4th EucheMs chemistry congress

Poster Session 1
s1052
chem. Listy 106, s587–s1425 (2012)
Poster session 1 - organic chemistry
P - 0 3 8 1
AnALySiS of therMAL deGrAdAtion BehAviorS
of PoLyKetone/PoLyAMide-6 BLendS
C. S. Lee 1 , C. yiM 1 , S. KiM 1 , C. dreyer 2 , J. AhLerS 2 ,
h. J. GLAeSeL 2 , S. K. yoon 3 , J. y. Jho 4
1 Hyundai Motor Group Automotive R&D Division, Polymeric
Materials Research Team, Whasung city, Republic of Korea
2 Fraunhofer Institution Polymeric Materials and Composites,
PYCO, Teltow, Germany
3 Hyosung, Technology Commercialization Center, Anyang city,
Republic of Korea
4 Seoul National University, School of Chemical and Biological
Engineering, Seoul, Republic of Korea
An aliphatic polyketone (PK) terpolymer consisting of
carbon monoxide, ethylene, and propylene has excellent
properties such as low water absorption, superb chemical
resistance, low gas permeability, and high heat distortion
temperature. Polyketone is well miscible with polyamide-6 due
to H-bonding between –C=O in polyketone and –NH- in
polyamide-6, and the mechanical properties of polyketone are to
be easily controlled through blending with polyamide-6. So the
blends are thought to be the promising materials for the
automotive parts, especially under the hood. During the residence
at the processing temperatures, however, the blends have a
chance to degrade easily. The thermal degradation behaviors of
the blends with additives were observed. After long time
residence for more than 60 min at 250 °C (the upper limit
temperature recommended for injection molding of the blends),
the initial single melting peak split into two peaks corresponding
to polyketone and polyamide-6 moiety, respectively. With
increasing content of polyamide-6 in the blends, the melting
points of polyketone moiety in the blends showed the tendency
of significant decrease with increasing content of polyamide-6 in
the blend, but the melting points of polyamide-6 moiety were
almost constant. TGA isothermal measurement at 250 °C for
60 min showed the weight reduction was enlarged with increasing
content of polyamide-6 in the blends. Inorganic particles were
compounded in the blends in order to improve the thermal
stability at the processing temperature. With decreasing the size
of the particles, the thermal stability of the materials was more
improved, especially in tens of nano size. In conclusion,
polyamide-6 tends to accelerate the thermal degradation of
polyketone in the blends, but polyamide-6 itself will not degrade
at high processing temperature. Nano inorganic particles are good
additives for the improvement of thermal stability of polyketone
and its blends with polyamide-6.
Keywords: Polymers; Amides; Ketones;
4 th EucheMs chemistry congress
P - 0 3 8 2
GoLd-CAtALyzed SyntheSiS of fLuorinAted
2,5-dihydrofurAnS And 3,4-dihydroPyrAnS
L. LeMPKe 1 , n. KrAuSe 1
1 TU Dortmund, Organic Chemistry, Dortmund, Germany
The enormous potential of fluorine-substituted molecules in
organic chemistry is reflected in a special interest of new synthetic
strategies. Based on the significant change of chemical and
physiological properties there exist many pharmaceutical and
industrial applications. [1] These include solubility, lipophilicity,
metabolic stability and bioavailability by replacement of hydrogen
with fluorine. [2–3]
In terms of heterocyclic structures several methods for
C-F-bond formation have been developed using electrophilic and
nucleophilic fluorination reagents. Examples to form
fluorinated precursors as well as fluorination of the heterocyclic
products are known. [4–5] Particularly interesting are
tandem-fluorination-cyclization reactions using Selectfluor or
NFSI (N-Fluorobenzenesulfonmide) as fluorelectrophiles. [6–7]
The gold-catalyzed cycloisomerization of α- and
β-hydroxyallenes forming 2,5-dihydrofurans and
3,4-dihydropyrans, respectively, is a well-known reaction. [8]
Using this selective formation to prepare fluorinated
cycloisomerization products is of particular value for the total
synthesis of natural compounds and their derivatives.
In this project, the gold-catalyzed cycloisomerization of
α- and β-hydroxyallenes forming fluorinated cyclization products
is pursued. First results of our investigations and their perspectives
are reported.
references:
1. Dolbier Jr., W. R.; J. Fluorine Chem. 2005, 126, 157–163.
2. O’Hagan, D.; Chem. Soc. Rev. 2008, 37, 308–319.
3. Fluorine in Bioorganic Chemistry (Eds.: J.T. Welch,
S. Eswarakrishman); Plenum, New York, 1991.
4. Li, Y.; Wheeler, K. A.; Dembinski, R.; Adv. Synth. Catal.
2010, 352, 2761–2766.
5. Coe, P. L.; Taleker, R. R.; Walker, R. T.; J. Fluorine Chem.
1994, 69, 19-24.
6. Qian, J.; Liu Y.; Zhu, J.; Jiang, B.; Xu, Z.; Org. Lett. 2011,
13, 4220–4223.
7. Xu, T.; Mu, X.; Peng, H.; Liu, G.; Angew. Chem. 2011,
113, 8326–8329.
8. Winter, C.; Krause, N.;.Chem. Rev. 2011, 111, 1994-–2009.
Keywords: Gold; Allenes; Cyclization; Fluorine; Heterocycles;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc