PENTAMETHYLDIETHYLENETRIAMINE (PMDETA) / PENTAMETLDETLENTRAMN

PENTAMETHYLDIETHYLENETRIAMINE (PMDETA) / PENTAMETLDETLENTRAMN

PENTAMETHYLDIETHYLENETRIAMINE (PMDETA) / PENTAMETLDETLENTRAMN

CAS NO: 3030-47-5

SYNONYMS: 3030-47-5; 1,1,4,7,7-Pentamethyldiethylenetriamine;Pentamethyldiethylenetriamine; PMDT; PMDETA;PMDTA;PENTAMETHYLDIETHYLENETRIAMINE;N,N,N,N,N-PENTAMETHYLDIETHYLENETRIAMINE;N,N,N,N,N-PENTAMETHYLDIETHYLENETRIAMINE;n-[2-(dimethylamino)ethyl]-n,n,n-trimethyl-1,2-ethanediamine;1,1,4,7,7-pentamethyl-diethylenetriamin;2,5,8-trimethyl-2,5,8-triazanon; N,N,N`,N“,N“-Pentamethyldiethylenetriamine; PMDETA; pentamethyl diethylenetriamine; N,N,N`,N“,N“-Pentamethyldiethylenetriamine; methyl-bis-dimethylaminoethylamine; 1,2-Ethanediamine, N-[2-(dimethylamino)ethyl]-N,N,N-trimethyl-; BIS-(2-DIMETHYLAMINOETHYL)METHYLAMINE; Pentamethyldiethylenetriamine; PMDETA,PMDTA; LUPRAGEN(R) N 301; PMDTAPMDETA; PMDETA; 1,1,4,7,7-pentaMEthyl; 1,1,4,7,7-Pentamethyldiethylenetriami; Pentamethyldiethylen; N1-(2-(dimethylamino)ethyl)-N1,N2,N2-trimethylethane-1,2-diamine; N1-(2-(Dimethylamino)ethyl)-N1,N2,N2-trimethylethane-1,2-diamine; pmdt; 2,5,8-trimethyl-2,5,8-triazanonane; PMDTA; PMDTA; N1-(2-(Dimethylamino)ethyl)-N1,N2,N2-trimethylethane-1,2-diamine; Pentamethyldiethylenetriaminek; Bis(2-dimethylaminoethyl)(methyl)amine; N,N,N`,N`,N“-Pentamethyldiethylenetriamine; 2,5,8-Trimethyl-2,5,8-triazanonane; N,N`,N“-Pentamethyldiethylenetriamine; pmdien; UNII-3274UTY3HL; NSC 65659; 1,2-Ethanediamine, N-[2-(dimethylamino)ethyl]-N,N`,N`-trimethyl-; Diethylenetriamine, 1,1,4,7,7-pentamethyl-; EINECS 221-201-1; n,n,n,n,n-pentamethyldiethylenetriamine; BRN 1741396; 3274UTY3HL; (2-{[2-(dimethylamino)ethyl](methyl)amino}ethyl)dimethylamine; CHEBI:39475; UKODFQOELJFMII-UHFFFAOYSA-N; MFCD00014876; 1,2-Ethanediamine, N-(2-(dimethylamino)ethyl)-N,N`,N`-trimethyl-; N-[2-(dimethylamino)ethyl]-N,N`,N`-trimethylethane-1,2-diamine; 2,2`-(methylazanediyl)bis(N,N-dimethylethanamine); N-(2-(dimethylamino)ethyl)-N,N`,N`-trimethyl-1,2-ethanediamine; 1,2-Ethanediamine, N1-(2-(dimethylamino)ethyl)-N1,N2,N2-trimethyl-; 1,2-Ethanediamine, N1-[2-(dimethylamino)ethyl]-N1,N2,N2-trimethyl-; N1-(2-(dimethylamino)ethyl)-N1,N2,N2-trimethyl-1,2-ethanediamine; 1,1,4,7,7-Pentamethyldiethylenetriamine, 98+%; N-[2-(Dimethylamino)ethyl]-N,N`,N`-trimethyl-1,2-ethanediamine; PubChem16644; Pentamethyldethylenetramne; ACMC-1BFS6; DSSTox_CID_9249; pentamethyldiethyenetriamine; EC 221-201-1; pentamethyl diethylentriamine; pentamethyl-diethylentriamine; DSSTox_RID_78732; DSSTox_GSID_29249; pentamethyl diethylenetriamine; PMDETA; PMDTA; pentamethyldiethylene-triamine; Pentamethyldiethylenetriamine; SCHEMBL37515; pentamethyl diethylene triamine; N,N,N;,N;,N;;-Pentam; CHEMBL3183641; DTXSID7029249; CTK5E2059;UKODFQOELJFMII-UHFFFAOYSA-; KS-000009PO; N,N“-Pentamethyldiethylenetriamine; NSC65659; Tox21_200681; ANW-72547; NSC-65659; ZINC19366286; Bis-(2-dimethylaminoethyl)methylamine; AKOS015915357; 1,4,7,7-Pentamethyldiethylenetriamine; MCULE-7227243002; NE10756; RTR-013028; TRA0000880; WLN: 1N1&2N1&2N1&1; 1,1,4,7,7-pentamethyldiethlenetriamine; NCGC00248795-01; NCGC00258235-01; 1,1,4,7,7-pentamethyldiethlene triamine; AK-34595; Diethylenetriamine,1,4,7,7-pentamethyl-; LS-61897; SC-22742; CAS-3030-47-5; N,N`,N`,N“-Pentamethyldiethylenetriamine; ST2419733; TR-013028; CS-0077160; FT-0606020; N,N,N`,N`,N”-Pentamethyldiethylenetriamine; P0881; N,N`,N“,N“-pentamethyldiethylene triamine; N,N,N`,N`,N“-Pentamethyidiethylenetriamine; N,N,N`, N“,N“-pentamethyldiethylenetriamine; N,N,N`,N“,N“-pentamethyldiethylene triamine; Q965311; J-017894; J-523896; 1, N-[2-(dimethylamino)ethyl]-N,N`,N`-trimethyl-; N,N,N`,N“,N“-Pentamethyldiethylenetriamine, 99%; N`-(2-dimethylaminoethyl)-N,N,N`-trimethyl-ethane-1,2-diamine; N-(2-dimethylamino-ethyl)-N,N`,N`-trimethyl-ethane-1,2-diamine; N-(2-dimethylaminoethyl)-N,N`,N`-trimethyl-ethane-1,2-diamine; InChI=1/C9H23N3/c1-10(2)6-8-12(5)9-7-11(3)4/h6-9H2,1-5H3; 75831-40-2; pmdt;PMDTA;PMDETA;PMDTA PMDETA;LUPRAGEN(R) N 301;Pentamethyldiethylen;1,1,4,7,7-pentaMEthyl-;PENTAMETHYLDIETHYLENETRIAMINE;N-PentaMethyl Diethylene TriaMine;PENTAMETHYLDIETHYLENETRIAMINE 99%; pentamethyldiethylenetriamine,1,1,4,7,7-pentamethyldiethylenetriamine,pmdt,n,n,n`,n,n-pentamethyldiethylenetriamine,pmdeta,pmdta,pentamethyldiethylenetriaminek,bis 2-dimethylaminoethyl methyl amine,2,5,8-trimethyl-2,5,8-triazanonane,n,n`,n-pentamethyldiethylenetriamine; penthametildietilentriamin; penthametil dietilen triamin; penthametildietilentriamine; pentha metil di etilen triamine; penta; metil; dietilen; di etilen; triamin; tri amin; triamine; tri amine; pentametil; penta metil; pentadietilen; penta dietilen; pentatriamin; penta triamin; pentatriamine; penta triamine; penta tri amine; penta tri amin; penthan metil di ethiylentiriamin; penthanmetildiethiylentiriamin; pentenmethiyldiethylenetiriamin; penten methiyl diethylene tiriamin; pentenemethiyldiethylenetiriamin; pentene methiyl diethylenetiriamin; penten methiyl di ethylene tiri amin; pentene methiyl di ethylene tiriamin; penta; methyl; diethylene; triamine; pentamethyl; pentadiethylene; pentadiethylenetriamine; methyldiethylenetriamine; pentamethldiethlenetriamin; penta methl di ethlene triamin; penta methl diethlenetriamin; pentametldietltiriamin; penta metl di etl tiri amin; pentametl dietltiriamin; penthameytildiethiylentriamin; pentha meytil diethiylen triamin; pentha meytildi ethiylen tri amin; pentametilendietilentriamin; penta metilen dietilen triamin; penten metilen dietiylen tiriamine; penten metilen dietiylen tiriamin; penten metilen dietiylen triamin; pentene metilen dietiylen tiriamine; penten metilene dietiylen triamine; penten metilene dietiylen triamin; penthanemetildietilentriamin; penthane metil dietilen triamin; penthane metil di etilen tri amin; penthane methil diyetilen triyamin; penthane methil di etilen tri amin; penthane methil di etilen tri amine; penthane methilo di etilen tri amin; penthane methilo di etilen triyamin; enthane methilo di etilen triyamino; enthane methilodietilentriyamin; pento metiyldietihlentriamin; pentometiyldietihlentriamin; pentometiyl dietihlentriamin; pentometiyl dietihlen tiriamin; pentometiyldietihlentiriamin; N-PENTAMETHYLDIETHYLENETRIAMINE; PENTHAMETILDIETILENTRIAMIN; PENTHAMETIL DIETILEN TRIAMIN; PENTHAMETILDIETILENTRIAMINE; PENTHA METIL DI ETILEN TRIAMINE; PENTA; METIL; DIETILEN; DI ETILEN; TRIAMIN; TRI AMIN; TRIAMINE; TRI AMINE; PENTAMETIL; PENTA METIL; PENTADIETILEN; PENTA DIETILEN; PENTATRIAMIN; PENTA TRIAMIN; PENTATRIAMINE; PENTA TRIAMINE; PENTA TRI AMINE; PENTA TRI AMIN; PENTHAN METIL DI ETHIYLENTIRIAMIN; PENTHANMETILDIETHIYLENTIRIAMIN; PENTENMETHIYLDIETHYLENETIRIAMIN; PENTEN METHIYL DIETHYLENE TIRIAMIN; PENTENEMETHIYLDIETHYLENETIRIAMIN; PENTENE METHIYL DIETHYLENETIRIAMIN; PENTEN METHIYL DI ETHYLENE TIRI AMIN; PENTENE METHIYL DI ETHYLENE TIRIAMIN; PENTA; METHYL; DIETHYLENE; TRIAMINE; PENTAMETHYL; PENTADIETHYLENE; PENTADIETHYLENETRIAMINE; METHYLDIETHYLENETRIAMINE; PENTAMETHLDIETHLENETRIAMIN; PENTA METHL DI ETHLENE TRIAMIN; PENTA METHL DIETHLENETRIAMIN; PENTAMETLDIETLTIRIAMIN; PENTA METL DI ETL TIRI AMIN; PENTAMETL DIETLTIRIAMIN; PENTHAMEYTILDIETHIYLENTRIAMIN; PENTHA MEYTIL DIETHIYLEN TRIAMIN; PENTHA MEYTILDI ETHIYLEN TRI AMIN; PENTAMETILENDIETILENTRIAMIN; PENTA METILEN DIETILEN TRIAMIN; PENTEN METILEN DIETIYLEN TIRIAMINE; PENTEN METILEN DIETIYLEN TIRIAMIN; PENTEN METILEN DIETIYLEN TRIAMIN; PENTENE METILEN DIETIYLEN TIRIAMINE; PENTEN METILENE DIETIYLEN TRIAMINE; PENTEN METILENE DIETIYLEN TRIAMIN; PENTHANEMETILDIETILENTRIAMIN; PENTHANE METIL DIETILEN TRIAMIN; PENTHANE METIL DI ETILEN TRI AMIN; PENTHANE METHIL DIYETILEN TRIYAMIN; PENTHANE METHIL DI ETILEN TRI AMIN; PENTHANE METHIL DI ETILEN TRI AMINE; PENTHANE METHILO DI ETILEN TRI AMIN; PENTHANE METHILO DI ETILEN TRIYAMIN; ENTHANE METHILO DI ETILEN TRIYAMINO; ENTHANE METHILODIETILENTRIYAMIN; PENTO METIYLDIETIHLENTRIAMIN; PENTOMETIYLDIETIHLENTRIAMIN; PENTOMETIYL DIETIHLENTRIAMIN; PENTOMETIYL DIETIHLEN TIRIAMIN; PENTOMETIYLDIETIHLENTIRIAMIN

Properties
Related Categories ATRP, ATRP Ligands, Amine Monomers, Materials Science, Monomers,
More…
vapor pressure 0.23 mmHg ( 20 C)
assay 99%
autoignition temp. 311 F
expl. lim. 5.6 %
refractive index n20/D 1.442 (lit.)
bp 198 C (lit.)
mp -20 C (lit.)

PMDTA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) is an organic compound with the formula [(CH3)2NCH2CH2]2NCH3. PMDTA is a basic, bulky, and flexible, tridentate ligand that is a used in organolithium chemistry. It is a colorless liquid, although impure samples appear yellowish.

Synthesis
PMDTA is prepared from diethylenetriamine by the Eschweiler-Clarke reaction, involving the use of formaldehyde and formic acid.[1]

[H2N(CH2)2]2NH + 5 CH2O + 5 HCO2H → [Me2NCH2CH2]2NMe + 5 CO2 + 5 H2O

Comparison with diethylenetriamine

Unlike diethylenetriamine, all three amines in PMDTA are tertiary. Both PMDTA and diethylenetriamine are tridentate ligands that form two five-membered chelate rings. The σ-donating properties of the amino groups of diethylenetriamine are greater than that of PMDTA in copper(II) complexes.[2] Both ligands can coordinate metal complexes in arrangements where the three nitrogen centers are co-planar or mutually cis.

Organolithium compounds and PMDTA
PMDTA is used to modify the reactivity of organolithium compounds, which deaggregate in the presence of Lewis bases to enhance their reactivity.[3] Commonly, the ditertiary amine TMEDA is used in these applications; it binds to the lithium center as a bidentate ligand. PMDTA behaves analogously, but since it is tridentate, it binds more strongly to lithium. In contrast to TMEDA, PMDTA forms monomeric complexes with organolithium compounds. Both amines affect the regiochemistry of metalation.[3][4]

In the PMDTA/n-BuLi adducts, the Li-C bonds are highly polarized, thus increasing the basicity of the butyl group.[5]

The effect of PMDTA on lithium anilide is illustrative of PMDTA`s complexing power. The complex, [{PhN(H)Li}32PMDTA], is trinuclear, featuring approximately colinear Li+ centers that are three-, four-, and five-coordinate. The central three-coordinate lithium atom is not bonded to PMDTA. One of the terminal Li centers is pseudo-tetrahedral in an N4 coordination sphere. The other terminal lithium atom is five-coordinate and binds to two anilino N centers and the PMDTA.[6]

Transition metal and aluminium complexes
PMDTA often forms five-coordinate complexes due to steric bulk of the methyl groups. PMDTA stabilize unusual cations. The first cationic derivative of alane, [H2Al(PMDTA)]+[AlH4]- was prepared by treating H3AlNMe3 with PMDTA.[5]

Description and features
AminCat PMDETA catalyst (Pentamethyldiethylenetriamine) is a highly active, pure liquid tertiary amine which has C9H23N3 as chemical formula. This substance is suitable for use as a blowing catalyst in a number of applications.

Pentamethyldiethylenetriamine is also known as PMDETA, PMDTA, PMDT and N-[2-(dimethylamino)ethyl]-N,N`,N`-trimethylethane-1,2-diamine.

Storage
Store Pentamethyldiethylenetriamine in a cool, dry and well-ventilated area and in line with legal requirements.
Keep AminCat PMDETA away from heat sources and oxidizing agents.

ntamethyldiethylenetriamine | CAS: 3030-47-5 | Disclaimer. This information is supplied solely for informational purposes and Vesta Chemicals bv makes no guarantees or warranties, either expressed or implied, with respect to the accuracy and use of this data. All product warranties and guarantees shall be governed by the Standard Terms of Sale. Nothing in this document is legal advice or is a substitute for competent legal advice.

Molecular and structural information
Molecular formula C9H23N3
Molecular weight 173.30 g/mol
Smiles notation CN(C)CCN(C)CCN(C)C
InChi key UKODFQOELJFMII-UHFFFAOYSA-N

Application
AminCat PMDETA catalyst is very effective in pour-in place polyurethane systems (such as rigid appliance systems), which are based on MDI. At a use level of 1.5 php, AminCat PMDETA catalyst provides the necessary flow ability and cure rates required in the production environment. AminCat PMDETA catalyst is also recommended for TDI, TDI/MDI and MDI HR flexible molded foams, as well as for use in integral skin and microcellular systems. It can also be as a raw material to make quaternary ammonium salt.

Pentamethyldiethylenetriamine Chemical Properties,Uses,Production
Chemical Properties
colourless liquid with an amine odour
Safety Profile
Poison by skin contact. Moderately toxic by ingestion.When heated to decomposition it emits toxic fumes of NOx.
Pentamethyldiethylenetriamine Preparation Products And Raw materials

Reaction of phenylsodium with MgPh2 in the presence of pentamethyldiethylenetriamine (PMDTA) gives crystals of structurally characterized (113), in which tetrahedral MgPh42-, containing typical σ Mgsingle bondC bonds (mean distance 0.229 nm), is bonded by asymmetrically bridging phenyl groups to two Na(PMDTA)+ groups producing five-coordination at the larger sodium centre; the Nasingle bondC(ipso) interactions are orthogonal to the aromatic plane and must involve the π electrons.263

pentamethyldiethylenetriamine (PMDTA)Li-SnPh3, for example, confirmed that the Sn-Li bond observed in the solid state (2.87 (av)) persists in solution.227

In perhaps the best studied copper-mediated ATRP, the lower oxidation state metal is copper(I) species complexed by an appropriate ligand such as 2,2′-bipyridine (bpy), pentamethyldiethylenetriamine (pmdta)

The alkali metal coordination can be further reduced to an η2-mode by using the tridentate pentamethyldiethylenetriamine (PMDETA) ligand for Li+ solvation.83 The molecular structure of the corresponding adduct, [{Li(PMDETA)+}Ind] (33), is depicted in Fig. 3.19E. Most recently, it was demonstrated that intramolecular C-H⋯π interactions between the H-atoms of the coordinated solvent and the indenyl benzene ring in 30, 32, and 33 cause additional gluing of the moieties to anions to complement the primary Li⋯indenyl interactions.83

HAZARDS IDENTIFICATION OF PENTAMETHYLDIETHYLENETRIAMINE
EMERGENCY OVERVIEW
Flammable. Harmful if swallowed. Toxic in contact with skin. Causes burns.
Potential Health Effects
Eye:
Causes eye burns.
Skin:
Harmful if absorbed through the skin. Causes skin burns. Amines have been known to cause skin irritation and sensitization.
Ingestion:
May cause severe and permanent damage to the digestive tract. Causes gastrointestinal tract burns. May be harmful if swallowed.
Inhalation:
Causes chemical burns to the respiratory tract.
Chronic:
No information found.

eaction of H3AlNMe3 with N,N,N′,N″,N″-pentamethyldiethylenetriamine (pmdien) in diethyl ether or 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (Me4cyclam) in tetrahydrofuran yields [H2Al(pmdien)]+[AlH4]-, which possesses a trigonal bipyramidal cation with the hydrides in the trigonal plane [Al-N′ 2.158(7), Al-N,N″ 2.01(1), Al-H 1.62 ] or [H2Al(Me4 cyclam)]+[AlH4], where the metal centre in the cation is trans-octahedral [Al-N(mean) 2.13, Al-H 1.60, 1.64 ].

Abstract
A homogeneous reverse atom transfer radical polymerization (RATRP) of methyl methacrylate (MMA) was successfully carried out in N, N-dimethylformamide(DMF) (25%, v/v) at 69C, using an initiating system azobisisobutyronitrile (AIBN)/CuBr2/N, N, N′, N″, N″-pentamethyldiethylenetriamine (PMDETA). The kinetics of homogeneous solution polymerizations showed linear first-order rate plots, indicating a constant number of growing species throughout the polymerization as well as a negligible contribution of termination or transfer reactions; a linear increase of the number-average molecular weight with conversion, and relatively low polydispersities, but low initiator efficiency. The dependence of the rate of polymerization on the concentrations of initiator, catalyst, ligand and temperature were presented.

Keywords: Reverse atom transfer radical polymerization, Living polymerization, Methyl methacrylate, Homogeneous polymerization, N, N, N′, N″, N″-pentamethyldiethylenetriamine, Radical polymerization

Product Description
Pentamethyldiethylenetriamine is a colorless transparent liquid, soluble in water, soluble in benzene, alcohol and so on.It is mainly used for sulfonylurea herbicides, pesticides, pharmaceutical intermediates important raw materials for chemical synthesis, but also polyamide, chemical luminescent agent, liquid crystal.

Application
1. Mainly used for sulfonylurea herbicides, pesticides
2. As an important chemical synthesis of pharmaceutical raw materials intermediates
3. As polyamide, chemical luminescent agent, liquid crystal and other chemical industry, high-quality acylating agents and other fields

Product Introduction:
Pentamethyldiethylenetriamine is called PMDETA for short, and another name in Chinese is N N N` N“ N“-pentamethyldiethylene triamine. The product is colorless or yellowish transparent liquid, light odor, soluble in water, ether and alcohol solvent. It can absorb moisture and carbon dioxide in the air.

Applications:
As the highly active catalyst in polyurethane reaction, it mainly catalyzes foaming reaction, also is used to balance overall foaming and gel reaction.
PMDETA is widely applied to various polyurethane rigid foams, including rigid foam for polyisocyanurate (PIR) panel. Because of its strong foaming effect, it can improve the foam flowability, thus to improve the production technology and the quality of products. PMDETA can be used together with N,N-Dimethylcyclohexylamine (DMCHA) or other catalysts.
PMDETA alone can be used as the catalyst in polyurethane foam plastic formula, also can be used together with other catalysts. When used alone, it is used in the range of 1.0 to 2.0 parts in 100 parts of polyol.
Besides of using in rigid foam, PMDETA also can be used in polyether type of polyurethane flexible block foam and molded foam. PMDETA is of high catalyst activity, and rapid foaming speed, making the foam product high toughness and high load bearing.

Storage:
Pay attention to waterproof and sealing. Keep away from open flame in transportation and storage. Stored in cool, dry and well-ventilated place.

Sealed. stored in cool, dry and well-ventilated place. Keep away from spark, fire and heat source. Stored in an airtight container. Keep away from incompatible substances and corrosive area.

The invention discloses a preparation method of pentamethyldiethylenetriamine. The method comprises the following steps: using formaldehyde and diethylenetriamine to perform hydrogenation reaction under the action of platinum or palladium supported catalyst and obtaining pentamethyldiethylenetriamine. The raw materials of the method of the invention are accessible, the reaction pressure is reduced, the reaction time is shortened, the product yield is increased and the production and post-treatment costs are reduced.

GENERAL DESCRIPTION: JD PMDETA catalyst is a highly active, pure liquid tertiary amine that is suitable for use as a blowing catalyst in a number of rigid and flexible polyurethane foam applications.

ADVANTAGES: In model systems, JD PMDETA catalyst has proven to have catalytic activity equivalent to other established blowing catalysts for the urea reaction. However, JD PMDETA catalyst has a greater affect than established blowing catalysts on the urethane or gelling reaction.

APPLICATIONS: JD PMDETA catalyst is very effective in pour-inplace polyurethane systems (such as rigid appliance systems), which are based on MDI. At a use level of 1.5 php, JD PMDETA catalyst provides the necessary flowability and cure rates required in the production environment. JD PMDETA catalyst is also recommended for TDI, TDI/MDI and MDI HR flexible molded foams, as well as for use in integral skin and microcellular systems. It can also be as a raw material to make quaternary ammonoum salt.

Linear poly(N-methylethylenimine), LPMEI, a methylated derivative of linear poly(ethylenimine), shows potential as a polymer electrolyte host. The interactions of LPMEI with lithium and sodium cations are modeled by solutions of N,N,N,N,N -pentamethyldiethylenetriamine, PMDETA, containing either dissolved LiCF3SO3 (LiTf) or NaCF3SO3 (NaTf). During these studies, crystalline compounds were discovered and characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy (IR), and Raman spectroscopy. Crystals of the NaTf complex, (PMDETA)NaTf, were of sufficient size to allow a structure determination by X-ray diffraction. The (PMDETA)NaTf crystallizes as two dimers with different symmetries in a monoclinic unit cell in the P21/c space group. A spectroscopic comparison of PMDETA, the crystalline complex PMDETA-LiTf, crystalline (PMDETA)NaTf, and their corresponding salt solutions over a composition range of 1.7:1 to 6.7:1 (PMDETA:MTf molar ratio, M = Li+, Na+) was carried out with IR and Raman spectroscopy. The dominant species in the (PMDETA)xNaTf solutions is the triple cation [Na2Tf]+, even at a 6.7:1 PMDETA:NaTf molar composition.

ngilizceden evrilmitir-PMDTA, [(CH₃) ₂NCH₂CH₂] ₂NCH₃ formlne sahip organik bir bileiktir. PMDTA, organolityum kimyasnda kullanlan temel, hacimli ve esnek, l bir liganddr. Saf olmayan rnekler sarms grnmesine ramen renksiz bir svdr.

PMDTA ( N , N , N ` , N` ` , N` ` -pentametildietilentriamin ) forml [(CH olan bir organik bileik olup, 3 ) 2 NCH 2 CH 2 ] 2 NCH 3 . PMDTA, organolityum kimyasnda kullanlan temel, hacimli ve esnek, l bir liganddr . Saf olmayan rnekler sarms grnmesine ramen renksiz bir svdr.

Sentez
PMDTA hazrlanr dietilentriamin ile Eschweiler-Clarke reaksiyonu formaldehit ve kullanmn kapsayan, formik asit . [1]

[E 2 , N (CH 2 ) 2 ] 2 , NH + 5 CH 2 O + 5 HCO 2 H → [Me 2 NCH 2 , CH 2 ] 2 NMe + 5 CO 2 + 5H 2 O

Dietilentriamin ile karlatrlmas
Dietilentriaminden farkl olarak, PMDTA`daki aminin hepsi ncldr. Hem PMDTA hem de dietilentriamin, be yeli iki elat halkas oluturan tridentat ligandlardr. Dietilentriaminin amino gruplarnn σ verici zellikleri, bakr (II) komplekslerinde PMDTA`nnkinden daha byktr. [2] Her iki ligand, azot merkezinin e dzlemli veya karlkl cis olduu dzenlemelerde metal komplekslerini koordine edebilir .

Organolityum bileikleri ve PMDTA
PENTAMETLDETLENTRAMN (PMDTA), Lewis bazlarnn varlnda reaktivitelerini arttrmak iin ayran organolityum bileiklerinin reaktivitesini deitirmek iin kullanlr . [3] Genel olarak, di ncl amin TMEDA Bu uygulamalarda kullanlr; iki dili bir ligand olarak lityum merkezine balanr. PMDTA benzer ekilde davranr, ancak tidentat olduundan lityuma daha gl balanr. TMEDA`nn aksine PMDTA, organolityum bileikleri ile monomerik kompleksler oluturur. Her iki amin de metalasyonun biyokimyasn etkiler. [3] [4]

PENTAMETLDETLENTRAMN (PMDTA)/ n- BuLi eklentilerinde, Li-C balar yksek oranda polarize edilir, bylece butil grubunun baziklii artar. [5]

PENTAMETLDETLENTRAMN (PMDTA)`nn lityum anilid zerindeki etkisi PMDTA`nn kompleks yapc gcn gstermektedir. [{PhN (H) Li} 3 2PMDTA] kompleksi ekirdekli olup, , drt ve be koordinatl yaklak dorusal dorusal Li + merkezlerine sahiptir. Merkezi koordinatl lityum atomu PMDTA`ya bal deildir. Terminal Li merkezlerinden biri, bir N pseudo-yzl olan 4 koordinasyon kresinde. Dier terminal lityum atomu be koordinatldr ve iki anilino N merkezine ve PMDTA`ya balanr. [6]

Gei metali ve alminyum kompleksleri
PENTAMETLDETLENTRAMN (PMDTA), metil gruplarnn sterik ktlesi nedeniyle sklkla be koordinat kompleksleri oluturur. PMDTA olaand katyonlar stabilize eder. Alane ilk katyonik trevi [E 2 , Al (PMDTA)] + [AlH 4 ] – lH ilenmesiyle hazrland 3 AlNMe 3 PMDTA ile. [5]

Hidroksil u gruplarna sahip 5-kollu ve yldz-ekilli poli(etilen oksit) (PEO-OH), PEO-esasl makrobalatcnn sentezi iin kullanld. Brom u gruplar ieren 5-kollu ve yldz-ekilli poli(etilen oksit) (PEO-Br), tert-butil akrilat monomerin Atom Transfer Radikal Polimerizasyonunda (ATRP) makrobalatc olarak kullanld ve bylece 5-kollu ve yldz-ekilli poli(etilen oksit)-blok-poli(tert-butil akrilat) (PEO-b-PtBA) blok kopolimerler sentezlendi. Polimerizasyon, asetonitril zc ortamnda ve bakr(I)bromr/ N,N,N′,N′′,N′′-pentametil dietilentriamin (CuBr/PMDETA) katalizr sistemi kullanlarak kontroll bir ekilde yrtld. Yldz-ekilli PEO-b-PtBA blok kopolimerin tert-butil gruplarnn hidrolizi diklorometan zc ortamnda oda scaklnda trifluoroasetik asit ile gerekletirildi ve bylece yldz-ekilli ve ift-hidrofilik PEO-b-PAA blok kopolimerler sentezlendi. Daha sonra, yldz-ekilli ve ift-hidrofilik PEO-b-PAA blok kopolimerlerin metillenmesi trimetilsilil diazometann metilleyici reaktif olarak kullanlmasyla oda scaklnda gerekletirildi.

Yukarda elde ettiimiz bir kollu polimer olan 3`l balatc (0.65 gr; 0.0001144 mol), MMA (3.671 ml), Toluen (3.671 ml), Pentametildietilentriamin (PMDTA) (0.02388 ml), CuCl (0.01132 gr) bir shlenk tpne alnr. 3 kez degaz sisteminden geirilip ierisindeki hava ve nem alnr. Sonra 90oC`de 2 saat tutulur. Saflandrma iin nce silika kolondan geirilir. Daha sonra zc uurulur, biraz THF`de zlp metanolde ktrlr (%14 verimle elde edilir) [30].

Bakr ve primer aminler arasndaki koordinasyon kompleksleri, bakr-bipy komplekslerine gre daha dk redoks potansiyeline sahip olduklarndan, polimerizasyon hzn artrr ve daha iyi kontrol salar [12-13]. Bundan dolay primer aminler bipy ve trevleri olan ligantlarn nemli alternatifleridir [14]. CuCl/Pentametildietilentriamin (PMDTA) kompleks sistemi ilk defa Gnanou,Y., Hzal G. [15] tarafndan kullanlmtr. Pentametildietilentriamin (PMDTA) kullanldnda Cu/Ligand oran 1:1 bipy veya TEMDA kullanldnda ise oran 1:2 olduunda maksimum reaksiyon hz ve polimerizasyon kontrol salanr [13].

Polimerlerin sayca ortalama molekl arl : Polimerlerin arlka ortalama molekl arl
Poli(metilmetakrilat) : Polistiren : N,N,N,N,N-pentametil dietilentriamin : Poli N-butil okzabornan imid polimeri : Radikal polimerizasyon aktivasyon ve deaktivasyon hz sabitleri : Radikal polimerizasyon sonlanma byme ve balama hz
sabitleri : Atom Transfer Radikal Polimerizasyonu : Halka Alma Metatez Polimerizasyonu : Stiren

rn, N, N-dimetilformamid, N, N-dimetil-aminoetanol, sikloheksanon, trietilendiamin, bis (2- (dimetilamino) etil) eter ve 1,1,4,7,7-pentametil-dietilentriamin maddeleri ierir.
Gzlerde ve mukoza zarnda tahri ve karaciere zarar verme riski vardr.rn Oyuncak Gvenlik Direktifinin gerekliliklerine uymaz.

Bu almada, sv kristal (6-(4-syanobifenil-4`oksi)heksil akrilat) (LC6) ve Stiren (St) monomerleri kullanlarak, Atom Transfer Radikal Polimerizasyon (ATRP) ve Foto Balatlm Radikal Polimerizasyon (PIRP) yntemleriyle ABA tip blok kopolimerler sentez edilmitir. lk aamada, foto-aktif α-metilol benzoin eter, 2-bromopropionil bromr ile esterletirilmi ve ele geen fonksiyonel balatc, LC6/Stiren monomerlerinin ATRP yntemiyle CuBr/N,N,N`,N“,N“` pentametil-dietilentriamin (PMDETA) varlnda polimerletirilmesinde kullanlmtr.kinci aamada ise; foto-aktif sv kristal polimer (PLC6) ve foto aktif polistiren (PSt) homopolimerleri bir sonraki aamada stiren ve LC6 monomerinin PIRP yntemiyle kopolimerletirilmesinde balatc olarak kullanlmtr.

3.2.4. N,N,N`,N“,N“ Pentametil dietilentriamin zeltisi 1 ml N,N,N`,N“,N“ Pentametil dietilentriamin 100 mL su iinde zld. PEO jellerin kimyasal olarak hazrlanmasnda hzlandrc olarak kullanlmtr.

Hazrlanan (5 g PEO+ 1000mL su) 2 mL(0,01g) ( PEO zeltisine srayla, apraz balayc PEGDA`tan 0,24 mL (0,269g), balatc AP zeltisi-1`den 0,4 mL, hzlandrc Pentametil dietilentriamin zeltisinden 0,25 mL eklenmitir. Hazrlanan zelti kartrldktan sonra 3 mm apndaki plastik pipetlere doldurulmu, oda scaklnda (25oC) jellemeye braklmtr. 25oC de 15 dakikada jelleme tamamland. Jeller plastik pipetlerden karlarak oda scaklnda 1 hafta kurumaya braklmtr. Kuruyan jellere iletkenlik lmleri ve dier analizler yaplmtr.

2`er mL(0,01g) PEO zeltisi alnr, bunlara ayr ayr izelge 3.1 de belirlenen oranlardan 1`er mL LiClO4 zeltisinden eklendi, daha sonra srayla, apraz balayc PEGDA`tan 0,24 mL (0,269 g), balatc AP zeltisi-1`den 0,4 mL, hzlandrc Pentametil dietilentriamin zeltisinden 0,25 mL eklenmitir. Hazrlanan zelti kartrldktan sonra 3 mm apndaki plastik pipetlere doldurulmutur, oda scaklnda (25oC) jellemeye brakld. 25oC de 60 dakikada jelleme tamamlanmtr. Jeller plastik pipetlerden karlarak oda scaklnda 1 hafta kurumaya braklmtr. Kuruyan jellere iletkenlik lmleri ve dier analizler yaplmtr. Daha sonra srayla apraz balayc PEGDA`tan 0,24 mL (0,269g), balatc AP zeltisi-1`den 0,4 mL, hzlandrc Pentametil dietilentrianim zeltisinden 0,25 mL eklenmitir. Hazrlanan zelti kartrldktan sonra 3 mm apndaki plastik pipetlere doldurulmu, oda scaklnda (25oC) jellemeye braklmtr. 25oC de 15 dakikada jelleme tamamlanmtr. Jellemeler tamamlandktan sonra anilinin polimerleme hzlar incelenmitir. Polimerlemelerde tamamlandktan sonra jeller plastik pipetlerden karlarak oda scaklnda 1 hafta kurumaya braklm. Kuruyan jellere iletkenlik, SEM ve infrared lmleri yaplmtr.

2,2-bipiridin trevleri ve azot esasl N,N,N`,N“,N“-pentametil dietilen triamin (PMDETA), tetrametilendiamine (TMEDA), tris[2-(dimetilamino)etil]amin (Me6-TREN) and alkilpiridilmetanimin gibi ligandlar ATRP de sklkla kullanlr.

Temiz ve kuru tek boyunlu bir balon ierisine srasyla hesaplanan miktarlarda 5 mL kuru toluen, pentametil dietilen triamin (PMDETA) (ligand), glisidil metakrilat (monomer) ve yzeyine balatc balanm olan nanolif (makro balatc) konuldu. Monomer ve ligandn homojen bir ekilde karmas salandktan sonra CuBr ilave edildi. CuBr`n znmesi iin 10 dakika daha kartrld. Balonun az hava geirmez kauuk kapak ile kapatldktan sonra glove boxdan kartld. Balon nceden stlm 60 C deki ya banyosu ierisine daldrld. 3 saatin sonunda balon alnarak az ald ve reaksiyon sonlandrld.

Bu almada kullanlm baz simgeler ve ksaltmalar, aklamalar ile birlikte aada sunulmutur. Simgeler Aklama m Metre R Diren k Kilo ohm Ksaltmalar Aklama AP Amonyum Perslfat PEO Poli(etilen oksit) PEGDA Polietilen Glikol Diakrilat PMDT N,N,N`,N“,N“ Pentametil dietilentrian 1 1. GR letken polimerler; metallerin elektriksel iletkenliklerini polimerlerin kimyasal ve mekaniksel zellikleriyle birletirerek, metallerle yar iletkenler arasnda iletkenlie sahip olan polimerlerdir. Polimerlerle modifiye edilmi elektrot kavramnn ilk olarak 1970lerin sonlarnda MacDiarmid ve arkadalarnn, poliasetilenin doplanmas ile iletkenliinin arttnn bulmasyla kullanlmaya balanmtr. Kimyasal olarak modifiye edilmi elektrotlar zerine en nemli gelime 1984 ylnda Murray tarafndan yaplan elektrotlarn hazrlanmas, karakterizasyonu ve uygulanmalar ile ilgili almada gzlenmitir. Polimer elektrotlar esnek lamine yaps ve smarlama geometrileriyle sarj edilebilir lityum pillerin gelimesinde nemli rol oynamaktadr.

Daha sonra bu aratrmaclar anilinle beraber sbstite anilinlerin ktlece 1:1 kopolimerlerini sentezleyerek, iletkenliklerinin 1,0×10-2 Scm-1e ykseldiini belirlemilerdir. 40 3. MATERYAL VE METOT 3.1. Materyal 3.1.1. Kullanlan kimyasallar Kullanlan Kimyasal Maddeler Temin Edilen Firma Poli(etilen oksit) (OCH2CH2)n Aldrich Lityum perklorat (LiClO4) Aldrich Polietilen glikol diakrilat (PEGDA) Aldrich Amonyum perslfat ((NH4)2S2O8) Merck N,N,N`,N“,N“ Pentametil dietilentriamin Merck Anilin (C6H5NH2) Hidroklorik asit (HCl) Slfrik asit (H2SO4) 3.1.2. Aletler ve cihazlar letkenlik lmleri Bir polimerin elektriksel iletkenlii akm younluunun (J) elektrik alanna (E) oran eklinde tanmlanr. = J/E letken polimerlerin yaygn zclerdeki zayf znrl kat halde iletkenlik lmlerinin alnmas iin nemli bir nedendir.

Amonyum perslfat zeltisi-1 1g Amonyum perslfat 20 mL su iinde zlm ve PEO jellerin kimyasal olarak hazrlanmasnda balatc olarak kullanlmtr. 43 3.2.4. N,N,N`,N“,N“ Pentametil dietilentriamin zeltisi 1 ml N,N,N`,N“,N“ Pentametil dietilentriamin 100 mL su iinde zld. PEO jellerin kimyasal olarak hazrlanmasnda hzlandrc olarak kullanlmtr. 3.2.5. 1M HCl zeltisi ie zerinde bulunan asidin spesifikasyonlar (d = 1.19 g/cm3, %37 lik) kullanlarak yaklak olarak 1 M HCl zeltisi hazrlanmtr. 3.2.6. Amonyum Perslfat zeltisi-2 2,6 g Amonyum Perslfat 100 mL 1 M HCl iinde zld. Anilinin polimerletirilmesinde kullanlmtr. 3.2.7. Anilin/HCl tuzu 2 mL Anilin behere konulmu, zerine yaklak 2 mL, d = 1.19 g/cm3, %37 lik HCl anilinin tamam kene kadar damlatlmtr.

Pentametil dietilentriamin zeltisinden 0,25 mL eklenmitir. Hazrlanan zelti kartrldktan sonra 3 mm apndaki plastik pipetlere doldurulmu, oda scaklnda (25oC) jellemeye braklmtr. 25oC de 15 dakikada jelleme tamamland. Jeller plastik pipetlerden karlarak oda scaklnda 1 hafta kurumaya braklmtr. Kuruyan jellere iletkenlik lmleri ve dier analizler yaplmtr. LiClO4 bazl PEO jel sentezi 2er mL(0,01g) PEO zeltisi alnr, bunlara ayr ayr izelge 3.1 de belirlenen oranlardan 1er mL LiClO4 zeltisinden eklendi, daha sonra srayla, apraz balayc PEGDAtan 0,24 mL (0,269 g), balatc AP zeltisi-1den 0,4 mL, hzlandrc Pentametil dietilentriamin zeltisinden 0,25 mL eklenmitir. Hazrlanan zelti kartrldktan sonra 3 mm apndaki plastik pipetlere doldurulmutur, oda scaklnda (25oC) jellemeye brakld. 25oC de 60 dakikada jelleme tamamlanmtr. Jeller plastik pipetlerden karlarak oda scaklnda 1 hafta kurumaya braklmtr. Kuruyan jellere iletkenlik lmleri ve dier analizler yaplmtr.. PEO ve polianilinin yarmal polimerizasyonu (Anilin/HCl tuz bazl PEO jel sentezi) 0,001 g, 0,005g, 0,01g anilin/HCl tuzlar tartld. Tartlan tuzlara ayr ayr hazrlanan 2 mL(0,01g) PEO zeltisi eklenmi ve tuz zlmtr. Daha sonra srayla apraz balayc PEGDAtan 0,24 mL (0,269g), balatc AP zeltisi-1den 0,4 mL, 45 hzlandrc Pentametil dietilentrianim zeltisinden 0,25 mL eklenmitir. Hazrlanan zelti kartrldktan sonra 3 mm apndaki plastik pipetlere doldurulmu, oda scaklnda (25oC) jellemeye braklmtr. 25oC de 15 dakikada jelleme tamamlanmtr.

Bakr esasl ATRP de ligand olarak ift dili bir ligand olan bipiridin (bpy) olduka yaygn kullanlmaktadr. Byle bir katalizr kullanldnda polimerlerin heterojenlik indisinin olduka kk olduu grlmtr (Mw/Mn

zcler: 1,4-dioksan, tetrahidrofuran, monoklor aseton, diklormetan, N,N
dimetil formamid, aseton, difenil eter, hidroklorik asit ve NMR spektrumlar
iin dteryumlanm kloroform (CDCl3) ve dimetil slfoksit(D6-DMSO)

Katalist sistem: 2,2`- bipiridin, CuBr , N,N,N`,N`,N“ penta metil dietilen triamin

Balatc: Bromasetonitril

Monomerler: Metilmetakrilat (monomer Merck olup %5`lik sodyum hidroksit
zeltisi ile ykanp vakum altnda damtlarak kullanld).

Kauuk kapakl polimerizasyon tpne 0.20 mmol CuBr 0.40 mmol N,N,N`,N“N“ penta metil dietilen triamin ligantndan srasyla konulduktan sonra argon gazndan geirildi. Balatc olarak 0.2 mmol Kalkon 2 konuldu ve zerine 20 mmol MMA konuldu, karm tekrar argon gazndan yaklak 10 dakika geirildi. Tpn az kapatlp 120 0C`ye ayarlanm ya banyosuna daldrlarak polimerizasyon balatld. 60 saat sren polimerizasyon sonunda, polimer diklorometanda zlp, etil alkol iinde damla damla ktrld. Saflatrma amacyla, ayn ekilde iki kez zp-ktrme ilemi tekrarland. Szlen polimer nce oda scaklnda akta kurutuldu, sonra vakum altnda 400C`de 36 saat kurutuldu. Polimer 1H-NMR teknii ile karakterize edildi. Polimerin yaps ekil 2.5` de gsterilmitir.

Bipiridinin yan srapiridiniminler ve fenantrolinler gibi dier ift dili ligantlar ile pentametildietilentriamin Pentametil dietilentriamin (PMDETA) ve permetillenmi tetraminler gibi ok dili ligantlar da benzer olarak kullanlabilmektedir.

Gnmzde bakr esasl ATRP halen en nemli katalist sistem olarak grlmesine ramen Ru, Fe, Ni, Pd ve Pt gibi dier gei metalleri de baaryla kullanlmaktadr.

ATRP polimerizacijom uz korićenje CuBr kombinovanog sa pentametildietilentetraaminom kao katalizatorom. Reakcija se odigravala u zatvorenom sudu, u kojem je vazduh bio zamenjen atmosferom azota, u uljanom kupatilu na temperaturi od 90 0C u trajanju od 4,5 h [69]. Korićenjem PS mediatora (poli(4-vinilbenzil-4-oksi2,2,6,6-tetrametilpiperidin-1-oksil-ran-stirena) u reakciji foto-ţive radikalne polimerizacije nastali su kalemljeni kopolimeri PS i PMMK.