WO2004056880A1 - Processus de preparation d'un copolymere multisequence - Google Patents

Processus de preparation d'un copolymere multisequence Download PDF

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WO2004056880A1
WO2004056880A1 PCT/NL2003/000883 NL0300883W WO2004056880A1 WO 2004056880 A1 WO2004056880 A1 WO 2004056880A1 NL 0300883 W NL0300883 W NL 0300883W WO 2004056880 A1 WO2004056880 A1 WO 2004056880A1
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optionally substituted
group
poly
reaction
polymerization
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PCT/NL2003/000883
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Anna Maria Gabrielle Van Benthem-Van Duuren
Josephina Cornelia Maria Willem Brokken-Zijp
Vincent Georges Robert Lima
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Stichting Dutch Polymer Institute
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Priority to AU2003295256A priority Critical patent/AU2003295256A1/en
Publication of WO2004056880A1 publication Critical patent/WO2004056880A1/fr

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    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the invention relates to a process for the preparation of a multiblock copolymer, the process being carried out in the presence of multifunctional initiator, said process comprising a combination of a cationic Ring Opening Polymerization (ROP) reaction catalyzed by at least one Lewis acid, and a controlled (co)polymerization reaction.
  • ROP Ring Opening Polymerization
  • a process for the preparation of a diblock copolymer of methyl methacrylate (MMA) and ⁇ -caprolactone ( ⁇ -CL) is disclosed in D. Mecerreyes et al., Angew. Chem. Int. Ed., 37 (1998) 1274. Said process comprises a ROP reaction which is catalyzed by tri(isopropoxy)aluminium, and an Atom Transfer Radical Polymerization (ATRP) reaction, which is catalyzed by tri(phenylphosphate)nickel bromide, in the presence of a multifunctional initiator.
  • ROP reaction which is catalyzed by tri(isopropoxy)aluminium
  • ATRP Atom Transfer Radical Polymerization
  • a drawback of the known process is that tri(phenylphosphate)nickel bromide is used as a catalyst for the ATRP reaction.
  • Nickel compounds are known to be highly toxic. For many applications, for example in the biomedical and microelectronics field, the presence of such a compound in the product is undesired. As removal of the metal catalyst from the product necessitates the use of very complicated and expensive purification processes, such a process has a limited feasibility for industrial application.
  • the aim of the present invention is therefore to provide a new process for the preparation of a multiblock copolymer in which the use of a transition metal catalyst is avoided.
  • RAFT Reversible Addition Fragmentation Chain Transfer
  • an inicta is understood to be a compound having at least one moiety acting as an initiating site for a cationic ROP reaction, and acting as a chain transfer agent in a RAFT (co)polymerization process.
  • multiblock copolymers free of transition metal residues can be obtained by using the process according to the invention. Furthermore, the process according to the invention often results in the formation of a multiblock copolymer with a narrow molecular weight distribution, the M w /M n typically being smaller than 1.5.
  • the molecular weight distribution is defined as the weight average molecular weight divided by the number average molecular weight (M w /M n ), which is measured by Gel Permeation Chromatography (GPC).
  • RAFT (co)polymerization processes are known per se and described in for example WO-A-98/01478 and WO-A-99/31144.
  • the RAFT (co)polymerization reaction according to the invention is carried out in the presence of at least one dithiocarbonyl compound, which acts as a chain transfer agent in said (co)polymerization process.
  • the process according to the invention is carried out in the presence of an inicta.
  • the inicta is a dithiocarbonyl compound of formula (I) or (II):
  • R 3 is a free-radical leaving group, comprising a moiety that initiates the ROP reaction
  • R 4 is selected from the group comprising H, an optionally substituted C-i - C-] 8 alkyl, an optionally substituted C 2 - C 18 alkenyl, an optionally substituted aryl, an optionally substituted heterocyclyl, an optionally substituted aralkyl, and an optionally substituted alkaryl, wherein the substituents are independently selected from the group that comprises epoxy, hydroxy, alkoxy acyl, acyloxy, carboxy (and salts), sulphonic acid (and salts), alkoxycarbonyl or aryloxycarbonyl, isocyanato, cyano, silyl, halogen, phosphonate and dialkylamino; in general the derived carboxy and sulphonic acid salts should not lead to cleavage or inactivation of the inicta and initiator of the RAFT and/or iniferter (co)polymerization reaction;
  • the inicta according to formula (I) or (II) acts as a transfer agent in the RAFT (co) polymerization reaction.
  • the group in R 3 that initiates the ROP reaction is generally a group that easily converts into or represents an active initiating species such as a radical, an ion or any other reactive group for ROP reactions, and which can form a covalent bond with the polymer chain that is formed subsequently.
  • the group in R 3 that initiates the ROP reaction is chosen from the group comprising an hydroxy, thiol, or carboxylic acid group.
  • R 3 is represented by the formula R 7 - A, wherein A represents hydroxy, thiol, epoxy, carboxylic acid, or an optionally substituted amide and R 7 is selected from the group comprising an optionally substituted saturated or unsaturated alkyl; an optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring, a silyl, an optionally substituted alkylthio, an optionally substituted alkoxy, an organometallic species, and a saturated or unsaturated polymer chain.
  • the derived salt compounds should not lead to cleavage or inactivation of the inicta or initiator
  • Z is selected from the group comprising:
  • R 6 is selected from the group comprising H, an optionally substituted C ⁇ - C 18 alkyl, an optionally substituted C 2 - C 18 alkenyl, an optionally substituted aryl, an optionally substituted heterocyclyl, an optionally substituted aralkyl, and an optionally substituted alkaryl, wherein the substituents are independently selected from the group that comprises epoxy, hydroxy, alkoxy acyl, acyloxy, carboxy (and salts), sulphonic acid (and salts), alkoxycarbonyl or aryloxycarbonyl, isocyanato, cyano, silyl, halogen, phosphonate and dialkylamino; in general the derived carboxy and sulfonic acid salts should not lead to cleavage or inactivation of the inicta and initiator of the RAFT (co)polymerization reaction.
  • the dithiocarbonyl compound acts as a chain transfer agent in the process according to the invention and has a chain transfer constant (C ⁇ ) in the range of from 0.01 to 10000 for the RAFT (co)polymerization.
  • C ⁇ is preferably in the range of from 1-8000, more preferably in the range of from 10 to 500.
  • the chain transfer constant (C ⁇ ) is defined as the ratio of the transfer and propagation rate coefficients (see: G. Odian, Principles of Polymerization, 3rd edition, John Wiley & Sons Inc., New York (1991), page 244):
  • k tr rate coefficient for transfer
  • k p rate coefficient for propagation. If the C-rof the dithiocarbonyl compound exceeds the upper limit of the above range substantially no (co)polymerization occurs; if it falls below the lower limit it is not possible to produce polymers having a narrow molecular weight distribution.
  • the RAFT reaction according to the invention is carried out in the presence of a free radical source. Free radicals can be subdivided into initiating radicals and propagating radicals. Initiating radicals are free radicals that are derived from the free radical source which add to a monomer to produce propagating radicals. Propagating radicals are radical species that have added to one or more monomer units and are capable of adding further monomer units.
  • the free radicals may be obtained by any suitable known method of generating free radicals, such as by the thermally induced homolytic scission of a suitable compound(s), i.e. thermal initiators such as peroxides, peroxyesters, or azo compounds; by the spontaneous generation from monomer, e.g. styrene; by redox initiating systems; photochemical initiating systems or high energy radiation such as electron beam, X- or gamma-radiation.
  • the free radical source is chosen such that under the reaction conditions there is no substantial adverse interaction of the free radical source with the monomers, solvents and additives. In the case of non-radiative initiating source(s) the free radical source should also have the required solubility in the reaction medium.
  • Thermal initiators are chosen to have an appropriate half life, i.e. being of the same order of magnitude as the reaction time, at the temperature and pressure of the (co)polymerization.
  • These initiators can include one or more of the following compounds: 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-cyano-2-butane), dimethyl 2,2'-azobisdimethylisobutyrate, 2,2'-azobis-(2,4-dimethyl valeronitrile), 1 ,1 '-azobis(cyclohexanecarbonitrile), 2-(t-butylazo)-2-cyanopropane, 2,2'-azobis (N,N'- dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis(isobutyramide) dihydrate, 2,2'-azobis (2,2,4-trimethylpentane), 2,2'-azobis(
  • Photochemical initiator systems are chosen to have the required solubility in the reaction medium or monomer mixture and have an appropriate quantum yield for radical production under the conditions of the (co)polymerization.
  • examples include benzoin derivatives, benzophenone, acyl phosphine oxides, and photoredox systems.
  • the wavelength of the radiation is chosen such that the radiation is hardly absorbed by the monomers or catalyst(s) for ROP.
  • Dithiocarbonyl compounds may also be used as photoinitiators in combination with UV and/or visible light. Other suitable initiating systems are described in recent literature.
  • the vinyl monomer is generally of formula (III):
  • Y 1 is selected from the group comprising hydrogen, R 2 , CO 2 R 2 , COR 2 , CN, CONR 2 2 , O 2 CR 2 , OR 2 , halogen, and aldehyde;
  • R 1 and R 2 are each independently selected from the group comprising optionally substituted Ci - C 18 alkyl, C 2 - C 18 alkenyl, aryl, heterocyclyl (for example pyridyl or pyrrolidyl), aralkyl, and alkaryl, wherein the substituents can independently be selected from the group comprising epoxy, alkoxy acyl, acyloxy, alkoxycarbonyl or aryloxycarbonyl, isocyanato, cyano, silyl, halogen, dialkylamino, and an optionally unsaturated polymer chain.
  • the factors which determine the radical copolymerizability of various monomers are well documented in the art, for example, in: R.Z. Greenley, Polymer Handbook 3rd Edition (Brandup, J., and Immergut, E.H Eds.) Wiley, New York, 1989, p. II/53.
  • the vinyl monomer may also be selected from the group comprising maleic anhydride, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate, dialkyl maleate and monomers polymerizable by ring-opening (co)polymerization.
  • substituents are halogen, alkoxy with for example 1 to 20 C atoms, (hetero)aryl with for example 1 to 20 C atoms and aryloxy with for example 1 to 20 C atoms.
  • X 1 preferably represents an unsubstituted linear alkyl with 1 - 10 carbon atoms, more preferably an unsubstituted linear alkyl with 2 - 6 carbon atoms.
  • the substituents should not activate the ring openings (co)polymerization or cleave/inactivate the inicta to circumvent homopolymerisation by ROP.
  • the vinyl monomer may also be a conjugated or non-conjugated
  • olefin having at least two double bonds.
  • olefins include 1 ,3-butadiene and triethylglycoldimethacrylate.
  • Q is an optionally substituted saturated or unsaturated polymer chain, which does not have substituents activating cationic ROP or radical (co)polymerization, prepared by any (co)polymerization mechanism, for example poly(ethyleneoxide) or poly(ethylene-co-butylene), and wherein X 1 and Y 1 are defined as above.
  • type and concentration of initiator(s), solvents, surfactants (which do not have substituents activating cationic ROP or radical polymerisation), if any, and any other components, as well as the reaction temperature and the pressure are chosen such that, at any time during the (co)polymerization reaction, the total number of moles of initiating radicals R» formed during the (co)polymerization is in the range of 10 "6 to 0.5 times that of the total number of moles of the dithiocarbonyl compound.
  • the molecular weight distribution (M w /M n ) of the block polymerized via RAFT can be controlled.
  • a narrower molecular weight distribution of the block polymerized via RAFT is obtained when the molar ratio dithiocarbonyl compound : R « is increased.
  • the molar ratio dithiocarbonyl compound : R* is chosen such that the block polymerized via RAFT has an M w /M n smaller than about 1.5.
  • the vinyl monomer concentration may vary between broad ranges and depends on e.g. the type of monomers used. Usually the total monomer concentration is between 1 mol/l and bulk, preferably between 3 and 8 mol/l.
  • the molar ratio dithiocarbonyl compound : vinyl monomer determines, among other reaction parameters (such as the temperature), the molecular weight of the block polymerized via RAFT, and is generally between 1 :2 and 1 :1000, preferably between 1 :3 and 1 :500, more preferably between 1 :5 and 1 :20.
  • ROP reactions are described in for example E.F. Connor et al., J. Am. Chem. Soc, 124 (2002) 914, and involve the (co)polymerization of a cyclic monomer in the presence of a Lewis acid.
  • Lewis acids include alkali metals, for example triethyl aluminium (AI(Et) 3 ), and metal alkoxides, for example Sn(octyl) 2 or AI(OiPr) 3 .
  • lactones cyclic esters
  • cyclic ethers for example tertrahydrofuran (THF)
  • epoxides cyclic acid anhydrides
  • cyclic carbonates preferably lactides
  • lactones include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprylolactone, ⁇ -caprolactone, ⁇ -stearolactone, ⁇ -caprylolactone, and ⁇ -palmitolactone, ⁇ -thiobutyrolactone;
  • Iactams include ⁇ -propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ -valerolactam, ⁇ -caprolactam, and hectolactam;
  • examples of cyclic acid anhydrides include succinic anhydride, maleic anhydride, glutamic anhydride, and phtalic anhydride;
  • examples of cyclic carbonates include ethylene carbonate, propylene carbonate, and trimethylene carbonate; and examples of lactides include dilactide, diglycollide and digly
  • lactones are used, for example an optionally substituted ⁇ -CL.
  • Possible substituents to ⁇ -CL include for example a halogen, an amide group, an alkoxy group with for example 1 to 20 C atoms, a (hetero)aryl group with for example 1 to 20 C atoms and an aryloxy group with for example 1 to 20 C atoms.
  • substituted ⁇ -CL's are 2-bromo- ⁇ -caprolactone, 4-methyl- ⁇ -caprolactone, 4-ethyl- ⁇ -caprolactone, 4-phenyl- ⁇ -caprolactone, and 3,5-dimethyl- ⁇ -caprolactone, as mentioned in for example M.
  • the substituent(s) should not activate cationic ROP or cleave/inactivate the inicta.
  • the process according to the invention may be carried out in solution or suspension in either a batch, semi-batch, continuous or feed mode. The process according to the invention may also be performed in bulk as well. If (a) solvent(s) is/are used, less-polar organic solvents are preferred, for example aromatic hydrocarbons, for example optionally substituted benzene, toluene or xylene.
  • Suitable solvents or mixtures are typically aromatic hydrocarbons (for example benzene, toluene, or xylene); halogenated hydrocarbons (for example chlorobenzene, 1 ,1,2-trichlorotrifluoroethane, chloroform or o-dichlorobenzene); and ethers (for example diethyl ether, dipropyl ether, dibutyl ether, and diisopropyl ether), or mixtures thereof.
  • aromatic hydrocarbons for example benzene, toluene, or xylene
  • halogenated hydrocarbons for example chlorobenzene, 1 ,1,2-trichlorotrifluoroethane, chloroform or o-dichlorobenzene
  • ethers for example diethyl ether, dipropyl ether, dibutyl ether, and diisopropyl ether, or mixtures thereof.
  • the chosen solvent(s) should not be polymerizable in the ROP and RAFT (co)polymerization reaction, and should not lead to cleavage or inactivation of the inicta and initiator of the ROP/RAFT (co)polymerization reaction.
  • the process is generally performed at a reaction temperature between -20 and 200 °C, preferably between 0 and 110 °C, more preferably between 20 and 70 °C. At temperatures lower than -20 °C the reaction will be relatively slow, while at temperatures higher than 120 °C the number of side reaction increase, resulting in a broader molecular weight distribution.
  • the pressure at which the process is carried out is not particularly critical and depends on for example the monomers and solvent used and the reaction temperature. When higher boiling monomers and/or solvents and/or additives are applied, for practical reasons the process is preferably carried out at atmospheric pressure.
  • a specific class of acrylates i.e. the ⁇ -substituted acrylates (e.g. methyl ethacrylate)
  • the use of an elevated pressure for example between 0.12 and 1 MPa is preferred.
  • the reaction time is not particularly critical and is dependent on for example the types and amounts of the dithiocarbonyl compound, the free radical source, the monomers, the catalyst used for the ROP reaction, the temperature, the pressure and the solvent.
  • a reaction time of at least 1 hour to 4 days is applied, more preferably a reaction time between 2 and 48 hours, most preferably a reaction time between 3 and 24 hours.
  • the reaction conditions may vary between the different (co)polymerization reactions, i.e. the ROP and the RAFT reaction, and also within one (co)polymerization reaction.
  • the combination of a ROP reaction and a RAFT reaction may be carried out in any order, in a one-pot or a multi-pot reaction set-up, simultaneously or one after the other.
  • Preferably said (co)polymerization reactions are performed in one pot. Carrying out the (co)polymerization reactions in one pot avoids intermediate work- up steps and limits the amount of equipment needed. More preferably said
  • A is chosen from the group comprising poly(acrylates), poly(methacrylates), poly(methyl methacrylates), poly(ethyl methacrylates), poly(butyl methacrylates) poly(styrenics), poly(vinylpyridines), poly(acrylamides), poly(N- isopropylacrylamides), poly(N-acryloylmorpholine), copolymers of acrylates, methacrylates, methyl methacrylates, ethyl methacrylates, butyl methacrylates, styrenics, vinylpyridines, acrylamides, N-isopropylacrylamides or N- acryloylmorpholine with ⁇ -olefins and mixtures of such (co)polymers;
  • B is chosen from the group comprising poly(lactones), and poly(ethers);
  • B represents poly( ⁇ -caprolactone) or poly( ⁇ -thiobutyrolactone).
  • a nucleophilic substitution reaction using a base, for example a primary amine (such as 1-hexylamine or 1-butylamine), a secondary amine, a metal oxide, a metal hydride, or a (bi)carbonate.
  • a base for example a primary amine (such as 1-hexylamine or 1-butylamine), a secondary amine, a metal oxide, a metal hydride, or a (bi)carbonate.
  • Such reaction may be performed in solution, the solvent being for example an aromatic hydrocarbon (such as toluene), an ether (such as tetrahydrofuran or diphenyl ether), a keton (such as acetone or methyl ethyl ketone) or dimethyl sulphoxide.
  • Such reaction may also be performed in bulk, in emulsion, in suspension, or in dispersion. Preferably the reaction is performed in solution.
  • Thiolfunctional polymers produced by the process according to the invention, may be used for grafting on (noble) metal substrates, for example thiopolymers grafted on Au, Ag, Pt, or Rh nanoparticles to obtain thiol-stabilized nanoparticles (see for example A.B.
  • a hydroxy group may be introduced by using hydroxyethyl(meth)acrylate.
  • R 8 and R 9 are each independently chosen from the group comprising H, CH 2 CH 2 COOR 10 , CH 2 CH(CH 3 )COOR 10 , wherein R 10 is the estergroup of a (meth)acrylate.
  • the multiblock copolymers as described above may for example be applied as a compatibilizer, a toughener, a crosslinking agent, a component for adhesives, a surfactant, a dispersing agent, and an elastomeric material.
  • Methyl methacrylate, ethyl methacrylate and all lactones were purchased from Aldrich; butyl methacrylate and styrene were purchased from Merck. All monomers were purified by distillation over CaH 2 prior to utilization. Toluene was distilled over CaH 2 before use. Tetrahydrofuran (THF) was refluxed over LiAIH prior to use. 4,4'-azobis(4-cyanopentanol) (ACPH) was prepared according to the method described by G. Clouet et al., Polym. Bull., ___ (1984) 337.
  • 2-cyanoprop-2-yl- dithiobenzoate was synthesized according to the procedure described in WO-A- 9801478. Tri(isopropoxy)aluminium was sublimated twice. Other chemicals were purchased from Aldrich and used without further purification. As mentioned in the description, dithiocarbonyl compounds can be prepared using different methods, wherein oxygen was removed by three cycles of vacuum/argon. Below the synthesis of 4-cyano-1 -hydroxypent-4-yl-dithiobenzoate is given as an example: Synthesis of 4-cyano-1-hydroxypent-4-yl-dithiobenzoate
  • Bromobenzene (125.6 g, 0.8 mol) was added dropwise to a 3-neck round-bottom flask containing dry THF (500 ml), and magnesium turnings (20 g, 0.82 mol). After completion of the bromobenzene addition, the solution was refluxed for 2 hours. An ice bath was then placed around the reaction flask and carbon disulfide (61 g, 0.80 mol) was added dropwise. After 30 minutes, ice-water (30 ml) was added to the reaction mixture and the precipitated magnesium salts were isolated by filtration. THF was removed under reduced pressure and the obtained aqueous solution was treated with concentrated hydrochloric acid. The purple dithioacid then separated from the pink aqueous solution.
  • GPC Gel Permeation Chromatography
  • WATERS WATERS model 510 pump model 486 UV detector (at 254 nm) and model 410 refractive index detector (at 313K).
  • the columns used were a PLgel guard (5 ⁇ m particles) 50 x 7.5 mm guard column, followed by two PLgel mixed-C (5 ⁇ m particles) 300 x 7.5 mm columns (313 K) in series.
  • THF was used as an eluent at a flow rate of 1 mLJmin.
  • Low polydispersity index polystyrene standards Polymer Labs
  • the samples (1mg/ml tetrahydrofuran) were filtered through a 0.2 ⁇ m syringe filter prior to injection. Data acquisition and processing were performed using Waters Millenium32 (v3.00) software.
  • MALDI-TOF-MS measurements were performed on a Voyager-DE STR (Applied Biosystems, Framingham, MA) instrument equipped with a 337 nm nitrogen laser. Positive-ion spectra were acquired in reflector mode. Dithranol was used as the matrix.
  • 4-cyano-1-hydroxypen-4-yl-dithiobenzoate (0.0770 g) as a dithiocarbonyl compound, 4,4'-azobis(4-cyanopentanol) (ACPH) (0.0244 g) as a thermal initiator, ⁇ -caprolactone ( ⁇ -CL) (2.06 g) as a monomer for a ROP reaction, AI(OCH(CH 3 ) 2 ) 3 (0.0802 g), and toluene (25 ml) as a solvent were mixed in a 3-neck-round bottom flask. Oxygen was removed and the flask was immersed in an oil bath preheated at 70 °C.
  • Example II Preparation of polv(butyl methacrylate-block- ⁇ -caprolactone.
  • Styrene (4.425 g), 4-cyano-1-hydroxypen-4-yl-dithiobenzoate (0.084 g), ACPH (0.026 g), ⁇ -caprolactone (1.92 g) and AI(OCH(CH 3 ) 2 ) 3 (0.0810 g) were mixed in a 3-neck-round bottom flask. Oxygen was removed and the flask was immersed in an oil bath preheated at 110°C. After 23.5 hours the resulting polymer was isolated by precipitation in acidic methanol.
  • Methyl methacrylate (0.8781 ml), 4-cyano-4- ((thiobenzoyl)sulphanyl)pentanoic acid (0.010 g), ACP ⁇ (0.004 g), ⁇ -caprolactone (0.412 g), AI(OC ⁇ (C ⁇ 3 ) 2 ) 3 (0.04 g) in 10.5 ml toluene were mixed in a 3-neck-round bottom flask. Oxygen was removed and the flask was immersed in an oil bath preheated at 70°C. After 24 hours the resulting polymer was isolated by precipitation in acidic methanol.
  • Example VII Preparation of polv(methyl methacrylate-block- ⁇ -thiobutyrolactone) Methyl methacrylate (1.009 g), 4-cyano-1 -hydroxypen-4-tyl- dithiobenzoate (0.083 g), ACPH (0.0266 g), ⁇ -thiobutyrolactone (1.77 g), AI(OCH(CH 3 ) 2 ) 3 (0.0776 g) in 25 ml toluene were mixed in a 3-neck-round bottom flask. Oxygen was removed and the flask was immersed in an oil bath preheated at 70°C. After 21.3 hours the final polymer was isolated by precipitation in acidic methanol.

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Abstract

L'invention concerne un processus de préparation d'un copolymère multiséquencé réalisé en présence d'un amorceur multifonctionnel. Ledit processus consiste en une combinaison d'une réaction de polymérisation par ouverture d'anneau cationique catalysée par au moins un composé sélectionné parmi le groupe qui renferme des acides de Lewis, des métaux alcalins et des alcoxydes métalliques, et d'une réaction de (co)polymérisation régulée. Ladite réaction de copolymérisation régulée est une polymérisation de transfert de chaîne de fragmentation d'addition réversible et l'initiateur multifonctionnel est un inicta.
PCT/NL2003/000883 2002-12-23 2003-12-12 Processus de preparation d'un copolymere multisequence WO2004056880A1 (fr)

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Cited By (11)

* Cited by examiner, † Cited by third party
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FR2868072A1 (fr) * 2004-07-28 2005-09-30 Coatex Soc Par Actions Simplif Polymeres obtenus par l'utilisation de composes soufres comme agents de transfert pour la polymerisation radicalaire controlee de l'acide acrylique et leurs applications
WO2007048423A1 (fr) * 2005-10-26 2007-05-03 Stichting Dutch Polymer Institute Micelles unimoleculaires contenant des nanoparticules metalliques et leur utilisation en tant que catalyseurs pour la synthese de liaisons carbone-carbone
EP1950232A1 (fr) * 2007-01-26 2008-07-30 Polymers Australia PTY Limited Procédé pour la préparation de polymères greffes par Reversible Addition Fragmentation Chain Transfer (RAFT) et par polymérisation par ouverture de cycle (ROP)
WO2008122576A1 (fr) * 2007-04-05 2008-10-16 Dsm Ip Assets B.V. Émulsion oligomère/polymère aqueuse présentant une fonctionnalité cationique
WO2010012712A1 (fr) * 2008-07-28 2010-02-04 Total Petrochemicals France Procédé de préparation d'un copolymère dibloc comprenant un bloc polymère monovinylaromatique
CN102604310A (zh) * 2012-03-09 2012-07-25 同济大学 一种硅包覆聚合物纳米粒子的水相制备方法
CN102746474A (zh) * 2012-08-27 2012-10-24 同济大学 一种温度和pH敏感性的壳交联聚合物胶束的制备方法
CN103204981A (zh) * 2013-04-23 2013-07-17 江苏大学 一种聚乳酸-嵌段-聚n-异丙基丙烯酰胺温敏材料的合成方法
CN103664722A (zh) * 2012-08-31 2014-03-26 陶氏环球技术有限公司 光致生酸化合物，聚合物及其制备方法
US9052589B2 (en) 2012-08-31 2015-06-09 Dow Global Technologies Llc Polymer comprising end groups containing photoacid generator, photoresist comprising the polymer, and method of making a device
CN113480703A (zh) * 2021-07-08 2021-10-08 安阳工学院 一种光控自由基聚合协同开环共聚制备双亲嵌段共聚物的方法

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FR2868072A1 (fr) * 2004-07-28 2005-09-30 Coatex Soc Par Actions Simplif Polymeres obtenus par l'utilisation de composes soufres comme agents de transfert pour la polymerisation radicalaire controlee de l'acide acrylique et leurs applications
WO2007048423A1 (fr) * 2005-10-26 2007-05-03 Stichting Dutch Polymer Institute Micelles unimoleculaires contenant des nanoparticules metalliques et leur utilisation en tant que catalyseurs pour la synthese de liaisons carbone-carbone
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WO2008089518A1 (fr) * 2007-01-26 2008-07-31 Polymers Crc Ltd Synthèse de polymères
WO2008122576A1 (fr) * 2007-04-05 2008-10-16 Dsm Ip Assets B.V. Émulsion oligomère/polymère aqueuse présentant une fonctionnalité cationique
US9340699B2 (en) 2007-04-05 2016-05-17 Dsm Ip Assets B.V. Aqueous oligomer / polymer emulsion with cationic functionality
WO2010012712A1 (fr) * 2008-07-28 2010-02-04 Total Petrochemicals France Procédé de préparation d'un copolymère dibloc comprenant un bloc polymère monovinylaromatique
EP2151457A1 (fr) * 2008-07-28 2010-02-10 Total Petrochemicals France Procédé de fabrication d'un copolymère biséquencé doté d'une séquence de polymère monovinylaromatique
CN102604310A (zh) * 2012-03-09 2012-07-25 同济大学 一种硅包覆聚合物纳米粒子的水相制备方法
CN102604310B (zh) * 2012-03-09 2014-04-02 同济大学 一种硅包覆聚合物纳米粒子的水相制备方法
CN102746474B (zh) * 2012-08-27 2014-07-16 同济大学 一种温度和pH敏感性的壳交联聚合物胶束的制备方法
CN102746474A (zh) * 2012-08-27 2012-10-24 同济大学 一种温度和pH敏感性的壳交联聚合物胶束的制备方法
CN103664722A (zh) * 2012-08-31 2014-03-26 陶氏环球技术有限公司 光致生酸化合物，聚合物及其制备方法
US9052589B2 (en) 2012-08-31 2015-06-09 Dow Global Technologies Llc Polymer comprising end groups containing photoacid generator, photoresist comprising the polymer, and method of making a device
CN103664722B (zh) * 2012-08-31 2016-02-10 陶氏环球技术有限公司 光致生酸化合物，聚合物及其制备方法
US9279027B1 (en) 2012-08-31 2016-03-08 Dow Global Technologies Llc Photoacid generator compound, polymer comprising end groups containing the photoacid generator compound, and method of making
CN103204981B (zh) * 2013-04-23 2015-06-10 江苏大学 一种聚乳酸-嵌段-聚n-异丙基丙烯酰胺温敏材料的合成方法
CN103204981A (zh) * 2013-04-23 2013-07-17 江苏大学 一种聚乳酸-嵌段-聚n-异丙基丙烯酰胺温敏材料的合成方法
CN113480703A (zh) * 2021-07-08 2021-10-08 安阳工学院 一种光控自由基聚合协同开环共聚制备双亲嵌段共聚物的方法
CN113480703B (zh) * 2021-07-08 2023-09-01 安阳工学院 一种光控自由基聚合协同开环共聚制备双亲嵌段共聚物的方法

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