Kinetics of the microemulsion polymerization of styrene with short‐chain alcohols as the cosurfactant

The kinetics of styrene microemulsion polymerization stabilized by sodium dodecyl sulfate (SDS) and a series of short‐chain alcohols (n‐C_iH_2i+1OH, abbreviated as C_iOH, where i = 4, 5, or 6) at 60 °C was investigated. Sodium persulfate was used as the initiator. The microemulsion polymerization process can be divided into two intervals: the polymerization rate (R_p) first increases to a maximum at about a 20% conversion (interval I) and thereafter continues to decrease toward the end of the polymerization (interval II). For all the SDS/C_iOH‐stabilized polymerization systems, R_p increases when the initiator or monomer concentration increases. The average number of free radicals per particle is smaller than 0.5. The molecular weight of the polymer produced is primarily controlled by the chain‐transfer reaction. In general, the reaction kinetics for the polymerization system with C₄OH as the cosurfactant behaves quite differently from the kinetics of the C₅OH and C₆OH counterparts. This is closely related to the different water solubilities of these short‐chain alcohols and the different concentrations of the cosurfactants used in the preparation of the microemulsion. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 898–912, 2001     

Effect of short-chain alcohols on the oil-in-water microemulsion polymerization of styrene

The influence of short-chain alcohols, 1-butanol (C₄OH), 2-pentanol (C₅OH) and 1-hexanol (C₆OH), on the formation of oil-in-water styrene microemulsions and the subsequent free-radical polymerization was studied. Sodium dodecyl sulfate was used as the surfactant. The overall performance of C₄OH as the cosurfactant is quite different from C₅OH and C₆OH. The range of the microemulsion region in decreasing order is C₄OH > C₅OH > C₆OH. The primary parameters selected for the microemulsion polymerization study were the concentrations of cosurfactant and styrene. Only a small fraction of microemulsion droplets initially present in the reaction system can be successfully transformed into latex particles and the remaining droplets serve as a reservoir to supply the growing particles with monomer. Limited flocculation of latex particles also occurs during polymerization and the degree of flocculation is most significant for the C₄OH system. Received: 24 August 1999/Accepted in revised form: 22 October 1999     

Microemulsion polymerization of styrene stabilized by sodium dodecyl sulfate and short‐chain alcohols

Styrene microemulsion polymerizations with different short‐chain alcohols [n‐C_iH_2i+1OH (C_iOH), where i = 4, 5, or 6] as the cosurfactant were investigated. Sodium dodecyl sulfate and sodium persulfate (SPS) were used as the surfactant and initiator, respectively. The desorption of free radicals out of latex particles played an important role in the polymerization kinetics. An Arrhenius expression for the radical desorption rate coefficient was obtained from the polymerizations at temperatures of 50–70 °C. The polymerization kinetics were not very sensitive to the alkyl chain length of alcohols compared with the temperature effect. The maximal polymerization rate in decreasing order was C₆OH > C₄OH > C₅OH. This was related to the differences in the water solubility of C_iOH and the structure of the oil–water interface. The feasibility of using a water‐insoluble dye to study the particle nucleation mechanisms was also evaluated. The parameters chosen for the study of the particle nucleation mechanisms include the cosurfactant type (C_iOH), the SPS concentration, and the initiator type (oil‐soluble 2,2′‐azobisisobutyronitrile versus water‐soluble SPS). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3199–3210, 2001     

Excess Volumetric and Spectroscopic Properties of Mixtures of Some <Emphasis Type="Italic">n</Emphasis>-Alkoxyethanols and of Some Polyethers with 2-Pyrrolidinone and <Emphasis Type="Italic">N</Emphasis>-Methyl-2-Pyrrolidinone at 298.15 K

Excess molar volumes V_m^E for binary liquid mixtures of n-alkoxyethanols or polyethers + 2-pyrrolidinone or N-methyl-2-pyrrolidinone have been measured with a continuous dilution dilatometer at 298.15 K and atmospheric pressure as a function of composition. The alkoxyethanols are diethylene glycol monomethylether, 2-(2-methoxyethoxy) ethanol, CH₃(OC₂H₄)₂OH; diethylene glycol monoethylether, 2-(2-ethoxyethoxy) ethanol, C₂H₅(OC₂H₄)₂OH; and diethylene glycol monobutylether, 2-(2-butoxyethoxy) ethanol, C₄H₉(OC₂H₄)₂OH; whereas the polyethers are diethylene glycol dimethylether, bis(2-methoxyethyl)ether, CH₃(OC₂H₄)₂OCH₃; diethylene glycol diethylether, bis(2-ethoxyethyl)ether, C₂H₅(OC₂H₄)₂OC₂H₅; and diethylene glycol dibutylether, bis(2-butoxyethyl)ether, C₄H₉(OC₂H₄)₂OC₄H₉. In all mixtures the excess molar volumes are negative and symmetric across the entire composition range. The excess volumes are fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors. The experimental results have also been discussed on the basis of IR measurements.     

Interfacial and Thermodynamic Properties of Formation of Water‐in‐Oil Microemulsions with Surfactants (SDS and CTAB) and Cosurfactants (n‐Alkanols C5–C9)

The interfacial and thermodynamic properties of water‐in‐oil microemulsion systems consisting of water, isopropyl myristate, n‐alkanol, and surfactant have been investigated using the method of dilution. The surfactants used were hexadecyl trimethylammonium bromide and sodium dodecylsulfate, and the cosurfactants were n‐alkanols with varying chain length from (C₅–C₉). The distribution of cosurfactant (n‐alkanol) between the interface of water and oil regions at the threshold level of stability as well as the energetics of the transfer of the cosurfactant from the oil to the interfacial region have been examined as a function of varying cosurfactant chain length (C₄–C₉) and temperature. The structural parameters (including dimension, population density and effective water pool radius) of the dispersed water droplets in the oil phase have also been evaluated and correlated with alkanol chain length.     

SDS/n－C5H11OH/n－C7H16/H2O体系中W/O－BI微乳液界面电性质

In the system of SDS/n-C5H11OH/n-C7H16/H2O with the weight ratio of SDS/n-C5H11OH/H2O system at5.0/47.5/47.5, the upper phase of the system was W/O microemulsion, and the lower phase was the bicontinuous microemulsion. When the n-heptane content was less than 1%, with the increase of the n-heptane content, the capacitance (Co, Cod) in the upper phase (W/O) dropped, the capacitance (CB1, CBld) in the lower phase (BI) raised. At the same time, the W/O-BI inteffacial potential (ΔE), capacitance (Ci), and charge-transfer current (ict) decreased.After the n-heptane content reached 1%, with the increase of the n-heptane content, ΔE, Ci and ict demonstrated no significant change.     

Samarium(II) Monoalkyl Complex Supported by a β-Diketiminato-Based Tetradentate Ligand: Synthesis,Structure, and Catalytic Hydrosilylation of Internal Alkynes

The synthesis and catalytic applications of trivalent rare-earth metal alkyl complexes have been well developed, but the chemistry of divalent rare-earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β-diketiminato-based tetradentate ligand, [LSmCH(SiMe₃)₂] (L=[MeC(NDipp)CHC(Me)NCH₂CH₂N(Me)CH₂CH₂NMe₂]⁻, Dipp=2,6-(iPr)₂C₆H₃). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ-I)]₂ and KCH(SiMe₃)₂ in 63 % yield. Its structure is characterized by single-crystal X-ray diffraction, showing a distorted square-pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl-substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α-(E) products in high yields.     

Alkyl polyglucoside microemulsion phase behavior

We review several key elements of alkyl polyglucoside (C_mG_n) microemulsion phase behavior. The low solubility of C_mG_n surfactants in oils such as alkanes makes producing C_mG_n microemulsions and subsequent study of their phase behavior difficult. Increasing the solubility of C_mG_n in oil is therefore helpful for the systematic study of C_mG_n-based microemulsion formulations. To this end, the role of cosurfactants in producing microemulsions with water, alkanes, and n-alkyl β-d-glucopyranosides is first discussed. Adding C₁₀βG₁ to mixtures of water–alkane–ethoxylated alcohol surfactants (C_iE_j) produces a region of the three-phase body (a ‘chimney’) that is independent of temperature; thus C_mβG₁ are not completely soluble in the co-oil formed of alkane and C_iE_j at higher temperatures. Then, through a novel approach using oxygenated ether oils (C_kOC₂OC_k), microemulsions are formed with water, C_kOC₂OC_k, and C_mβG₁ and the phase behavior studied as a function of temperature and composition. Increased C_mβG₁ solubility in the more hydrophilic ether oils produces patterns of phase behavior in water–C_kOC₂OC_k–C_mβG₁ mixtures that are identical to those observed in water–alkane–C_iE_j mixtures. Using the water–ether oil–C_mβG₁ mixtures as a base case, the role of C_mG_n surfactant structure in setting C_mG_n microemulsion phase behavior is explored. The solubility of the α-d anomer (n-alkyl α-d-glucopyranosides, C_mαG₁) in water is much less than that of the β-d surfactant, and these solubility boundaries extend to high surfactant and oil concentrations in water–C_kOC₂OC_k–C_mαG₁ mixtures. Adding C_mG₂ compounds to water–C_kOC₂OC_k–C_mβG₁ mixtures shifts the phase behavior to high temperatures, again demonstrating the extreme hydrophilic nature of the sugar headgroup. Finally, adding small amounts of ionic alkyl sulfate surfactants to water–C_kOC₂OC_k–C_mβG₁ mixtures dramatically reduces the total amount of surfactant needed to form a single-phase microemulsion.     

Mixed micelle behavior of poly(ethylene glycol) alkyl ethers with series of monomeric cationic, phosphonium cationic, and zwitterionic surfactant

The steady state fluorescence measurements have been carried out for the binary mixtures of poly(ethylene glycol) alkyl ethers (C _i E _j ) with series of monomeric cationic (MC), zwitterionic (ZI), and phosphonium cationic (PC) surfactants over the whole mole fraction range by using pyrene as fluorescence probe. The cmc values for all the binary mixtures, thus, determined have been further evaluated by using the regular solution theory. The various micellar parameters such as regular solution interaction parameter (β), micropolarity (I ₁/I ₃), and mean micelle aggregation number (N _agg) have been determined. A strong influence of hydrophobicity of both nonionic as well as cosurfactant (CS) components has been observed on the nature of mixed micelles. The presence of bulky head groups of PC surfactants significantly contributes towards the unfavorable mixing.     

Miniemulsion polymerization of styrene using alkyl methacrylates as the reactive cosurfactant

 Stable styrene miniemulsions were prepared by using alkyl methacrylates as the reactive cosurfactant. Like conventional cosurfactants (e.g., cetyl alcohol (CA) and hexadecane (HD)), alkyl methacrylates (e.g., dodecyl methacrylate (DMA) and stearyl methacrylate (SMA)) may act as a cosurfactant in stabilizing the homogenized miniemulsions. Furthermore, the methacrylate group may be chemically incorporated into latex particles in subsequent miniemulsion polymerization. The data of the monomer droplet size, creaming rate and phase separation of monomer as a function of time were used to evaluate the shelf-life of miniemulsions stabilized by sodium dodecyl sulfate in combination with various cosurfactants. Polystyrene latex particles were produced via both monomer droplet nucleation and homogeneous nucleation in the miniemulsion polymerization using CA or DMA as the cosurfactant, with the result of a quite broad particle size distribution. On the other hand, the miniemulsion polymerization with HD or SMA showed a predominant monomer droplet nucleation. The resultant particle size distribution was relatively narrow. In miniemulsion polymerization, the less hydrophobic DMA is similar to CA, whereas the more hydrophobic SMA is similar to HD. Received: 19 November 1996 Accepted: 20 February 1997     

The effect of cosurfactants and the initiator concentration on the polymer to surfactant concentration in nanolatexes

The effect of cosurfactant and initiator concentration on the ab initio production of nanolatexes using low surfactant levels was investigated. While the use of cosurfactants (acrylic acid and pentanol) increased the amount of monomer that can be used in styrene‐SDS microemulsion formulations to 13 wt %, high surfactant concentrations are still required, resulting in polymer‐to‐surfactant ratios (Pol/Surf) <1. Latexes with particle size of 30 ± 5 nm were produced upon polymerization of these microemulsions. The Pol/Surf can be significantly increased by increasing the initiator concentration of emulsion polymerization recipes. Particle sizes are comparable with microemulsion latexes, however, less surfactant is required. The reduction in the particle size with higher initiator concentration is attributed to a higher efficiency of particle nucleation and to a higher nucleation rate relative to the rate of monomer transfer. Nanolatexes (particle size < 30 nm) were obtained with 19 wt % solids content and Pol/Surf of 3.6 in ab initio. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Magnesium, zinc, and calcium complexes based on tridentate nitrogen ligands: Syntheses, structures, and catalytic activities to the ring opening polymerization of rac-lactide

A series of magnesium, zinc, and calcium monoalkyl or monoamide complexes containing tridentate nitrogen ligands, CH₃C(2,6-(ⁱPr)₂C₆H₃N)CHC(CH₃) (NCH₂CH₂-D) (D = NMe₂, N((CH₂CH₂)₂CH₂)), have been synthesized, and six of which were characterized by single-crystal X-ray diffraction. The X-ray diffraction results show that the metal complexes are all solvent-free monomers and the pendant arm D bonds to the metal ion. These metal complexes are highly active for the ring-opening polymerization of rac-lactide and give preference for heterotactic polylactide.     

Acid-catalyzed degradation of poly(2-butyl-1, 3, 6-trioxocane)

Acid-catalyzed degradation of poly(2-butyl-1,3,6-trioxocane) (1) has been studied. With ethyl tosylate as the catalyst, the cyclic monomer 2 was the major product. The minor products are cis and trans isomers of C₃H₇CH?CH? OCH₂CH₂OCH₂CH₂OH, and three stereoisomers of C₃H₇CH?CH? OCH₂CH₂OCH₂CH₂O? CH?CH? C₃H₇ elucidated by ¹H and ¹³C NMR, IR, electron impact and chemical ionization MS, and in the case of 2 also by comparison with an authentic sample. With 98% H₂SO₄ as the catalyst 2 is only a minor product. The major products are diethylene glycol, valeraldehyde, and 1,4-dioxane with some 2-butyl-1,3-dioxolane. Capillary GC/mass spectrometry led to identification of the following less abundant products: tri-n-propylbenzene, α,β-unsaturated aldehydes, and cyclic dimer. The products of H₂SO₄-catalyzed decomposition of polymer were also obtained by heating monomer 2 with H₂SO₄. A detailed mechanism for the formation of the eight-member ring 2 in the decomposition is proposed which involves unzipping proceeds via open carbocation intermediates. According to the principle of microscopic reversibility, the same open carbocation is the propagating species in the polymerization of 2 under similar conditions.     

基团贡献法估算线性烷基醇分子体系电子相关能

在本文中,提出了极性基团电子相关能贡献的定义,并在MP2-OPT2/6-311++G(d)水平上计算了CH₃(CH₂) _mOH( m=0-4)体系中HO-、CH₃-和-CH₂-基团电子相关能贡献值。计算结果表明,在CH₃(CH₂) _mOH( m=0-4)体系中端基HO-、CH₃-基团电子相关能贡献值 E_corr(HO-)和 E_corr(cH₃-)的数值随着 m的增加而逐渐减小。同一体系中a -CH₂-基团电子相关能贡献值大于其它-CH₂-基团电子相关能贡献值,在CH₃(CH₂) _mOH( m=1-4)体系中,距离端基HO-基团越远的-CH₂-基团其电子相关能贡献值越小;通过计算结果可以推断,在CH₃(CH₂) _mOH体系中随着 m的逐渐增加,相对远离端基HO-的-CH₂-基团的电子相关能贡献值表现出收敛趋向并将趋于不变,此-CH₂-基团可看作一个标准的亚甲基而且其 E_corr(-cH₂-)的数值在CH₃(CH₂) _mOH体系中具有传递性。在MP2-OPT2/6-311++G(d)水平上对CH₃(CH₂) _mOH( m=2-4)体系的计算结果和应用Gaussian 98程序在MP2/6-311++G(d)//HF/6-311++G(d)水平上对CH₃(CH₂) _mOH( m=2-7)体系的计算结果均表明,体系总电子相关能与（ m-1）呈 中 m是体系中亚甲乙烯基的数值。     

Asymmetric Synthesis of Novel Ferrocenyl Ligands with Planar and Central Chirality

A stereogenic center at the position β to the metallocene backbone is present in ferrocenyl ligands 2 , which are interesting for asymmetric catalysis. These planar-chiral compounds are accessible for the first time by a highly diastereoselective and enantioselective synthesis (de=93–97 %; ee≥96 %) from the ferrocenyl ketones 1 . A variety of donor groups (E¹=Ph₂P⋅BH₃, SMe, SiPr; E²=SMe, STol, SePh, Ph₂P⋅BH₃, iPr₂P⋅BH₃) can be introduced as electrophiles. Tol=tolyl=CH₃C₆H₄.     

Stereospecific post-metallocene polymerization catalysts: the example of isospecific styrene polymerization

In the context of developing single-site stereoselective post-metallocene catalysts, the case for isospecific styrene polymerization catalysts based on methylaluminoxane-activated group 4 metal bis(phenolato) complexes is summarized. Ligands derived from the 1,4-dithiabutanediyl-linked bis(phenol)s have been found to induce stereochemical rigidity by the presence of the hemi-labile sulfide donor functions. Isospecific styrene polymerization was achieved using easily accessible catalyst precursors of the type [MX₂(OC₆H₂-^tBu₂-4,6)₂{S(CH₂)₂S}] (M = Ti, Zr, Hf; X = Cl, OⁱPr, CH₂Ph). Activating the dibenzyl titanium complex [Ti(CH₂Ph)₂(OC₆H₂-^tBu₂-4,6)₂{S(CH₂)₂S}] with B(C₆F₅)₃ and AlⁱBu₃, controlled isotactic polymerization became possible at lower temperatures. A remarkable dependence of both the activity and stereoselectivity on the ligand substitution pattern was observed. Analogous precursors with the 1,5-dithiapentanediyl-linked bis(phenolato) ligand gave syndiotactic polystyrene with lower activity.     

Styrene polymerization with nickel complexes/methylaluminoxane catalytic system

Polymerization of styrene using β‐diketiminate nickel (II) bromide complexes CH{C(R)NAr}₂NiBr (R = CH₃, Ar = 2,6‐ⁱPr₂C₆H₃, 1 ; R = CH₃, Ar = 2,6‐Me₂C₆H₃, 2 ; R = CF₃, Ar = 2,6‐ⁱPr₂C₆H₃, 3 ; R = CF₃, Ar = 2,6‐Me₂C₆H₃, 4 ) in the presence of methylaluminoxane was studied. Compound 3 is the most active styrene polymerization catalyst of all the nickel complexes tested. The activity of these catalysts increases with increases in steric bulk of the substituents on the aryl rings. The electronic nature of the ligand backbone also affects the activity. Weight‐average molecular weight of the prepared polystyrene ranges from 21 000 to 72 000, with polydispersity indexes of 1.95–2.78. The microstructure of the obtained products is atactic polystyrenes from NMR analyses. Copyright © 2008 John Wiley & Sons, Ltd.     

Liquid properties of oligomers. Comparison of relaxational properties of propylene glycol oligomers with those of ethylene glycol oligomers

Liquid properties such as dielectric relaxation and viscous flow of the two structurally homologous propylene glycol oligomers HO(CH(CH₃)CH₂O)_nH (n=1, 2, 3, 4, 5 and 34) and ethylene glycol oligomers HO(C₂H₄O)_nH (n=1, 2, 3, 4, 5 and 6) are studied in pure liquid state to clarify the degree of polymerization dependences of chain molecules on their liquid properties. These oligomers are, at room temperature, viscous liquid which shows dielectric relaxations in the frequency range from 10 Hz to 3 MHz. Propylene glycol oligomers (n=from 1 to 5) show the Davidson-Cole-type relaxations, but the higher glycol (n=34) shows superposition of the two different relaxations, i. e., small Debye-type relaxation in the lower-frequency region and large principal Havriliak-Negami-type relaxation in the higher-frequency region. Relaxation times vs. degree of polymerization do not increase linearly, but vary in zigzag lines. Above all, the dimers (dipropylene glycol and diethylene glycol) show longer relaxation times than the other glycols. This dielectric result does not agree with the degree of polymerization dependence of viscous flow.     

Salt Effects on Volumetric Properties of Some n-Alkoxyethanols (C1Em, m = 1, 2, and 3) in Aqueous Solutions at 298.15 K

Accurate density measurements over the whole composition range were made at a temperature of 298.15 K under ambient pressure for the mixtures of ethylene glycol monomethyl ether (2-methoxyethanol, C₃H₇O₂; C₁E₁), or diethylene glycol monomethyl ether (2-(2-methoxyethoxy)ethanol, C₅H₁₂O₃; C₁E₂), or triethylene glycol monomethyl ether [2-{2-(2-methoxyethoxy)ethoxy}ethanol, C₇H₁₆O₄; C₁E₃) in aqueous salt solutions having a common anion with a view to examining the cationic effect on the volumetric properties. To gain insight into the mixing behavior, results of the density measurements were used to estimate excess molar volumes, V_m^E, apparent molar volumes, V_{, i}, partial molar volumes, , excess partial molar volumes, V_m,i^E, and their limiting values at infinite dilution, V_{, i}, V_m,i, and V_m,i^E,, respectively. Aqueous solutions of the chlorides of lithium, sodium, potassium, and calcium in a concentration range to ca. 1 mol-kg^–1 were chosen for investigation as this concentration is used most frequently in applied chemistry. All mixtures except that containing lithium chloride show a decrease in the magnitude of V_m^E with the addition of a salt when compared to salt-free mixtures. Comparison of the derived volumes at infinite dilution suggested modification of the water structure as well as an electrostatic interaction between the ionic species and an alkoxyethanol molecule.     

Synthese und Charakterisierung neuer intramolekular stickstoffstabilisierter Organoaluminium‐ und Organogalliumalkoxide

Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me₂Al{μ‐O(CH₂)₃NMe₂}]₂ ( 1a ), Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6 ( 2a ), [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]₂ ( 3a ) and [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]₂ ( 4 ) are formed by reacting equimolar amounts of AlMe₃ and Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH₂OH, or (S)‐PhCH₂NHCH(i‐Pr)CH₂OH, respectively. An excess of AlMe₃ reacts with Me₂N(CH₂)₂OH, Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH₂OH producing the “pick‐a‐back” complexes [Me₂AlO(CH₂)₂NMe₂](AlMe₃) ( 5 ), [Me₂AlO(CH₂)₃NMe₂](AlMe₃) ( 1b ), [Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6](AlMe₃)₂ ( 2b ), and [(S)‐Me₂AlOCH₂CH(i‐Pr)NH‐i‐Pr](AlMe₃) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 6 ) and [{CH₂=C(CH₃)}(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 8 ) are to obtain from Me₂AlCl and Me₂N(CH₂)₂OH and from [Cl₂Al{μ‐O(CH₂)₂NMe₂}]₂ ( 7 ) and CH₂=C(CH₃)MgBr, respectively. The analogous dimethylgallium alkoxides [Me₂Ga{μ‐O(CH₂)₃NMe₂}]₂ ( 9 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]_n ( 10 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]_n ( 11 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)N(Me)CH₂Ph}]_n ( 12 ) and [(S)‐Me₂Ga{μ‐OCH₂(C₄H₇NHCH₂Ph)}]_n ( 13 ) result from the equimolar reactions of GaMe₃ with the corresponding alcohols. The new compounds were characterized by elemental analyses, ¹H‐, ¹³C‐ and ²⁷Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction.