t ⁇ methylphenyl, t-butylphenyl, di-t-butylphenyl, 3,5-d ⁇ -t-butyl-4-methylphenyl, methoxyphenyl, ethoxyphenyl and butoxyphenyl.
• polycyclic cycloaliphatic ring systems examples include adamantane, cubane, twistane, norbornane, bycyclo[2.2.2]octane or bycyclo[3.2.1 ]octane
• polycyclic heterocycloaliphatic ring system is hexamethylentetramme (urotropine)
• monocarboxylic acids with 1 to 18 carbon atoms are formic acid, acetic acid, propionic acid phenyl acetic acid, cyclohexane carbonic acid, mono-, di- and trichlor-acetic acid or mono-, di- and tnfluor-acetic acid
• suitable acids are benzoic acid, chlor-benzoic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, chlorbenzenesulfonic acid, trifluormethanesulfonic acid, methylphosphonic acid or phenylphosphonic acid
• Examples of a monovalent radical of a carboxylic acid are an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, cyclohexylcarboxyiic acid, benzoyl or ⁇ -(3,5-d ⁇ -tert-butyl-4-hydroxyphenyl)- propionyl radical.
• a cycloaliphatic carboxylic acid is for example cyclohexane carboxylic acid or cyclopentane carboxylic acid
• An example of an aromatic carboxylic acid is benzoic acid
• Typical unsaturated carboxylic acids are acrylic acid methacry c acid or crotonic acid.
• Examples of a monovalent silyl radical are of the formula -(C,H 2] ) S ⁇ (Z') 2 Z", in which j is an integer in the range from 2 to 5, and Z' and Z", independently o ⁇ one another, are C 1 -C 4 alkyl or d-C 4 alkoxy
• di-, tn- and tetra valent acids are for example malonyl, succmyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl(3,5-d ⁇ - tert-butyl-4-hydroxybenzyl)malonyl or bicycloheptenedicarbonyl radical or a group of the formula ,trimellitoyl, citryl or nitrilotriacetyl, butane-
• Examples of a dicarbamic acid are the hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radicals.
• C 2 -C 12 alkanoyl is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.
• Hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted alkyl can be, for example, 2- hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.
• Any C 2 -C 12 alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
• C 4 -C 12 alkenylene is for example butenylene, pentenylene, hexenylene, heptenylene or nonenylene including their isomers.
• C 6 -C 12 aryiene is, for example, o-, m- or p-phenylene, 1 ,4-naphthylene or 4,4'-diphenylene.
• C 4 -C 22 acyloxyalkylene is, for example, 2-ethyl-2-acetoxymethylpropylene.
• Any C 2 -C 6 alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
• d-dsalkanoyloxy is, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, paimitoyloxy and stearoyloxy.
• the nitroxyl-ethers of formula (X) are known and may be prepared according to WO 99/03984, EP-A-0 891 986 or WO 98/13392.
• nitroxyl-ethers of formula XXa, b and c are also known and may be prepared according to European Patent Application No. 98810741.3.
• nitroxyl-ethers of formula XXX are also known and can be prepared as described in European Patent Application No. 98810531.8.
• tetramethylpipe ⁇ dine precursors are partially commercially available or can be prepared according to known methods.
• US 5 096 950 and the documents cited therein describe the preparation of the precursors.
• the oxidation and ether forming process can be done as described above.
• G, , G 2 , G 3 and G 4 are methyl or ethyl and G 5 and G 6 are hydrogen or methyl. More Preferably G, , G 2 , G , and G , are methyl and G- and G are hydrogen.
• Another preferred group of compounds are those wherein G , and G 3 are ethyl and G 2 and G 4 are methyl, or G, and G 4 are ethyl and G 2 and G 3 are methyl, and one of G 5 or G 6 is hydrogen and the other methyl or both are hydrogen.
• X is selected from the group consisting of C Cisalkyl, C 3 -C ⁇ 8 alkenyl, C 3 -C 18 alk ⁇ nyl, phenyl, phenyl(C 7 -Cn)alkyl, phenyl or phenyl(C 7 -Cn)alkyl substituted by CrC 12 alkyl, d- C ⁇ 2 alkoxy, OH, ammo, CrC 12 alkylam ⁇ no, d-C ⁇ dialkylammo, N0 2 or halogen, C 2 -C 7 cycloalkyl,
• R 22 are hydrogen or CrC 12 alkyl, C 2 -C, 2 alkenyl, phenyl or C 3 -C 7 cycloalkyl.
• X is selected from the group consisting of C ,-C, B alkyl, benzyl, allyl, cyclopentyl or cyclohexyl.
• a preferred subgroup are compounds of the structural formulae A, B, O or P, wherein m is 1 ,
• R is hydrogen, CrCisalkyl 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 ⁇ , ⁇ - unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having
• R is CrC, 2 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C, 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl;
• R 2 is CrC ⁇ 8 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.
• R is hydrogen, C ,-C ⁇ 8 alkyl, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid, having 2 to 18 carbon atoms;
• R is CrC ⁇ 2 alkyl, C 7 -C 8 aralkyl, C 2 -C, 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl;
• R 2 is CrC ⁇ 8 alkyl, glycidyl a group of the formula -CH 2 CH(OH)-Z or of the formula -CO-Z, wherein Z is hydrogen, methyl or phenyl
• nitroxyl-ether is a compound of formula (X),
• R1 01 is cyano
• Ri 02 and R ⁇ 03 are each independently of one another unsubstituted C, -C 12 alkyl or phenyl; or R 102 and R 103 , together with the linking carbon atom, form a C 5 -C 7 cycloalkyl radical,
• R 110 is C -C 12 alkyl bound via a tertiary C-atom to the nitrogen atom, Cg-Cnphenylalkyl or phenyl; or
• R 110 and R together form a C 2 -C 6 alkylene bridge which is unsubstituted or substituted with
• R 112 is d-C alkyl
• a further preferred subgroup is wherein the nitroxyl-ether is a compound of formula (XXa),
• R 20 ⁇ is tertiary C -C 8 alkyl
• R 202 and R 203 are methyl, ethyl or together with the carbon atom form a C 5 -C 6 cycloalkyl ring;
• R 20 is C ⁇ -C 18 alkoxy, benzyloxy or NR 223 R 224 , wherein R 2 3 and R 224 are independently of each other hydrogen or C,-C 8 alkyl, or of formula (XXb), wherein Q, is O,
• R 207 and R 208 are independently of each other methyl or ethyl; or
• R 209 and R 210 are independently of each other formyl, C 2 -C 8 alkylcarbonyl, benzoyl, CrC 8 alkyl, benzyl or phenyl, or of formula (XXc), wherein Y, is O,
• R 205 and R 206 and/or R 207 and R 208 together with the carbon atom form a C 5 -C 6 cycloalkyl ring;
• R 2 n is formyl, C 2 -C 18 alkylcarbonyl, benzoyl, d-C 18 alkyl, benzyl or phenyl and
• R 212 is OH, CrC 18 alkoxy, benzyloxy, NR 223 R 224 , wherein R 223 and R 22 are independently of each other hydrogen or C r C 18 alkyl
• the polymer to be grafted on contains unsaturated moieties selected from the group consisting of polydienes, co-, block-, random- and tapered polymers of styrene, terpolymers with diolefms and copolymers with diolefms
• unsaturated polymers are polybutadiene polyisoprene styrene-isoprene-block- copolymers (SI SIS) styrene butadiene block-copolymers (SB SBS SEBS) ABS EPDM, butyl rubber chloroprene rubber and nit ⁇ le rubber having a content of unsaturated repeating units from 0 1 to 85%
• SB SBS EPDM having a content of unsaturated repeating units from 1 to 70%
• the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolem, vinyl acetate, (alkyl)acryl ⁇ c acidanhydrides, (alkyl)acryl ⁇ c acid salts, (alkyl)acryl ⁇ c esters or (alkyl)acrylam ⁇ des
• R a is hydrogen or methyl
• R b is NH 2 , gycidyl, unsubstituted or with hydroxy substituted CrC 4 alkoxy, unsubstituted C,-C 4 alkylam ⁇ no, d ⁇ (C,-C 4 alkyl)am ⁇ no, hydroxy- substituted d-C 4 alkylam ⁇ no or hydroxy-substituted d ⁇ (C,-C 4 alkyl)am ⁇ no
• Z is oxygen
• ethylenically unsaturated monomers are methylacrylate, ethylacryiate, butylacrylate, isobutylacrylate, tert butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, d ⁇ methylam ⁇ noethyl(meth)acrylate glyc ⁇ dyl(meth)acrylates, acrylonitrile, acrylamide or methacrylamide
• the temperature applied in the first reaction step depends on the polymer and is for example 50° to 150° C above the glass transition temperature (Tg) for amorphous polymers and 20° to 180° C above the melting temperature (Tm) for semi-crystalline polymers Typical are following temperatures
• the temperature in the first step A) is from 150° C to 300° C, more preferred from 170° C to 280° C.
• the temperature in the second step B) is from 70° to 280° C, more preferably from 70° to 210° C.
• the group X is preferably allyl or benzyl.
• the group X is preferably benzyl or cyclohexyl.
• the group X is preferably cyclohexyl or alkyl.
• the compound containing a structural element of formula (I) is present in an amount from 0.1 % to 30%, more preferably in an amount from 1 % to 20% and most preferably in an amount from 1 % to 10% based on the weight of the polymer.
• the ratio of the reaction product of step A) to the ethylenically unsaturated monomer or oligomer added in step B) is from 1 -10000 to 10:1 , more preferably from 1 :1000 to 1 :1 and most preferably from 1.500 to 1.1
• Step A) of the process may be performed in any reactor suitable for mixing a polymer melt.
• the reactor is an extruder or kneading apparatus as for example described in "Handbuch der Kunststoffextrusion” Vol I, editor F. Hensen, W. Knappe and H. Potente, 1989, pages 3-7.
• an extruder is used the process may be described as reactive extrusion process. Examples of reactiv extrusion equipment and processes are given by G. H Hu et al., in "Reactive Modifiers for Polymers", first edition, Blackie Academic & Professional an Imprint of Chapman & Hall, London 1997, chapter 1 , pages 1-97.
• a reduced pressure of less than 200 mbar is applied during extrusion. Volatile byproducts are removed thereby
• the reaction time for step A) depends on the desired amount of grafted ONR'R" initiator moieties. Typical reaction times are from a few minutes to an hour Preferably the reaction time is from 1 mm to 1 h, most preferably from 2 mm to 20 m .
• the reaction step B) may be performed immediately after step A), however it is also possible to store the intermediate polymeric radical initiator at room temperature for some time The intermediate polymeric radical initiator is stable at room temperature and no loss of activity occurs up to several months
• the reaction for step B) may be performed in any reactor suitable for mixing a polymer melt with a monomer.
• the degree of grafting depends on the reaction time, on the temperature used and the activity of the polymeric initiator
• the reaction time for step B) is from 1 mm to 20 hours, more preferably from 30 mm to 5 hours.
• reaction step B) is performed in an extruder, a reaction time of 2 to 20 minutes is preferred.
• the grafted polymers are useful in many applications such as compatibilizers in polymer blends or alloys, adhesion promoters between two different substrates, surface modification agents, nucleating agents, coupling agents between filler and polymer matrix or dispersing agents.
• the process is particularly useful for the preparation of grafted block copolymers.
• Grafted block copolymers are, for example, grafted block copolymers of polystyrene and polyacrylate (e.g., poly(styrene-co-acrylate) or poly(styrene-co-acrylate-co-styrene). They are usefull as adhesives or as compatibilizers for polymer blends or as polymer toughening agents.
• Poly(methylmethacrylate-co- acrylate) diblock graft copolymers or poly(methyiacrylate-co- acrylate-co-methacrylate) t ⁇ block graft copolymers are useful as dispersing agents for coating systeme, as coating additives (e.g rheological agents, compatibilizers, reactive diluents) or as resin component in coat ⁇ ngs(e.g high solid paints)
• Graft block copolymers of styrene, (meth)acryiates and/or acrylonitrile are useful for plastics, elastomers and adhesives.
• graft block copolymers of this invention wherein the grafted blocks have polar monomers on a non polar polymer are useful in many applications as amphiphilic surfactants or dispersants for preparing highly uniform polymer blends
• the present invention also encompasses in the synthesis novel graft block, multi-block, star, gradient, random, hyperbranched and dendritic copolymers
• the polymers prepared by the present invention are particularly useful for following applications: adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubricants, rheology modifiers, thickeners, crosslmkers, paper treatment, water treatment, electronic materials, paints, coatings, photography, ink materials, imaging materials, superabsorbants, cosmetics, hair products, preservatives, biocide materials or modifiers for asphalt, leather, textiles, ceramics and wood
• the present graft polyme ⁇ zaton is a "living" polymerization, it can be started and stopped practically at will Furthermore, the polymer product retains the functional alkoxyamme group allowing a continuation of the polymerization in a living matter.
• a second monomer can then be added to form a second block on the growing graft polymer chain in a second polymerization step Therefore it is possible to carry out additional graft polymerizations with the same or different monomer(s) to prepare multi-block graft copolymers.
• this is a radical polymerization, graft blocks can be prepared in essentially any order.
• Another subject of the invention are the grafted polymers obtainable by according to A) and B) of the process descibed above
• polymeric radical initiator obtainable by step A) of the above process is schematically represented in formula (P1 )
• R 498 is hydrogen, substituted or unsubstituted CrC ⁇ 8 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alk ⁇ nyl; C 3 - C 20 cycloalkyl or C 3 -C 12 cycloalkyl containing at least one nitrogen or oxygen atom or C 3 - C 12 cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by N0 2 , halogen, ammo, hydroxy, cyano, carboxy, C,-C 4 alkoxy, C,-C 4 alkylth ⁇ o, CrC 4 alkylam ⁇ no or d ⁇ (d- C 4 alkyl)am ⁇ no, 0(d-C 18 alkyl), 0(C 2 -C 1B alkeny), C 7 -Cnphenylalkyl, O-phenyl, OC 7 -C 9 phenylalkyl or halogen or phenyl and naphth
• R 99 is the stable nitroxyl radical, bound at the oxygen atom
• R 500 is substituted or unsubstituted d-C 18 alkyl, C 2 -C 18 alkenyl, C 3 -C 20 cycloalkyl, phenyl, C 7 -
• R 50 ⁇ is hydrogen, substituted or unsubstituted d-C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkinyl, C 3 -
• R502, R503, R504, R5 05 , Rsoe, R507, Rsos, R509, R510, R511, R512 and R513 independently of each other are hydrogen, substituted or unsubstituted C ⁇ -C 18 alkyl, C 2 -C 18 aikenyl, C 2 -C 18 alkinyl, C 3 -
• n is a number from 1 to 10
• y is a number from 1 to 25000 and
• z is a number from 0 to 25000.
• R 50 ⁇ is H or methyl
• Q 5 is CRso ⁇ Rsos, wherein R 502 and R 503 is H, methyl or C 2 -C 9 alkenyl and R 504 , R505, Rsoe and R 507 are independently H or methyl.
• polyethylene polypropylene and polybutadiene, SBS and EPDM are especially preferred.
• a further subject of the invention is a polymer of formula (P2) obtainable by step B) of the above process.
• Q 6 is a homo-, co- or tapered polymer resulting from the monomers as described above, t is a number from 0 to 25000
• R 499 may be removed thermally or chemically.
• the polymer (P2) is grafted with a monomer selected from the groups described above and more preferably with styrenes, (meth)acrylates, butadiene, isoprene.
• SB-g-styrenes Most preferred are SB-g-styrenes, SB-gf-(meth)acryiates, Sl-g-styrenes, Sl-sr-(meth)acrylates, SBS- 7-styrenes, SBS-sf-(meth)acrylates, EPDM-g-styrenes, EPDM-gr-(meth)acrylates.
• a grafted polymer according to step A) of the above described process as macroinitiator for radical polymerization, and the use of the polymer obtained according to the process as adhesive or as compatibilizer for polymer blends or as polymer toughening agent
• the granulated polymer is dissolved, reprecipitated and high temperature NMR spectra are taken to determine whether polymer bound NO-moieties are present

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