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
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • 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
  • C08F4/00—Polymerisation catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups

Definitions

• the present invention relates to a polymerizable composition
• a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b1) at least one multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1 -oxyl and a free radical initiator or b2) at least one multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1 -oxyl-ether.
• Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, the (co)polymers obtainable by this process and the use of multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1 -oxyls in combination with a free radical initiator, or a multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1 -oxyl-ethers for controlled polymerization.
• this invention relates to stable free radical-mediated polymerization processes which provide homopolymers, random copolymers, block copolymers, multiblock copolymers, graft copolymers and the like, at enhanced rates of polymerization and enhanced monomer to polymer conversions.
• US-A-4 581 429 to Solomon et al. discloses a free radical polymerization process which controls the growth of polymer chains to produce short chain or oligo- meric 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.
• the reactions typically have low conversion rates.
• radical R'R"N-O « groups are derived from 1 ,1 ,3,3 tetraethylisoindoline, 1 ,1 ,3,3 tetrapropylisoindoline, 2,2,6,6 tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine or di-t-butylamine.
• the suggested compounds do not fulfill all requirements.
• the polymerization of acrylates does not proceed fast enough and/or the monomer to polymer conversion is not as high as desired.
• EP-A-735 052 discloses a method for preparing thermoplastic polymers of narrow poly- dispersities by free radical-initiated polymerization, which comprises adding a free radical initiator and a stable free radical agent to the monomer compound.
• a free radical initiator and a stable free radical agent to the monomer compound.
• JP 08-269117 published 31.3.1995 describes the polymerization of vinyl monomers with nitroxides such as the nitroxides of bis(2,2,6,6-tetramethyl-4-piperidy!) sebaic acid ester and tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1 ,2,3,4 butanetetracarboxylate.
• the compounds of the present invention provide polymeric resin products having low polydispersity, particularly when the polymer is heated for a certain time after polymerization is completed. In addition the monomer to polymer conversion proceeds in a short time. Thus making the compounds particularly suitable for industrial polymerization processes.
• One subject of the invention is a polymerizable composition, comprising a) at least one ethylenically unsaturated monomer or oligomer, and b) a compound of formula (I)
• n is the number 1 or 2
• R is a group of the formula
• E is -O- or -ND 3 -
• A is C 2 -C 6 alkylene or -(CH 2 ) 3 -0- and
• X! is the number 0 or 1
• D 3 is hydrogen, d-C ⁇ alkyl, C 2 -C 5 hydroxyalkyl or C 5 -C 7 cycloalkyl
• R 2 is identical to R, or is one of the groups -N(G 21 )(G 22 ), -OG 23 , -N(H)(CH 2 OG 23 ) or
• G 2 ⁇ is CrC ⁇ alkyl, cyclohexyl, benzyl or CrC ⁇ hydroxyalkyl or a group of the formula
• G 22 is CrC ⁇ alkyl, cyclohexyl, benzyl or C 1 -C 4 hydroxyalkyl, and
• G 23 is hydrogen, C C 12 alkyl or phenyl, or
• G 21 and G 22 together are C 4 -C 5 alkylene or C 4 -C 5 oxaalkylene, for example -CH 2 CH 2 -0-
• G 11 is 0» or -O-X, wherein
• X represents a group such that the free radical X» derived from X is capable of initiating polymerization of ethylenically unsaturated monomers; and if G 11 is 0 «, a source of free radicals is additionally present.
• Any d-C ⁇ alky! substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert- butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
• Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
• C 5 -C 7 cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.
• C 2 -C 6 alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
• G 2 ⁇ and G 22 together are C 4 -C 5 alkylene or oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.
• n 1 in formula (I).
• Particularly preferred compounds of formula (I) are, wherein n is 1 , R 1 and R 3 are a group
• R 2 is identical to Ri and R 3 or is a group -N(G 2 ⁇ )(G 22 )
• R 2 is identical to Ri and R 3 , or is a group -N(G 2 ⁇ )(G 2 2),
• X is selected from the group consisting of -CH(aryl) 2 , -CH 2 -aryl,
• R 30 is hydrogen or d-C 12 alkyl; the aryl groups are unsubstituted or substituted with C ⁇ -C 12 alkyl, halogen, d-C 12 alkoxy, d-
• Aryl is phenyl or naphthyl.
• Examples of groups of poiyalkylpiperidine compounds according to formula (I) are the compounds of the following formulae:
• Gn represents -0», or -O-X, wherein X is as defined above.
• the compound of formula (I) is present in an amount of from 0.01 mol-% to 30 mol-% , based on the monomer or monomer mixture, more preferably in an amount of from 0.05 mol-% to 20 mol-%, and most preferably in an amount of from 0.1 mol-% to 10 mol-% based on the monomer or monomer mixture.
• the compounds according to formula (I) are in principal known and may be prepared according to standard procedures as for example described in US 5 216 156 , US 5 004 770 or 5 204 473 .
• the source of a free radical initiator is a bis-azo compound, a peroxide or a hydroperoxide.
• the source of free radicals 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-amidinopropan
• Preferred peroxides and hydroperoxides are acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl pemeodecanoate, t-butyi 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-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-buty
• the molar ratio of the free radical source to the compound of formula I is from 1 :2 to 20:1 , more preferably from 1 :1 to 5:1.
• the ethylenically unsaturated monomer or oligomer is selected from the group consisting of alkene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides.
• R a is hydrogen
• R b is NH > unsubstituted or with hydroxy substituted C C 4 alkoxy, unsubstituted d-C 4 alkylamino, di(d-C 4 alkyl)amino, hydroxy-substituted C C 4 alkylamino or hydroxy-substituted di(C 1 -C 4 alkyl)amino
• Z is oxygen
• the ethylenically unsaturated monomer is styrene, ⁇ -methyl styrene or p- methyl styrene and ethylene.
• organic sulfonic or organic carboxylic acids (US 5,322,912), sulfonic acid salts(US 5,608,023), acid anhydrides (Malmstr ⁇ m, E.; Miller, R. D.; Hawker, C. J. Tetrahedron 1997, 53, 15225-15236) or vinyl monomers containing acid groups (WO 96/18663) can be added to the polymerization process.
• the polymerization rate can be enhanced by the addition of phosphorous compounds (US 5,610,249), electron accepting compounds (EP 0 773 232), dimethylsulfoxide (US 5,412,012), reducing agents (EP 0 897 930) or metal catalysts and stable free radical complex catalysts (US 5,744,560).
• phosphorous compounds US 5,610,249
• electron accepting compounds EP 0 773 232
• dimethylsulfoxide US 5,412,012
• reducing agents EP 0 897 930
• metal catalysts and stable free radical complex catalysts US 5,744,560.
• Another subject of the present invention is a process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically unsaturated monomer or oligomer, which comprises (co)polymerizing the monomer or monomers/oligomers in the presence of a compound of formula (I) as described above, wherein if
• Gn is -O-X a) under reaction conditions capable of effecting scission of the O-X bond to form two free radicals, the radical *X being capable of initiating polymerization; or if
• Gn is O» b) additionally in the presence of a free radical source, liberating a free radical which is capable of initiating polymerization.
• a further subject of the invention is a process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically unsaturated monomer or oligomer, which comprises (co)polymerizing the monomer or monomers/oligomers in the presence of
• ni is a number from 2 to 4
• G and G independently of one another, are hydrogen or methyl
• Gn is 0 « or O-X
• Gi 2 if n, is 2, is C 2 -C 12 alkylene, C 4 -C 12 alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus- containing acid or a divalent silyl radical, preferably a 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 12 groups,
• G ⁇ 2 if n, 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 12 of an aromatic tricarbamic acid or of a phosphorus-containing acid, or is a trivalent silyl radical
• G 12 if ni is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
• 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-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
• G 12 is a divalent radical of a dicarboxylic acid, it is, for example, a 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
• G 12 is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitoyl, citryl or nitrilotriacetyl radical. If G 12 is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-1 ,2,3,4-tetracarboxylic acid or of pyromellitic acid.
• G 12 is a divalent radical of a dicarbamic acid, it is, for example, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.
• n 2 and G 12 is the diacyl radical of an aliphatic dicarboxylic acid having 4-12 carbon atoms.
• a typical example is di(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate. These compounds are in principal known and partially commercially available.
• the initiator/regulator compound useful in the above process is of formula (I) including the preferences as described above.
• the additional heating step may be performed directly in the polymerization apparatus or the polymer may be first isolated cooled down to room temperature stored for a while and then heated again to a temperature between 140° C and 280° C, more preferably between 140° C to 200° C and most preferably between 150° C to 180° C.
• the heating step may be applied from 10 seconds to 2 hours, preferably from 1 minute to 60 minutes and more preferably from 1 minute to 30 minutes.
• the polymer is isolated with conventional techniques.
• the isolating step of the present process may be carried out by known procedures, e.g. by precipitation, distilling and filtering off unreacted monomer. After completing the reaction the polymer may be filtered off, followed by evaporation of the solvent or by precipitation of the polymer in a suitable liquid phase, filtering the precipitated polymer, washing and drying.
• the above described additional heating step is then applied to the dried polymer.
• the heating step may be performed in every suitable vessel. It is also possible to heat the polymer in an extruder, mixer or kneading apparatus.
• the advantage of the heating step lies in the formation of a more uniform polymer as is proven by the reduced molecular weight distribution after thermal exposure compared to the original material.
• Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyi-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'
• Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioc- tylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl- 4-nonylphenol.
• Hydroguinones and alkylated hvdroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert- butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4- hydroxyphenyl) adipate.
• 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydr
• Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (Vitamin E).
• Hydroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl- 2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphe- nyl)disulfide.
• Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-me- thylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ , ⁇ ,
• N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl)suifide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
• Hvdroxybenzylated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hy- droxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di- dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyi]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
• Aromatic hvdroxybenzyl compounds for example 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
• Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hy- droxyanilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5- triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6- tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxy- benzyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di
• Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
• esters of ⁇ -(3.5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxymethyl
• esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl.propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,
• esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenvQpropionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyiene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyloipropane, 4-hy- droxymethyl-1-phospha-2,6,7-trio
• esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyiene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyloipropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicycl
• Phosphites and phosphonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di- tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyioxypentaerythhtol diphosphite, bis
• Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos ® 168, Ciba-Geigy), tris(nonylphenyl) phosphite,
• initiators/regulators of the present invention there may be other compounds present during polymerization having a monofunctional N-0» moiety.
• Suitable compounds are for example described in EP-A-621 878, WO 96/24620, US 4 581 429, US 5 721 320, US 5627 248, WO 98/13392 , WO98/30601 or in WO 98/44008
• Preferred is a compound of formula (X) , wherein R 101 is H, -OH,
• the compounds of formula (X) are preferably present in an amount of from 0.1 % to 30% by weight based on the monomer or monomer mixture. They may replace the amount of compounds of formula (I) of from 1 % to 50%.
• the process may be carried out in the presence of an organic solvent or in the presence of water or in mixtures of organic solvents and water. Additional cosolvents or surfactants, such as glycols or ammonium salts of fatty acids, may be present. Other suitable cosolvents are described hereinafter.
• Preferred processes use as little solvents as possible.
• suitable solvents or mixtures of solvents are typically pure alkanes (hexane, heptane, octane, isooctane), aromatic hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons (chlorobenzene), ethylene glycol, ethylene glycol monomethyl ether), esters (ethyl acetate, propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether), or mixtures thereof.
• the aqueous polymerization reactions can be supplemented with a water-miscible or hydrophilic cosolvent to help ensure that the reaction mixture remains a homogeneous single phase throughout the monomer conversion.
• a water-miscible or hydrophilic cosolvent Any water-soluble or water-miscible cosolvent may be used, as long as the aqueous solvent medium is effective in providing a solvent system which prevents precipitation or phase separation of the reactants or polymer products until after all polymerization reactions have been completed.
• Exemplary cosolvents useful in the present invention may be selected from the group consisting of aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkyl pyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids and salts thereof, esters, organosulfides, sulfoxides, sulfones, alcohol derivatives, hydroxyether derivatives such as butyl carbitol or cellosolve, amino alcohols, ketones, and the like, as well as derivatives thereof and mixtures thereof.
• the water to cosolvent weight ratio is typically in the range of about 100:0 to about 10:90.
• the process is particularly useful for the preparation of block copolymers.
• Block copolymers are, for example, block copolymers of polystyrene and polyacrylate (e.g., poly(styrene-co-acrylate) or poly(styrene-co-acrylate-co-styrene). They are useful as adhesives or as compatibilizers for polymer blends or as polymer toughening agents.
• block copolymers of this invention wherein the blocks alternate between polar monomers and non-polar monomers, are useful in many applications as amphiphilic surfactants or dispersants for preparing highly uniform polymer blends.
• the (co)polymers of the present invention may have a number average molecular weight from 1 000 to 1000 000 g/mol, preferably from 2 000 to 250 000 g/mol and, more preferably, from 2 000 to 200 000 g/mol.
• the number average molecular weight may be determined by size exclusion chromatography (SEC), matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) or, if the initiator carries a group which can be easily distinguished from the monomer(s), by NMR spectroscopy or other conventional methods.
• the polymers or copolymers of the present invention have preferably a polydispersity of from 1.1 to 2, more preferably of from 1.2 to 1.8. Particularly when an additional heating step is applied, the polydispersity is preferably between 1.2 and 1.8.
• the present invention also encompasses the synthesis of block, multi-block, star, gradient, random, hyperbranched and dendritic copolymers, as well as graft copolymers.
• the polymers prepared by the present invention are useful for following 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.
• the present 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.
• a second monomer can then be added to form a second block on the growing polymer chain in a second polymerization step. Therefore it is possible to carry out additional polymerizations with the same or different monomer(s) to prepare multi-block copolymers. Furthermore, since this is a radical polymerization, blocks can be prepared in essentially any order.
• a multi-block copolymer in which a polyacrylonitrile or a poly(meth)- acrylate block is prepared first, then a styrene or diene block is attached thereto, and so on.
• a plurality of specifically designed polymers and copolymers are accessible by the present invention, such as star and graft (co)polymers as described, inter alia, by C. J. Hawker in Angew. Chemie, 1995, 107, pages 1623-1627, dendrimers as described by K. Matyaszewski et al. in Macromolecules 1996, Vol 29, No. 12, pages 4167-4171 , graft (co)polymers as described by C. J. Hawker et al. in Macromol. Chem. Phys. 198, 155-166(1997), random copolymers as described by C. J. Hawker in Macromolecules 1996, 29, 2686-2688, or diblock and triblock copolymers as described by N. A. Listigovers in Macromolecules 1996, 29, 8992-8993.
• a further subject of the invention is a polymer or oligomer having attached at least one oxyamine group of formula (I), obtainable by the above described process.
• Still another subject of the invention is the use of a compound of formula (I) for the polymerization of ethylenically unsaturated monomers or oligomers.
• nitroxyl stable free radical and radical initator given Table 1 are dissolved in 50 ml freshly distilled styrene.
• the solution is degassed in three consecutive freeze-thaw-cycles and then purged with argon.
• the stirred mixture/solution is then immersed in an oil bath and polymerized at 130°C for 6 hours. After polymerization, residual monomer is removed under vacuum at 60°C and the polymer is dried at 70°C in vacuo until constant weight is achieved.
• Control polymerizations without a stable free radical were carried out identically, at 80°C.
• Molecular weight and molecular weight distributions are determined by GPC on a HP 1090 liquid chromatograph (software: winGPC/Polymer Standard Services, Mainz, Germany) using THF as eluent and a column combination calibrated with narrow polystyrene standards (Polymer Laboratories).
• BPO Dibenzoyl peroxide
• BPO is Dibenzoyl peroxide.
• the samples 1 A, 2A, 6A and 9A described above were subjected to an additional heating step of different time and temperature and M n and M w are measured thereafter.
• Antiox I is Irganox® 1076 supplied by Ciba Specialty Chemicals Table 6

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