Poly /methanol

Diffraction data for the alkoxy-substituted materials are scarce. For PMEEMT x-ray diffraction patterns were recorded [44] at two temperatures, room temperature and 150°C, showing in both cases three to four rather broad peaks on a diffuse background. The peaks correspond to interplanar distance d= 17.8 A, 7.0 A, 3.8 A and 2.4 A, the latter two being close to two values also found for PATs as the 6-axis parameter and a diffuse feature at 0 = 2.6 A related to the main chain periodicity. It is remarkable that the diffraction pattern survives heating to 150"C, which is above the thermochromic transition for PMEEMT. A recent diffraction study of poly methanol-thiophene) prepared electrochemically showed only broad amorphous scattering around 0= 1.4 A [94],... 

Prepared generally by ester interchange from polyvinylacelate (ethanoate) using methanol and base also formed by hydrolysis of the acetate by NaOH and water. The properties of the poly(vinyl alcohol) depend upon the structure of the original polyvinyl acetate. Forms copolymers. Used as a size in the textile industry, in aqueous adhesives, in the production of polyvinyl acetates (e.g. butynal) for safety glasses. U.S. production 1980... 

Hydroxy-2-methylpropanenitrile is then reacted with methanol (or other alcohol) to yield methacrylate ester. Free-radical polymerization is initiated by peroxide or azo catalysts and produce poly(methyl methacrylate) resins having the following formula ... 

Ester interchange reactions are valuable, since, say, methyl esters of di-carboxylic acids are often more soluble and easier to purify than the diacid itself. The methanol by-product is easily removed by evaporation. Poly (ethylene terephthalate) is an example of a polymer prepared by double application of reaction 4 in Table 5.3. The first stage of the reaction is conducted at temperatures below 200°C and involves the interchange of dimethyl terephthalate with ethylene glycol... 

Currently, almost all acetic acid produced commercially comes from acetaldehyde oxidation, methanol or methyl acetate carbonylation, or light hydrocarbon Hquid-phase oxidation. Comparatively small amounts are generated by butane Hquid-phase oxidation, direct ethanol oxidation, and synthesis gas. Large amounts of acetic acid are recycled industrially in the production of cellulose acetate, poly(vinyl alcohol), and aspirin and in a broad array of other... 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

Formaldehyde is produced and sold as water solutions containing variable amounts of methanol. These solutions are complex equiUbrium mixtures of methylene glycol, CH2(OH)2, poly(oxymethylene glycols), and hemiformals of these glycols. Ultraviolet spectroscopic studies (13—15) iadicate that even ia highly concentrated solutions the content of unhydrated HCHO is <0.04 wt%. 

Manufacture. The manufacture of 1,4-cyclohexanedimethanol can be accompHshed by the catalytic reduction under pressure of dimethyl terephthalate ia a methanol solution (47,65). This glycol also may be prepared by the depolymerization and catalytic reduction of linear polyesters that have alkylene terephthalates as primary constituents. Poly(ethylene terephthalate) may be hydrogenated ia the presence of methanol under pressure and heat to give good yields of the glycol (see Polyesters) (66,67). 

The overall yield of the process is at least 87 mol %, and 2.3 mol of methanol per mole of final product are needed, an excess of 15% over the 2.0 theoretical amount. The methanol can be recycled from the manufacture of poly(ethylene terephthalate). Reported utilities consumptions per kilogram of product are 1.2 kg of 1400-kPa steam, 420 kj of boiler fuel, and 0.5 kWh of electricity (72). 

Poly(ethylene oxide) associates in solution with certain electrolytes (48—52). For example, high molecular weight species of poly(ethylene oxide) readily dissolve in methanol that contains 0.5 wt % KI, although the resin does not remain in methanol solution at room temperature. This salting-in effect has been attributed to ion binding, which prevents coagulation in the nonsolvent. Complexes with electrolytes, in particular lithium salts, have received widespread attention on account of the potential for using these materials in a polymeric battery. The performance of soHd electrolytes based on poly(ethylene oxide) in terms of ion transport and conductivity has been discussed (53—58). The use of complexes of poly(ethylene oxide) in analytical chemistry has also been reviewed (59). 

On the basis of bulk production (10), poly(ethylene terephthalate) manufacture is the most important ester producing process. This polymer is produced by either the direct esterification of terephthaHc acid and ethylene glycol, or by the transesterification of dimethyl terephthalate with ethylene glycol. In 1990, poly(ethylene terephthalate) manufacture exceeded 3.47 x 10 t/yr (see Polyesters). Dimethyl terephthalate is produced by the direct esterification of terephthaHc acid and methanol. 

An industrial example of acidolysis is the reaction of poly(vinyl acetate) with butyric acid to form poly(vinyl butyrate). Often a butyric acid—methanol... 

Either methanol or ethanol may be used to effect alcoholysis but the former is often preferred because of its miscibility with poly(vinyl acetate) at room... 

The solution of poly(vinyl butyral) is diluted with methanol and the polymer precipitated by the addition of water during vigorous agitation. The polymer is then stabilised, washed and dried. 

The first methacrylic esters were prepared by dehydration of hydroxyisobutyric esters, prohibitively expensive starting points for commercial synthesis. In 1932 J. W. C. Crawford discovered a new route to the monomer using cheap and readily available chemicals—acetone, hydrocyanic acid, methanol and sulphuric acid— and it is his process which has been used, with minor modifications, throughout the world. Sheet poly(methyl methacrylate) became prominent during World War II for aircraft glazing, a use predicted by Hill in his early patents, and since then has found other applications in many fields. 

In addition to its water solubility poly(vinyl pyrrolidone) is soluble in a very wide range of materials, including aliphatic halogenated hydrocarbons (methylene dichloride, chloroform), many monohydric and polyhdric alcohols (methanol, ethanol, ethylene glycol), some ketones (acetyl acetone) and lactones (a-butyrolactone), lower aliphatic acids (glacial acetic acid) and the nitro-paraffins. The polymer is also compatible with a wide range of other synthetic polymers, with gums and with plasticisers. 

Methyl 2-methoxy-2-polyfluoroalkyl-2-fluoroacetates, generated from poly-fluoroalkyltrifluoroethylene oxides and methanol, give, on heating with concentrated or fuming sulfuric acid, methyl polyfluoroalkylglyoxylates [29] (equation 32). 

Cationic, hydrophilic, and hydrophobic Chitosan, poly-2-vinyl pyridine 0.3-1.0 M salt/buffer, pH 2-7 with the addition of methanol for more hydrophobic polymers... 

The GBR resin works well for nonionic and certain ionic polymers such as various native and derivatized starches, including sodium carboxymethylcel-lulose, methylcellulose, dextrans, carrageenans, hydroxypropyl methylcellu-lose, cellulose sulfate, and pullulans. GBR columns can be used in virtually any solvent or mixture of solvents from hexane to 1 M NaOH as long as they are miscible. Using sulfonated PDVB gels, mixtures of methanol and 0.1 M Na acetate will run many polar ionic-type polymers such as poly-2-acrylamido-2-methyl-l-propanesulfonic acid, polystyrene sulfonic acids, and poly aniline/ polystyrene sulfonic acid. Sulfonated columns can also be used with water glacial acetic acid mixtures, typically 90/10 (v/v). Polyacrylic acids run well on sulfonated gels in 0.2 M NaAc, pH 7.75. 

Commercial grades of PVP, K-15, K-30, K-90, and K-120 and the quaternized copolymer of vinylpyrrolidone and dimthylaminoethylmethacrylate (poly-VP/ DMAEMA) made by International Specialty Products (ISP) were used in this study. PEO standard calibration kits were purchased from Polymer Laboratories Ltd. (PL), American Polymer Standards Corporation (APSC), Polymer Standards Service (PSS), and Tosoh Corporation (TSK). In addition, two narrow NIST standards, 1923 and 1924, were used to evaluate commercial PEO standards. Deionized, filtered water, and high-performance liquid chromatography grade methanol purchased from Aldrich or Fischer Scientific were used in this study. Lithium nitrate (LiN03) from Aldrich was the salt added to the mobile phases to control for polyelectrolyte effects. 

The strongest known producer of j8-poly(L-malic acid) has been identified as Aureobasidium sp. providing 61 g of polymer from 1 liter of culture medium [5,6]. 8-Poly(L-malate, Ca -salt) of the culture broth was first separated from accompanying bulk pullulan by methanol precipitation. The water-redisolved precipitate was converted to the polymer acid by passage over Amberlite IR-120B (H -form). Thus, the best to-day producers of... 

The purification of j8-poly(L-malic acid) from A o-basiae has been reported involving methanol precipitation of the polymer in the form of the Ca salt [5]. This is possible because a high concentration of CaCOs is present in the growth medium. Unfortunately, the polymer acid is not soluble in aceton thus missing an additional purification step. In our hands, purification of jS-poly(L-malate) from several Aureobasidiae strains was unsatisfactory because of low yields and resisting impurities. 

Figure 3 Reversed-phase chromatography of products after alkaline hydrolysis of /3-poly(L-malate), Discrete polymer products are formed, which differ in length by several units of L-malate. The absorbance at 220-nm wavelength was measured, (a) /3-Poly(L-malate) before hydrolysis, (b) After 10-min incubation in 20 mM NaOH at 37°C. (c) After 15 h in 20 mM NaOH at 37°C. (d) After I h in 500 mM NaOH at 100°C. High pressure chromatography (HPLC) on Waters reversed-phase Ci8- i-Bondapak. The methanol gradient (in water-trifluoro acetic acid, pH 3.0) was programmed as follows 0-40 min 0.3-23%, 40-47 min 23-40%, 47-49 min 40%, 49-54 min 40-0%. (d) Inset size exclusion chromatography after 3-min alkaline hydrolysis at pH 10.2. BioSil SEC 250 column of 300 mm x 7.8 mm size, 0.2 M potassium phosphate buffer pH 7.0.

Paine et al. [99] tried different stabilizers [i.e., hydroxy propylcellulose, poly(N-vinylpyrollidone), and poly(acrylic acid)] in the dispersion polymerization of styrene initiated with AIBN in the ethanol medium. The direct observation of the stained thin sections of the particles by transmission electron microscopy showed the existence of stabilizer layer in 10-20 nm thickness on the surface of the polystyrene particles. When the polystyrene latexes were dissolved in dioxane and precipitated with methanol, new latex particles with a similar surface stabilizer morphology were obtained. These results supported the grafting mechanism of stabilization during dispersion polymerization of styrene in polar solvents. 

In another study, uniform composite polymethyl-methacrylate/polystyrene (PMMA/PS) composite particles in the size range of 1-10 fim were prepared by the seeded emulsion polymerization of styrene [121]. The PMMA seed particles were initially prepared by the dispersion polymerization of MMA by using AIBN as the initiator. In this polymerization, poly(7V-vinyl pyrolli-done) and methyl tricaprylyl ammonium chloride were used as the stabilizer and the costabilizer, respectively, in the methanol medium. Seed particles were swollen with styrene monomer in a medium comprised of seed particles, styrene, water, poly(7V-vinyl pyrollidone), Polywet KX-3 and aeorosol MA emulsifiers, sodium bicarbonate, hydroquinone inhibitor, and azobis(2-methylbu-... 

There have been very few examples of PTV derivatives substituted at the vinylene position. One example poly(2,5-thienylene-1,2-dimethoxy-ethenylene) 102 has been documented by Geise and co-workers and its synthesis is outlined in Scheme 1-32 [133]. Thiophene-2,5-dicarboxaldehyde 99 is polymerized using a benzoin condensation the polyacyloin precursor 100 was treated with base to obtain polydianion 101. Subsequent treatment with dimethyl sulfate affords 102, which is soluble in solvents such as chloroform, methanol, and DMF. The molar mass of the polymer obtained is rather low (M = 1010) and its band gap ( ,.=2.13 eV) is substantially blue-shifted relative to PTV itself. Despite the low effective conjugation, the material is reasonably conductive when doped with l2 (cr=0.4 S cm 1). 

Fig. 9. Variation of Xmax in the fluoroscence spectra of solutions of poly(propynoic acid)s in water 1(1) and (2)] and methanol [(3) and (4)1 as a function of the ph of the solution. (1) and (3) Poly(propynoic acid) obtained by polymerization in liquid phase (PPAL) (2) and (4) poly(propynoie acid) obtained by polymerization in solid phase (PPAS)...

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