2,4,4-Tetramethyl-1, 3 -cyclobutanediol

Materials. 2,2,4,4-Tetramethyl-1,3-cyclobutanediol. The diol was a commercial product (Tennessee Eastman Co.). Unless otherwise indicated, the diol consisted of a cis-/trans- mixture with about a 1 to 1 isomer ratio. The cis-isomer was obtained from the isomer mixture by transforming the trans- isomer into an unsaturated aldehyde with aqueous sulfuric acid (4). The mrw-diol was obtained by preparing the diformate of the isomer mixture, separating the trans-derivative from the cis- derivative by recrystallization, and converting the transdiformate to the diol by methanolysis (5). 

Paraformaldehyde Method. 2,2,4,4-Tetramethyl-1,3-cyclobutanediol. A 2-liter, three-necked flask was fitted with a glass stirrer, thermometer, and Dean-Stark trap which was filled with distilled cyclohexane and attached to a water-cooled condenser. In the flask were placed 216 grams (1.5 moles) of 2,2,4,4-tetramethyl-l,3-cyclobutanediol (1 to 1 cis-/trans- mixture), 52.2 grams (1.65 moles, if 95% pure) of paraformaldehyde, 1200 ml. of distilled cyclohexane, and 0.20 gram of methanedisulfonic acid in a 10 to 25% aqueous solution. (The catalyst solution had been treated with Darco G-60 to remove all color.) While this mixture was stirred at 60° C., the paraformaldehyde depolymerized to formaldehyde, which reacted with the diol. Complete reaction of these two components was indicated when they had gone into solution. This required about 1 hour. 

Cyclic VMS Cyclic volatile methyl siloxane. See Dodecamethylcyclohexasiloxane Cycloamylase. See Cyclodextrin 1,3-Cyclobutanediol, 2,2,4,4-tetramethyl-. See 2,2,4,4-Tetramethyl-1,3-cyclobutanediol Cyclocarboxypropyloleic acid CAS 53980-88-4 EINECS/ELINCS 258-987-1 Synonyms Acrylinoleic acid 5(or 6)-Carboxy-4-... 

CeHi6O2 f cis-2,2,4,4-Tetramethyl-1,3-cyclobutanediol, 42B, 100 C9H9NO1, 2,3-Diacetyl-5-nitrocyclopentadiene, 41B, 159 C9H10, Phenylcyclopropane (gas-ed), 30B, 404... 

Neopentyl glycol adipate Cyclohexane dimethanol adipate Tetramethyl cyclobutanediol adipate Neopentyl glycol succinate Butane-1,4-diol succinate Phenyl diethanolamine succinate Ethylene glycol sebacate Neopentyl glycol sebacate Ethylene glycol isophthalate Ethylene glycol phthalate... 

Polymerizations of 1 with 2,5-hexanediol and 1,3-cyclohexanediol afforded polymers 3 and 4, respectively. These polymers had molecular wdghts which were substantially lower than 2a-d. This is attributable to an elimination process involving the choroformate-pyridine complex as a side reaction, which becomes more important with the less reactive secondary diols (26), Daly reported polymerizations of cyclo-hexanediol with tetramethyl cyclobutanediol dichloroformate afforded high molecular weight polymer, this being a case where elimination cannot occur due to the metbyl substitution at the p- position (27). 

Alternative monomers for elimination of crystallinity in PET have been recently proposed. In each of these cases, cyclic monomers were employed, and in most cases, these monomers were alicyclic, and potentially possess sub-7 g molecular motions that could also be of help in dissipating impact energy through molecular motions. The four-membered ring monomer, 2,2,4,4-tetramethyl-l,3-cyclobutanediol (CBDO), first developed by the Shell Chemical Company, has... 

After the butyl alcohol was removed, the polymers were built up by heating the melt under reduced pressure. Since these polyformals of aliphatic diols had very low melting points (below 75° C.), their utility was limited. Apparently, no higher melting points have been reported for polyformals. In attempts to obtain higher-melting polyformals, the following alicyclic diols were used cis-, trans-, and 1 to 1 cis-/trans- mixture of 2,2,4,4-tetramethyl-l,3-cyclobutanediol (I) trans-1,4-cyclohexanediol (II) tmiw-l,4-cyclohexanedimethanol (III) and 2,5- or 2,6-norbomanediol (IV). 

The solid-phase method of building up polyformals is applicable only to high-melting polymers. The required melting point is not known, but the poly-formal of trarw-l,4-cyclohexanediol melted at 206°—10° C. and that of the cis-/ trans- mixture of 2,2,4,4-tetramethyl-l,3-cyclobutanediol melted appreciably higher. The solution method did not appear to be applicable to building up the polyformals of these two diols, since inherent viscosities below 0.4 were obtained. The solution method may be most applicable to primary diols, such as cyclohexanedimethanol and decanediol, which gave polyformals with inherent viscosities of 0.9. 

BPA is a known endocrine disrupting chemical (EDC), but this effect is sUght and has been known since the 1930s. This fear of EDC activity led to a total ban of BPA in polycarbonate plastic bottles intended for babies. The chemical industry was not really shaken by this ban as this use was only a tiny fiaction of the market. On the other hand, finding substances that rival the favorable properties BPA is not easy, and more significantly, not cheap. Isosorbide, which can be produced by artificial sweetener sorbitol, is a possible replaeement. A promising alternative of polycarbonate plastics is named Tritan co-polyester, and is made from dimethyl terephthalate, 1,4-cyclohexanedimethanol (CHDM), and 2,2,4,4-tetramethyl-l,3-cyclobutanediol (CBDO). However, replacing BPA in all current apphcatiorrs would be difficult, very expensive, and—most importantly—unlikely to save anyone from any harm. 

Another copolyester is prepared from two diols, CHDM and 2,4,4-tetramethyl-l,3-cyclobutanediol (TMCD). These diols, which have cis and trans con-hgurations, are reacted with dimethyl terephthalate to give an amorphous, transparent copolyester [36]. This amorphous copolyester features good chemical and heat resistance, which make this copolyester suitable for hot-fill cosmetics packaging, personal care and fragrance packaging. These polymers are available from Eastman Chemical under that Tritan trade name. The structure of CHDM/TMCD copolyester is depicted in Fig. 1.21. 

Stress whitening (indicating cavitation during stress) for the montmorillonite containing elastomer-toughened epoxy was much more extensive that the stress whitening with the elastomer-toughened epoxy without montmorillonite. This unusual behavior will be discussed in Chapter 7 with the review of montmorillonite-elastomer nanocomposites and an unusual amorphous polyester nanocomposite, terephthal-ate copolyester prepared with 2,2,4,4-tetramethyl-l,3-cyclobutanediol and propanediol. 

An amorphous polyester-montmorillonite nanocomposite prepared from condensation of 2,2,4,4-tetramethyl-l,3-cyclobutanediol, 1,3-propanediol, and dimethylterephthalate produced unexpected mechanical properties [45]. Cloisite 20A was melt blended with the polymer at 2.5,5, and 10 wt.% with a Haake HBI System 90 drive attached to a Rheomex CTW 100 twin-screw extruder. The r/min of the extruder was 60 and the temperature was 120°C. The test samples were prepared in two different injection molders. The test samples from the polyester-montmorillonite composite at 5% Cloisite 20A content were prepared with a Demag Ergotech 35 at 150°C with a pressure range of 10000 to 11000 psi. The test samples from the polyester-montmorillonite composites with 2.5, 5.0, and 10% Cloisite 20A content were prepared with a mini-jector molding machine at a temperature range of 190-200°C. 

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