Monochlorodimethyl ether

The preparation and properties of SDVB copolymers have been described in the preceding section. SDVB copolymers can be converted to anion-exchange resins through chloromethylation with monochlorodimethyl ether using a FriedehCrafts catalyst followed by treatment with different aminesAnderson studied in detail the influence of various Friedel-Crafts catalysts for the diloromethylation of SDVB copolymers. A chlorosulfonic acid — methylal mixture has also been used for the chloromethylation of SDVB copolymers... 

SYNS CHLORDIMETHYLETHER (CZECH) CMME DIMETHYLCHLOROETHER ETHER METHYLIQUE MONOCHLORE (FRENCH) METHYLCHLOROMETH-YL ETHER (DOT) METHYL CHLOROMETHYL ETHER, anhydrous pOT) MONOCHLORODIMETHYL ETHER (MAK) RCRA WASTE NUMBER U046... 

MONOCHLOROBENZENE see CEJ125 MONOCHLORODIFLUOROMETHANE see CFX500 MONOCHLORODIMETHYL ETHER (MAK) see CIO250... 

Synonym chloromethyl ether, chloromethoxymethane, CMME, monochlorodimethyl ether... 

Beilstein Handbook Reference) BRN 0506943 CCRIS 138 Chlordimethylether Chlorodimethyl ether Chloromethoxymethane Chloromethyl methyl ether a,a-Dichlorodimethyl ether Dimethylchloroether EINECS 203-480-1 Ether, chloromethyl methyl Ether, dimethyl chloro Ether methylique monochlore HSDB 908 Methane, chloromethoxy- Methoxychloromethane Methoxy-methyl chloride Methyl chloromethyl ether Monochlorodimethyl ether Monochloromethyl methyl ether NSC 21208 RCRA waste number U046 UN1239, Liquid mp = -103,5° bp = 59.5° d = 1.063 soluble in EtOH, Et20, Me2CO, CHCI3. 

SYNONYMS Chlorodimethyl ether, chloromethyoxymethane, dimethylchloroether, methylchloromethyl ether, monochlorodimethyl ether. 

O—CH3, an aliphatic monochloro ether Synonyms monochlorodimethyl ether methyl chloromethyl ether chloromethoxy-methane... 

Monochlorodimethyl ether, CH3OCH2CI (MCDE) [1, 13, 14], though a rather toxic compound, is also considered to be a suitable bifunctional crosslinking reagent. Its reaction with polystyrene proceeds quantitatively through the intermediate stage of chloromethylation the introduced... 

Figure 6.1 FTIR spectra of (a) linear atactic polystyrene with molecular weight of 400 kDa, (b) poly(p-methylstyrene), and hypercrosslinked polystyrenes prepared by crosslinking styrene-0.5% DVB copolymer with (c) 0.3, (d) 0.5, (e) 1.0, and (0 1.5 mol of monochlorodimethyl ether per styrene repeating unit.

Figure 7.1 Equilibrium swelling in toluene vs concentration of initial polystyrene solution for the networks crosslinked with (1, 2) p-xylylene dichloride and (3) monochlorodimethyl ether to crosslinking degrees (1) 11, (2) 100, and (3) 43%.

Figure 7.2 Dependence of equilibrium swelling in toluene on the summarized crosslinking degree for the networks prepared by crosslinking gel-type styrene-DVB copolymers with (1, 2, 4, 5) 1.4-bis(chloromethyl)diphenyl or (3) monochlorodimethyl ether (6) styrene-DVB copolymers. (After [128]).

Figure 7.3 Dependence of equilibrium swelling in toluene on the crosslinking degree of networks prepared by crosslinking with monochlorodimethyl ether of (1) linear polystyrene at the concentration of Co = 0.125mg/mL (2) styrene-0.3% DVB copolymer swollen to a maximum, Q, = 0.111 mg/mL (3) styrene-0.3% DVB copolymer partially swollen to Q = 0.485 mg/mL (4) styrene-1 % DVB copolymer swollen to a maximum, Q, = 0.485 mg/mL. (After [129]).

Figure 7.6 Dependence of equilibrium swelling in n-hexane on the crosslinking degree of networks prepared by crosslinking linear polystyrene with (1) monochlorodimethyl ether (2) tris-(chloromethyl)-mesitylene and (3) 1,4-bls(p-chloromethylphenyl)butane.

Figure 7.7 Dependence of swelling ratio in (1) methanol (2) ethanol (3) n-hexane and (4) toluene on the concentration of starting solution for the networks prepared by crosslinking linear polystyrene with monochlorodimethyl ether to 66% crosslinking degree. (Reprinted from [133] with permission of Elsevier Publishing Company.)...

Figure 7.15 Toluene regain of the networks prepared by crosslinking with monochlorodimethyl ether in ethylene dichloride of polystyrene with molecular weight of (1) 8800 and (2) 300,000 Da.

Figure 7.17 Kinetics of swelling in toluene of gel-type copolymers (1) the network prepared by crosslinking styrene-0.2% DVB copolymer with monochlorodimethyl ether to 25% and conventional styrene copolymers with (2) 1.4, (3) 2.7, and (4) 5.3% DVB, as measured on Individual beads (full lines) and averaged over 10 measurements (dotted lines). (Reprinted from [159] with permission ofAkademizdattsentr Nauka RAN.)...

Figure 7.19 Kinetics of swelling in (1, 2) toluene and (3, 4) ethanol of hypercrosslinked networks prepared by crosslinking styrene-0.2% DVB copolymer with monochlorodimethyl ether to (1,3) 100 and (2,4) 200%. (After [159]).

Table 7.7 Apparent density (papp g/cm ) and total pore volume (Mfo/CmVg) of hypercrosslinked networks based on linear polystyrene with a molecular weight of 3 X 10 Da and crosslinked with p,p-bis-chloromethyl-diphenyl, p-xylylene dichloride, or monochlorodimethyl ether...

Figure 7.26 Sorption isotherm of nitrogen at 77 K on the hypercrosslinked polymer prepared by post-crosslinking styrene-0.3% DVB copolymer with monochlorodimethyl ether to 100%. Measured by Micromeritics Instrument Corporation.

Hypercrosslinked networks were prepared by crosslinking linear polystyrene (I) with p-xylylene dichloride and styrene—0.7% DVB copolymer (II) with monochlorodimethyl ether X= 100%. 

Figure 7.30 Electron macrographs of the networks prepared by post-crosslinking linear polystyrene (/M = 300,000 Da) with (a, b) p-xylylene dichloride (a) X=100%, (b) X=43% and (c, d) monochlorodimethyl ether (c) X=100%, (d) X=5% (a, b) two-step replicas, transmission electron microscopy, 46,600x (c, d) scanning electron microscopy, (c) 40,000x, (d) 100,000x. (After [198]).

Figure 7.32 Texture of the network prepared by post-crosslinking linear polystyrene of 3,000,000 Da molecular weight with monochlorodimethyl ether to 100% in 6.7% ethylene dichloride solution scanning electron microscopy, 40,000x. (After [198]).

Figure 7.33 Texture of three-dimensional material based on hypercrosslinked nanosponges additional crosslinking degree with monochlorodimethyl ether is 11% ultrathin section, transmission electron microscopy, 42,000x. (After [198]).

Figure 7.34 Plots of small-angle X-ray scattering (logarithm of intensity vs modulus of scattering vector s = 47rsin ( s/A), normalized on the thickness of a sample and attenuation for (1, 2) the network obtained by post-crosslinking styrene-2% DVB copolymer with monochlorodimethyl ether to 100% and for (3) initial copolymer (1) the sample swollen in n-hexane and (2, 3) dry samples.

Figure 735 Diffraction patterns under large angles for (1) the dry hypercrosslinked network obtained by post-crosslinking styrene-2% DVB copolymer with monochlorodimethyl ether to 100% and (2) for the conventional copolymer precursor.

Figure 7.43 Effect of the pretreatment of the network obtained by crosslinking styrene-0.57% DVB copolymer with monochlorodimethyl ether to 100% on the position and form of thermomechanical curves (1) control sample (2) the sample heated up to 136°C under a loading of 400 g and relaxed at 164°C for 2h without pressure (3) the sample heated up to 136°C and then cooled under a loading of 400g (12% residual deformations), then subjected to swelling and drying (4) the sample heated up to 136°C and then cooled under a loading of 400 g (10% residual deformations). (Reprinted from [202] with permission of Wiley Sons, Inc.)...

The first represents the direct interaction of polystyrene with, for example, 0.5 mol of monochlorodimethyl ether (MCDE) [230]. In this case, however, the reaction medium proves to be extremely dduted with respect to aU reacting components, including the crosslinking reagent and the catalyst (stannic tetrachloride), and completing the process requires approximately 100 h. Also, smaU traces of impurities in the large amount of the solvent can deactivate the catalyst. These factors result in poor reproducibdity of the reaction product, especiaUy at very low concentrations of about 0.05% (Table 8.1). 

The third group, Styrosorb 2, represents nanoporous single-phase polymers derived from spherical beads of gel-type styrene copolymers with largely 0.7% DVB, post-crosslinked in swollen state with monochlorodimethyl ether. The size of the micropores is approximately 10—30 A, and the apparent specific surface area reaches very large values of 1000—1900 m /g, which is comparable to the range of the best activated carbons. On the other hand, the pore volume of these materials is rather small, 0.2—0.3 cm /g. 

Figure 10.1 Sorption isotherms for nitrogen at -196°C on Styrosorb 1 (monochlorodimethyl ether, MCDE) with the crossiinking degree of (1) 25, (2) 43, (3) 66, (4) 80, and (5) 100% presented (a) in usuai coordinates and (b) iinear coordinates of BET equation.

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