DOCSLIB.ORG

Crystallization of Isotactic Polypropylene : the Influence of Stereo-Defects

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Crystallization of Isotactic Polypropylene : the Influence of Stereo-Defects Crystallization of isotactic polypropylene : the influence of stereo-defects Citation for published version (APA): Burgt, van der, F. P. T. J. (2002). Crystallization of isotactic polypropylene : the influence of stereo-defects. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR559498 DOI: 10.6100/IR559498 Document status and date: Published: 01/01/2002 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement: www.tue.nl/taverne Take down policy If you believe that this document breaches copyright please contact us at: [email protected] providing details and we will investigate your claim. Download date: 10. Oct. 2021 Crystallization of isotactic polypropylene The influence of stereo-defects CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN Burgt, Frank P.T.J. van der Crystallization of isotactic polypropylene : The influence of stereo-defects / by Frank P.T.J. van der Burgt. - Eindhoven : Technische Universiteit Eindhoven, 2002. Proefschrift. - ISBN 90-386-2674-6 NUR 952 Trefwoorden: polymeren; reologie / polymeerstructuur / kristallisatie / polyolefinen; isotactisch polypropylene / tacticiteit / polymerisatiekatalysatoren / Ziegler-Natta / metallocenen Subject headings: polymers; rheology / polymer morphology / crystallization / polyolefins; isotactic polypropylene / tacticity / polymerization catalysts / Ziegler-Natta / metallocenes Printed by the University Press Facilities, Eindhoven, the Netherlands. This research was financially supported by the Dutch Polymer Institute (DPI; pro- ject #132). Crystallization of isotactic polypropylene The influence of stereo-defects PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Technische Universiteit Eindhoven, op gezag van de Rector Magnificus, prof.dr. R.A. van Santen, voor een commissie aangewezen door het College voor Promoties in het openbaar te verdedigen op woensdag 20 november 2002 om 16.00 uur door Frank Peter Theodorus Johannes van der Burgt geboren te Eindhoven Dit proefschrift is goedgekeurd door de promotoren: prof.dr. P.J. Lemstra en prof.dr.ir. W.H. de Jeu Copromotor: dr. S. Rastogi Dedicated to Arend Eshuis y 7 December 1999 Contents Summary xi 1 Introduction 1 1.1 Polypropylene . 1 1.1.1 History . 1 1.1.2 Properties and economic relevance . 1 1.1.3 Development of metallocene catalysis . 2 1.2 Stereo-isomerism and stereo-regularity . 2 1.3 Catalysis and stereo-defect distribution . 4 1.3.1 Single stereo-defects . 4 1.3.2 Stereo-defect distribution . 5 1.4 The outline of the thesis . 6 2 Experimental methods 7 2.1 Introduction . 7 2.2 Electron microscopy and thin film preparation . 7 2.3 Differential scanning calorimetry . 8 2.4 Wide-angle x-ray scattering . 8 2.4.1 Subtraction of the amorphous halo . 9 2.4.2 Determining the ratio / ¡ phase . 10 2.5 High-pressure treatment . 11 2.6 Rheometry . 11 2.6.1 Melt characterization . 12 2.6.2 Crystallization experiments . 12 3 Polymorphism in polypropylene 13 3.1 The phase . 13 3.1.1 The crystal structure . 13 3.1.2 Crosshatched lamellae . 15 3.2 The ¢ phase . 15 3.3 The ¡ phase . 15 3.3.1 The crystal structure . 16 3.3.2 Morphological features . 16 viii Contents 3.4 Pressure treatment . 16 3.5 Useful data on polymorphism . 17 4 Crystallization of metallocene derived polypropylenes 21 4.1 Introduction . 21 4.2 Materials . 21 4.3 Ambient conditions . 22 4.3.1 Morphology . 22 4.3.2 Differential scanning calorimetry . 24 4.3.3 Wide-angle x-ray scattering . 26 4.4 High Pressure studies . 29 4.4.1 High pressure crystallization . 29 4.4.2 In-situ high pressure experiments . 29 4.5 Discussion . 34 4.5.1 Crystal structure and morphology . 34 4.5.2 Polymorphism . 36 4.5.3 High pressure crystallization . 39 4.6 Conclusions . 40 5 Crystallization of Ziegler-Natta derived polypropylenes 43 5.1 Introduction . 43 5.2 Materials . 43 5.3 Ambient Conditions . 44 5.3.1 Microscopy . 44 5.3.2 Differential scanning calorimetry . 44 5.3.3 Wide-angle x-ray scattering . 47 5.4 High-pressure studies . 48 5.4.1 High-pressure crystallization . 48 5.4.2 In-situ high-pressure experiments . 50 5.5 Discussion . 51 5.6 Conclusions . 55 6 Metallocene versus Ziegler-Natta derived polypropylenes 57 6.1 Introduction . 57 6.2 Morphology . 57 6.3 Melting temperatures . 58 6.4 Crystallinity and polymorphism . 61 6.4.1 (hkl) reflections of the phase and isotactic perfection . 61 6.4.2 Polymorphism versus tacticity . 61 6.4.3 Crystallinity versus tacticity . 62 6.4.4 Pressure influence and growth direction . 62 6.5 Modelling with disordered structures . 63 6.5.1 Model of disordered structures . 63 Contents ix 6.5.2 Method of calculation of the x-ray diffraction patterns . 65 6.5.3 Results of the calculations . 66 6.6 Line broadening analysis . 70 6.7 Conclusions . 71 7 Correlation of molecular structure and rheological parameters 73 7.1 Introduction . 73 7.2 Theoretical aspects . 74 7.2.1 Moments of the molecular weight distribution . 74 7.2.2 The Cross model . 75 7.2.3 The polydispersity index . 76 7.2.4 The Maxwell relaxation-time spectrum . 76 ¦¨§ 7.2.5 £¥¤ versus . 77 7.2.6 The plateau modulus . 77 7.3 Influence of molecular weight distribution . 78 7.3.1 The storage and loss modulus. 79 7.3.2 The complex dynamic viscosity. 79 7.3.3 The Cross model . 80 7.3.4 The polydispersity index . 82 7.3.5 The Maxwell relaxation-time spectrum . 82 7.4 Influence of molecular weight . 85 ¦¨§ 7.4.1 £¥¤ versus . 85 7.4.2 Small MwD differences in metallocene samples . 86 7.5 General Correlations . 87 7.5.1 Correlation between © and . 87 £ ¤ 7.5.2 Molecular weight distribution dependency on © and . 88 7.5.3 The plateau modulus . 88 7.6 Example: Influence of molecular weight distribution on crystal- lization . 90 7.7 Conclusions . 93 A Shift-factors and simple constitutive equations 95 A.1 Shift factor and WLF-fits . 95 A.2 Data-fitting with simple constitutive equations . 96 A.3 Relaxation-time spectra . 97 Bibliography 99 Technology assessment 107 Samenvatting 109 Acknowledgements 111 x Contents Curriculum Vitae 113 Summary Polypropylene (PP) was discovered in the early 1950s. Since then PP has grown to a commodity polymer with numerous grades for specific end uses. By con- trolling the polymer chemistry it is now feasible to generate a range of poly- propylenes possessing mechanical properties varying from a thermoplast to an elastomer. Stereo-regularity and its distribution along the chain play a crucial role in the development of these polymers. The degree of stereo-regularity as well as the stereo-defect distribution of poly- propylene are strongly dependent on the catalyst and on the polymerization con- ditions. In this thesis we have investigated the crystallization behavior of iPPs with varying isotacticity as a function of the stereo-defect distribution based on the origin of the catalyst. More specifically, Ziegler-Natta catalysts introduce a block-like distribution of stereo-defects, and the samples used derived from metallocene catalysis, yielded a random distribution. For this purpose various techniques were used, such as: wide-angle x-ray scattering, electron microscopy, differential scanning calorimetry and rheometry. With respect to crystallization behavior it was observed that for both molecular structures an increasing amount of stereo-defects suppresses the crystallinity and gives rise to larger amounts of the ¡ polymorph, especially on slow cooling. The metallocene derived iPPs show a stronger dependence on the stereo-defects com- pared to the Ziegler-Natta derived materials. Differences in molecular structure are displayed in the melting temperatures which are for Ziegler-Natta derived iPP structurally higher compared to the metallocene samples. The morphologies observed for Ziegler-Natta derived iPP are rather similar to those presented in literature. For example in stereo-irregular Ziegler-Natta samples an overgrowth of the lamellae with ¡ phase is observed. However, metallocene samples show considerable morphological variations with varying tacticity. In poorly isotac- tic metallocene PP curved lamellar morphologies are observed which may be caused by incorporation of a part of randomly distributed stereo-defects within the crystal lattice. After solid state analysis of various polypropylenes, the behavior in the melt was investigated. Different catalysts systems, especially in Ziegler-Natta cataly- sis, can also yield different molecular weight distribution or, for example add a xii Summary high molecular weight tail to the distribution.
Load more

Recommended publications
  • Tacticity in Vinyl Polymers
    TACTICITY IN VINYL POLYMERS Introduction Tacticity in polymers refers to a configurational order in molecular structures. Definition of polymer tacticity is properly given in a review article by Jenkins and co-workers (1), which reads The orderliness of the succession of configurational repeating units in the main chain of a regular macromolecule, a regular oligomer molecule, a regular block or a regular chain. Tacticity should not be confused with the conformational states of the poly- mer chains in space. The conformation refers to different arrangements of atoms and/or substituents of the polymer chain brought about by rotations about single bonds. Examples of different polymer conformations include the fully extended planar zig-zag, helical, folded chains, and random coils, etc. By contrast, the tac- tic configuration of the molecular chains refers to the organization of the atoms along the chain and configurational tactic isomerism involves the different struc- tural arrangements of the atoms and substituents in a polymer chain, which can be interconverted only by the breakage and reformation of primary chemi- cal bonds. There are three tactic forms in polymers: atactic, isotactic, and syn- diotactic. Isotactic and syndiotactic polymers are both stereoregular and thus are crystallizable. Atactic polymers, on the other hand, are usually completely amorphous, unless the side group is so small or highly polar as to permit crys- tallinity, e.g. poly(vinyl fluoride) (PVF) or polyacrylonitrile (PAN). Like some or- ganic compounds or naturally occurring polymers such as poly(L,D-lactic acid)s or poly(amino acid)s that differ in chirality, vinyl polymers differ in tacticity, which may be viewed as a pseudochirality form.
    [Show full text]
  • Multi-Headed Chain Shuttling Agents and Their Use for the Preparation of Block Copolymers
    (19) TZZ¥ ¥ T (11) EP 3 243 846 A2 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 15.11.2017 Bulletin 2017/46 C08F 4/659 (2006.01) C07F 3/02 (2006.01) C08F 10/00 (2006.01) C07F 3/06 (2006.01) (2006.01) (2006.01) (21) Application number: 17164138.4 C07F 5/02 C07F 5/06 (22) Date of filing: 20.07.2010 (84) Designated Contracting States: • Clark, Thomas AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Midland, MI Michigan 48640 (US) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • Frazier, Kevin PL PT RO SE SI SK SM TR Midland, MI Michigan 48642 (US) • Klamo, Sara (30) Priority: 29.07.2009 US 229610 P Midland, MI Michigan 48642 (US) • Timmers, Francis (62) Document number(s) of the earlier application(s) in Midland, MI Michigan 48642 (US) accordance with Art. 76 EPC: 10737196.5 / 2 459 598 (74) Representative: V.O. P.O. Box 87930 (71) Applicant: Dow Global Technologies Llc Carnegieplein 5 Midland, MI 48674 (US) 2508 DH Den Haag (NL) (72) Inventors: Remarks: • Arriola, Daniel This application was filed on 31-03-2017 as a Midland, MI Michigan 48642 (US) divisional application to the application mentioned under INID code 62. (54) MULTI-HEADED CHAIN SHUTTLING AGENTS AND THEIR USE FOR THE PREPARATION OF BLOCK COPOLYMERS (57) This disclosure relates to olefin polymerization shuttling agents (CSAs or MSAs) and for their use in pre- catalysts and compositions, their manufacture, and the paring blocky copolymers.
    [Show full text]
  • Chain Structure Characterization
    CHAIN STRUCTURE CHARACTERIZATION Gregory Beaucage and Amit S. Kulkarni Department of Chemical and Materials Engineering, University of Cincinnati, Cincinnati, Ohio 45221-0012 I. Introduction to Structure in Synthetic Macromolecules a) Dimensionality and Statistical Descriptions b) Chain Persistence and the Kuhn Unit c) Coil Structure and Chain Scaling Transitions d) Measures of Coil Size Rg and Rh II. Local Structure and its Ramifications a) Tacticity c) Branching d) Crystallization e) Hyperbranched Polymers III. Summary 1 I. Introduction to Structure in Synthetic Macromolecules a) Dimensionality and Statistical Descriptions Synthetic polymers display some physical characteristics that we can identify as native to this class of materials, particularly shear thinning rheology, rubber elasticity, and chain folded crystals. These properties are inherent to long-chain linear and weakly branched molecules and are not drastically different across a wide range of chemical make-ups. We can consider these features to define synthetic macromolecules as a distinct category of materials. The realization of this special category of materials necessitated the definition of a structural model broad enough to encompass nylon to polyethylene yet specific enough that detailed analytically available features could be used to define the major properties of interest, especially those native to this class of materials. This structural model for polymer chains is based on the random walk statistics observed by Robert Brown in studies of pollen grains and explained by Einstein in 1905. It is a trivial exercise to construct a random walk on a cubic lattice using a PC, Figure 1. From such a walk we can observe certain features of the general model for a polymer chain.
    [Show full text]
  • Chem3020: Polymer Chemistry
    CHEM3020: POLYMER CHEMISTRY Unit-5: Preparation, structure, properties and application of polymers Polyethylene, polystyrene and styrene copolymers Prof. Rafique Ul Islam Department of Chemistry, MGCU, Motihari CHEM3020: POLYMER CHEMISTRY UNIT-5 Polyethylene, polystyrene and styrene copolymers Polyethylene: The first commercial ethylene polymer was branched polyethylene commonly designated as Low density polyethylene. Polyethylene was first prepared using ethylene under 1400 atm pressure at 1700 C. Ethylene is made from the thermal and catalytic cracking of different hydrocarbons ranging from ethane obtained from natural gas to fuel oil. Presence of traces of oxygen initiate the polymerization process of ethylene readily. Rapid exothermic reaction can occur, and violent explosion have take place. Impurities present in the monomer, such as hydrogen and acetylene, may act as chain transfer agents and yield low molecular weight polyethylene. To obtained high molecular weight polymeric product, the imputiies must be carefully removed. Besides oxygen, peroxides, hydroperoxides and azo compounds can also be used as initiators for the polymerization process. Manufacturing: The manufacture of polyethylene follows addition polymerization kinetics involving catalysis of purified ethylene. Its melting point is 85–110oC. Under high pressure process, the density of polyethylene is 0.91-0.93 , whereas under low pressure the density is 0.96. CHEM3020: POLYMER CHEMISTRY UNIT-5 There are three ways by which polyethylene is manufactured – a. High Pressure Process : In this process, peroxide is used as a catalyst at 100-300oC and produces low density randomly oriented polymer of low melting point. The process is carried out at pressure of 1000–2500 atms. In this process Low Density Polyethylene (LDPE) is obtained.
    [Show full text]
  • Tacticity Control of Polypropylene Using a C2-Symmetric Family of Catalysts
    TACTICITY CONTROL OF POLYPROPYLENE USING A C2-SYMMETRIC FAMILY OF CATALYSTS A Thesis by NATHAN PRENTICE RIFE Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE December 2007 Major Subject: Chemistry TACTICITY CONTROL OF POLYPROPYLENE USING A C2-SYMMETRIC FAMILY OF CATALYSTS A Thesis by NATHAN PRENTICE RIFE Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Approved by: Chair of Committee, Stephen A. Miller Committee Members, David E. Bergbreiter Jaime C. Grunlan Head of Department, David H. Russell December 2007 Major Subject: Chemistry iii ABSTRACT Tacticity Control of Polypropylene Using a C2-Symmetric Family of Catalysts. (December 2007) Nathan Prentice Rife, B.S., McMurry University Chair of Advisory Committee: Dr. Stephen A. Miller A family of C2-symmetric catalysts was designed and synthesized with the intent to polymerize propylene. The catalyst was designed to be C2-symmetric for the specific goal that the catalyst would have two identical sites for the propagation of the polymer and therefore eliminate some of the stereoerrors that occur in the propagation of the polymer chain. This catalyst would also operate under simple enantiomorphic site control and therefore the insertion of the monomer would be governed by the ligand surrounding the active site. The ligands were synthesized with increasing degrees of steric bulk with the intention to determine if a catalyst system could generate elastomeric polypropylene. Enantiomorphic site control polypropylene utilizes statistical methods to determine the Si and Re content of a given polymer chain as a function of the variable .
    [Show full text]
  • Effects of Branch Points and Chain Ends on the Thermodynamic Interaction Parameter in Binary Blends of Regularly Branched and Linear Polymers
    Macromolecules 2006, 39, 5113-5121 5113 Effects of Branch Points and Chain Ends on the Thermodynamic Interaction Parameter in Binary Blends of Regularly Branched and Linear Polymers Jae S. Lee and Mark D. Foster* Maurice Morton Institute of Polymer Science, The UniVersity of Akron, Akron, Ohio 44325 David T. Wu Chemical Engineering Department and Chemistry Department, Colorado School of Mines, Golden, Colorado 80401 ReceiVed January 4, 2006; ReVised Manuscript ReceiVed May 15, 2006 ABSTRACT: The architectural effects of branch points and chain ends on the bulk thermodynamic interaction parameter, øeff, in binary blends of branched polymers with their linear analogues have been investigated using small-angle neutron scattering (SANS) and a series of well-defined, regularly branched polystyrenes with the same molecular weight and differing only in the number of branch points or chain ends. The value of øeff increases as the number of branch points increases for constant number of chain ends or as the number of chain ends increases for constant number of branch points. A Gaussian field theory for an athermal blend predicts the general trend in bulk øeff with the number of chain ends but does not capture the changes in øeff with changes in the number of branch points. Differences in chemistry among the various branch points probably have to be included to quantitatively predict changes in øeff for shorter branches. Qualitative variations in the size of the branched molecules in solution compare favorably with a Gaussian model for the branched chain’s radius of gyration. The variation in the average statistical segment length with chain architecture was also determined from the SANS data.
    [Show full text]
  • Polymer Chemistry
    Polymer Chemistry Properties and Application Bearbeitet von Andrew J Peacock, Allison Calhoun 1. Auflage 2006. Buch. XIX, 399 S. Hardcover ISBN 978 3 446 22283 0 Format (B x L): 17,5 x 24,5 cm Gewicht: 1088 g Weitere Fachgebiete > Chemie, Biowissenschaften, Agrarwissenschaften > Biochemie > Polymerchemie Zu Inhaltsverzeichnis schnell und portofrei erhältlich bei Die Online-Fachbuchhandlung beck-shop.de ist spezialisiert auf Fachbücher, insbesondere Recht, Steuern und Wirtschaft. Im Sortiment finden Sie alle Medien (Bücher, Zeitschriften, CDs, eBooks, etc.) aller Verlage. Ergänzt wird das Programm durch Services wie Neuerscheinungsdienst oder Zusammenstellungen von Büchern zu Sonderpreisen. Der Shop führt mehr als 8 Millionen Produkte. Produktinformation Seite 1 von 1 Polymer Chemistry Allison Calhoun, Andrew James Peacock Properties and Application ISBN 3-446-22283-9 Leseprobe Weitere Informationen oder Bestellungen unter http://www.hanser.de/3-446-22283-9 sowie im Buchhandel http://www.hanser.de/deckblatt/deckblatt1.asp?isbn=3-446-22283-9&style=Leseprobe 05.05.2006 5 Molecular Characterization of Polymers 5.1 Introduction Polymers differ from most chemicals in that they do not consist of identical molecules. All polymers comprise a distribution of molecules that share certain chemical characteristics, but may vary widely in terms of their lengths and precise compositions. Polymer scientists typically describe polymers in terms of their average molecular characteristics or some readily measurable value that represents the average composition of the ensemble of molecules. Thus, we commonly describe the lengths of polymers in terms of one or more averages that reflect moments of their overall molecular weight distribution. Similarly, we describe chemical composition in terms of the average comonomer content, which does not completely describe the distribution of comonomers within a given chain.
    [Show full text]
  • Model Prediction, Experimental Determination, and Control of Emulsion Copolymer Microstructure
    Model prediction, experimental determination, and control of emulsion copolymer microstructure Citation for published version (APA): van Doremaele, G. H. J. (1990). Model prediction, experimental determination, and control of emulsion copolymer microstructure. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR340343 DOI: 10.6100/IR340343 Document status and date: Published: 01/01/1990 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal.
    [Show full text]
  • Wo 2010/147798 A2
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date 23 December 2010 (23.12.2010) WO 2010/147798 A2 (51) International Patent Classification: hara, Asaka-shi, Saitama-ken, 35 1-0025 (JP). BRANT, BOlD 67/00 (2006.01) C08J 5/18 (2006.01) Patrick [US/US]; 1038 Shorewood Drive, Seabrook, TX BOlD 71/00 (2006.01) HOlM 2/16 (2006.01) 77586 (US). (21) International Application Number: (74) Agents: HUGHES, Gerard J. et al; Exxon Mobil Chem PCT/US2010/037755 ical Company, Law Technology, P.O. Box 2149, Bay- town, TX 77522-2149 (US). (22) International Filing Date: 8 June 2010 (08.06.2010) (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, English (25) Filing Language: AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, (26) Publication Language: English CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (30) Priority Data: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, 61/218,720 19 June 2009 (19.06.2009) US KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, 09168193.2 19 August 2009 (19.08.2009) EP ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, 61/298,756 27 January 2010 (27.01 .2010) US NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, 61/298,752 27 January 2010 (27.01 .2010) US SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, 61/346,675 20 May 2010 (20.05.2010) US TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
    [Show full text]
  • Engineering of Syndiotactic and Isotactic Polystyrene-Based Copolymers Via Stereoselective Catalytic Polymerization
    Review Engineering of Syndiotactic and Isotactic Polystyrene-Based Copolymers via Stereoselective Catalytic Polymerization Eva Laur, Evgueni Kirillov * and Jean-François Carpentier * Université de Rennes 1, CNRS, Institut des Sciences Chimiques de Rennes, UMR 6226, F-35042 Rennes CEDEX, France; [email protected] * Correspondence: [email protected] (E.K.); [email protected] (J.-F.C.); Tel.: +33-223-236-118 (E.K.); +33-223-236-939 (J.-F.C.) Academic Editor: Kotohiro Nomura Received: 18 March 2017; Accepted: 5 April 2017; Published: 7 April 2017 Abstract: This contribution presents an updated overview of the different copolymers containing stereoregular polystyrene blocks. Special emphasis is placed on syndiospecific and isospecific copolymerization of styrene with co-monomers (ethylene and α-olefins, conjugated and non-conjugated dienes, styrene derivatives, etc.). The catalytic systems involved are described and the polymerization mechanisms are discussed. Alternative approaches (simultaneous, living, chain-transfer and graft copolymerization) and the resulting detailed structures and characteristics of the copolymers are also reported. Keywords: styrene; syndiotactic polystyrene; isotactic polystyrene; copolymers; stereoselective catalysis; polymerization 1. Introduction Production of plastic materials is one of the most important processes of the contemporary chemical industry (some 322 million tons of plastic materials were produced in 2015) and represents an ever-increasing market. Besides commodity polymers, numerous efforts are focused on the development of new generations of materials with more specific properties (engineering and specialty polymers) designed to replace other materials like ceramics or metals. Copolymerization of two (or more) monomers is one of the ways to create new materials, as copolymers have unique properties different from those of the corresponding homopolymers.
    [Show full text]
  • Lecture 22 Notes 140415
    1 ;> ^ c^ ^ ^£S V K^* f ^ ^ 5 ^\ E \ • ' OV>£MAVW ,57 feC.W\ _ *itf-' ' J!.< '* 5 r \ I' \-J ft w^sVjnC ACS Macro Letters Scheme 1. Synthesis of 4,7-Substituted ACSMacr(Uetter£> pubs.acs.org/macroletters [2.2.2]Paracyclophane-Trienes 4a-c [2.2.2]Paracyclophane-Trienes—Attractive Monomers for ROMP Dominic Maker, Christopher Maier, Kerstin Brodner, and Uwe H. F. Bunz* Organisch-Chemisches Institut, Ruprecht-Karls-Universitat Heidelberg, INF 270, D-69120 Heidelberg, Germany 0 Supporting Information ABSTRACT: Three derivatives of 4,7-substituted [2.2.2]- paracyclophane-trienes were synthesized and used in ring-opening metathesis polymerization (ROMP), resulting in well-soluble poly(para-phenylenevinylene)s (PPV). The paracyclophane-tri- enes were prepared using an iterative buildup of a phenylene— ethynylene backbone, followed by a cis selective Grignard reduction and an intramolecular McMurry reaction. The monomers were applied in ROMP to result in well-soluble PPV derivatives with an unusual substituent pattern. The PPVs were spin-coated into amorphous, highly fluorescent films. To the best of our knowledge, we are the first to synthesize 4,7- Figure 2. Photographs of (A) absorption and (B) emission under substituted [ 2.2.2 Jparacyclophane-trienes and use them as ROMP monomers. ultraviolet illumination (365 nm) of polymer and monomer solutions in CHClj. (C) Photographs of spin-coated films out of C6HSC1 under ultraviolet illumination (365 nm). ue to their spectacular optical and optc"'l'"-Trn"L6 ring-opened into PPV, whereas the (Z,Z,Z,Z)-isomer does not D^properties, conjugated polyrqe/s such as polyfluorene.1 have enough strain energy to be active (Figure 1)." hydrochloric acid, overnight in the dark.
    [Show full text]
  • Crystallization Kinetics of Ipp: Influence of Operating Conditions
    CORE Metadata, citation and similar papers at core.ac.uk Provided by Archivio istituzionale della ricerca - Università di Palermo Crystallization Kinetics of iPP: Influence of Operating Conditions and Molecular Parameters V. La Carrubba, S. Piccarolo, V. Brucato Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita` di Palermo, Viale delle Scienze, 90128 Palermo, Italy Received 5 September 2006; accepted 21 November 2006 DOI 10.1002/app.25871 Published online in Wiley InterScience (www.interscience.wiley.com). ABSTRACT: An analysis of the crystallization kinetics of dif- the crystalline phases. The whole body of results (including cal- ferent grades of isotactic polypropylene (iPP) is here presented. orimetric ones) provides a wide basis for the identification To describe the crystallization kinetics as a function of molecu- of a crystallization model suitable to describe solidification in lar and operating parameters, the methodological path fol- polymer-processing operations, based on the Kolmogoroff– lowed was the preparation of quenched samples of known Avrami–Evans nonisothermal approach. The kinetic parame- cooling histories, calorimetric crystallization isotherms tests, dif- ters, determined for all the materials, are discussed, highlight- ferential scanning calorimetry cooling ramps, wide angle X-ray ing the effect of molecular parameters on the crystallization diffraction (WAXD) measurements, and density determination. kinetics: molecular mass and distribution, tacticity, nucleating The WAXD analysis performed
    [Show full text]