WO2012066016A1 - Procédé de fabrication de matières de polystyrène diblocs comprenant des blocs syndiotactiques et atactiques - Google Patents

Procédé de fabrication de matières de polystyrène diblocs comprenant des blocs syndiotactiques et atactiques Download PDF

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WO2012066016A1
WO2012066016A1 PCT/EP2011/070204 EP2011070204W WO2012066016A1 WO 2012066016 A1 WO2012066016 A1 WO 2012066016A1 EP 2011070204 W EP2011070204 W EP 2011070204W WO 2012066016 A1 WO2012066016 A1 WO 2012066016A1
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sps
aps
block
polymerisation
styrene
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PCT/EP2011/070204
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Liana Annunziata
Pierre De Fremont
Yann Sarazin
Jean-François Carpentier
Michel Duc
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Total Petrochemicals Research Feluy
Centre National De La Recherche Scientifique (Cnrs)
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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
    • C08F2/00—Processes of polymerisation
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Definitions

  • the present invention concerns the use of a metal-based catalyst alone or in combination with a metallic compound of formula M 2 (R') n , acting as chain transfer agent, to initiate the stereospecific chain-growth polymerisation of styrene and eventually prepare stereoblock polystyrenic materials by subsequent radical polymerisation of styrene, possibly in the presence of elastomers.
  • Syndiotactic polystyrene has been first described by Ishihara et al. (Ishihara, N.; Seimiya, T.; Kuramoto, M.; Uoi, in M. Macromolecules 1986, 19, 2464; JP-A- 62187708; EP-A-210615). Its unique mechanical properties make it valuable for industrial purposes and specialty materials. However, despite the remarkable heat and chemical resistance properties induced by its crystalline phase, sPS is, just as aPS, inherently brittle, which is an acute issue since it has to compete with inherently tough engineering plastics such as polyamides. For many applications, sPS toughness appears insufficient and its impact-modification is often highly desirable.
  • glass fibres often used to reinforce sPS, remains a palliative solution as they only enhance stress energy dissipation when the strain applied is perpendicular to their orientation direction.
  • Such fillers are far less effective than rubbery particles as impact modifiers.
  • aPS impact modification has been practiced for a long time, either by blending aPS with multi-block rubbery copolymers, mainly of the styrene-butadiene- styrene (SBS) type, or by merely polymerising styrene by a radical pathway in the presence of polybutadiene (PB) rubber leading to high-impact polystyrene, commonly referred to as HiPS.
  • PB polybutadiene
  • HiPS high-impact polystyrene
  • polybutadiene rubber chains are partly grafted in situ by polystyrene chain.
  • the resulting PB-g-PS emulsifies the rubbery particles formed within the aPS continuous phase.
  • HiPS are consequently composite thermoplastics made of soft particles well-dispersed and anchored within a stiff polystyrene matrix and exhibiting excellent elongation and impact properties.
  • sPS impact-modification through compounding with specialty rubbers resulted in significant extra-costs compared to direct-reaction processes, not to mention the price of the impact modifiers.
  • sPS and aPS are miscible in the amorphous state, i.e. mostly in the molten state, as long as the sPS fraction has not extensively developed crystallinity.
  • a major advantage of the present invention is that it makes possible the versatile production of impact-resistant polystyrene of very high thermal and chemical resistance.
  • sPS-Jb-aPS block copolymers either made by chain-growth polymerisation in presence of chain transfer agents (CTAs), or by any other means.
  • CTAs chain transfer agents
  • Synthesis of sPS under homogenous conditions relies usually on hemi- or post- metallocene titanium (IV/III) complexes activated with MAO or B(C6F 5 ) 3 or [CPh)][B(C6F 5 ) 4 ].
  • Suitable Ti complexes were selected, for instance, from:
  • the active catalyst was a Ti(lll) species derived from the Ti(IV) precursor.
  • pentamethylcyclopentadienyl-titanium-tribenzyl (Cp * TiBn 3 ) is known to produce almost pure sPS, giving better polymer yield and control of the average molecular weight in comparison to the corresponding trimethyl-titanium complex, as described for example by Grassi et al (Grassi, A.; Lamberti, C; Zambelli, A.; Mingozzi, I in. Macromolecules 1997, 30, 1884-1889).
  • sPS-graff-aPS copolymers were synthesized by a three- step process consisting of:
  • Endo involved a two-step process with the preliminary preparation of an atactic polystyrene macromer bearing a styryl end- group and its syndiospecific copolymerisation with styrene using CpTiCl3/MAO as catalyst.
  • Grassi et al. (Pastorino, R.; Capacchione, C; Ferro, R.; Milione, S.; Grassi, A. Macromolecules 2009, 42, 2480-2487) reported the preparation of syndiotactic polystyrene macromers end-capped with a bromine atoms, using stereospecific polymerisation of styrene with a CpTiR 3 -B(C6F 5 ) 3 catalyst and sequential reaction of living Ti-sPS chains with N-bromosuccinimide (NBS).
  • NBS N-bromosuccinimide
  • Styrene is a very versatile monomer, which can be polymerised either by radical, anionic, cationic or coordination-insertion mechanism. Radical pathways proved to be quite useful. In particular, the past few years have witnessed the rapid growth in development and understanding of new controlled radical polymerisation (CRP) methods.
  • CRP controlled radical polymerisation
  • One of the most efficient CRP method is nitroxide-mediated polymerisation (NMP) that requires stable-free nitroxide radicals or alkoxyamines as disclosed by Hawker et al. (Hawker, C. J.; Bosman, A. W.; Harth, E. Chem. Rev.
  • alkyl-lithium compounds are efficient reagents for neutralising an excess of TEMPO, yielding the corresponding diamagnetic alkylated alkoxy-amines.
  • the reaction has been extended to other alkyl metals, including Grignard reagents, and was found to be very efficient with dialkyl-samarium compounds as disclosed in Whitesides and Newirth (Whitesides, G. M.; Newirth, T. L. in J. Org. Chem. 1975, 40, 3443) or in Nagashima and Curran (Nagashima, T.; Curran, D. P. in Synlett 1996, 4, 330).
  • ATRP atom transfer radical polymerisation
  • Figure 1 represents the MALDI-ToF-MS spectrum of the reaction product of Mg(sPS) 2 and TEMPO.
  • Figure 2 represents the SEC trace of the material recovered via nitroxide-mediated polymerisation (NMP) of styrene with sPS-TEMPO using the first embodiment of the invention, respectively for the starting block having a number average molecular weight M n of 3 620 g/mol as indicated and for the final diblock copolymer having blocks of 4 900 g/mol and 35 780 g/mol as indicated.
  • NMP nitroxide-mediated polymerisation
  • Figure 3 represents the SEC trace of the material recovered via nitroxide- mediated polymerisation (NMP) of styrene with sPS-TEMPO using the first embodiment of the invention, respectively for the starting block having M n of 4 630 g/mol as indicated and for the final diblock copolymer having blocks of 3 840 g/mol and 90 740 g/mol as indicated.
  • NMP nitroxide- mediated polymerisation
  • Figure 4 represents the SEC trace of the material recovered via thermal polymerisation of styrene with Mg(sPS)2 using the second embodiment of the invention respectively for the starting block having M n of 4 630 g/mol as indicated and for the final copolymer with M n of 44 470 g/mol as indicated.
  • Figure 5 represents the SEC trace of the material recovered via thermal polymerisation of styrene with Mg(sPS)2 using the second embodiment of the invention respectively for the starting block M n of 8 810 g/mol as indicated and for the final copolymer with M n of 32 990 g/mol as indicated.
  • Figure 6 represents the SEC trace of the material recovered via catalytic polymerisation of styrene with Mg(aPS)2 using the third embodiment of the invention respectively for the starting block M n of 5 020 g/mol as indicated and for the final copolymer with M n of 12 030 g/mol as indicated.
  • Figure 7 represents the SEC trace of the material recovered via catalytic polymerisation of styrene with Mg(aPS)2 using the third embodiment of the invention respectively for the starting block M n of 10 560 g/mol as indicated and for the final copolymer with M n of 10 970 g/mol as indicated.
  • Figure 8 represents the DSC curve of a sPS-b-aPS diblock copolymer.
  • Figure 9 represents the conversion rate expressed in % as function of polymerisation time expressed in minutes for styrene polymerisation catalysed by Cp * Ti(CH 2 Ph)3/B(C 6 F5)3/AI(Oct)3 in ratio 1/1/1 at a temperature of 0°C using 65 equivalents of styrene (Table 4, lines 10-14) for conversion represented by ⁇ and for number-average molecular weight M n represented by o.
  • Figure 10 represents the conversion rate expressed in % as function of polymerisation time expressed in minutes for styrene polymerisation catalysed by Cp * Ti(CH 2 Ph)3/B(C 6 F5)3/AI(Oct)3 in ratio 1/1/1 at a temperature of 0°C using 325 equivalents of styrene (Table 4, lines 10-14) for conversion represented by ⁇ and for number-average molecular weight M n represented by o.
  • Figure 1 1 represents the 1 H NMR spectrum (C2D2CI4, 353 K) of sPS-end capped bromine atoms.
  • Figure 12 represents high temperature Gel Permeation Chromatography (GPC) chromatograms of the copolymers; the dashed line represents the starting sPS-Br block and the solid line represents the final copolymer.
  • GPC Gel Permeation Chromatography
  • Figure 13 represents the 1 H NMR spectrum (C 2 D 2 CI 4 , 353 K) of sPS-b-aPS copolymer
  • Figure 14 represents a plot of melting enthalpy ⁇ in terms of % of syndiotactic polystyrene present either in sPS/aPS blends, represented by squares or in sPS-b- aPS diblock copolymers represented by circles.
  • Figure 15 represents a plot of crystallisation enthalpy ⁇ in terms of % of syndiotactic polystyrene present either in sPS/aPS blends, represented by squares or in sPS-b-aPS diblock copolymers represented by circles.
  • Figure 16 represents a plot of melting enthalpy ⁇ (squares) and of melting temperature (circles) in terms of % of syndiotactic polystyrene present in sPS-b-aPS diblock copolymers.
  • Figure 17 represents the DSC curve for a aPS/sPS blend of composition 90/10 (blend 6 in table 7).
  • Figure 18 represents the DSC curve for a aPS/sPS blend of composition 90/10 additivated with 15 wt%, based on the total weight of the mix, of sPS-b-aPS block copolymer (blend 1 1 in table 7).
  • Figure 19 represents a plot of the reciprocal value t p "1 of the crystallisation peak time (t p ) as a function of crystallisation temperature Tc for syndiotactic polystyrene, represented by squares, and for a sPS-b-aPS copolymer with similar amount of aPS and sPS represented by circles.
  • Figure 20 represents a plot of the reciprocal value t p "1 of the crystallisation peak time (t p ) as a function of crystallisation temperature Tc for syndiotactic polystyrene, represented by squares ( ⁇ ), for a aPS/sPS blend represented by triangles ( A), for a sPS-b-aPS block copolymer with similar amount of aPS and sPS blocks represented by circles ( ⁇ ), and for a blend aPS/sPS additivated with 15 wt%, based on the total weight of the mix, of sPS-aPS copolymer represented by rhombuses ( ⁇ ) at a crystallisation temperature Tc of 244 °C.
  • Figure 21 represents an Avrami plot for syndiotactic polystyrene, represented by squares, and for a sPS-b-aPS copolymer with similar amount of aPS and sPS blocks represented by circles at a crystallisation temperature Tc of 245 °C.
  • Figure 22 represents an Avrami plot for syndiotactic polystyrene, represented by squares ( ⁇ ), for a aPS/sPS blend represented by triangles ( A), for a sPS-b-aPS block copolymer with similar amount of aPS and sPS blocks represented by circles ( ⁇ ), and for a blend aPS/sPS additivated with 15 wt%, based on the total weight of the mix, of sPS-aPS copolymer represented by rhombuses ( ⁇ ) at a crystallisation temperature Tc of 244 °C.
  • Figure 23 represents the 1 H NMR spectrum (300 MHz, C 2 D 2 CI 4 , 333K) of the crude sPS-Jb-aPS/PBD produced in Run 1 of Table 10. SUMMARY OF THE INVENTION.
  • sPS-Jb-aPS copolymers as crystallisation accelerators in mixtures comprising atactic and syndiotactic polystyrenes.
  • a purpose of the present invention is the versatile production of semi-crystalline impact-modified polystyrene dedicated to applications requiring a high thermal and chemical resistance.
  • the present invention discloses a method for preparing polystyrene materials containing a syndiotactic polystyrene block linked to an atactic polystyrene block, namely sPS-Jb-aPS block copolymers, wherein a metal-based catalyst component of formula [L n Xx]M 1 R n , alone or in combination with a compound M 2 (R') n ' acting as a chain transfer agent (CTA), initiates the stereospecific chain-growth polymerisation of styrene, and wherein M 1 is a metal selected from Group 3-5 of the Periodic Table, LnXx is a monanionic or a dianionic ligand selected from cyclopentadienyl-type ligands and related compounds or a phenolate or an amido-type ligand, all of these ligands possibly bearing additional donor groups, M 2 is an element selected from Group 1 to 13 of the Periodic Table, R is hydrogen or an alkyl
  • the M 2 (R) n ' compound which acts as a chain-tranfer agent (CTA), leads to the formation of M 2 (sPS) n ' species.
  • This intermediate product can be used as such, but it can optionally be end-capped with (a) a nitroxide radical thereby allowing the nitroxide-mediated polymerisation (NMP) of styrene, or (b) with dioxygen in the case of boryl-sPS species leading to boryl-O-O-sPS species, allowing radical polymerisation upon simple heating ( ⁇ ), , or (c) with halogens thereby allowing either atom transfer radical polymerisation (ATRP) or reversible iodine transfer polymerisation (RITP) of styrene.
  • ATRP atom transfer radical polymerisation
  • RITP reversible iodine transfer polymerisation
  • LnXx is preferably selected from cyclopentadienyl-type ligands of general formula C5R"5 where R" are equal or different and selected from hydrogen, alkyl, aryl, trialkylsilyl or hetero-functionalized substituents, and all related Cp-type ligands such as indenyl and fluorenyl derivatives, substituted or not.
  • L can also be a non- cyclopentadienyl ligand and selected from regular ligands used in post-metallocenes derivatives, for instance imino-phenolate derivatives, amido derivatives and all combinations derived from such phenolate and amido derivatives, with possible donor functionalities including imino, alkoxy, amino... . groups.
  • M 1 is preferably selected from Nd, Y, Sc, Ti, Zr
  • M 2 is preferably selected from Mg, Zn, Al, B
  • R is preferably selected from methyl or higher alkyl groups such as ethyl, butyl, hexyl and octyl, benzyl, allyl (C3H5) or allyl groups substituted at the 1 and/or 3 positions
  • R' is preferably selected from methyl or higher alkyl groups such as ethyl, butyl, hexyl and octyl, or benzyl groups, or allyl (C3H5) groups, or allyl groups substituted at the 1 and/or 3 positions
  • a Lewis acid such as B(C6F 5 ) 3 or [Ph 3 C][B(C6F 5 )4] or [HNMe 2 Ph][B(CeF 5 )4]
  • the method for preparing the aPS-b-sPS copolymer comprises the steps of: a) growing a first syndiotactic sPS block in the presence of a metal-based catalyst system [L n Xx]M 1 R n , and a M 2 (R') n ' chain transfer agent to generate a M 2 (sPS)n' product;
  • This embodiment can be schematically represented in Scheme 6 wherein M 1 is Nd M 2 is Mg and the functional group capped on sPS chain ends is a nitroxide introduced via TEMPO.
  • the method for preparing the aPS-b-sPS copolymer can be carried out in a one-pot process and comprises the steps of: a) growing a first syndiotactic sPS block in the presence of a metal-based catalyst system [L n Xx]M 1 R n , and a M 2 (R') n ' chain-transfer agent to generate a M 2 (sPS)n' product;
  • the selective deactivation of the Nd catalyst, required for growing aPS segments onto Mg(sPS)2, and thus for producing aPS-Jb-sPS stereoblock copolymers, is carried out with ethers, nitriles, simple amines or other species coordinating to lanthanides.
  • This deactivation step is necessary to stop the production of sPS that otherwise takes over that of aPS.
  • Both polymerisation steps are carried out at temperatures ranging from 20 °C to 160 °C, more preferably from 80 °C to 150 °C.
  • the method for preparing the aPS-Jb-sPS copolymer can be carried out in one-pot process and comprises the steps of: a) chain growing a first atactic aPS block by a thermal process in the presence of a M 2 (R')n' chain transfer agent to generate a M 2 (aPS) n ' product;
  • step b) chain-growing a second sPS block in the presence of a metal-based catalyst system [L n Xx]M 1 R n , and the M 2 (aPS) product of step a) to generate M 2 (sPS-Jb- aPS)n' product and forming a aPS-Jb-sPS block upon hydrolysing/quenching of the previous M 2 (aPS-Jb-sPS) n product.
  • Both polymerisation steps are carried out at temperatures ranging from 20 °C to 160 °C, more preferably from 80 °C to 150 °C.
  • the method for preparing the aPS-Jb-sPS block copolymer comprises the steps of: a) growing a first sPS block in the presence of a metal-based catalyst system [L n Xx]M 1 Rn, and in situ end-capping said sPS block with a halogen atom; b) growing an aPS block via atom transfer radical polymerisation (ATRP) or reversible iodine transfer polymerisation (RITP) and eventually forming sPS-Jb- aPS copolymers.
  • ATRP atom transfer radical polymerisation
  • RITP reversible iodine transfer polymerisation
  • the stereospecific polymerisation step is carried out at temperatures ranging from -20 °C to 160 °C, more preferably from 0 to 100 °C, in an hydrocarbon solvent such as heptanes, toluene and xylenes.
  • the ATRP polymerisation step is carried out at temperatures ranging from 60 °C to 180 °C, more preferably from 100 °C to 150 °C and in an organic solvent, preferably an ether such as anisole.
  • the syndiospecific and atactic blocks are grown sequentially by different methods.
  • the length of the sPS is selected when catalysed with a metal-based catalyst system and that of the aPS block is selected during the radicalar graft of styrene onto the sPS block.
  • the present methods thus produce sPS-b-aPS block copolymers that can be accurately tailored.
  • the same approaches can be used using a rubber in styrene solution as starting material, preferably a polybutadiene in styrene solution.
  • This approach leads to impact-modified semi-crystalline polystyrene composites.
  • the metallocene polymerisation of the rubber-in-styrene solution produces first a sPS and rubber in styrene solution.
  • the subsequent radical polymerisation of the remaining styrene is used advantageously to generate in situ some polystyrene- grafted rubber chains that stabilise the final rubber in polystyrene composites which contains crystalline domains resulting from the partial crystallisation of the syndiotactic PS produced in the first step.
  • This versatile and inexpensive process leads consequently to impact-modified semi-crystalline styrenic composites that can compare with polyamide or ABS in terms of impact resistance, ductility and stress- cracking resistance.
  • Impact-resistant semi-crystalline polystyrene can thus be obtained by using sPS-Jb- aPS block copolymer as a crystallisation accelerator in the preparation of sPS/HiPS blends.
  • This impact-resistant semi-crystalline polystyrene can advantageously be used in applications requiring a high heat and/or chemical resistance, such as the manufacturing of refrigerator liners, electrical & electronic appliances or automotive parts.
  • the sPS-b-aPS block copolymers of the present invention are characterised by a faster crystallisation rate than that of homopolymers of styrene. It is further observed that:
  • the diblock copolymers crystallise faster than blends for comparable Mn values.
  • aPS-Jb-sPS block copolymers can thus be used as accelerators in the polymerisation of styrene or in sPS/aPS blends, wherein the crystallisation rate increases with increasing amount of sPS in the block copolymer.
  • HPLC grade heptanes, toluene and m-xylene were purchased from VWR. Dry diethyl ether was purchased from Aldrich. These solvents were distilled under argon from a sodium mirror prior to use.
  • dichloromethane DCM
  • chloroform acetone
  • MEK methylbutylketone
  • methanol methanol
  • the initiator ⁇ Me 2 C(Cp)(Flu) ⁇ Nd(1 ,3-(SiMe 3 )2-C 3 H 3 ) was prepared with all steps performed under argon accoding to the method disclosed by Rodrigues et al. (Rodrigues, A. S.; Kirillov, E.; Roisnel, T.; Razavi, A.; Vuillemin, B.; Carpentier, J.-F. Angew. Chem. Int. Ed. 2007, 46, 7240).
  • reaction mixture was stirred for 1 day at room temperature, turning red, and diethyl ether was replaced by toluene (10 ml_) prior addition of 1 ,3-bis(trimethylsilyl)allyl potassium (1 .60 g, 7.13 mmol, 1 .01 equivalent(s)).
  • the solution was filtered, the solids were washed with pentane (2 x 10 ml_) and the deep red solution was evaporated in vacuo to afford a sticky solid. It was then triturated twice with heptanes to afford a crimson brittle powder after extensive drying (Yield: 3.77 g, 74%).
  • TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
  • Styrene 99.5%) was supplied by Aldrich, dried over CaH 2 overnight, distilled by heating at a temperature of 50 °C under dynamic vacuum at 10 "2 Bar and stored at a temperature of 4 °C away from light under argon.
  • Pentamethylcyclopentadienyltitanium(IV)tribenzyl (Cp * TiBn 3 ) was synthesised according to the method described by Mena et al. (Mena, M.; Royo, P.; Serrano, R. Organometallics 1989, 8, 476-482).
  • Trispentafluorophenylborane B(C6F 5 ) 3 was synthesised according to the method disclosed by Massey et al. (Massey, A.G.; Park, A. J. J. Organomet. Chem. 1964, 2, 245-250).
  • N-bromosuccinimmide (NBS), CuBr, 1 , 1 ,4,7,7- pentamethyldiethylenetriamine (PMDETA) were purchased from Aldrich, while 1 , 1 ,2,2-tetrachloroethane-d 2 was purchased from Acros.
  • reaction mixture was stirred for 3 h, cooled down to room temperature.
  • the mixture was quenched by addition of a dichloromethane solution containing 5% of acidified methanol (1 M/HCI).
  • Polystyrene-TEMPO materials were fully dissolved in dichloromethane (or chloroform), precipitated and washed with methanol to be dried out at 70 °C under vacuum.
  • the polymerisation was stopped by cooling down the reaction media to room temperature and, for analytical purposes, the Mg(aPS)2 chains were converted to two distinct aPS chains by addition of a solution of dichloromethane containing 5% of acidified methanol (1 M/HCI). Polystyrenes were fully dissolved in dichloromethane precipitated and washed with methanol to be dried out at 70 °C under vacuum.
  • the mixture was quenched to room temperature by addition of a dichloromethane solution containing 5% of acidified methanol (1 M/HCI). Polystyrenes were fully dissolved in dichloromethane (or chloroform), precipitated and washed with methanol to be dried out at 70 °C under vacuum.
  • the resulting solution was thermostated at 27 °C and the polymerisation was started by injection of the catalytic solution (dark red solution), prepared by adding a colourless solution of B(C6F 5 ) 3 (23 mg, 44 pmol in 2 mL of toluene) to a red solution of Cp * TiBn 3 (20 mg, 44 pmol in 3 mL of toluene). After 12 min, the mixture was poured into acidified methanol. When present, the polymers were recovered by filtration and dried at 45 °C in a vacuum oven.
  • the catalytic solution dark red solution
  • Cp * TiBn 3 20 mg, 44 pmol in 3 mL of toluene
  • the reaction was started by injecting the catalytic solution (dark red solution), prepared by adding a colourless solution of B(C6F 5 ) 3 (69 mg, 132 pmol in 2 mL of toluene) to a red solution of Cp * TiBn 3 (60 mg, 132 pmol in 3 mL of toluene).
  • the polymerisation was terminated after the prescribed time by adding the brominating agent NBS (N-bromosuccinimide, 6.6 mmol) and keeping the mixture under stirring for 1 h at room temperature.
  • the polymer was coagulated in acidified methanol, recovered by filtration, washed with large excess of acetonitrile, and dried in vacuo at 45 °C. ATRP of styrene and formation of sPS-b-aPS according to the second step of the fourth embodiment of the invention.
  • T m Melting points (T m ) of the polystyrene and copolymers were measured by differential scanning calorimetry (DSC) using a DSC 131 Setaram instrument in argon flow with a heating and cooling rate of 10 "C.min "1 in the range 30 °C to + 300 °C. Melting temperatures were reported for the second heating cycle.
  • NMR spectra of polymers and copolymers were recorded on a Bruker AM-500 spectrometer in 1 , 1 ,2,2-tetrachloroethane-d 2 at several temperature 353K, 333K, 323K and reported relative to tetramethylsilane.
  • reaction was tolerant to aromatic solvents such as toluene or xylenes, allowing homogenous polymerisation at temperature of 100 °C and above.
  • a MALDI-ToF-MS analysis of the polymers after reaction with TEMPO revealed two distributions as seen in Figure 1 .
  • One of these distributions fitted the expected capped sPS-TEMPO macromolecules while the second fitted the sPS-H chains.
  • the latter chains could arise from hydrolysis of Mg(sPS)2 during functionalisation with TEMPO and/or from fragmentation of sPS-TEMPO during the MS analysis.
  • This analysis revealed the presence of the targeted sPS-TEMPO materials but was not an indication of the efficiency of the functionalisation reaction.
  • the first polymer distribution had its M n close to that of the starting sPS-TEMPO and likely arose from some sPS-H chains formed during the synthesis of PS-TEMPO.
  • the second polymer had its M n way above the expected M n at 14 000 g.mol "1 . This can be explained by the fact that there is less macro-initiator than expected, due to the presence of inactive sPS-H chains. Both distributions overlapped on the SEC, but NMP was controlled and the (co)polymer sPS-Jb-aPS exhibited a narrow M n distribution characterised by a low PDI as seen in Figure 2.
  • MgBu 2 did not initiate the polymerisation in these experiments, but acted as chain transfer agent (CTA), narrowing the PDI below 3 for this type of free radical polymerisation. Under these conditions, the polymerisations were quite sluggish and the yields decreased with decreasing quantities of styrene for the same reaction time as seen in Table 2.
  • CTA chain transfer agent
  • a first series of experiments was undertaken to search a suitable chain transfer agent to be used in combination with the Cp * TiBn 3 /B(C6F 5 ) 3 catalyst, in order to produce sPS blocks via chain growth polymerisation.
  • Different CTAs and different titanium/CTA ratios were evaluated. Diethylzinc, dibutylmagnesium and triethylborane turned out to be poisons for the catalytic system and, in all cases, the solution immediately changed colour once the dark red catalytic solution was added to the solution containing the CTA. It changed from red to deep yellow, green and clear yellow, respectively.
  • some AIR 3 compounds proved to be compatible with the Cp * TiBn 3 /B(C6F 5 ) 3 catalyst system. Therefore, several polymerisations were performed by changing the Al/Ti ratio.
  • the polymerisations were carried out as follows: 44 ⁇ of Ti catalyst; 44 ⁇ of boron cocatalyst; 35 mL of toluene; 5 mL of styrene; at a temperature of 27 °C ; during a period of time of 12 minutes.
  • M n values calculated by 1 H NMR were in good agreement with the M n values obtained by HT-GPC analysis; on the other hand, there was a systematic discrepancy between the theoretical M n values, determined from the styrene-to-Ti ratio and conversion values, and the M n values obtained from either NMR or GPC measurements.
  • NBS is an efficient brominating agent.
  • the present conditions allowed the preparation of nearly perfectly functionalised syndiotactic polystyrene.
  • the efficiency of this functionalisation step was assessed by NMR spectroscopy.
  • copolymers were fully characterised by HT-GPC, NMR spectroscopy and by DSC. Formation of diblock sPS-Jb-aPS copolymers were confirmed by GPC analysis, by the shift of the trace toward higher molecular weight values after the ATRP as seen in Figure 12.
  • compositions of the synthesised sPS-Jb-aPS are displayed in Table 6. TABLE 6.
  • the diblock copolymers sPS-Jb-aPS were characterised by 1 H and 13 C NMR spectroscopy.
  • Figure 13 shows the 1 H NMR spectrum of a copolymer where the signals of the aPS and sPS blocks are clearly visible.
  • no signals of the starting sPS-Br were detected, indicating that all the functionalised chains initiated the ATRP of styrene.
  • the bromine atoms were found at the end of the atactic block, and the signals were attributed according to the literature for related atactic polystyrene obtained via ATRP, for example in Liu and Sen (Lui, S.; Sen, A. Macromolecules 2000, 33, 5106-51 10) or in Chen et al. (Chen, J.; Cui, K.; Zhag, S.; Xie, P.; Zhao, Q.; Huang, J.; Shi, L; Li, G.; Ma, Z. Macromol. Rapid. Commun. 2009, 30, 532-538).
  • the sPS-Br samples and their corresponding sPS-Jb-aPS copolymers were characterised by DSC and all data are reported for the second heating cycle.
  • a melting temperature was observed around 270-272 °C, which is characteristic of sPS.
  • a lower melting temperature ranging between 264 °C and 266 °C was observed.
  • a maximun decrease of ca. 5 °C in the melting temperature was observed for the block copolymers sPS-Jb-aPS.
  • Thermal properties of the aPS-Jb-sPS diblock copolymers have also been carried out and compared with blends of aPS and sPS homopolymers having comparable percentage of aPS and sPS components and with blends of aPS and sPS homopolymers additivated with aPS-Jb-sPS diblock copolymers.
  • the last two diblock copolymers of Table 4 have been characterised using different crystallisation flow rates.
  • DSC Differential scanning calorimetry
  • T c values were found to be related to the percentage of aPS in the blends: the more aPS in the blends, the lower the crystallisation temperature, as seen in Figure 19. This trend is even more obvious at high flow rates (20 °C/min).
  • the diblock copolymers showed a similar behavior but in all cases, for a given aPS/sPS ratio, the crystallisation of the diblock copolymer proceeded faster (i.e., at a higher T c value) than for the corresponding sPS/aPS blend. That can be seen by comparing lines 1 and 5 and lines 2 and 7 of Table 7.
  • the effect of sPS-Jb-aPS stereoblock materials on the crystallysation behavior of aPS/sPS blends was tested by adding from 5 to 15% of stereoblock copolymer to aPS/sPS blends. The results are reported in Table 7. Interestingly, the addition of 15% of copolymer affected positively the crystallysation behaviour of the blends.
  • Crystallisation proceeded faster when the stereoblock materail was added. This effect was amplified in the blends with high contents (90%) of aPS. It was further observed that the beneficial effect of the stereoblock copolymers on the crystallisation behavior blends increased with increasing crystallisation flow rate. isothermal crystallisation studies were also performed in order to better understand the crystallisation behaviour of this copolymer, used either alone or as additive in the aPS/sPS blends. For comparative purposes the same studies were also conducted on pure sPS and on aPS/sPS blends.
  • the pure sPS crystallizes the fastest (i.e., the highest t p "1 value), followed by copolymer and aPS/sPS blend modified with sPS-Jb-aPS (i.e. similar t p "1 values) and by aPS/sPS blend which showed the lowest t p "1 value.
  • the new diblock copolymer alone or used as additive in the aPS/sPS blends crystallised faster than regular aPS/sPS blend having the same relative amounts of sPS and sPS as the diblock copolymer.
  • V c 1 - expt(-Kt n ) wherein K is the rate constant, containing the nucleation and the growth parameter in an isothermal crystallisation process, and n is the Avrami exponent whose value depends on the nucleation mechanism and on the nature of crystal growth.
  • n and K were calculated by plotting Log(-ln(1 -V c )) vs. Log (t) and evaluating the slope and intercept of the best fitting line. For consistency, the slope (n) and intercept (Log K) values were taken from the portion 0.05 ⁇ V c ⁇ 0.50 of the Avrami plot.
  • the diblock copolymers crystallise faster than blends for comparable Mn values.
  • aPS-Jb-sPS block copolymers can thus be used as accelerators in the polymerisation of styrene or in sPS/aPS blends, wherein the crystallisation rate increases with increasing amount of sPS in the block copolymer.
  • T max 300 °C.
  • the same treatments brought significantly lower Tc values. It was also observed that copolymers crystallised faster than the corresponding blends. This trend was amplified at high flow rates, for example at 20 °C/min.
  • a 25 mL glass flask equipped with a magnetic stirring bar was charged sequentially with sPS-Br (0.200 g, 1 1.6 pmol), purified polybutadiene (50 mg), CuBr (35 pmol), anisole (15 mL), pentamethyldiethylenetriamine (PMDETA) (35 pmol) and styrene (1 .50 mL).
  • 3 freeze-pump-thaw cycles were performed to de-oxygenate the reaction medium, and finally the flask was filled with argon.
  • the resulting degassed suspension was stirred for 10 min. at room temperature and then was placed in an oil bath at 130 °C for the requested polymerisation time.
  • the reaction was terminated by pouring the clear homogeneous solution into a large excess of acidic methanol.
  • the copolymer was recovered by filtration, washed with fresh methanol, and dried under vacuum at 45

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Abstract

La présente invention concerne l'utilisation d'un catalyseur à base de métal, seul ou en combinaison avec un composé métallique de formule M2(R')n, agissant en tant qu'agent de transfert de chaîne, pour amorcer la polymérisation de croissance de chaîne stéréospécifique du styrène et préparer ultérieurement des matières polystyréniques stéréoblocs sPS-b-aPS, éventuellement renforcées par un caoutchouc, et utiles pour des applications nécessitant une résistance élevée thermique et/ou chimique.
PCT/EP2011/070204 2010-11-18 2011-11-16 Procédé de fabrication de matières de polystyrène diblocs comprenant des blocs syndiotactiques et atactiques WO2012066016A1 (fr)

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* Cited by examiner, † Cited by third party
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WO2018007869A1 (fr) 2016-07-02 2018-01-11 Rheomod De Mexico, S.A.P.I. De C.V. Polymères greffés
CN108070041A (zh) * 2017-07-11 2018-05-25 衢州蓝然新材料有限公司 一种醇溶性磺酸型阳离子交换树脂的制造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018007869A1 (fr) 2016-07-02 2018-01-11 Rheomod De Mexico, S.A.P.I. De C.V. Polymères greffés
US11046801B2 (en) 2016-07-02 2021-06-29 Rheomod de México, S.A.P.I. de C.V. Grafted polymers
CN108070041A (zh) * 2017-07-11 2018-05-25 衢州蓝然新材料有限公司 一种醇溶性磺酸型阳离子交换树脂的制造方法
CN108070041B (zh) * 2017-07-11 2020-12-01 衢州蓝然新材料有限公司 一种醇溶性磺酸型阳离子交换树脂的制造方法

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