WO2012156237A1 - Utilisation d'un initiateur multifonctionnel pour préparer des copolymères diséquencés comprenant une séquence de polymère monovinylaromatique - Google Patents

Utilisation d'un initiateur multifonctionnel pour préparer des copolymères diséquencés comprenant une séquence de polymère monovinylaromatique Download PDF

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WO2012156237A1
WO2012156237A1 PCT/EP2012/058486 EP2012058486W WO2012156237A1 WO 2012156237 A1 WO2012156237 A1 WO 2012156237A1 EP 2012058486 W EP2012058486 W EP 2012058486W WO 2012156237 A1 WO2012156237 A1 WO 2012156237A1
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monomer
group
block
monovinylaromatic
catalyst
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PCT/EP2012/058486
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English (en)
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Valentin Poirier
Yann Sarazin
Jean-François Carpentier
Michel Duc
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Total Research & Technology Feluy
Centre National De La Recherche Scientifique (Cnrs)
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Publication of WO2012156237A1 publication Critical patent/WO2012156237A1/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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides

Definitions

  • the present invention concerns a process to make a diblock copolymer having a monovinylaromatic polymer block and a block having ester and/or carbonate monomer units such as by way of example lactic acid, glycolic acid, lactones, and/or trimethylene carbonate.
  • the mixtures of the said diblocks with a monovinylaromatic polymer have a high transparency similar to the transparency of the monovinylaromatic polymer alone.
  • These diblocks are useful as compatibilisers in mixtures comprising at least a polymer made essentially of the same monomer units as one of the blocks and at least a polymer made essentially of the same monomer units as the other block.
  • PLA Poly(lactic acid)
  • bio-polymers presenting the highest potential in terms of physical and mechanical properties, but also processability, considered as very close to polystyrene' ones.
  • Thermogravimetric analysis (TGA) of these block copolymers shows a two-step degradation curve with the first step corresponding to the degradation of poly(lactide) segment and the second step associated with the poly(styrene) segment of the block copolymer.
  • the bifunctional initiators were prepared by the esterification of 3-hydroxy-, 4- hydroxy-, and 3,5-dihydroxy-benzyl alcohols with a-bromoisobutyryl bromide and 2-bromobutyryl bromide.
  • the esterified benzyl alcohols were employed in the polymerisation of styrene under copper (Cu)-catalysed ATRP conditions to yield macroinitiators with low polydispersity.
  • the functional macroinitiator (2) was then used in solution ATRP of styrene with the in situ-generated ruthenium catalyst [RuCl2(p-cymene)(PRs)] to generate a diblock type poly(£-caprolactone)-b-polystyrene (4) with vacant bipyridine binding sites at one polymer chain termination.
  • the two mechanisms of polymerisation must be compatible and tolerant of one another, as well as of the monomers, the reaction temperature must remain constant, and the kinetics must be nearly identical.
  • the dual- functionalised initiator possesses a primary hydroxyl functionality, which is the initiation center for the living ROP of cyclic lactones or lactides, and an azo group, which initiates the radical polymerisation of vinyl monomers upon its thermal decomposition.
  • a monomer mixture of styrene (S) and ⁇ -caprolactone (CL) that is initiated by the dual initiator in the presence of Sn(oct) 2 as the ROP catalyst produces the diblock copolymer PS-b-PCL.
  • S styrene
  • CL ⁇ -caprolactone
  • the TEMPO-supported PCL behaved as a polymeric counter radical for the radical polymerisation of styrene, giving poly(CL-block-styrene) in quantitative efficiency.
  • the radical polymerisation was found to proceed in accordance with a living mechanism, because the conversion of styrene linearly increased over time, and the molecular weight was directly proportional to the reciprocal of the initial concentration of the PCL.
  • the resulting copolymers have two glass transition temperatures due to the PCL and polystyrene blocks and one melting endotherm based on the crystalline phases of PCL. Craig J. Hawker has described in Macromolecules, 1998, 31, 213-219, the making of diblock polymers of ⁇ -caprolactone and styrene. Basic of the process involving functional ised alkoxyamine initiators is shown hereunder:
  • the dual, or double headed initiator, 1 contains a single primary alcohol which is used as the initiating centre for the living ROP of lactones, as well as a secondary benzylic group which is an efficient initiator for the nitroxide-mediated "living" free radical polymerisation of vinyl monomers.
  • the living ROP of ⁇ -CL, 2, by 1 as the initiator was studied using a catalytic amount of aluminum tris(isopropoxide) as a promoter.
  • TEMPO-OH hydroxyl functional TEMPO
  • AIEt.3 an initiator for the ROP of lactide to produce the poly(lactide) functionalised TEMPO mediator (PLAT) shown in (a).
  • the PLAT mediator is then used to polymerise styrene or te/t-butyl styrene with a conventional initiator such as benzoyl peroxide (BPO) to make the desired styrenic-based block copolymer.
  • BPO benzoyl peroxide
  • the ROP of lactide is made in the presence of toluene as solvent, styrene is introduced only at step b). More, TEMPO-OH is used in a nearly stoechiometric amount versus the Al precursor to generate the polymerisation initiator.
  • the present inventors have recently discovered a more efficient process to make a diblock copolymer having a monovinylaromatic polymer block and a block having ester or carbonate monomer units. It is described in co-pending application WO/2010/012712. It discloses a process to make a composition comprising a block copolymer A-B that comprises the steps of:
  • a) forming a mixture comprising: one or more cyclic component polymerisable by ring-opening polymerisation (ROP) dispersed in at least one monovinylaromatic monomer,
  • ROP ring-opening polymerisation
  • step b) contacting the mixture of step a) with a mixture of b1 and b2 such that : b1 ) is M[N(SiR 8 3)2]x in which M is a metal, R 8 is an hydrocarbon group and x is the valency of the metal M,
  • M is a metal
  • R 9 is an hydrocarbon group
  • x is the valency of the metal M
  • BDI bulky ⁇ -diiminate ligands
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from hydrogen, unsubstituted or substituted hydrocarbyl, or inert functional group and wherein two or more of said groups can be linked together to form one or more rings, wherein X is an hydrocarbyl radical having from 1 to 12 carbon atoms, an alkoxide group OR * , an amido group NR ** 2 or a borohydride group (BH ).
  • step b) polymerising the solution obtained at step b) optionally in the presence of a free radical initiator, optionally in the presence of chain transfer agents, at conditions effective to produce:
  • step d) optionally degassing the product of step c) to separate the optional unpolymerised monomers and comonomers and recovering optionally a composition comprising at least the block copolymer A-B.
  • diblock copolymers having a monovinylaromatic polymer block and a block having ester and/or carbonate monomer units.
  • Figures 3a and 3b represent respectively the Size Exclusion Chromatography (SEC) of aliquots and final material resulting from experiments 1 and 2 in Table 2.
  • Figures 4a and 4b represent respectively the retention time curves of the polymers obtained with the one-step procedure and with the multi-step procedure.
  • the present invention discloses a process for preparing a diblock copolymer having a monovinylaromatic polymer block and a block having ester and/or carbonate monomer units that comprises the steps of:
  • step b) carrying out ROP of the monomer(s) of step b) in the presence of a suitable metallic or organic catalyst, in order to form P1-R-Y- R-P2;
  • the process is carried out in one-pot, one-step.
  • the compound of formula HO-R-Y-R'-OH, the one or more carbonate and/or ester monomers and the styrene are placed simultaneously in the reactor, and the mixture is heated to a temperature of at least 100 °C, resulting in the formation of P1-P3 and P2-P3 block copolymers.
  • R and R' are the same and are selected from tertiary alkyl groups or secondary benzylic groups, both possibly containing functionalities. More preferably the compound of step a) is
  • That compound is stable up to a temperature of 80 °C and offers the advantage of being easily available.
  • Suitable compounds of that type can be found in US-A- 5,079,310 and can be represented for example by formulae
  • An excess of the compound of formula HO-R-Y-R'-OH of step a) can be used with respect to the metallic/organic catalyst of c).
  • the molar excess is in the range 1 to 200, preferably of 50 to 200. That compound acts as an activator of some metallic catalysts, eventually transforming in situ these catalyst precursors into an active metal-alkoxide species.
  • Wako acts as an external initiator of the ROP process.
  • excess HO-R-Y-R'-OH is used, the alcohol functions act as transfer agent, thus generating as many polymer chains P1-R-Y-R -P2 as excess HO-R-Y- R'-OH molecules are introduced.
  • a portion of the monovinylaromatic monomer may also be polymerised as an homopolymer (or a copolymer when two or more monovinyl aromatic monomers are present) independantly of the diblocks P1-P3 and P2-P3.
  • the mixtures of said diblocks with a monovinylaromatic polymer made by the above process are nanostructured. When there is essentially no rubber, they have a high transparency similar to the transparency of the monovinylaromatic polymer alone. In said mixtures, the monovinylaromatic polymer is made of the same monomer units as the P3 block.
  • said diblocks recovered at step g) can be used as compatibilisers.
  • the diblocks P1-P3 and P2-P3 are useful as compatibilisers in mixtures comprising at least a polymer made essentially of the same monomer units as blocks P1 and P2 and at least a polymer made essentially of the same monomer units as the block P3.
  • the present invention also relates to said mixtures. These mixtures are often nanostructured.
  • the present invention also relates to a mixture comprising the diblock P1-P3 or P2-P3 and : - either one or more polymers made essentially of the same monomer units as the block P1 or P2,
  • the cyclic component(s) polynnerisable by ROP can be selected from cyclic monomers or dimers of aliphatic hydroxycarboxylic acids. Examples of these include lactide, glycol ide, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ - valerolactone, ⁇ -valerolactone, ⁇ -caprolactone and the like.
  • each of the D-form and the L-form as well as mixtures of both may be used. Racemic mixtures can also be used.
  • the D-lactide is the cyclic dimer made of two D-lactic acid
  • the L-lactide is the cyclic dimer made of two L-lactic acid
  • the meso lactide is the dimer made of one D-lactic acid and one L-lactic acid.
  • L, D-lactide or rac-lactide (rac-LA) designates a racemic mixture of L-lactide and D-lactide.
  • cyclic components polymerisable by ROP comprise cyclic carbonates and advantageously the 5- to 7-membered cyclic carbonates.
  • this polymerisation process is operative for 5- and 6-membered cyclic carbonates.
  • trimethylenecarbonate (TMC) 2- benzyloxy-trimethylenecarbonate (BTMC), 2-hydroxy-trimethylenecarbonate (TMCOH), 4-(benzyloxymethyl)-1 ,3-dioxolan-2-one (BDMC), 4-(hydroxymethyl)- 1 ,3-dioxolan-2-one (DMCOH).
  • cyclic carbonates such as 2-oxy-trimethylenecarbonate (OTMC), dehydrotrimethylenecarbonate (DHTMC) and 2,2 dimethoxy trimethylene carbonate (TMC(OMe) 2 ).
  • ROP of trim ethylene carbonate is as follows:
  • the preferred monomer polymerisable by ROP is lactide (LA) and/or trimethylenecarbonate (TMC), more preferably L-LA.
  • the monovinylaromatic monomer can be selected from any aromatic bearing a vinyl function.
  • styrene vinyl toluene, alphamethylstyrene, alphaethylstyrene, methyl-4-styrene, methyl-3- styrene, methoxy-4-styrene, hydroxymethyl-2-styrene, ethyl-4-styrene, ethoxy- 4-styrene, dimethyl-3,4-styrene, chloro-2-styrene, chloro-3-styrene, chloro-4- methyl-3-styrene, tert.-butyl-3-styrene, dichloro-2,4-styrene, dichloro-2,6- styrene,vinyl-1 -naphtalene and vinylanthracene.
  • a part of the monovinylaromatic monomer may be replaced by unsaturated monomers copolymerisable with styrene.
  • unsaturated monomers copolymerisable with styrene By way of example, mention may be made of alkyl esters of acrylic or methacrylc acid, acrylonitrile and methacrylonitrile.
  • the proportion of comonomer may be from 0 to 50% by weight for respectively 100 to 50% of the monovinylaromatic monomer.
  • the preferred monovinylaromatic monomer is styrene.
  • the catalyst components that may be used in the ring-opening polymerisation of the cyclic monomer of step c) depend upon the nature of the monomer and are well known from the prior art and can be selected from metal complex or Lewis acidic metal salt or metal-free organic base.
  • Metallic complexes can be represented by formula MR" n wherein M is a metal Group 2, 3 (including the lanthanide series, hereafter referred as Ln), 8, 12 or 13 of the periodic Table, wherein each R" is selected independently from hydrogen, an hydrocarbyl radical having from 1 to 12 carbon atoms, an alkoxide group OR * wherein R * is a linear or branched hydrocarbyl having from 1 to 12 carbon atoms, an amido group NR ** 2 wherein R ** is of general formula YR # 3 wherein Y is Si or C and each R# is independently selected from hydrogen or hydrocarbyl having from 1 to 12 carbon atoms, a borohydride group or an halide, and wherein n is the valence of M.
  • R is selected independently from hydrogen, an hydrocarbyl radical having from 1 to 12 carbon atoms, an alkoxide group OR * wherein R * is a linear or branched hydrocarbyl having from 1 to 12 carbon atoms, an amido group
  • M is Mg(ll), Ca(ll), Y(lll), Fe(ll), Fe(lll), Zn(ll), or Al(lll).
  • each R is selected independently from an amido group such as N(SiMe 3 )2, N(SiHMe 2 )2, an alkoxide group OR' such as OiPr, OMe, OBn, or a borohydride group (BH 4 )...
  • BDI bulky ⁇ -diiminate ligands
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from hydrogen, unsubstituted or substituted hydrocarbyl, or inert functional group andwherein two or more of said groups can be linked together to form one or more rings, wherein X is an hydrocarbyl radical having from 1 to 12 carbon atoms, an alkoxide group OR * wherein R * is a linear or branched hydrocarbyl having from 1 to 12 carbon atoms, an amido group NR ** 2 wherein R ** is of general formula YR # 3 wherein Y is Si or C and each R# is independently selected from hydrogen or hydrocarbyl having from 1 to 12 carbon atoms, a borohydride group (BH 4 ).
  • X is an hydrocarbyl radical having from 1 to 12 carbon atoms, an alkoxide group OR * wherein R * is a linear or branched hydrocarbyl having from 1 to 12 carbon atoms, an amido group NR **
  • R a is (CH 2 ) m NCH2CH2(OCH 2 CH2) n wherein m is 1 , 2 or 3 and n ⁇ 1 );
  • R b is hydrocarbyl group having 1 to 10 carbon atoms and is preferably selected from methyl, ethyl, iso-propyl, tert-butyl or neo-pentyl;
  • R c is the same as R a or is hydrocarbyl group having 1 to 20 carbon atoms and is preferably alkyl selected from methyl, ethyl, iso-propyl, tert- butyl, neo-pentyl, cumyl, trityl or aryl selected from phenyl, 2,4,6- trimethylphenyl, 2,6-diisopropylphenyl.
  • the key element in the substitution pattern is R a which must simultaneously comprise a nitrogen function and an oxygen atom engaged in the cycle. It is a cycloazoether.
  • the metallic salt can be selected from metallic complexes of formula M'(OSO 2 CF 3 )n, hereafter referred to as triflates or OTf or M'(N(OSO 2 CF 3 )2)n, hereafter referred to as triflimidates or NTf 2 or M'(R $ C(O)CR 2 C(O) R $ ) n , hereafter referred to as acetylacetonates or acac or (R"CO 2 ) n M', hereafter referred to as carboxylates, wherein M' is a metal Group 2, 3, including the lanthanide series, hereafter referred as Ln, 4, 12, 13, 14 or 15 of the periodic Table, wherein each R $ is selected independently from a linear or branched hydrocarbyl radical having from 1 to 12 carbon atoms, substituted or not by for instance an halogen or heteroatom, wherein each R" is selected independently from a perfluorinated alkyl or aryl residue having from 1 to 12
  • I is Mg(ll), Ca(ll), Sc(lll), Ln(lll) ,Y(III), Sm(lll), Yb(lll), Ti(IV), Zr(IV), Fe(ll), Fe(lll), Zn(ll), Al(lll) Sn(IV) or Bi(lll). More preferably, it is Al, Bi, Zn or Sc, Al and Zn being the most efficient metals, and most preferably Zn.
  • each R $ is selected independently from alkyl group such as CH 3 or a substituted alkyl group such as CF 3 , More preferably, they are all the same and they are CR 3 or CF 3 .
  • R" is (C6F 5 ) or (CF 3 ), or CF 3 (CF 2 ) m wherein m is an integer from 1 to 6.
  • AI(OTf) 3 AI(NTf 2 ) 3 , Mg(OTf) 2 , Ca(OTf) 2 , Zn(OTf) 2 , Sc(OTf) 3 , Bi(OTf) 3 , Fe(acac) 3 , AI(OCOCF 3 ) 3 , Zn(OCOCF 3 ) 2 , Zn(BF 4 ) 2 , Zn(acac) 2 .
  • These catalysts act by an activated monomer pathway, in the combination with an external nucleophile, typically the PC-(OH) n compound.
  • the non-metallic organic compounds can be selected, as non limitative examples, from dimeric phosphazene bases as disclosed for example in Zhang et al. (Zhang L, Nederberg F., Messman J.M., Pratt R.C., Hedrick J.L., and Wade C.G., in J. Am. Chem. Soc, 2007, 129, 12610-1261 1 ) or phosphazene bases as disclosed for example in Zhang et al.
  • Nederberg F. Lohmeijer G.B., Leibfarth F., Pratt R.C., Choi J., Dove A.P., Waymouth R.M., Heidrich J.L., in Biomacromolecules, 8, 153, 2007
  • Mindemark et al. Mindemark J., Hilborn J., Bowden T., in Macromolecules, 40, 3515, 2007).
  • the amount of catalyst used for the ROP in step c) is advantageously selected to obtain a ratio of the cyclic component(s) polymerisable by ROP to catalyst ranging between 100 to 100 000, preferably of at least 1 000 and more preferably of at least 1 500.
  • the ratio of the number of equivalent of functional alcohol-to-catalyst ranges between 1 and 200.
  • the polyester and/or polycarbonate blocks thus prepared show typically a unimodal molecular weight distribution that ranges from 1 .1 to 5.0, more typically from 1 .5 to 2.5.
  • the number average molecular weight Mn can be tuned by the monomer-to- functional alcohol ratio and ranges from 1 000 to 1 000 000 g/mol, more typically from 10 000 to 250 000 g/mol.
  • the ROP of step c) can be carried out at moderate temperature.
  • said temperature is below 100 °C, preferably below 80 °C.
  • a portion of the monovinylaromatic monomer may also be polymerised as a monovinylaromatic polymer independently of the above mechanism, following a usual radical mechanism.
  • the proportion of the monovinylaromatic polymer is increasing with the presence of a chain transfer agent.
  • the amount of monovinyl aromatic monomer is high enough and the temperature high enough, a substantial portion of the monovinyl aromatic monomer is also polymerised as an homopolymer (or a copolymer when two or more monovinyl aromatic monomers are present) independently of the diblocks P1 -P3 and P2-P3.
  • the catalyst used in the ROP of lactide was Ln 3 OZn(N(TMS) 2 ), wherein TMS is trimethylsilyl. e 3
  • Wako was obtained from Wako Chemicals Gmbh. Styrene (99+%) was received from Aldrich, dried over CaH 2 for a minimum of 48 hours, distilled by heating under dynamic vacuum and stored at 4 °C over activated molecular sieves; it was used within two weeks to avoid contamination by polystyrene. Toluene was pre-dried over sodium, and systematically distilled under Argon from a sodium mirror prior to use.
  • the reaction was terminated by addition of acidified MeOH (HCI, 1 wt-%) and the polymer was precipitated in hexane. It was purified by several re-precipitations, using THF as solvent and hexane as a non-solvent. The polymer was then dried to constant weight by heating at 60 °C under dynamic vacuum ( ⁇ 10 "2 mbar).
  • GPC Gel Permeation Chromatography
  • the ROP of lactide is carried out in the presence of metallic compound Ln 3 OZnN(TMS) 2 .
  • Mn represents the number average molecular weight.
  • PDI represents the polydispersity index defined as the ratio Mw/Mn of the weight average molecular weight over the number average molecular weight.
  • Figure 1 represents the gel permeation chromatography (GPC) traces of polymers for various monomer to alcohol ratios. It can be seen that the retention time increases when the ratio monomer/alcohol decreases, indicating that the molecular weight of the resulting polymer decreases.
  • GPC gel permeation chromatography
  • Figure 2 represents the IR spectrum of the polylactide formed hereabove which is seen to be a combination of the IR spectra of classical PLLA and WAKO (VA- 086 stands for WAKO in this Figure).
  • FIGS 3a and 3b represent respectively:
  • Example 2 The preparation of PLA-b-PS block copolymer was carried out in a one-step, one-pot process according to scheme
  • the block copolymer obtained had a number average molecular weight Mn of 56000 g/mol and a polydispersity index PDI of 2.56 as measured by GPC.
  • the retention time curves were the same as those obtained with the multi-step procedure as can by comparing Figures 4a and 4b representing respectively the retention time curve of the polymer obtained with the one-step procedure and with the multi-step procedure.

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Abstract

La présente invention concerne un procédé de fabrication d'un copolymère diséquencé comprenant une séquence de polymère monovinylaromatique et une séquence contenant des unités monomères ester ou carbonate utilisant à la fois une polymérisation par ouverture de cycle (ROP) et une polymérisation radicalaire.
PCT/EP2012/058486 2011-05-19 2012-05-09 Utilisation d'un initiateur multifonctionnel pour préparer des copolymères diséquencés comprenant une séquence de polymère monovinylaromatique WO2012156237A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017144385A1 (fr) * 2016-02-22 2017-08-31 AZ Electronic Materials (Luxembourg) S.à.r.l. Copolymères séquencés avec des groupes de jonction linéaires tensioactifs, leurs compositions et leurs procédés

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5079310A (en) 1989-11-27 1992-01-07 General Electric Company Free-radical generating aromatic diols, polycarbonates containing thermal labile groups and their conversion to polycarbonate block copolymers
EP0929031A2 (fr) 1998-01-08 1999-07-14 Seiko Epson Corporation Procédé et imprimante de vréseau
WO2010012712A1 (fr) 2008-07-28 2010-02-04 Total Petrochemicals France Procédé de préparation d'un copolymère dibloc comprenant un bloc polymère monovinylaromatique
WO2010066597A2 (fr) 2008-12-12 2010-06-17 Total Petrochemicals Research Feluy Procédé pour préparer des copolymères biséquencés et multiséquencés
EP2253637A1 (fr) 2009-04-30 2010-11-24 Total Petrochemicals Research Feluy Systèmes catalytiques pour la polymérisation immortelle d'ouverture de cycle d'esters et carbonates cycliques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5079310A (en) 1989-11-27 1992-01-07 General Electric Company Free-radical generating aromatic diols, polycarbonates containing thermal labile groups and their conversion to polycarbonate block copolymers
EP0929031A2 (fr) 1998-01-08 1999-07-14 Seiko Epson Corporation Procédé et imprimante de vréseau
WO2010012712A1 (fr) 2008-07-28 2010-02-04 Total Petrochemicals France Procédé de préparation d'un copolymère dibloc comprenant un bloc polymère monovinylaromatique
WO2010066597A2 (fr) 2008-12-12 2010-06-17 Total Petrochemicals Research Feluy Procédé pour préparer des copolymères biséquencés et multiséquencés
EP2253637A1 (fr) 2009-04-30 2010-11-24 Total Petrochemicals Research Feluy Systèmes catalytiques pour la polymérisation immortelle d'ouverture de cycle d'esters et carbonates cycliques

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
ABDIAZIZ A. FARAH ET AL., POLYMER, vol. 47, 2006, pages 4282 - 4291
ASAWIN LIKHITSUP ET AL., J. POLYM. SCI., PART A: POLYM. CHEM., vol. 46, no. 1, 2008, pages 102 - 116
CHIH-FENG HUANG ET AL.: "A new strategy for the one-step synthesis of block copolymers through simultaneous free radical and ring-opening polymerisations using a dual-functional initiator", POLYMER, vol. 46, 2005, pages 1561 - 1565
CRAIG J. HAWKER, MACROMOLECULES, vol. 31, 1998, pages 213 - 219
ERI YOSHIDA; YUSUKE OSAGAWA: "Synthesis of Poly(E-caprolactone) with a Stable Nitroxyl Radical as an end-functional Group and Its application to a Counter Radical for Living Radical Polymerization", MACROMOLECULES, vol. 31, 1998, pages 1446 - 1453, XP000739212, DOI: doi:10.1021/ma970944h
HUANG C-F ET AL: "A new strategy for the one-step synthesis of block copolymers through simultaneous free radical and ring opening polymerizations using a dual-functional initiator", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 46, no. 5, 14 February 2005 (2005-02-14), pages 1561 - 1565, XP004727571, ISSN: 0032-3861, DOI: 10.1016/J.POLYMER.2004.12.013 *
MINDEMARK J.; HILBORN J.; BOWDEN T., MACROMOLECULES, vol. 40, 2007, pages 3515
NEDERBERG F.; LOHMEIJER G.B.; LEIBFARTH F.; PRATT R.C.; CHOI J.; DOVE A.P.; WAYMOUTH R.M.; HEIDRICH J.L., BIOMACROMOLECULES, vol. 8, 2007, pages 153
RIFAT JABBAR ET AL., J. APPL. POLYM. SCI., vol. 109, 2008, pages 3185 - 3195
TEMEL OZTURK ET AL: "One Step Synthesis of Multiphase Block Copolymers via Simultaneus Free Radical and Ring Opening Polymerization Using Poly(ethylene oxide) Possessing Azo Group", JOURNAL OF MACROMOLECULAR SCIENCE : PART A - CHEMISTRY, MARCEL DEKKER, NEW YORK, NY, US, vol. 45, no. 7, 1 January 2008 (2008-01-01), pages 572 - 577, XP009152544, ISSN: 0022-233X *
ZHANG L.; NEDERBERG F.; MESSMAN J.M.; PRATT R.C.; HEDRICK J.L.; WADE C.G., J. AM. CHEM. SOC., vol. 129, 2007, pages 12610 - 12611
ZHANG L.; NEDERBERG F.; PRATT R.C.; WAYMOUTH R.M.; HEDRICK J.L.; WADE C.G., MACROMOLECULES, vol. 40, 2007, pages 4154 - 4158

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017144385A1 (fr) * 2016-02-22 2017-08-31 AZ Electronic Materials (Luxembourg) S.à.r.l. Copolymères séquencés avec des groupes de jonction linéaires tensioactifs, leurs compositions et leurs procédés

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