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Title:
GRAFTING OF ETHYLENICALLY UNSATURATED MONOMERS ONTO POLYMERS
Document Type and Number:
WIPO Patent Application WO/2000/014135
Kind Code:
A1
Abstract:
The present invention relates to a process for the preparation of a grafted polymer wherein in a first step A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a nitroxyl-ether containing a group (=NO-X), wherein 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 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 he polymer radical; maintaining said temperature for further polymerization and afterwards cooling down the mixture to a temperature below 60 °C. Further subjects are grafted thermoplastic 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 thermoplastic polymers.

Inventors:
ROTH MICHAEL (DE)
PFAENDNER RUDOLF (DE)
NESVADBA PETER (CH)
Application Number:
PCT/EP1999/006172
Publication Date:
March 16, 2000
Filing Date:
August 23, 1999
Export Citation:
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Assignee:
CIBA SC HOLDING AG (CH)
ROTH MICHAEL (DE)
PFAENDNER RUDOLF (DE)
NESVADBA PETER (CH)
International Classes:
C08F2/38; C08F4/00; C08F4/32; C08F255/00; C08F255/04; C08F4/04; C08F255/06; C08F257/02; C08F279/02; C08F285/00; C08F287/00; C08F291/00; C08F293/00; C09J151/00; (IPC1-7): C08F291/00; C08F293/00; C08F4/00; C08F2/38
Domestic Patent References:
WO1999025749A11999-05-27
WO1997036944A11997-10-09
WO1994011412A11994-05-26
Foreign References:
US4581429A1986-04-08
EP0837080A11998-04-22
US5723511A1998-03-03
US5627248A1997-05-06
Other References:
MALSTROEM E E ET AL: "MACROMOLECULAR ENGINEERING VIA "LIVING" FREE RADICAL POLYMERIZATION", MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 199, no. 6, June 1998 (1998-06-01), pages 923 - 935, XP000776016
Attorney, Agent or Firm:
CIBA SPECIALTY CHEMICALS HOLDING INC. (Patentabteilung Klybeckstrasse 141 Basel, CH)
CIBA SPECIALTY CHEMICALS HOLDING INC. (Patentabteilung Klybeckstrasse 141 Basel, CH)
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Claims:
Table 1 Grafting of N-OR to polvpropylene Example Additives Polymer bound (230/2.16) NO [%] A11.0 % compound 1 0.26 2.03 A2 1.5 % compound 1 0.37 2.14 A3 1.0 % compound 1 + 0.2 % 0.37 2.89 | peroxide 1 compound 1:
1. allyloxy. 4. propoxy. 2,2,6,6. tetramethylpiperidine peroxide 1: 2,5. dimethyl. 2,5. di (tert. butylperoxy) hexane on chalk (45 %) *MFR according to ISO 1133 B) Graftinq of N. OR to the polymer and subsequent polymer analoqous reaction Commercially available SBS (styrene/butadiene/styrene copolymer, Kraton D 1102 CU, supplier: Shell) is extruded together with the compound given in Table 2 in a twin screw extruder (TW 100 of Haake, Germany) at 180. 210° C (heating zones 1. 5) and 40 rpm. In an evacuated Schlenk reactor, purged with argon, 5 g of the granulated polymer is dissolve in 50. 100 mL monomer under argon atmosphere. Dissolve oxygen is removed in freeze. thaw. cycles (liquid nitrogen). The reaction mixture is stirred and heated under argon atmosphere. Remaining monomer is removed under vacuum and the residue is dried under vacuum until constant weight is achieved. Molecular weights and molecular weight distributions are determined by gel permeation chromatograpgy (GPC). The results are shown in Table 3. Table 2 Graftinq of N. OR to the po ! ymer Example Polymer type Additives Molecular weight (Mp*, GPC) Comparison 1 SBS not processed 105.500 Starting material for SBS 0.25 % compound 2 106.700 inventive example 1 + 2 compound 2: benzoic acid 1. cyclohexyloxy. 2,2,6,6. tetramethyl. piperidin. 4. yl ester *bimodal distribution; peak molecular weight (Mp) from high MW peak Table 3 Polvmeranaloqous reactions Example Polymer type MonomerRection) Molecular conditions weight (Mp*, GPC) Comparison 2 SBS styrene 1 h, 130° C 102.700 Inventive example 1 SBS styrene 1 h, 130° C 112.200** Inventive example 2 SBS styrene 4h, 130°C 267.400** *bimodal distribution ; peak molecular weight (Mp) from high MWpeak **tailing in high MW area Claims 1. A process for the preparation of a grafted polymer wherein in a first step A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a nitroxyl. ether containing a group (=NO. X), wherein 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 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.
2. A process according to claim 1, wherein a free radical source is additionally present.
3. A process according to claim 2, wherein the free radical source is a bis. azo compound, a peroxide or a hydroperoxide.
4. A process according to claim 3 wherein the free radical source is 2,2'. azobisisobutyronitrile, 2,2'. azobis (2. methyl. butyronitrile), 2,2'. azobis (2,4. dimethylvaleronitrile), 2,2'. azobis (4. methoxy. 2,4. dimethylvaleronitrile), 1,1'. azobis (1. cyclohexanecarbonitrile), 2,2'. azobis (isobutyramide) dihydrate, 2. phenylazo. 2,4. dimethyl. 4. methoxyvaleronitrile, dimethyl. 2,2'. azobisisobutyrate, 2. (carbamoylazo) isobutyronitrile, 2,2'. azobis (2,4,4. trimethylpentane), 2,2'. azobis (2. methylpropane), 2,2'. azobis (N, N'. dimethyleneisobutyramidine), free base or hydrochloride, 2,2'. azobis (2. amidinopropane), free base or hydrochloride, 2,2'. azobis {2. methyl. N. [1,1. bis (hydroxymethyl) ethyl propionamide} or 2,2'. azobis (2. methyl. N. 1,1. bis (hydroxymethyl). 2. hydroxyethyl propionamide; acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t. amyl perneodecanoate, t. butyl perneodecanoate, t. butyl perpivalate, t. amylperpivalate, bis (2,4. dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis (2. methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, t. butyl per 2. ethylhexanoate, bis. (4. chlorobenzoyi). peroxide, t. butyl perisobutyrate, t. butyl permaleinate, 1,1. bis (t. butylperoxy) 3,5,5. trimethylcyclohexane, 1,1. bis (t. butylperoxy) cyclohexane, t. butyl peroxy isopropyl carbonate, t. butyl perisononaoate, 2,5. dimethylhexane 2,5. dibenzoate, t. butyl peracetate, t. amyl perbenzoate, t. butyl perbenzoate, 2,2. bis (t. butylperoxy) butane, 2,2 bis (t. butylperoxy) propane, dicumyl peroxide, 2,5. dimethylhexane. 2, 5. di. t. butylperoxide, 3. t. butylperoxy 3. phenylphthalide, di. t. amyl peroxide, a, a'. bis (t. butylperoxy isopropyl) benzene, 3,5. bis (t. butylperoxy) 3,5. dimethyl 1,2. dioxolane, di. t. butyl peroxide, 2, 5. dimethylhexyne. 2,5. di. t. butylperoxide, 3,6,6,9,9. hexamethyl 1,2,4,5. tetraoxa cyclononane, p. menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono. a. hydroperoxide, cumene hydroperoxide or t. butyl hydroperoxide.
5. A process according to claim 1 wherein the polymer is polyethylene, polypropylene, polystyrene, styrene block. copolymers, polybutadiene or polyisoprene, EPDM (ethylene. propylene diene monomer) or EPR (ethylene. propylene rubber).
6. A process according to claim 1, wherein the nitroxyl. ether is of formula (X) wherein n, is 0 or 1 R101, R102, R103 are each independently of one another hydrogen, halogen, N02, cyano, . CONR105R106, . (R109)COOR104,. C(O). R107, . OR108,. SR108, . NHR108, . N(R108)2, carbamoyl, di (C1. C, ealkyl) carbamoyl,. C (=NR, os) (NHR106); unsubstituted C,. C, Baikyl, Cz. C, 8alkenyl, C2. C, 8alkynyl, C7. Cgphenylalkyl, C3. C2cycloalkyl or C3. C12cycloalkyl containing at least one nitrogen or oxygen atom; or C,. C, eatkyl, Cz. C, 8alkenyl, C2. C, 8 alkynyl, C7. Cgphenylalkyl, C3. C, 2cycloalkyl or C3. C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, amino, hydroxy, cyano, carboxy, C,. C4alkoxy, C,. C4alkylthio, C,. C4alkylamino or di (C1. C4alkyl) amino; or phenyl, which is unsubstituted or substituted by C,. C4alkyl, C,. C4alkoxy, C,. C4alkylthio, halogen, cyano, hydroxy, carboxy, C,. C4alkylamino or di (C,. C4alkyl) amino; or R102 and R, o3, together with the linking carbon atom, form a C3. C, 2 cycloalkyl radical, a (C4. C12 cycloalkanon). yl radical or a C3. C, 2cycloalkyl radical containing at least one O atom and/or a Nu108 group; or if n, is 1 Roi are a group i ; R0o3 R104 is hydrogen, Ct. C, 8alkyl, phenyl, an alkali metal cation or a tetraalkylammonium cation; Pics and R106 hydrogen, C,. C, ealkyl, Cz. C, aalkyl which is substituted by at least one hydroxy group or, taken together, form a C2. C, 2alkylene bridge or a C2. C12. alkylene interrupted by at least one O or/and NR, o8 atom; Rio ? ! s hydrogen, C,. C, 8alkyl or phenyl; R, 08 is hydrogen, C,. C, 8alkyl or C2. C, 8alkyl which is substituted by at least one hydroxy group; Riog is C,. C12alkylen or a direct bond; R110 is C4. C18alkyl bound via a tertiary C. atom to the nitrogen atom, Cg. C"phenylalkyl, C3. C12cycloalkyl or C3. C12cycloalkyl containing least one nitrogen or oxygen atom; or C4. C18alkyl bound via a tertiary C. atom to the nitrogen atom, Cg. C"phenytalkyl, C3. C, 2cycloalkyl or C3. Cl2CYCloalkyl containing at least one nitrogen or oxygen atom, which are substituted by N02, halogen, amino, hydroxy, cyano, carboxy, C,. C4alkoxy, C,. C4alkylthio, C,. C4alkylamino or di (C,. C4alkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by C,. C4alkyl, C,. C4alkoxy, C,. C4alkylthio, halogen, cyano, hydroxy, carboxy, Cl. C4alkylamino or di (C,. C4alkyl) amino; if n, is 1 Rm is C,. C, Balkyl, C7. Cgphenylalkyl, C3. C, 2cycloalkyl or C3. C, 2cycloalkyl containing at least one nitrogen or oxygen atom; or C,. C, salkyl, C7. Cgphenylalkyl, C3. C, 2cycioalkyl or C3. C, 2cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C,. C4alkoxy, C,. C4alkylthio, C,. C4alkylamino or di (C,. C4alkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by Cl. C4alkyl, C,. C4alkoxy, C,. C4alkylthio, halogen, cyano, hydroxy, carboxy, C,. C4alkylamino or di (C,. C4alkyl) amino; or a polycyclic cycloaliphatic ring system or a polycyclic cycloaliphatic ring system with at least one di. or trivalent nitrogen atom; or R110 and R111 together form a C2. C, 2alkylene bridge, a C3. C, 2 alkylen. on bridge or a C2. C, 2alkylene bridge which is interrupted by at least one O or N atom, which bridges are unsubstituted or substituted with C,. C, 8alkyl, hydroxy (Cl. C4) alkyl, phenyl, C7. Cgphenylalkyl, NO2, halogen, amino, hydroxy, cyano, carboxy, C,. C4alkoxy, C1. C4alkylthio, C1. C4alkylamino or di (C,. C4alkyl) amino, R"2 is hydrogen,. (R109)COOR104, cyano, . OR108, . SR108, . NHR108, . N(R108)2, . NH. C(O). R108, unsubstituted C1. C18alkyl, C2. C18alkenyl, C2. C18alkynyl, C7. C9phenylalkyl, C3. C12cycloalkyl orC3. C, 2cycloalkyl containing at least one nitrogen or oxygen atom; or C,. C,8alkyl, C2. C, aalkenyl, C2. C, 8 alkynyl, C7. Cgphenylalkyl, C3. C, 2cycloalkyl or C3. Cr2cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, amino, hydroxy, cyano, carboxy, C,. C4alkoxy, C,. C4alkylthio, C,. C4alkylamino or di (C,. C4alkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by Cl. C4alkyl, Cl. C4alkoxy, C,. C4alkylthio, halogen, cyano, hydroxy, carboxy, Cl. C4alkylamino, di (C,. C4alkyl) amino; or R", and R, 12 together with the linking atom form a C3. C, 2cycloalkyl radical.
7. A process according to claim 1, wherein the nitroxyl. ether of formula XXa, XXb or XXc wherein Y, is O or CH2 ; Q is O or NR220, wherein R220 is hydrogen or Ci. Caikyi; R201 is tertiary C4. C, 8alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C (O). R222 wherein R221 is a alkali metal atom or C,. C, 8alkyl and R222 is C,. C, 8alkyl; or R20, is C5. C12cycloalkyl, C5. C12cycloalkyl 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; R202 and R203 are independently C,. C, ealkyi, benzyl, Cs. C, 2cycioalkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 C (O). R222 or together with the carbon atom form a Cs. C, 2cycloalkyl ring; if Y1 is O, R2o4 and R2, 2 are OH, O (alkali. metal) C1. C18alkoxy, benzyloxy, NR223R224, wherein and R224 are independently from each other hydrogen, C,. C, 8alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 C (O). R222; if Y, is CH2, R2o4 is OH, C,. C, 8alkoxy, benzyloxy, O. C (O). (C,. C, ) alkyl or NR223R224; R2, 2 are a group C (O) R225, wherein R225 is OH, C1. C18alkoxy, benzyloxy, wherein R223 and R224 are independently from each other hydrogen, C1. C18alkyl orphenyl, which are unsubstituted or substituted by halogen, OH, COOR221 C (O). R222; R205, R206, R207 and R208 are independently of each other C1. C18alkyl, C5. C12cycloalykyl or phenyl; or R2o5 and R206 and/or R207 and R208 together with the carbon atom form a C5. C, 2cycloalkyl ring; R2o9 and R2, are independently of each other hydrogen, formyl, C2. C, 8alkylcarbonyl, benzoyl, C,. C, 8alkyl, Cs. C, 2cycloalkyl, Cs. C, 2cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR22, or C (O). R222; R2", is formyl, C2. C18alkylcarbonyl, benzoyl, C1. C18alkyl, C5. C12cycloalkyl C5. C12cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR221 C (O). R222.
8. A process according to claim 1, wherein the nitroxyl. ether contains a structural element of formula (XXX) wherein Gi, G2, G3, G4 are independently C,. C6alkyl or G, and G2 or G3 and G4, or G, and G2 and G3 and G4 together form a C5. C, 2cycloaikyl group; Gs, G6 independently are H, C,. C, 8alkyl, phenyl, naphthyl or a group COOC,. C, ealkyl.
9. A process according to claim 8, wherein the the structural element of formula (XXX) is any of formulae A to S wherein Gi, G2, G3 and G4 are independently alkyl of 1 to 4 carbon atoms, or G, and G2 together and G3 and G4 together, or G, and G2 together or G3 and G4 together are pentamethylene; Gs and G6 are independently hydrogen or C,. C4 alkyl; R, if m is 1, is hydrogen, C,. C, 8alkyl 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 a, p. 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, 2 groups, in which Z12 is H, C,. C2oalkyl, C3. C12alkenyl, C5. C7CYCloalkyl, phenyl or benzyl; or R is a monovalent radical of a carbamic acid or phosphorus. containing acid or a monovalent silyl radical; R, if m is 2, is C2. C, 2alkylene, C4. C, 2alkenylene, 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 8. 14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two. COOZ, 2 groups; or R is a divalent radical of a phosphorus. containing acid or a divalent silyl radical; R, if m is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by . COOZ, 2, of an aromatic tricarbamic acid or of a phosphorus. containing acid, or is a trivalent silyl radical, 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, 2alkyl, C5. C, cycloalkyl, C7. C8aralkyl, C2. C, ealkanoyl, C3. Csalkenoyl or benzoyl; when p is 1, R2 is C,. C, 8alkyl, C5. C7cycloalkyl, C2. C8alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula. CH2CH (OH). Z or of the formula. CO. Z. or. CONH. Z wherein Z is hydrogen, methyl or phenyl; or when p is 2, R2 is C2. C, 2alkylene, C6. C, 2. arylene, xylylene, a. CH2CH (OH) CH2. O. B. O. CH2CH (OH) CH2. group, wherein B is Cz. C, oalkylene, C6. ClSarylene or C6. C, 2cycloalkylene; or, provided that R, is not alkanoyl, alkenoyl or benzol, R2 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 R2 together when p is 1 can be the cyclic acyl radical of an aliphatic or aromatic 1,2. or 1,3. dicarboxylic acid; or R2 is a group where T7 and T8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T7 and T8 together are alkylene of 4 to 6 carbon atoms or 3. oxapentamethylene; when p is 3, R2 is 2,4,6. triazinyl; when n is 1, R3 is Cz. Cgaikytene or hydroxyalkylene orC4. C22acyloxyalkylene; or when n is 2, R3 is (. CH2) 2C (CH2. ) 2; when n is 1, R4 is hydrogen, C,. C, 2alkyl, C3. C5alkenyl, C7. Cgaralkyl, C5. C7cycloalkyl, C2. C4hydroxyalkyl, C2. C6. alkoxyalkyl, C6. C, o. aryl, glycidyl, a group of formula. (CH2) m. COO. Q or of the formula. (CH2) m. O. CO. Q wherein m is 1 or 2 and Q is C,. C4. alkyl or phenyl; or when n is 2, R4 is C2. C12alkylene, C6. C12. arylene, group. CH2CH (OH) CH2. O. D. O. CH2CH (OH) CH2. wherein D is C2. C, oalkylene, C6. C, 5arylene or C6. C, 2cycloalkylene, or a group. CH2CH (OZ1) CH2. (OCH2CH (OZ,) CH2) 2. wherein Z, is hydrogen, C1. C18alkyl allyl, benzyl, C2. C, 2alkanoyl or benzoyl; R5 is hydrogen, C,. C, 2alkyl, allyl, benzyl, glycidyl or C2. C6alkoxyalkyl; Q, is. N (R7). or. 0. ; E is C1. C3alkylene, the group. CH2CH (R8). O. wherein R8 is hydrogen, methyl or phenyl, the group. (CH2) 3. NH. or a direct bond; R7 is C,. C, 8alkyl, C5. C7. ycloalkyl, C7. C12aralkyl, cyanoethyl, C6. C10aryl, group. CH2CH (R8). OH; or a group of the formula or a group of the formula wherein G is C2. C6alkylene or C6. C, 2arylene and R is as defined above; or R7 is a group. E. CO. NH. CH2. OR6; R6 is hydrogen or C,. C, 8alkyl ; 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 a. olefin copolymer with an alkyl acrylate or methacrylate; k is 2 to 100; and Rio is hydrogen, C,. C, 2alkyl or C,. C, 2alkoxy; T2 has the same meaning as R4; T3 and T4 are independently alkylene of 2 to 12 carbon atoms, or T4 is a group T5 is C2. C22alkylene, C5. C7cycloaikylene, C,. C4alkylenedi (C5. C, cycloalkylene), phenylene or phenylenedi (C,. C4alkylene); <BR> <BR> <BR> <BR> <BR> <BR> Tris<BR> . NH (CH2) a. N (CH2) b. N (CH2) c. N. dH where a, b and c are independently 2 or 3, and d is 0 or 1; e is 3 or 4; E, and E2, being different, are each oxo or imino; E3 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; E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms; or E3 and E4 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; and E6 is an aliphatic or aromatic or aromatic tetravalent radical.
10. A process according to claim 8, wherein Gi, Gs, 63 and G4 are methyl and G5 and G6 are hydrogen.
11. A process according to claim 1, wherein X is selected from the group consisting of C,. C,8alkyl, C. <. C, 8alkenyl, C3. C, 8alkinyl, phenyl, phenyl (C7. C") alkyl, phenyl or phenyl (C7. C") alkyl substituted by C,. C, 2alkyl, C,. C, 2alkoxy, OH, amino, C1. C12alkylamino, C1. C12dialkylamino, NO2 or halogen, C2. C7cycloalkyl, or a group wherein R20, R21, and R22 are hydrogen or C,. C, 2alkyl, C2. C, 2alkenyl, phenyl or C3. C7cycloalkyl.
12. A process according to claim 11, wherein X is selected from the group consisting of C,. C, 8alkyl, benzyl, allyl, cyclopentyl or cyclohexyl.
13. A process according to claim 9, wherein the nitroxyl. ether is of the structural formulae A, B, O or P, wherein m is 1, R is hydrogen, C,. C,! ky ! 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 a, P. unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; p is 1; R, is C,. C, zalkyl, C5. C, cycloalkyl, C7. C8aralkyl, C2. C, ealkanoyl, C3. Csaikenoyl or benzoyl; R2 is C1. C18alkyl, C5. C7cycloalkyl, C2. C8alkenyl or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula. CH2CH (OH). Z or of the formula. CO. Z or. CONH. Z wherein Z is hydrogen, methyl or phenyl.
14. A process according to claim 13, wherein the nitroxyl. ether is of the structural formula A or B, wherein R is hydrogen, C,. C, 8alkyl, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid, having 2 to 18 carbon atoms; R, is C,. C, 2alkyl, C7. C8aralkyl, Cz. C, Balkanoyl, C3. C5alkenoyl or benzoyl; R2 is C,. C, 8alkyl, glycidyl, a group of the formula. CH2CH (OH). Z or of the formula. CO. Z, wherein Z is hydrogen, methyl or phenyl.
15. A process according to claim 6, wherein the nitroxyl. ether is a compound of formula (X), n, is 1 Rio, is cyano; R, 02 and R, o3 are each independently of one another unsubstituted C,. C, 2alkyl or phenyl; or Pics and Rions, together with the linking atom, form a C5. C7cycloalkyl radical; R110 is C4. C, 2alkyl bound via a tertiary C. atom to the nitrogen atom, Cg. C"phenylalkyl or phenyl; or Rue and R", together form a C2. C6alkylene bridge which is unsubstituted or substituted with C,. C4alkyl; and R"2 is C,. C4aikyl.
16. A process according to claim 6, wherein the nitroxyl. ether is a compound of formula (XXa), Y is O; R201 is tertiary C4. C8alkyl; R202 and R203 are methyl, ethyl or together with the carbon atom form a C5. C6cycloalkyl ring; R204 is C,. C, 8alkoxy, benzyloxy or NR223R224, wherein R223 and R224 are independently of each other hydrogen or C,. C8alkyl; or of formula (XXb), wherein Q, is O; R205, R206, R207 and R208 are independently of each other methyl or ethyl; or R205 and R206 and/or R207 and R208 together with the carbon atom form a Cg. Cecyctoaikyt ring; R209 and R2, o are independently of each other formyl, C2. CBalkylcarbonyl, benzoyl, C,. C8aikyl, benzyl or phenyl; or of formula (XXc), wherein Y, is O; R205, R206, R207 and R208 are independently of each other methyl or ethyl; or R205 and R206 and/or R207 and R208 together with the carbon atom form a Cg. Cecyctoaikyt ring; RZ"is formyl, C2. C, ealkylcarbonyl, benzoyl, C,. C, 8alkyl, benzyl or phenyl and R2, 2 is OH, C,. C, 8alkoxy, benzyloxy, NR223R224, wherein R223 and R224 are independently of each other hydrogen or C1. C18alkyl.
17. A process according to claim 1, wherein the polymer be grafted on contains unsaturated moieties selected from the group consisting of polydienes, co. ,block. , random. and tapered polymers of styrene, terpolymers with diolefins and copolymers with diolefins.
18. A process according to claim 1, wherein the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl) acrylic acidanhydrides, (alkyl) acrylic acid salts, (alkyl) acrylic esters or (alkyl) acrylamides.
19. A process according to claim 18, whrein the ethylenically monomer is styrene, α. methyl styrene, p. methyl or a compound of formula CH2=C (Ra). (C=Z). Rb, wherein Ra is hydrogen or C,. C4alkyl, Rb is NH2, OCH3, glycidyl, unsubstituted C,. C, 8alkoxy or hydroxy. substituted C,. C, 8alkoxy, unsubstituted C,. C,! ky ! amino, di (C,. C18alkyl)amino, hydroxy. substituted C,. C, 8aikylamino or hydroxy. substituted di (C,. C18alkyl)amino ; Me is a monovalent metal atom Z is oxygen or sulfur.
20. A process according to claim 1, wherein the temperature in the first step A) is from 150° C to 300° C.
21. A process according to claim 1, wherein the temperature in the second step B) is from 70° to 280° C.
22. A process according to claim 1, wherein the compound containing a structural element of formula (I) is present in an amount of from 0.1% to 30% based on the weight of the polymer.
23. A process according to claim 1, wherein 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.
24. A process according to claim 1, wherein the first step A) is performed in an extruder.
25. A polymeric radical initiator obtainable according to step A) of claim 1 or claim 2.
26. A polymer obtainable according to steps A) and B) of the process of claim 1 or claim 2.
27. A polymeric radical initiator of formula (P1) wherein R498 is hydrogen, substituted or unsubstituted C,. C, $alkyl, C2. C, ealkenyl, C2. C, 8alkinyl; C3. C20cycloalkyl or C3. C, 2cycloalkyl containing at least one nitrogen or oxygen atom or C3. C, 2cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy; C,. C4alkoxy, C,. C4alkylthio, C,. C4alkylamino or di (C,. C4alkyl) amino, O (C,. C, ealkyl), O (C2. C, 8alkeny), C7. C"phenylalkyl, O. phenyl, OC7. Cgphenylalkyl or halogen or phenyl and naphthyl which are unsubstituted or substituted by C,. C4alkyl, C,. C4alkoxy, C,. C4alkylthio, halogen, cyano, hydroxy, carboxy, C,. C4alkylamino or di (C,. C4alkyl) amino; R499 is the stable nitroxyl radical, bound at the oxygen atom; Rsoo is substituted or unsubstituted C,. C, 8alkyl, C2. C, 8alkenyl, C3. C2ocycloalkyl, phenyl, C7. C"phenylalkyl; Rso, is hydrogen, substituted or unsubstituted C,. C18alkyl, C2. C, ealkenyl, C2. C8alkinyl, C3. C20cycloalkyl, phenyl, O(C1. C18alkyl), O(C2. C18alkeny), C7. C11phenylalkyl, O. phenyl, O. C7. Cgphenylalkyl or halogen, CN, COOR500, CONRsooRsoo ; Q5 is CR5o2Rso3, CH=CH2, (CR502R503) n, CRSo4=CR505. CRso6Rso79 (CRso4=CRsos. CRso6R5o7) n, C#CR508R509, (C=CR5o8R509) n, O, C=O, NR510, NR511. C=O, O. C(O). O, SO2 S, SiR512R513, O. SiR512R513. O; R502, R503, R504, Rsos, Rso6 Rsov, Rso8 Rsog, R510, R511, R512 andR5, 3 independently of each other are hydrogen, substituted or unsubstituted C,. C, 8alkyl, Cz. C, aalkenyl, C2. C, aalkinyl, C3. C7cycloalkyl, phenyl, O(C1. C18alkyl), O(C2. C18alkeny), C7. C11phenylalkyl, O. phenyl, O. C7. Cgphenylalkyl or halogen; 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.
28. A polymer of formula (P2) wherein Q6 is a homo. , co. or tapered polymer resulting from the monomers as defined in claims 18 and 19, t is a number from 0 to 25000 and the other substituents are as defined in claim 27.
29. Use of a nitroxyl. ether containing a group (=NO. X), wherein X is selected such, that cleavage of the O. X bond occurs and a radical Xe is formed at about the melting temperature of the polymer for the preparation of a grafted polymer with and without a free radical source.
30. Use of a grafted polymer according to step A) of claim 1 or claim 2 as macroinitiator for radicalpolymerization.
31. Use of the polymer obtained according to the process of claim1 or claim 2 as adhesive or as compatibilizer for polymer blends or as polymer toughening agent.
Description:
Grafting of Ethvlenicaliv Unsaturated Monomers onto Polymers 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.

Increasing activities have been directed towards chemical modifications of existing polymers in order to obtain functional and/or engineered new materials. Chemical modifications of existing polymers are important for at least two reasons: 1. They can be an inexpensive and rapid way of obtaining new polymers without having to search for new monomers; 2. they may be the only way to synthesize polymers with the intended new characteristics.

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.

The advantages of free radical-grafting are further gained with the use of batch mixers or screw extruders as chemical reactors, which allow the free radical-grafting reaction to occur without solvents. This is for example described 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.

These 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. However the use of 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. Typically 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 oligomeric homopolymers and copolymers, including block and graft copolymers. The process employs an initiator having the formula (in part) R'R"N-O-X, where X is a free radical species capable of polymerizing unsaturated monomers.

Surprisingly it has now been found that with specific R'R"N-O-X compounds it is possible to produce a polymeric radical initiator by grafting the group R'R"N-O to the polymer and to use this macroinitiator for further grafting reactions of olefinically 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 A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a nitroxyl-ether containing a group (=NO-X), wherein X is selected such, that cleavage of the O-X bond occurs and a radical Xe is formed at about the melting temperature of the polymer; 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 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.

The reaction mixture after step A) may also be cooled down to a temperature below 60° C before further reaction of step B) is performed.

Optionally a free radical source is additionally present.

The reaction mixture after step A) may also be cooled down to a temperature below 60° C before further reaction of step B) is performed.

Preferably the free radical source is a bis-azo compound, a peroxide or a hydroperoxide.

Specific preferred radical sources are 2,2'-azobisisobutyronitrile, 2, 2'-azobis (2-methyl- butyronitrile), 2, 2'-azobis (2, 4-dimethylvaleronitrile), 2. 2'-azobis (4-methoxy-2, 4-dimethylvalero- nitrile), 1,1'-azobis (l-cyclohexanecarbonitrile), 2, 2'-azobis (isobutyramide) dihydrate, 2- phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2, 2'-azobisisobutyrate, 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2, 2'-azobis (2- methylpropane), 2,2'-azobis (N, N'-dimethyleneisobutyramidine), free base or hydrochloride, 2,2'- azobis (2-amidinopropane), free base or hydrochloride, 2S2s-azobis {2-methyl-N-1l1 bis (hydroxymethyl) ethyl propionamide} or 2, 2'-azobis (2-methyl-N- 1,1-bis (hydroxymethyl)-2- hydroxyethyljpropionamide; acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, bis (2,4- dichlorobenzoyi) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate, bis- (4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butyl permaleinate, 1,1-bis (t-butylperoxy) 3,5, 5-trimethylcyclohexane, 1-bis (t- butylperoxy) cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl perisononaoate, 2,5- dimethylhexane 2,5-dibenzoate, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2 bis (t-butylperoxy) propane, dicumyl peroxide, 2,5- dimethylhexane-2, 5-di-t-butylperoxide, 3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, a, a'-bis (t-butylperoxy isopropyl) benzene, 3,5-bis (t-butylperoxy) 3,5-dimethyl 1,2-dioxolane, di-t- butyl peroxide, 2, 5-dimethylhexyne-2, 5-di-t-butylperoxide, 3,3,6,6, 9,9-hexamethyl 1, 2,4, 5- tetraoxa cyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-a-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

Peroxides are most preferred.

Examples of suitable polymers are mentioned below.

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut- 1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), 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), 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) radical polymerisation (normally under high pressure and at elevated temperature). b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or Vlil of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyis and/or aryis 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, titanium (III) 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, Ila and/or Illa 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).

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. 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 copo- lymers, 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 (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example Cs-Cg) including hydrogenated modifications thereof (e. g. tackifiers) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly (p-methylstyrene), poly (a-methylstyrene).

6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyi acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acryloni- trile/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, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl meth- acrylate 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 acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin 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 chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from a, p-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsatu- rated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acry- lonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcools and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers. polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines 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 11, 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 ela- stomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m- phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e. g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

17. Potyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.

18. 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-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Blends of the aforementioned polymers (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, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

Preferred polymers are polyethylene, polypropylene, polystyrene, styrene block-copolymers, polybutadiene or polyisoprene, EPDM (ethylene-propylene diene monomer) or EPR (ethylene- propylene rubber).

More preferred are polyethylene, polypropylene, polybutadiene, SBS and EPDM (ethylene- propylene diene monomer).

One preferred nitroxyl-ether is of formula (X) wherein n, is 0 or 1 R, 0"R, 02, R, 03 are each independently of one another hydrogen, halogen, N02, cyano, -CONR105R106, -(R109)COOR104, -C(O)-R107, -OR108, -SR108, -NHR108, -N (R108)2, carbamoyl, di (C,- C, ealkyl) carbamoyl,-C (=NR, os) (NHR,oe); unsubstituted C1-C18alkyl, C2-C18alkenyl, C2-C18alkynyl, C7-C9phenylalkyl, C3-C12cycloalkyl orC3- C, 2cycioalkyl containing at least one nitrogen or oxygen atom; or C1-C18alkyl,C2-C18alkenyl, C2-C18 alkynyl C7-C9phenylalkyl, C3-C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by N02, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl) ; or phenyl, which is unsubstituted or substituted by C,-C4alkyl, Ct-C4alkoxy, C1-C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino di (Ct-C4alkyl) amino; or R102 andRiva, together with the linking carbon atom, form a C3-C, 2 cycloalkyl radical, a (C4- C, 2 cycloalkanon)-yl radical or a C3-C : 2cycloalkyl radicai containing at least one O atom and/or a NR, 08 group; or if n, is 1 Rto1 l are agroup < R103 1 Rto4 is hydrogen, C1-C18alkyl, phenyl. analkali metal cation or a tetraalkylammonium cation; Rions and R, 06 are hydrogen, C1-C18alkyl, C2-C18alkyl is substituted by at least one hydroxy group or, taken together, form a C2-C, 2alkylene bridge or a C2-C, 2-alkylene bridge interrupted by at least one O or/and NR, 08 atom-.

Riz ? is hydrogen, C,-Ct8alkyl or phenyl; Rto8 is hydrogen, C1-C18alkyl or C2-C18alkyl which substituted by at least one hydroxy group; R109 is Ct-Ct2alkylen or a direct bond : Rno is C4-C, 8alkyl bound via a tertiary C-atom to the nitrogen atom, Cg-C"phenylalkyl, C3- C, 2cycloalkyl or C3-C, 2cycloalkyl containing at least one nitrogen or oxygen atom; or C4-C18alkyl bound via a tertiary C-atom to the nitrogen atom, Cg-C"phenylalkyl, C3-C, 2cycloalkyl or C3-C, 2cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C,-C4alkoxy, C,-C4alkylthio, C,-C4alkylamino or di (C,-Caalkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by C,-C4alkyl, C,-C4alkoxy, C,- C4alkylthio, halogen, cyano, hydroxy, carboxy, C,-C4alkylamino or di (C,-C4alkyl) amino; if n, is 1 R", is C,-C, kyl, C7-CAphenylalkyl, C3-C, 2cycloalkyl or C3-C, 2cycloalkyl containing at least one nitrogen or oxygen atom; or C,-C18alkyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C3-C12cycloalkyl containing least one nitrogen or oxygen atom, which are substituted by N02, halogen, amino, hydroxy, cyano, carboxy, C,-C4alkoxy, C,-C4alkylthio, C,-C4aikylamino or di (C,-C4alkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by C,-C4alkyl, C,-C4alkoxy, C,- C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino di (C,-C4alkyl) amino; or a polycyclic cycloaliphatic ring system or a polycyclic cycloaliphatic ring system with at least one di-or trivalent nitrogen atom; or Rucand Rm together form a C2-C, 2alkylene bridge, a C3-C, 2 alkylen-on bridge or a C2- C12alkylene bridge which is interrupted by at least one O or N atom, which bridges are unsubstituted or substituted with C,-C18alkyl, hydroxy(C,-C4) alkyl, phenyl, C7-Cgphenylalkyl, NOz, halogen, amino, hydroxy, cyano, carboxy, C,-C4alkoxy, C,-C4alkylthio, C,-C4alkylamino or di (C1-C4alkyl)amino, R, 12 is hydrogen, -(R109)COOR104, cyano, -OR108, -SR108, -NHR108, -N(R108)2, -NH-C(O)-R108, unsubstituted C,-C, 8alkyl, C2-C, 8alkenyl, C2-C, 8alkynyl, C7-Cgphenylalkyl, C3-C12cycloalkyl or C3- C, 2cycloalkyl containing at least one nitrogen or oxygen atom; or C,-C18alkyl, C2-C18alkenyl, C2-C18 alkynyl, C7-C9phenylalkyl, C3-C12cycloalkyl orC3-Ca2cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NOs, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino di (C,-C4alkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by C :-C4alkyl, C,-C4alkoxy, C,- C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino, di(C1-C4alkyl)amino or R", and Rnz together with the linking carbon atom form a C3-C : 2cycloalkyl radical.

Another preferred nitroxyl-ether of formula XXa, XXb or XXc wherein Y, is O or CH2; Q is O or NR220, wherein R220 is hydrogen or Ct-C, 8alkyl ; R201 is tertiary C4-C, ealkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR22, or C (O)-R222 wherein R22t is hydrogen, a alkali metal atom or C1-C18alkyl andR222 is C,-C, 8alkyl; or Foi is C5-C12cycloalkyl, C5-C12cycloalkyl interrupted interrupted at at least one O or N atom, a polycyclic alkyl radical a polycyclic alkyi radical which is interrupted by at least one O or N atom; R202 and R203 are independently C,-C, 8alkyl, benzyl, C5-C12cycloalkyl orphenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222 or together with the carbon atom form a C5-C12cycloalkyl ; if Y, is O, R2o4 and R212 are OH, O (alkali-metal) C,-C, 8alkoxy, benzyloxy, NR223R224, wherein R223 and R224 are independently from each other hydrogen, C,-C18alkyl orphenyl, which are unsubstituted or substituted by halogen, OH, COOR221 C (O)-R222; if Y, is CH2, R204 is OH, C,-C, 8alkoxy, benzyloxy, O-C (O)-(C,-C, 8) alkyl or NR223R224; R212 are a group C (O) R225, whereinR225 is OH, C1-C18alkoxy benzyloxy, NR223R224, R223 and R224 are independently from each other hydrogen, C,-C, 8alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR22, or C (O)-R222; R205, R206, R207 and R208 are independently of each other C,-C18alkyl, C5-C12cycloalykyl or phenyl ; or R2o5 and R206 and/orR207 and R208 together with the carbon atom form a Cs-cl2cycloalkyl ring; R2o9 and R210 independently of each other hydrogen, formyl, C2-Ct8alkylcarbonyl, benzoyl, Ci-C18alkyl, C5-C12cycloalkyl, C5-C12cycloalkyl is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222; R2", is formyl, C2-C18alkylcarbonyl, benzoyl, C1-C18alkyl C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O or N atom, benzyl orphenyl which are unsubstituted or substituted by halogen, OH, COOR22i or C (O)-R222.

Still another preferred nitroxyl-ether contains a structural element of formula (XXX) wherein Gi, Gz, Gg, 64 are independently C,-C6alkyl or G, and G2 or G3 and G4, or G1 andG2 and G3 and G4 together form a Cs-C, 2cycloalkyl group; G5, G6 independently are H, C,-C, 8alkyl, phenyl, naphthyl or a group COOC,-C, 8alkyl.

More preferred is a nitroxyl-ether, wherein the structural element of formula (XXX) is any of formulae A to S wherein Gi, Gz, Gg and G4 are independently alkyl of 1 to 4 carbon atoms, or G, and G2 together and G3 and G4 together, or G, and G2 together or G3 and G4 together are pentamethylene; G5 and G6 are independently hydrogen or C,-C4 alkyl; R, if m is 1, is hydrogen, C,-C, gaikyi 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 a, p-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, cycioaliphatic or aromatic moiety by 1 to 3-COOZ, 2 groups, in which Z, 2 is H, C-C20alkyl, C3- C, 2alkenyl, Cs-C7cycloalkyl, phenyl or benzyl; or R is a monovalent radical of a carbamic acid or phosphorus-containing acid or a monovalent silylradical; R, if m is 2, is C2-C>2alkylene, C4-C, 2alkenylene, 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 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two-COOZt2 groups; or R is a divalent radical of a phosphorus-containing acid or a divalent silyl radical; R, if m is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by -COOZ, 2, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or is a trivalent silyl radical, R, if m is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; pis 1, 2 or 3, R, is C,-C, 2alkyl, C5-C, cycloalkyi, C7-Cearalkyl, Cz-C, ealkanoyl, C3-Csalkenoyl or benzoyl; when p is 1, R2 is C ;-C, 8alkyl, C5-C7cycloalkyl, C2-Cealkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula-CH2CH (OH)-Z or of the formula-CO-Z-or-CONH-Z wherein Z is hydrogen, methyl or phenyl; or when p is 2, R2 is C2-C, 2alkylene, C6-C, 2-arylene, xylylene, a-CH2CH (OH) CH2-O-B-O-CH2CH (OH) CH2- group, wherein B is C2-C, oalkylene, C6-C, Sarylene or C6-C, 2cycloalkylene; or, provided that R, is not alkanoyl, alkenoyl or benzoyl, R2 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 R2 together when p is 1 can be the cyclic acyl radical of an aliphatic or aromatic 1,2- or 1,3- dicarboxylic acid; or R2 is a group where T7 and T8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T7 and T8 together are alkylene of 4 to 6 carbon atoms or 3-oxapentamethylene; when p is 3, R2 is 2,4,6-triazinyl ; when n is 1.

R3 is C2-C8alkylene or hydroxyalkylene or C4-C22acyloxyalkylene; or when n is 2, R3 is (-CH2) 2C (CH2-) 2; when n is 1, R4 is hydrogen, C1-C12alkyl, C3-C5alkenyl, C7-C9aralkyl, C5-C7 cycloalkyl, C2-C4hydroxyalkyl, C2- C6-alkoxyalkyl, C6-C, o-aryl, glycidyl, a group of formula -(CH2)m-COO-Q of the formula- (CH2) m-O-CO-Q wherein m is 1 or 2 and Q is Ct-C4-alkyl or phenyl; or when n is 2, R4 is C2-C, 2alkylene, C6-C : 2-arylene, a group-CH2CH (OH) CH2-O-D-O-CH2CH (OH) CH2- wherein D is C2-C, oalkylene, C6-C, Sarylene or C6-C, 2cycloalkylene, or a group- CH2CH (OZ1)CH2-(OCH2CH(OZ1)CH2)2- wherein Z1 hydrogen, C,-C, ealkyl, allyi, benzyl, C2- C, 2alkanoyl or benzoyl; Rs is hydrogen, C,-C, 2alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl; Q, is-N (R7)- or-0- ; E is C,-C3alkylene, the group-CH2CH (R8)-O- wherein R8is hydrogen, methyl or phenyl, the group- (CH2) 3-NH- or a direct bond; R7 is C,-C, 8alkyl, C5-C7-ycloalkyl, C7-C, 2aralkyl, cyanoethyl, C6-C, oaryl, the group-CH2CH (R8)- OH; or a group of the formula or a group of the formula wherein G is C2-C6alkylene or Ce-Cizarytene and R is as defined above; or R7 is a group-E-CO-NH-CH2-OR6; R6 is hydrogen or Ci-Ciga 8alkyl; 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 a-olefin copolymer with an alkyl acrylate or methacrylate; k is 2 to 100; and Riz ils hydrogen, C,-Cl2alkyl or Ct-C>2alkoxy T2 has the same meaning as R4; T3 and T4 are independently alkylene of 2 to 12 carbon atoms, or T4 is a group T5 is C2-C22alkylene, Cs-C, cycloaikylene, C,-C4alkylenedi (C5-C, cycloalkylene), phenylene or phenylenedi (Ct-C4alkylene); <BR> <BR> <BR> <BR> <BR> T6 is<BR> -NH (CH2) a-N (CH2) b-N (CH2) c-N- cjH where a, b and c are independently 2 or 3, and d is 0 or 1; e is 3 or 4; E, and E2, being different, are each oxo or imino; E3 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; E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms; or E3 and E4 together are polymethylene of 4 to 17 carbon atoms, or said polymethylene substituted by up to four alkyl of 1 to 4 carbon atoms; and E6 is an aliphatic or aromatic or aromatic tetravalent radical.

Further suitable heterocyclic nitroxyl-ether are for example mentioned in WO 98/30601 or in WO 98/44008, which are incorporated by reference.

Alkyl with up to 20 carbon atoms is, for example, methyi, ethyl, n-propyl, n-butyl, sec-butyl, tert- butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. The alkyl groups may be linear or branched.

C3-C, 8alkyl which is interrupted by one or more oxygen atoms is preferably derived from ethylene oxide or propylene oxide.

C3-C18alkyl interrupted by at least one O atom is for example-CH2-CH2-O-CH2-CH3,-CH2-CH2- O-CH3 or-CH2-CH2-O-CH2-CH2-CH2-O-CH2-CH3. It is preferably derived from polyethlene glycol. A general description is- ((CH2) a-O) b-H/CH3, wherein a is a number from 1 to 6 and b is a number from 2 to 10.

C3-C, 2alkenyl is linear or branched and for example propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, dodecenyl including their isomers.

C3-C8alkynyl is preferably propargyl.

Cs-C, 2cycloalkyl 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-yi Examples for alkali metal are lithium, sodium or potassium.

Alkyl substituted by-OH is typically 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl.

C,-C, ealkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.

C,-C, 8Alkyl substituted by C-C8alkoxy, preferably by C,-C4alkoxy, in particular by methoxy or ethoxy, is typically 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3- butoxypropyl, 3-octoxypropyl and 4-methoxybutyl.

C,-C, BAIkyl substituted by di (C,-C4alkyl) amino is preferably e. g. dimethylamino, diethylamino, 2- dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3- dibutylaminopropyl and 4-diethylaminobutyl.

Ct-C, 8Alkyl substituted by C,-C4alkylamino is preferably e. g. methylamino, ethylamino, 2- methylaminoethyl, 2-ethylaminoethyl, 3-methylaminopropyl, 3-ethylaminopropyl, 3-butylamino- propyl and 4-ethylaminobutyl.

C,-C4AIkylthio is typically thiomethyl, thioethyl, thiopropyl, thioisopropyl, thiobutyl and thioisobutyl.

C2-C18 alkylcarbonyl is for example acetyl, propionyl, butyryl, pentylcarbonyl, hexylcarbonyl or dodecylcarbonyl.

C7-Cgphenylalkyl or C7-Cgaralkyl is for example benzyl, phenylethyl, phenylpropyl, a, a- dimethylbenzyl or a-methylbenzyl.

Examples of C2-C12alkylene bridges, preferably ofC2-C^alkylene bridges, are ethylene, propylene, butylene, pentylene, hexylene.

C2-C, 2alkylene bridges interrupted by at least one N or O atom are, for example, -CH2-0-CH2-CH2,-CH2-0-CH2-CH2-CH2,-CH2-0-CH2-CH2-CH2-CH2-, -CH2-O-CH2-CH2-O-CH2-,-CH2-NH-CH2-CH2,-CH2-NH-CH2-CH2-CH2, -CH2-NH-CH2-CH2-CH2-CH2-,-CH2-NH-CH2-CH2-NH-CH2-or-CH2-NH-CH 2-CH2-0-CH2-.

Examples for C4-C, 2cycloalkanone-yl are cyclopentanone-yl, cyclohexanone-yl or cycloheptanone-yl.

Phenyl substituted by 1,2 or 3 C,-C4alkyl or C,-C4alkoxy is typically methylphenyl, dimethyl- phenyl, trimethylphenyl, t-butylphenyl, di-t-butylphenyl, 3,5-di-t-butyl-4-methylphenyl, methoxyphenyl, ethoxyphenyl and butoxyphenyl.

Examples of polycyclic cycloaliphatic ring systems are adamantane, cubane, twistane, norbornane, bycyclo [2.2.2] octane or bycyclo [3.2.1] octane.

An example of a polycyclic heterocycloaliphatic ring system is hexamethylentetramine (urotropine).

Examples of 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 trifluor-acetic acid. Other 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, cyclohexylcarboxylic acid, benzoyl or P- (3, 5-di-tert-butyl-4-hydroxyphenyl)- propionyl radical.

Further examples are derived from propionic acid, laurinic acid or methyl ethyl acetic acid or the other isomers of valeric acid.

Examples of 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, methacrylic acid or crotonic acid.

Examples of a monovalent silyl radical are of the formula- (C, H2,)-Si (Z') 2Z", in which j is an integer in the range from 2 to 5, and Z'and Z", independently of one another, are C,-C4alkyl or C,-C4alkoxy.

Examples of di-, tri-and tetra valent acids are for example malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl (3,5-di- tert-butyl-4-hydroxybenzyl) malonyl or bicycloheptenedicarbonyl radical or a group of the formula , trimellitoyl, citryl or nitrilotriacetyl, butane- 1,2,3,4-tetracarboxylic acid or pyromellitic acid.

Examples of a dicarbamic acid are the hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.

C2-C, 2alkanoyl 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 C2-C, 2alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

C4-C, 2alkenylene is for example butenylene, pentenylene, hexenylene, heptenylene or nonenylene including their isomers.

C6-C, 2arylene is, for example, o-, m-or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C4-C22acyloxyalkylene is, for example, 2-ethyl-2-acetoxymethylpropylene.

Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

C,-C, 8alkanoyloxy is, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy 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.

Some typical examples are given below. The nitroxyl-ethers of formula XXa, b and c are also known and may be prepared according to European Patent Application No. 98810741.3.

Typical examples are given below.

The nitroxyl-ethers of formula XXX are also known and can be prepared as described in European Patent Application No. 98810531.8.

Furthermore DE 26 21 841, US 4'131'599 and DE 26 30 798 for example describe the preparation of 2,6-diethyl-2,3, 6-trimethyl-4-oxopiperidine and 2,6-dipropyl-3-ethyi-2, 6-dimethyl- 4-oxo-piperidine, which are intermediates for the corresponding 1-oxo and nytroxyl-ether compounds.

Another method for the preparation of 2,2-dimethyl-6,6-dialkyl-4-oxopiperidine is described by F. Asinger, M. Thiel, H. Baltz, Monatshefte fur Chemie 88,464 (1957) or by J. Bobbittt et al. in J. Org. Chem. 58,4837 (1993).

The oxidation of the piperidine compound to 1-oxo-piperidine derivatives is well known in the art and for example described by L. B. Volodarsky, V. A. Reznikov, V. I. Ovcharenko in Synthetic Chemistry of Stable Nitroxides, CRC Press, Boca Raton 1994.

The tetramethylpiperidine precursors are partially commercially available or can be prepared according to known methods. For example 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.

Examples are given below.

Preferably G,, G2, G3 and G4 are methyl or ethyl and G5 and G6 are hydrogen or methyl.

More Preferably G1, G2, G3 and G4 aremethyl and G ; and G, : are hydrogen.

Another preferred group of compounds are those wherein G1 andG3 are ethyl and G2 and Gn <BR> <BR> <BR> are methyl, orG, and G@ areethyl and G2 and G3 are methyl, and one of Gs or G6 is hydrogen and the other methyl or both are hydrogen.

Preferably X is selected from the group consisting of C,-C, 8alkyl, C3-C, 8alkenyl, C3-C, saikinyl, phenyl, phenyl (C7-C") alkyl, phenyl or phenyl (C7-C") alkyl substituted by C,-C12alkyl, C,- C, 2alkoxy, OH, amino, C,-C, 2alkylamino, C,-C, 2dialkylamino, N02 or halogen, C2-C7cycloalkyl, or a group wherein R20, R21, and R22 are hydrogen or C1-C12alkyl, C2-C12alkenyl, phenyl orC3-C7cycloalkyl.

More preferably X is selected from the group consisting of C,-C, 8alkyl, benzyl, allyl, cyclopentyl or cyclohexyl.

Most preferred are allyl andcyclohexyl.

A preferred subgroup are compounds of the structural formulae A, B, O or P, wherein misl, R is hydrogen, C1-C18alkyl is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzol, 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 a, ß- unsaturated carboxylic having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; p is 1; R, is C1-C12alkyl, C5-C7cycloalkyl, C7-C8aralkyl, C2-C18alkanoyl, C3-C5alkenoyl or;benzoyl R2 is C,-C, 8alkyl, Cs-C, cycloalkyl, C2-CBalkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula-CH2CH (OH)-Z or of the formula-CO-Z or-CONH-Z wherein Z is hydrogen, methyl or phenyl.

More preferred are those of structure A or B, wherein R is hydrogen, C,-C18alkyl, cyanoethyl, benzol, glycidyl, a monovalent radical of an aliphatic carboxylic acid, having 2 to 18 carbon atoms; R, is Cl-Cl2alkyl, C7-C8aralkyl, C2-C, 8alkanoyl, C3-C5alkenoyl or benzoyl; R2 is C1-C18alkyl, glycidyl, group of the formula-CH2CH (OH)-Z or of the formula -CO-Z, wherein Z is hydrogen, methyl or phenyl.

Another preferred subgroup is wherein the nitroxyl-ether is a compound of formula (X), n, is 1 Rio, is cyano; R102 and R103 are each independently of one another unsubstituted C,-C12alkyl or phenyl, or R, o2 and R, o3, together with the linking carbon atom, form a Cs-C7cycloalkyl radical; R110 is C4-C12alkyl bound via a tertiary C-atom to the nitrogen atom, C9-C11phenylalkyl or;phenyl or R, 10 and Rm together form a C2-C6alkylene bridge which is unsubstituted or substituted with C,-C4alkyl; and R"2 is C,-C4alkyl.

A further preferred subgroup is wherein the nitroxyl-ether a compound of formula (XXa), Y is O ; R201 is tertiary C4-C8alkyl ; R202 and Rzo3 are methyl, ethyl or together with the carbon atom form a CS-C6cycloalkyl ring; R204 is C,-C, 8alkoxy, benzyloxy or NR223R224, wherein R223 and R224 are independently of each other hydrogen or C,-C8alkyl; or of formula (XXb), wherein Q, is O; R205, R206, R207 and R208 are independently of each other methyl or ethyl; or R205 and R206 and/or R207 and R2-¢ together with the carbon atom form a CS-C6cycioaikyl ring; R209 and R2io are independently of each other formyl, C2-C8alkylcarbonyl, benzoyl, C,-Csalkyl, benzyl or phenyl; or of formula (XXc), wherein Y, is O; R205, R206, R207 and R208 independently of each other methyl or ethyl; or R205 and R206 and/or R207 and R208 together with the carbon atom form a C5-C6cycloalkyl ring; R2"is formyl, C2-C18alkylcarbonyl, benzoyl, C1-C18alkyl, benzyl orphenyl and R2, 2 is OH, Ci-Ciga 8alkoxy, benzyloxy, NR223R224, wherein R223 and R224 are independently of each other hydrogen or C,-Cl8alkyl.

Preferably 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 diolefins and copolymers with diolefins.

Preferred 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 nitrile rubber having a content of unsaturated repeating units from 0.1 to 85%. Mostly preferred are SB. SBS, EPDM having a content of unsaturated repeating units from 1 to 70%.

Preferably the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl) acrylic acidanhydrides, (alkyl) acrylic acid salts, (alkyl) acrylic esters or (alkyl) acrylamides.

More preferably the ethylenically unsaturated monomer is styrene, a-methyl styrene, p-methyl styrene or a compound of formula CH2=C (Ra)- (C=Z)-Rb, wherein Ra is hydrogen or C,-C4alkyl, Rb is NH2, OCH3, glycidyl, unsubstituted C,-Cl8alkoxy or hydroxy-substituted C,-C, 8alkoxy, unsubstituted C,-C, 8alkylamino, di (Cl-C, 8alkyl) amino, hydroxy-substituted C,-C, 8alkylamino or hydroxy-substituted di (C,-C, 8alkyl) amino; Me is a monovalent metal atom Z is oxygen or sulfur.

Most preferably Ra is hydrogen or methyl, Rb is NH2, gycidyl, unsubstituted or with hydroxy substituted C,-C4alkoxy, unsubstituted C,-C4alkylamino, di (C,-C4alkyl) amino, hydroxy- substituted C,-C4alkylamino or hydroxy-substituted di (C,-C4alkyl) amino; and Z is oxygen.

Specifically preferred ethylenically unsaturated monomers are methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethylaminoethylacrylate, glycidylacrylates, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (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: low density polyethylene LDPE 170-260° C high density polyethylene HDPE 180-270° C polypropylene PP 180-280° C polystyrene PS 190-280° C styrene-block copolymers SB (S) 180-260° C ethylene-propylene-diene modified EPDM 180-260° C ethylene propylene rubber EPR 180-260° C In a preferred process the temperature in the first step A) is from 150° C to 300° C, more preferred from 170° C to 280° C.

Preferably the temperature in the second step B) is from 70° to 280° C, more preferably from 70° to 210° C.

If a temperature of 120° to 180° C is applied, the group X is preferably allyl or benzyl.

If a temperature of 180° to 240° C is applied the group X is preferably benzyl or cyclohexyl.

If a temperature of 240° to 300° C is applied the group X is preferably cyclohexyl or alkyl.

Preferably 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.

Preferably 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.

Preferably the reactor is an extruder or kneading apparatus as for example described in "Handbuch der Kunststoffextrusion"Vol. l, editor F. Hensen, W. Knappe and H. Potente, 1989, pages 3-7. if 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.

Preferably, if an extruder is used, 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 min to 1 h, most preferably from 2 min to 20 min.

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. Preferably the reaction time for step B) is from 1 min to 20 hours, more preferably from 30 min to 5 hours.

If the 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 (methylacrylate-co- acrylate-co-methacrylate) triblock 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 coatings (e. g. high solid paints) Graft block copolymers of styrene, (meth) acrylates and/or acrylonitrile are useful for plastics, elastomers and adhesives.

Furthermore, 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.

Thus, 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 foilowing applications: adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubricants, rheology modifiers, thickeners, crosslinkers, 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.

Because the present graft polymerizaton is a"living"polymerization, it can be started and stopped practically at will. Furthermore, the polymer product retains the functional alkoxyamine group allowing a continuation of the polymerization in a living matter. Thus, in one embodiment of this invention, once the first monomer is consumed in the initial polymerizing step 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.

Furthermore, since this is a radical polymerization, graft blocks can be prepared in essentially any order.

Consequently further subjects of the present invention are a polymeric radical initiator prepared according to step A) of the process without an additional free radical source and a polymeric radical initiator prepared according to step A) of the process with an additional free radical source.

Another subject of the invention are the grafted polymers obtainable by according to A) and B) of the process descibed above.

The polymeric radical initiator obtainable by step A) of the above process is schematically represented in formula (P1) wherein R498 is hydrogen, substituted or unsubstituted C,-C, 8alkyl, C2-C, 8alkenyl, C2-C, 8alkinyl; C3- C20cycloalkyl or C3-C, 2cycloalkyl containing at least one nitrogen or oxygen atom or C3- C, 2cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy; C,-C4alkoxy, C,-C4alkylthio, C,-C4alkylamino or di (C,- C4alkyl) amino, O (C,-C, 8alkyl), O (C2-C, Balkeny), C7-C"phenylalkyl, O-phenyl, OC7-Cgphenylalkyl or halogen or phenyl and naphthyl which are unsubstituted or substituted by C,-C4alkyl, C,- C4alkoxy, C,-C4alkylthio, halogen, cyano, hydroxy, carboxy, C,-C4alkylamino or di (C,- C4alkyl) amino; R499 is the stable nitroxyl radical, bound at the oxygen atom; Rsoo is substituted or unsubstituted C,-C,salkyl, C2-C, 8alkenyl, C3-C2ocycloalkyl, phenyl, C7- C"phenylalkyl; R50, is hydrogen, substituted or unsubstituted C,-C, 8aikyl, C2-C18alkenyl, C2-C, 8alkinyl, C3- C2ocycloalkyl, phenyl, O (C,-C, 8alkyl), O (C2-C, 8alkeny), C7-C"phenylalkyl, O-phenyl, O-C7- Cgphenylalkyl or halogen, CN, COOR500, CONR500R500 ; Q5 is CR502R503, CH=Ch2, (CR502R503)n, CR504=CR505-CR506R507,(CR504=CR505-CR506R507)n, C-CRsoaRsos, (C=CRso8R5o9) n, O, C=O, NR510, NR511-C=O, O-C(O)-O, SO2, S, SiR12R513, O- SiR512R513-0 ; Rsoz, Rsos, R504, Rsosl R506, Rso7l Rso8 Rsoss Rs1ol Rs11l Rs12 and Rs13 independently of each other are hydrogen, substituted or unsubstituted C,-C, 8alkyl, C2-C, ealkenyl, C2-C, 8alkinyl, C3- C7cycloalkyl, phenyl, O (C,-C, 8alkyl), O (C2-C, 8alkeny), C7-C"phenylalkyl, O-phenyl, O-C7- Cgphenylalkyl or halogen; 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.

Preferably Rso, is H or methyl; Q5 is CR502R503, CH=CH2, CR504=CR505CR506R507, wherein R502 and R5o3 is H, methyl or C2-C9alkenyl and R504, R505, R506 andR507 are independently H or methyl.

Examples for the different substituents have been already given.

Within this selection 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.

Definitions and examples of the substituents are as given above; Q6 is a homo-, co-or tapered polymer resulting from the monomers as described above, t is a number from 0 to 25000.

R499 may be removed thermally or chemically.

Preferably the polymer (P2) is grafted with a monomer selected from the groups described above and more preferably with styrenes, (meth) acrylates, butadiene, isoprene.

Most preferred are SB-g-styrenes, SB-g- (meth) acrylates, SI-g-styrenes, SI-g- (meth) acrylates, SBS-g-styrenes, SBS-g- (meth) acrylates, EPDM-g-styrenes, EPDM-g- (meth) acrylates.

Examples and preferences have been already given.

A further subject of the present invention is the use of a nitroxyl-ether containing a group (=NO- X), wherein 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 for the preparation of a grafted polymer with and without a free radical source.

Still further subjects are the use of 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 following examples illustrate the invention.

A) Grafting of N-OR compounds to the polymer (preparation of a polymeric initiator) Polypropylene (MFR230/2.16 = 1 43 according to ISO 1133) is extruded together with the compounds given in Table 2 in a twin screw extruder (TW 100 of Haake, Germany) at 180- 210° C (heating zones 1-5) and 40 rpm. The melt viscosity (MFR) is determined according to ISO 1133 (Table 1).

The granulated polymer is dissolved, reprecipitated and high temperature NMR spectra are taken to determine whether polymer bound NO-moieties are present.