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WO1998005691A1 - Polymeres en etoile a plusieurs branches de polyisobutylene partant d'un noyau de calixarene et leur synthese - Google Patents

Polymeres en etoile a plusieurs branches de polyisobutylene partant d'un noyau de calixarene et leur synthese Download PDF

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Publication number
WO1998005691A1
WO1998005691A1 PCT/US1997/014017 US9714017W WO9805691A1 WO 1998005691 A1 WO1998005691 A1 WO 1998005691A1 US 9714017 W US9714017 W US 9714017W WO 9805691 A1 WO9805691 A1 WO 9805691A1
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Prior art keywords
composition
polymerization
arene
star
isobutylene
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PCT/US1997/014017
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English (en)
Inventor
Joseph P. Kennedy
Istvan J. Majoros
Sunny Jacob
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The University Of Akron
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Priority claimed from US08/693,433 external-priority patent/US5844056A/en
Priority claimed from US08/862,581 external-priority patent/US5804664A/en
Application filed by The University Of Akron filed Critical The University Of Akron
Priority to AU39748/97A priority Critical patent/AU3974897A/en
Priority to DE19781927T priority patent/DE19781927T1/de
Priority to JP50825098A priority patent/JP2002500682A/ja
Publication of WO1998005691A1 publication Critical patent/WO1998005691A1/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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type

Definitions

  • This invention relates generally to star polymers and, more particularly, to the carbocationic polymerization of monomers such as isobutylene via the "core first" method.
  • this invention relates to the synthesis of well-defined star polymers having well-defined arms of polyisobutylene and block copolymers thereof emanating from a calixarene core.
  • the synthesis is accomplished by the use of novel multifunctional calixarene derivative initiators which, in conjunction with certain Fricdel-Crafts acids which act as coinitiators, induce the living (carbocationic) polymerization of isobutylene.
  • the resultant star polymers have a well-defined core as well as well-defined arms and are advantageously directly telechelic.
  • star polymers are seen as useful as, inter alia, surfactants, lubricants, rheology modifiers, and viscosity modifiers or control agents.
  • star polymers are now considered by many to be state-of-the-art viscosity modifiers and oil additives, although the potential of some of these star polymers for these applications is still being evaluated and tested.
  • multifunctional linking agents such agents have proven useful, in conjunction with anionic polymerization techniques, in preparing homo-, block-, and hclero-arm star polymers with varying number of arms.
  • Multifunctional linking agents have also been used in conjunction with carbocationic polymerization techniques to prepare well defined tetra-arm poly(isob ⁇ tyl vinyl ether) stars, and multi-arm polyisobutylene stars.
  • the polyisobutylene stars were prepared by hydrosilation of allyl-terminated polyisobutylenes with siloxane cores.
  • Linking living polymer chains with divinyl monomer(s) is also well known and has been used for the synthesis of multi-arm stars by anionic, cationic and group transfer polymerization techniques.
  • multifunctional initiators for the synthesis of multi-arm star polymers has not been as thoroughly developed in certain respects.
  • the use of multifunctional initiators is somewhat limited due to relatively poor initiator solubility in hydrocaibon solvents.
  • at least two studies have shown that hydrocarbon-swollen polydivinylbcnzene can be used as multifunctional anionic initiators.
  • the dispcrsity of the star polymers was rather broad in each of these studies.
  • Still other studies have recently used a hydrocarbon-soluble trifunctional initiator for preparing homo-, block-, and functionalized star polymers.
  • directly telechelic it is meant that the resultant star polymer, e.g., polyisobutylene, will automatically have a functional group at the end of each arm of the star polymer upon termination of the polymerization reaction. That is, chain end functionality of the polyisobutylene arms is preserved during formation of the star. In comparison, other star polymers require an additional process step to provide end chain functionality.
  • ill-defined it is meant that the core of the star polymer, e.g., PDVB, is an uncontrolled, crosslinked, gel-like structure having unsaturation sites in the core.
  • well-defined cores are built of readily characterizable, soluble molecules which are precursors to the core.
  • the resultant star polymers having well-defined cores may impart better resistance to mechanical/chemical degradation than star polymers using ill-defined cores. That is, the presence of unsaturation sites (i.e., double bonds) in the ill-defined cores (PDVB) provides for the possibility that the resultant star polymers will be more sensitive to oxidative reactions than the star polymers having well-defined cores.
  • PDVB ill-defined cores
  • PIB stars with ill-defined cores have a polydispersity of at least 1.4 or larger. Quantification of the number of arms and arm molecular weight is also not readily determined using conventional analytical techniques.
  • calixarenes are seen as a potential solution to the existing problems of ill-defined cores.
  • Calixarenes are cyclic condensation products of a ⁇ -substituted phenol and formaldehyde.
  • Gutsche et al. Various procedures have been developed by Gutsche et al. for the selective synthesis of various calixarenes and calixarene derivatives. Detailed descriptions of these procedures are set forth in various publications by Gutsche et al., including Gutsche, CD., Calixarenes. The Royal Society of Chemistry, Thomas Graham House, Cambridge, (1989); Gutsche, CD. ct al. "Calixarenes, 4.
  • thermoplastic elastomers TPEs
  • core first thermoplastic elastomers
  • a composition of matter suitable for use as a cationic polymerization initiator having the structure
  • a cationic polymerization initiator comprising a material selected from the group consisting of the /e/7-methoxy, fe/7-hydroxy, and fe/7-CI derivatives of
  • the arms of the composition of matter may further include at least one segment, incompatible with polyisobutylene, formed by cationic polymerization of a monomer other than isobutylene which is connected to the terminus end of the polyisobutylene to provide a polyisobutylcne-based block copolymer.
  • the present invention also includes a method for the carbocationic polymerization of a monomer which results in the formation of a polymer, comprising reacting ( I) an initiator selected from the group consisting of the .c/7-methoxy, tert- hydroxy, and tert-Cl derivatives of
  • Fig. 1 is a representative IJJ N MR (CDCI3) spectrum of 2-(p- methoxyphenyl)-2-methoxypropane.
  • Fig. 2 is a representative l
  • Fig. 3 is a representative 13 C NMR (CDC1 3 ) spectrum of
  • Fig. 4 is a representative ⁇ H NMR (CDCI3) spectrum of 5,ll,17,23,29,35,41,47-(2-methoxypropyl)-49,50,51,52,53,54,55,56- octamethoxycalix[8]arene.
  • Fig. 5 is a representative ⁇ C NMR (CDCI3) spectrum of 5,ll,17,23,29,35,41,47-(2-methoxypropyl)-49,50,51,52,53,54,55,56- octamethoxycalix[8]arene.
  • the peak corresponding to /er/-C attached to -OMe group, ⁇ 76.7 ppm is superimposed on the CDCI3 peaks.
  • Fig 6 is a plot of -ln(l-I e ffi)-I e ffi versus jCj from results obtained by incremental monomer addition (IMA) polymerization experiments of isobutylene with 2-(p-methoxyphenyl)-2-methoxypropane as initiator and BCl3-TiC-4 coinitiators.
  • IMA incremental monomer addition
  • RI refractive index
  • Fig.9 is a set of gel permeation chromatograms of (a) a RI trace, and (b) a UV trace, of polymers obtained by using the 5,11,17,23,29,35,41,47-(2- methoxypropyl)-49,50,51 ,52,53,54,55,56-octamethoxycalix[8]arene/BCl3-TiC_4 initiating system under the conditions set forth in Example 1 hereinbelow.
  • Fig.10 is a set of gel permeation chromatograms of (a) a RI trace, and (b) a UV trace, of polymers obtained by using the 5,11,17,23,29,35,41,47-(2- methoxypropyl)-49,50,51,52,53,54,55,56-octamethoxycalix[8]areneBCl3-TiCl4 initiating system under the conditions set forth in Example 4 hereinbelow.
  • Fig.10 is a set of gel permeation chromatograms of (a) a RI trace, and (b) a UV trace, of polymers obtained by using the 5,11,17,23,29,35,41,47-(2- methoxypropyl)-49,50,51,52,53,54,55,56-octamethoxycalix[8]areneBCl3-TiCl4 initiating system under the conditions set forth in Example 4 hereinbelow.
  • 1 1 is a set of gel permeation chromatograms of (a) a RI trace, and (b) a UV trace, of polymers obtained by using the 5, 1 1 , 17,23,29,35,41 ,47-(2- melhoxypropyl)-49,50,51,52,53,54,55,56-octamcthoxycalix[8]arene/BCl3-TiCl4 initialing system under the conditions set forth in Example 5 hereinbelow.
  • Fig. 12 is a set of gel permeation chromatograms of (a) a laser light scattering (LLS) (90°) trace, and (b) a RJ (Optilab 903) trace of the resultant star polymer from Example 4 after fractionation.
  • LLS laser light scattering
  • Fig. 13 is a set of gel permeation chromatograms of RI traces, (a) before core destruction and (b) after core destruction of the star polymers from Example 4.
  • Fig. 14 is a plot of the molecular weight build-up of the block-arm
  • Fig. 15 is a set of gel permeation chromatograms of RI traces, (a) a homo- polyisobutylene star polymer and (b) a polystyrene-polyisobutylene star block copolymer.
  • Fig. 16 is a DSC thermogram, demonstrating heat flow (niV) as a function of temperature, of a representative octa-arm (polystyrene-b-polyisobutylene) star block copolymer.
  • Fig. 17 is a series of stress-strain curves of various octa-arm (polystyrene-b- polyisobutylene) star copolymers.
  • the present invention is directed toward the production or synthesis of aivionic polymerizable monomer such as, for example, isobutylene, styrene and its derivatives (such as the p-halo styienes and the p-alkyl styrenes).
  • a cationic polymerizable monomer such as, for example, isobutylene, styrene and its derivatives (such as the p-halo styienes and the p-alkyl styrenes).
  • a second segment, incompatible with the first, selected from a cationic polymerable monomer other than the monomer of the first and preferably aromatic, may also be added subsequent to the polymerization of the first segment to provide a star block copolymer.
  • a cationic polymerable monomer other than the monomer of the first and preferably aromatic may also be added subsequent to the polymerization of the first segment to provide a star block copolymer.
  • compositions of matter has been accomplished by the use of the "core first" method wherein a mono- or multi-functional initiator is used, in conjunction with at least one Freidel-Crafts acid, to induce the living (carbocationic) polymerization of a monomer such as isobutylene.
  • the resultant polymer composition is directly telechelic, meaning the chain end of the polymer arms remain functionalized upon termination of the polymerization reaction.
  • the subsequent addition of other cationic polymerizable monomers such as, for example, styrene, can be used to form various copolymers such as polyisobutylene- block-polystyrene, and other potentially useful thermoplastic elastomers.
  • a monofunctional initiator is used, only one arm will extend from the core. It will be appreciated that the monofunctional initiators suitable for use according to the concepts of the present invention are the . ⁇ ?;7-methoxy, /e/7-hydroxy, and (ert-C ⁇ derivatives of
  • monofunctional initiators suitable for use in the present invention include but are not necessarily limited to 2-(/;-methoxyphenyl)-2-propanol and 2-(/?-methoxyphenyl)-2- melhoxypropane. Where a multifunctional initiator is used, a plurality of arms equal to the number of functional sites on the initiator may extend from the core.
  • the number of arms, N will depend upon the number of cyclic units, n, in the calixarene product since each cyclic unit has one functional site. It is conventional in the art to refer to the number of cyclic units and, thus, the number of functional sites on a calixarene by denoting the product ns calix[n]arene where n equals the number of cyclic units.
  • the multifunctional initiators have the structure
  • the tert- methoxy derivative is used preferentially because it is soluble in polymerization charges (Cl ⁇ Cl/hexanes) at -80°C.
  • Examples of preferred multifunctional (octafunctional) initiators suitable for use in the present invention are the /t./7-methoxy, /e/7-hydroxy, and tert-C ⁇ derivatives of 5,1 l ,17,23,29,35,4 l ,47-octaacctyl-49,50,51,52,53,54,55,56- octamethoxycalix[8]arene, namely 5,1 l , 17,23,29,35,41 ,47-(2-hydroxypropyl)- 49,50,5 l ,52,53,54,55,56-oclamethoxycaIix[8]arene and 5,1 1 ,17,23,29.35,41 , 47-(2- mcthoxypropyl)-49,50,51,52,53,54,55,56-oclamethoxycalix[8]arene.
  • the monofunctional initiators may be considered analogues of the multifunctional initiators of the present invention. While the main constituents of the derivative initiators, i.e., the /7-methoxy cumyl group and calixarenes, are known in the art, this is believed to be the first synthesis of the / ⁇ ?/7-methoxy, /e/7-hydroxy, and tert-C ⁇ derivatives of these compounds.
  • At least one Friedel-Crafts acid may be used as a co-initiator in the polymerization process, and any known Friedel-Crafts acid suitable as a co-initiator for carrying out the polymerization reaction may be used in the present invention.
  • the monomer may be any carbocationic polymcrizable monomer.
  • examples of such monomers include isobutylene and styrene as well as derivatives of styrene such as, for example, / -chloro styrene.
  • the preferred monomer for the present invention is isobutylene which, upon carbocationic polymerization in the presence of a multifunctional calixarene initiator and a Friedel- Crafts acid as co-initiator, forms multiple polyisobutylene arms emanating from a calixarene core.
  • polyslyrcnc-polyisobutylene block copolymers can be formed.
  • Any cationic polymerizable monomer substantially incompatible with the monomer used in the first addition polymerization can be added to form the block copolymer.
  • derivatives of styrene are also particularly suitable for this subsequent addition.
  • Such derivatives include the / -halo styrenes such as /7-chloro styrene or -fluoro styrene, the -alkyl styrenes such as />-methyl styrene, ⁇ - ethyl styrene and indene.
  • Other potentially useful monomers include ⁇ -pinene and norbornene.
  • nl least one solvent should be used in the synthesis.
  • a solvent should be capable of solubilizing the initiator, the Friedel-Crafts acid, and the monomer as well as the polymer.
  • the solvent should not be capable of undergoing polymerization itself during the formation of the polymer and must not permit termination or chain transfer to occur.
  • certain solvents such as TIIF are specifically excluded.
  • exemplary solvents suitable for use in the present invention include but are not necessarily limited to the chlorinated alkanes, CI I2CI2, hexanes, carbon dioxide, and mixtures thereof, with CII3CI being preferred under certain conditions.
  • the polymerization reaction is further carried out in the presence of an electron pair donor and a proton scavenger.
  • Any known electron pair donor and proton scavenger suitable for use with the other constituents of the polymerization process as described herein may be used.
  • the preferred electron pair donor suitable for use are, inter alia, dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), dimethylphthalate (DMP), pyridine and its derivative tricthylamine (TEA), with DMA being most preferred.
  • Examples of proton scavengers include di-.c./7-butylpyridine (DtBP) and its methyl derivatives with DtBP being most preferred.
  • the polymerization process is carried out in two stages in one reactor.
  • the initiator is dissolved in a first solvent, followed sequentially by a portion of the amount of monomer required for polymerization, and a first Friedel-Crafts acid at a cryogenic temperature in the presence of an electron pair donor and a proton scavenger to induce polymerization.
  • a second stage an additional amount of solvent or a second and/or additional solvent(s), the balance of the monomer, and additional and/or a second Freidcl -Crafts acid are added in sequence.
  • a terminating agent such as methanol may be added.
  • compositions unlike many other star polymers, have been found to have well-defined cores as well as well-defined arms. Moreover, characterization of these resultant compositions have been found that they have a more definite number of arms, a more definite core molecular weight, a more definite arm molecular weight, and a narrower polydispersity as compared to compositions having an ill-defined core component. In fact, the composition of the present invention have been found to have a polydispersity far less than 1.4 and typically in the range of about 1.1 to about 1.15.
  • the resultant polymers were directly telechelic.
  • the terminating agent employed to quench the polymerization reaction is methanol
  • the end of each arm of the resultant composition will have a /e/7-Cl functional group.
  • the composition can easily be further functionalized based upon various known techniques such as dchydrochlorination or substitution of the /t ⁇ -CI group.
  • the polymerization is carried out in at least one solvent at cryogenic temperature and in the presence of an electron pair donor and a proton scavenger.
  • star polymer compositions comprising eight polyisobutylene (PIB) arms emanating from a calix[8]arene core were prepared as well as using other polyisobutylene compositions derived from the monofunctional analogues described hereinabove.
  • the synthesis of the star polymers was accomplished by the use of oclafunctional calixarene derivative initiators which, in conjunction with mixed BCl3/TiCl4 coinitiators, induce the living polymerization of isobutylene.
  • the initiators were /e/7-hydroxy- and /-./7-melhoxy derivatives of 5, 1 l , 17,23,29,35,41 ,47-octaacetyl-49,50,51 ,52,53,54,55,56- octamethoxycalix(8)arene.
  • the /er -methoxy derivative, 5, 1 1 , 17,23, 29,35,41 , 47-(2- mcthoxypropyl)-49,50,51,52, 53,54, 55,56-octamethoxycaIix[8]arene is soluble in induce the living polymerization of isobutylene to desirable arm lengths.
  • schemes have been included to help visualize the structures involved and the key steps of this "core-first" synthesis strategy.
  • compositions were also characterized using i NMR and ⁇ C NMR spectra recorded by a Varian Gemini-200 spectrometer using standard 5 mm tubes al room temperature.
  • Sample concentrations for l NMR and ⁇ C NMR spectroscopy were -30 mg and ⁇ 50 mg respectively in suitable solvents.
  • For ⁇ NMR spectroscopy 64 FIDs were collected and for ⁇ C NMR spectroscopy more than 4000 FIDs were collected. Melting points of the octafunctional initiators were determined by a Dupont's Differential Scanning Calorimeter in N2 atmosphere. Elemental analyses were performed by Galbrialh Laboratories Inc., Knoxville, Tennessee.
  • the molecular weight of the polymers was determined by GPC (Waters Co.) equipped with a series of five ⁇ -Styragel columns ( 100, 500, 10 3 , 10 4 , and 10$), RI detector (Waters 410 Differential Refractometer), UV detector (440 ⁇ bsorbance Detector), WISP 7103 with Nelson Analytical Interfaces.
  • the columns were calibrated using narrow molecular weight PIB standards.
  • Approximately 20 mg of polymer and a few crystals of sulfur (internal standard) were dissolved in 4 mL TIIF, the solution was filtered by using a 0.2 ⁇ m Acrodisc Filter (membrane type PTFE).
  • the polymer solution 100 ⁇ L was injected into the column using the auto injector.
  • the Nelson Analytical Gel Permeation Chromatography Software (version 4.0) was used for data analysis.
  • the molecular weights of the star polymers were determined by a laser light scattering (LLS) detector (Wyatt Technology Corporation). The dn/dc values were obtained by using an Optilab 903 (Wyatt Technology Corporation) instrument. Samples for light scattering were prepared with care to avoid the presence of particulate matter.
  • LLS laser light scattering
  • Samples for light scattering were prepared with care to avoid the presence of particulate matter.
  • polymers were dissolved in prefiltercd TI IF by 0.025 ⁇ m Whatman Anolop 25 filters, the solutions were filtered using 0.2 ⁇ m Acrodisc filters (membrane type PTFE), evaporated to dryness in air under dust-free conditions, and further dried in vacuum until all TI IF was removed. Polymer solutions of known concentrations (e.g.
  • the first four steps have been described by Gutsche et al. as reported hereinabove.
  • the first step involves the cyclic condensation ofp-ter/-butylphenol and ⁇ -formaldehyde in the presence of KOH to obtain the octafunctional 5,11,17,23,29,35,41,47-Octa-tert- butyl-49,50,51,52,53,54,55,56-octahydroxycalix[8]arene.
  • the second step is die dealkylation of the p-tert-butyl group by AICI3 in the presence of phenol in toluene to give 49,50,5 l,52,53,54,55,56-octahydroxycalix[8]arene.
  • the third step involves protection of the -OH group as the methyl ether to afford 49,50,51,52,53,53,54,55,56- octamethoxycalix[8]arene, which enables the subsequent Friedel-Crafts acylation to 5,l l,17,23,29,35,41,47-octaacetyl-49,50,51,52,53,54,55,56-octamethoxycalix[8]arene. From this point, a 1000 mL three-neck flask equipped with stirrer, condenser, and an addition funnel, was purged with nitrogen, and 339 g (1.01 mmol) of methyl magnesium bromide were added dropwise.
  • the aqueous layer was extracted five times with 50 mL portions of anisole and a small amount of ether.
  • the organic layer was dried over MgSO4, filtered, and the product precipitated using excess hexane.
  • the solid was filtered, washed with hexane to remove traces of anisole, and dried in vacuum to give a 72% yield of 5, 1 l ,17,23,29,35,41 ,47-(2-Hydroxypropyl)-49,50,51,52,53,54,55,56- octamethoxycalix[8]arene.
  • NMR analyses the product was essentially pure.
  • the new monofunctional initiator 2-(p-me(hoxyphenyl)-2-me(hoxypropane was used as a monofunctional model of the octafunctional initiator 5, l l , 1 7,23 ,29,35,4 1 ,47- (2 -methoxypropy l )-49, 50, 5 1 , 52 , 53 , 54 , 55 , 56- octamethoxycalix[8]arene to initiate the living (carbocationic) polymerization of isobutylene using mixed Freidel-Crafts acids, BCI3 and T1CI4, as coinitiators in Cl I3CI- hexanes mixture (40:60) as solvent at -80°C
  • the two stage procedure described hereinabove was followed wilh only minor variations.
  • the polymerizations were carried out in 75 mL culture tubes in a stainless steel glove box under dry nitrogen at -80°C The volume of the charge was 29 mL.
  • the addition sequence of the readmits was: CI ⁇ CI (7-8 mL), monomer (33% of the required amount), initiator 2-(/ -mcthoxyphenyl)-2- mcthoxypropane, dimcthylacetamide (DMA), di /07-butylpyridine (DtBP), nnd BCI3.
  • Stock solutions of initiator, DMA, DtBP, and BCI3 were prepared in CH3CI. Care was taken not to freeze the T1CI4, and the balance amount of monomer was added.
  • the polymerization is continued by the addition of TiCl4, plus the required amount of hexanes and the balance of isobutylene.
  • the reaction is carried to the conversion level.
  • the M n (g/mol) versus Wp,(g) plots indicate slow initiation, i.e., the observed molecular weights are initially higher than theoretical and converge to the theoretical value at higher conversions. Slow initiation is most likely due to the formation of a resonance stabilized carbonation, which causes cationation to be rate limiting.
  • Fig. 6 shows a plot of -ln(l -I e ffJ) - I e ff. versus jCj. The linearity of the plot starting from the origin indicates living polymerization with slow initiation. To determine whether the primary ether group stays intact during polymerization and work-up, isobutylene oligomers were prepared to facilitate analysis.
  • Figure 7 shows a representative h i NMR spectrum
  • the charge contained 10 mL CI I3CI, DMA (5.57 x I0' 2 M), DtBP ( 1.452 x 10' 2 M), 2 mL isobutylene and the polymerization was induced by the addition of BCI3 (4.45 x I 0" 1 M) at 80°C.
  • Initiator 5 1 1 , 17,23,29,35,4 l ,47-(2-methoxypropyl)-49,50,5 1 , 52,53, 54, 55,56-octamethoxycalix[8]arene, 8.45 x 10" 2 g (5.402 x I0'5 mol), was placed in a 75 mL culture tube.
  • the charge contained 10 mL CH3CI, DMA (5.57 x 10" 2 M), DtBP (1.03 x I0" 2 M), 2 mL isobutylene, and the polymerization was induced by the addition of BCI3 (2.23 x 10 * 1 M).
  • the charge contained 10 mL CII3CI, DMA (1.99 x 10" 2 M), DtBP ( 1.03 x 10" 2 M), I mL isobutylene, and the polymerization was induced by the addition of BCI3 (2.60 x 10" 2 M).
  • Initiator 5 1 1 ,17,23,29,35,41 ,47-(2-methoxypropyl)-49,50,51 ,52,53,54, 55,56-octamethoxycalix[8]arene, 4.85 x 10" 2 g (3.15 x 10"5 mol) was placed in a 75 mL culture tube. The charge contained 10 mL CI I3CI, 15 mL hexanes, DMA ( 1 .99 x
  • the slar polymer was isolated from the mixture by fractionation using hexanes solvent and acetone as the precipitating agent. Molecular weights of polymers are not reported because for these preliminary, RI and UV (GPC) analyses linear calibration plots were used which do not give correct values for the star polymers. 29
  • ⁇ gnin the following scheme set forth the rcnclions »s enrried out in two singes: The first singe wns induced by the addition of BC ⁇ 3 to n solution of initiator. pnrlinl amount of IB (-30%) nod olhcr nddilivcs in CI I3CI, and polymci i ⁇ in ⁇ for 90 minutes. Then the polymcrizntion wns continued by the nddilion 0 riie-.nt.es, 1 iC'l,
  • Fig. 9 shows the GPC liacc ol the products, .wo nnrrow dispcrsily penks. The nmount of the linc ⁇ r by-product wns -26%.
  • BCI3/T-CI4 gave 100% conversion and narrow dispersily product. Prior experiments with only BCI3 or only T1CI4 gave traces of product or less than 10% conversion respectively. These observations suggested haloboralion to be the major side reaction. This conclusion prompted a thorough investigation of the effect of BCI3, monomer, first stage reaction time, mode of addition of the coinitiators (whether added simultaneously or separately) and T1CI4 on Ihe molecular weight and conversion. In most cases, in both the presence of both BCI3 and T1CI4 and in the absence of initiator, conversions were -100%.
  • the RI and UV traces of the star polymers were symmetrical indicating a monodisperse product.
  • the small peak at 42 mL edition volume indicates unrcactcd initiator which escaped dissolution via the solvent.
  • BCI3 ⁇ 0.026M Gel formation was observed.
  • the simultaneous addition of the coinitiators further decreases the amount of linear product as shown in Fig. 1 1 , but its molecular weight was higher than thai obtained in the prior experiments indicating lower initiator efficiency.
  • the UV trace showed the presence of some high molecular weight stars (-31 mL).
  • the two stage procedure with low concentration of BCI3 is preferred over one-step simultaneous addition of coinitiators.
  • slow propagation in the presence of BCI3 in the first stage allows almost all the initiating sites to add a few units of isobutylene and grow rapidly in the second stage. This could also alleviate slow initiation as it simulates "seeding technique".
  • Molecular weights of these polymers are not rcporled because, for these optimization studies, RI and UV (GPC) analyses linear calibration plots were used which do not give correct values for the star polymers.
  • Mn weight average molecular weight
  • Mw polydispersity index
  • the molecular weight of the arms that survived oxidation was determined by LLS (GPC) and are shown in Fig. 13.
  • the dn/dc of surviving arms was found to be 0.107 cnvVg.
  • the distribution of the arms after core destruction was slightly broader than the stars which may be due to slow initiation and/or incomplete oxidation of the cores.
  • the number of arms were found to be slightly lower than theoretical (i.e., 8.0) which may be due to incomplete initiation and/or incomplete oxidation of the cores.
  • thermoplastic elastomers were prepared by the addition of aromatic (styrene) monomer to the polyisobutylene stars prepared hereinabove. That is, thermoplastic elastomers (TPEs) comprising poly(styrene-b-isobutylene) (PSt- ⁇ -PIB) arms emanating from a calixarene core were prepared using the "core first" method.
  • TPEs thermoplastic elastomers
  • PSt- ⁇ -PIB poly(styrene-b-isobutylene)
  • the synthesis was substantially similar to that used hereinabove. Polymerizations were carried out in 300mL stirred reactors in a glove box at -80°C. Isobutylene was polymerized by incremental monomer addition (IMA) to predetermined molecular weights and after reaching at least 95% conversion, styrene was added and polymerized for a predetermined time to get star block copolymers with varying polystyrene (PSt) compositions. Samples, in amounts ranging from about 0.5 mL to 1 mL, were withdrawn to follow conversions and molecular weight build up.
  • IMA incremental monomer addition
  • PSt polystyrene
  • Initiator 5 1 1 , 17,23,29,35,41 ,47-(2-methoxypropyl)-49,50,51 ,52,53,54, 55,56-octamelhoxycalix[8]arene, (4.91 X 10' 2 g, 3.19 x l ⁇ "5 mol) was dissolved in CI I3CI (10 mL), then, in sequence, isobutylene ( 1 mL), DMA (0.05 mL, 5.76 x 10" 4 38 mol), and DtBP (0.07 mL, 3.0 x 10-4 mo
  • Initiator 5 1 1 , 17,23,29,35,41 .47-(2-methoxypropyl)-49,50.51 ,52,53.54, 55,56-octamethoxycalix[8]arene, (4.91 x 10" 2 g, 3.19 x I 0"5 mol) was dissolved in CH3CI (10 mL), then, in sequence, isobutylene ( 1 mL), DMA (0.05 mL, 5.76 x 10" 4 mol), and DtBP (0.07 mL, 3.0 x I0 -4 mol) were added, and the polymerization was induced by the addition of BCI3 (0.06 L, 8.64 x 10 "4 mol) al -80°C.
  • 55,56-octamethoxycalix[8]arene (4.91 x 10" 2 g, 3.19 x 10" ⁇ mol) was dissolved in CH3CI (10 mL), then, in sequence, isobutylene (1 mL), DMA (0.05 mL, 5.76 x 10" 4 mol), and DtBP (0.07 mL, 3.0 x 10" 4 mol) were added, and the polymerization was induced by the addition of BCI3 (0.06 mL, 8.64 x 10" 4 mol) at -80°C.
  • the dn/dc values were obtained by using an Optilab 903 (Wyatt Technology) instrument. Polymers were dissolved in THF prefiltered by 0.025 ⁇ m Whatman Anotop 40
  • the final TiCl4 concentration in the presence of styrene was also critical for molecular weight control and for the preparation of linear (unalkylated, unbranched) polystyrene (PSt) segments.
  • PSt linear polystyrene
  • the use of too low ⁇ CI4 concentrations produces low molecular weight PSt segments, while the use of too high TiCl4 concentrations results in undesirable alkylation/branching.
  • moderate ⁇ CI4 concentrations (0.059 M) and relatively large concentrations of styrene were used.
  • the styrene concentration was determined by preliminary experimentation which showed that a 2-2.5 fold excess relative to the targeted molecular weight gave satisfactory results. Styrene was added after the isobutylene conversion had reached at least 95%. 41
  • Figure 14 shows the result of a representative experiment.
  • isobutylene polymerization in the presence of BCI3 (Stage 1 ) only a few isobutylene units were added to the initiator and after the introduction of TiCl Ihe molecular weights increased as expected (Stage II). After crossing over to styrene monomer, the molecular weight increased rapidly because the rate of styrene polymerization is much higher than that of isobutylene.
  • Fig. 15 shows a representative GPC (RI) trace of a PIB star and the corresponding PI -ft-PSl star. Both peaks arc monomodal and refiect narrow molecular weight distributions, M w /M ⁇ , of 1.18 and 1.23, respectively.
  • the small peak at -34 mL (Fig. 2, (a)) is due to linear PIB by-product, the origin of which has been explained.
  • the small peak al -33 mL (Fig.
  • (b)) is a mixture of linear diblocks (PIB- 6-PSt) formed by the crossover of living PIB + to styrene (-10%, by RI peak area after extracting the mono-PSt by MEK) and homo-PSt (3-5%, by extraction).
  • PIB- 6-PSt linear diblocks
  • the GPC (RI) traces showed shoulders indicating the formation of high molecular weight stars most likely by alkylation of the pendent phenyl rings in PSt by growing PSt + .
  • gel formed due to extensive alkylation.
  • the molecular weighls of the PIB stars and star-blocks were determined by triple-detector GPC. Even though Ihe RI traces of the star-block were monomodal, the molecular weights determined by LLS were higher than expected possibly due to the presence of a small amount of higher molecular weight stars formed by alkylation. Thus, Ihe molecular weight data of the star-blocks and PSt segments calculated from LLS data was viewed with caution.
  • TPEs One of the key features of TPEs is their high tensile strength.
  • the role of PSt domains in the stress absorbing mechanism is well known.
  • PSt-/_ - PBd/PIS-A-PSt TPEs
  • failure occurs in the PSt domains.
  • the lower strength of isobulylene-bascd thermoplastics compared to PSt- ⁇ -PBd/PIS- ⁇ -PSt has been postulated to be due to a different failure mechanism, or to the presence of diblock contamination, or to the existence of a broad interphase.
  • linear PSt- ⁇ -PIB- ⁇ -PSt triblock copolymer ionomers have showed higher tensile strength than the corresponding linear triblocks which contradicts the point of a different failure mechanism, i.e., failure in the rubbery region. More results are needed to substantiate these postulates.
  • multi-arm polyisobutylene stars arc well-defined, both at their arms and core, and that have comparatively a more definite number of arms, a more definite arm molecular weight and a narrower polydispersity than those stars having well-defined arms, but ill-defined cores.
  • Such multi-arm star polymers are seen as having utility as viscosity modifiers and motor oil additives and the like, although it will be appreciated that the subject star polymers may be readily useful in a variety of applications, including the manufacture of other materials as well.
  • the synthesis of star block copolymers provides for the preparation of useful TPEs as well.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La synthèse et caractérisation de nouveaux polymères linéaires et de polymères en étoile à plusieurs branches comprenant des branches de polyisobutylène reliées à un noyau de calixarène bien défini sont décrites. On a réalisé cette synthèse en utilisant le procédé 'noyau d'abord' selon lequel des dérivés polyfonctionnels de calix[n]arène (où n = 4-16) ou leurs analogues monofonctionnels sont utilisés comme des initiateurs qui, conjointement avec certains acides de Friedel-Crafts utilisés comme co-initiateurs, induisent la polymérisation vivante de l'isobutylène ou de monomères polymérisables carbocationiques semblables pour former des polymères en étoile ou des copolymères blocs. De nouveaux initiateurs convenant à l'induction de cette polymérisation sont également décrits.
PCT/US1997/014017 1996-08-07 1997-08-07 Polymeres en etoile a plusieurs branches de polyisobutylene partant d'un noyau de calixarene et leur synthese WO1998005691A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU39748/97A AU3974897A (en) 1996-08-07 1997-08-07 Star polymers having multiple polyisobutylene arms emanating froma calixarene core and the synthesis thereof
DE19781927T DE19781927T1 (de) 1996-08-07 1997-08-07 Sternpolymere mit mehreren Polyisobutylenarmen, die sich von einem Calixarenkern erstrecken und deren Synthese
JP50825098A JP2002500682A (ja) 1996-08-07 1997-08-07 カリクスアレーンコアから延びる多重ポリイソブチレンアームを有するスター重合体及びその合成

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US08/693,433 US5844056A (en) 1996-08-07 1996-08-07 Star polymers having multiple polyisobutylene arms emanating from a calixarene core, initiators therefor, and method for the synthesis thereof
US08/693,433 1996-08-07
US08/862,581 US5804664A (en) 1997-05-23 1997-05-23 Star polymers having multiple arms emanating from a calixarene core, initiators therefor, and method for the synthesis thereof
US08/862,581 1997-05-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999029744A1 (fr) * 1997-12-04 1999-06-17 The University Of Western Ontario Initiateurs destines a la polymerisation carbocationique d'olefines

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WO2011127562A1 (fr) * 2010-04-16 2011-10-20 Lanxess Inc. Polymères arborescents dotés d'un noyau présentant une température de transition vitreuse élevée et procédé de préparation de ceux-ci
JP5730150B2 (ja) * 2011-07-14 2015-06-03 Jsr株式会社 重合開始剤およびその製造方法並びにスターポリマーおよびその製造方法
KR102322754B1 (ko) * 2014-04-17 2021-11-05 에니 에스.피.에이. 칼리자렌을 기반으로 한 코어를 갖는 방사형 구조를 지닌 수소화된 폴리머 및 이의 윤활제 조성물 중에서의 용도
US11078437B2 (en) 2014-04-17 2021-08-03 Eni S.P.A. Hydrogenated polymers with a radial structure having a core based on calixarenes and use thereof in lubricant compositions

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US4914166A (en) * 1988-01-20 1990-04-03 The University Of Akron Non-fouling liquid nitrogen cooled polymerization process
US5169914A (en) * 1988-05-03 1992-12-08 Edison Polymer Innovation Corporation Uniform molecular weight polymers
US5248746A (en) * 1990-04-03 1993-09-28 Nippon Zeon Co., Ltd. Method of producing polymers

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US4914166A (en) * 1988-01-20 1990-04-03 The University Of Akron Non-fouling liquid nitrogen cooled polymerization process
US5169914A (en) * 1988-05-03 1992-12-08 Edison Polymer Innovation Corporation Uniform molecular weight polymers
US5248746A (en) * 1990-04-03 1993-09-28 Nippon Zeon Co., Ltd. Method of producing polymers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999029744A1 (fr) * 1997-12-04 1999-06-17 The University Of Western Ontario Initiateurs destines a la polymerisation carbocationique d'olefines
US6268446B1 (en) 1997-12-04 2001-07-31 The University Of Western Ontario Initiators for carbocationic polymerization of olefins
US6495647B2 (en) 1997-12-04 2002-12-17 The University Of Western Ontario Initiators for carbocationic polymerization of olefins

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