Formaldehyde 1, 4 butanediol

Butanediol. 1,4-Butanediol [110-63-4] made from formaldehyde and acetylene, is a significant market for formaldehyde representing 11% of its demand (115). It is used to produce tetrahydrofuran (THF), which is used for polyurethane elastomers y-butyrolactone, which is used to make various pyrroHdinone derivatives poly(butylene terephthalate) (PBT), which is an engineering plastic and polyurethanes. Formaldehyde growth in the acetylenic chemicals market is threatened by alternative processes to produce 1,4-butanediol not requiring formaldehyde as a raw material (140) (see Acetylene-derived chemicals). 

Biacetyl is produced by the dehydrogenation of 2,3-butanediol with a copper catalyst (290,291). Prior to the availabiUty of 2,3-butanediol, biacetyl was prepared by the nitrosation of methyl ethyl ketone and the hydrolysis of the resultant oxime. Other commercial routes include passing vinylacetylene into a solution of mercuric sulfate in sulfuric acid and decomposing the insoluble product with dilute hydrochloric acid (292), by the reaction of acetal with formaldehyde (293), by the acid-cataly2ed condensation of 1-hydroxyacetone with formaldehyde (294), and by fermentation of lactic acid bacterium (295—297). Acetoin [513-86-0] (3-hydroxy-2-butanone) is also coproduced in lactic acid fermentation. 

Formaldehyde. Worldwide, the largest amount of formaldehyde (qv) is consumed in the production of urea—formaldehyde resins, the primary end use of which is found in building products such as plywood and particle board (see Amino resins and plastics). The demand for these resins, and consequently methanol, is greatly influenced by housing demand. In the United States, the greatest market share for formaldehyde is again in the constmction industry. However, a fast-growing market for formaldehyde can be found in the production of acetylenic chemicals, which is driven by the demand for 1,4-butanediol and its subsequent downstream product, spandex fibers (see Fibers, elastomeric). 

Diol Components. Ethylene glycol (ethane 1,2-diol) is made from ethylene by direct air oxidation to ethylene oxide and ring opening with water to give 1,2-diol (40) (see Glycols). Butane-1,4-diol is stiU made by the Reppe process acetylene reacts with formaldehyde in the presence of catalyst to give 2-butyne-l,4-diol which is hydrogenated to butanediol (see Acetylene-DERIVED chemicals). The ethynylation step depends on a special cuprous... 

Butadiene could also be obtained by the reaction of acetylene and formaldehyde in the vapor phase over a copper acetylide catalyst. The produced 1,4-butynediol is hydrogenated to 1,4-butanediol. Dehydration of 1,4-butanediol yields butadiene. 

MethyloU2-Butanol (2-Methyl-l,3-butanediol or a >Dioxy-/3-methylbutane). CH3.CH(OH).CH(CH2OH).CH3 mw 104.15, viscous oil, bp 200° 98—99° at 9mm. Sol in w, v sol in ale and eth. Can be prepd either by reduction of the corresponding aldehyde, 2-methylbutanol(3)-al-(l) with A1 amalgam (Ref 1), or by electrolytic reduction in 10% sulfuric acid of the corresponding ketone ale. In the latter case, methyl-2-butanone-3-ol-(l), obtained by the condensation of methylethylketone with formaldehyde, can be used. On nitration, it yields an expl dinitrate Refs 1) Beil 1,482,(250) 2)L.P.Kyria-kides, JACS 36, 535(1914)... 

Finally, reaction of primary, secondary, or tertiary alcohols 11 with Me3SiCl 14 in the presence of equivalent amounts of DMSO leads via 789 and 790 to the chloro compounds 791 [13]. n-Pentanol, benzyl alcohol, yS-phenylefhanol or tert-butanol are readily converted, after 10 min reaction time, into their chloro compounds, in 89-95% yield, yet cyclohexanol affords after reflux for 4 h cyclohexyl chloride 784 in only 6% yield [13] (Scheme 6.5). 1,4-Butanediol is cyclized to tetrahydrofuran (THF) [13a], whereas other primary alcohols are converted in 90-95% yield into formaldehyde acetals on heating with TCS 14 and DMSO in benzene [13b] (cf also the preparation of formaldehyde di(n-butyl)acetal 1280 in Section 8.2.1). 

The hydroformylation of acrolein cyclic acetals has received considerable attention in the recent patent literature as a route to 1,4-butanediol (76-52). This diol is a comonomer for the production of polybutylene terephthalate, an engineering thermoplastic. The standard method for its manufacture has been from acetylene and formaldehyde, as shown in Eqs. (37) and (38) ... 

Methyl-1,3-dioxane, available from the Aldrich Chemical Company, Inc., is used as received. Alternatively, the formal may be prepared from 1,3-butanediol and aqueous formaldehyde as previously described.2... 

Uses. About 35-40% of the methanol made is converted to formaldehyde. That s not because the embalming business is so good. Formaldehyde is a feedstock for amino and phenolic resins, which are used as adhesives in plywood, and in the automotive and appliance industry to make parts (all the agitators in washing machines used to be made out of phenolic resins). It is used as feedstock for hexamethylene tetramine, used in electronic plastics for pentaerythritol, used for making enamel coatings and for floor polish and inks for butanediol, a chemical intermediate and for acetic acid, which is widely used itself as a feedstock and solvent and warrants its own treatrnent later on. In the textile business, formaldehyde is used to make fire retardants, mildew resistant linens, and permanent press clothing. 

The most recent entrant-to the. club of commodity chemicals is 1,4-butanediol (BDO), a petrochemical used in some of the more specialized applications such as chemical intermediates for the production of tetrahydro-furane and gama-butyrolactone, polybutylene terephthalate, and the more familiar polyurethanes. Traditionally, the Reppe process was the primary route to BDO, based bn acetylene and formaldehyde feeds. More recently, the share of BDO from butane and propylene oxide based production has grown rapidly. 

Table 12.3 summarizes the uses of formaldehyde. Two important thermosetting plastics, urea- and phenol-copolymers, take nearly one half the formaldehyde manufactured. Urea-formaldehyde resins are used in particleboard, phenol-formaldehyde resins in plywood. 1,4-Butanediol is made for some polyesters and is an example of acetylene chemistry that has not yet been replaced. Tetrahydrofiiran (THF) is a common solvent that is made by dehydration of 1,4-butanediol. 

Butanediol, also known as tetramethylene glycol, is produced by the hydrogenation of butynediol (made from acetylene and formaldehyde). 

Methanol Formaldehyde Ethylene Propylene oxide Phenol 1,4-Butanediol Tetrahydrofuran Ethylene glycol Adipic acid Isocyanates Styrene Methyl methacrylate Methyl formate Two-step, via CH4 steam reforming Three-step, via methanol Cracking of naphtha Co-product with t-butyl alcohol or styrene Co-product with acetone Reppe acetylene chemistry Multi-step Hydration of ethylene oxide Multi-step Phosgene chemistry Co-product with propylene oxide Two-step, via methacrolein Three-step, via methanol... 

Diacetoxy-2-butene. Mitsubishi commercialized a new proces, the acetoxy-lation of 1,3-butadiene, as an alternative to the Reppe (acetylene-formaldehyde) process for the production of l,4-diacetoxy-2-butene. l,4-Diacetoxy-2-butene is tranformed to 1,4-butanediol used in polymer manufacture (polyesters, polyurethanes). Additionally, 1,4-butanediol is converted to tetrahydrofuran, which is an important solvent and also used in polymer synthesis. 

Ethers are formed in the usual way the te-chloromethyl ether is obtained by using formaldehyde and hydrogen chloride. With aldehydes or their derivatives, butanediol forms acetals, either 7-membered rings (1,3-dioxepanes) or linear polyacetals the rings and chains are easily intraconverted. 

The Reppe process is used to make 1,4-1 butanediol from acetylene. In this process, acetylene and formaldehyde are reacted in the presence of a copper-bismuth catalyst. The resulting intermediate, 2-butyne-l,4-diol is hydrogenated over a Raney nickel catalyst ... 

Acetylene and formaldehyde are reacted in the presence of a highly active catalyst to form butynediol, which is hydrogenated to butanediol and then cyclodehydrogenated to form butyrolactone. Pyrrolidone is produced by reacting butyrolac-tone with ammonia. This is followed by a vinylation reaction in which pyrrolidone and acetylene are reacted under pressure. The monomer vinylpyrrolidone is then polymerized in solution, using a catalyst. Crospovidone is prepared by a popcorn polymerization process. 

Perlon U, which was manufactured in Germany to a small extent, is a polyurethane. It is formed by the action of hexamethylene di-isocyanate on 1 4 butanediol. d he butanediol is obtained by the action of formaldehyde on acetylene followed by reduction ... 

Low molecular weight acid phosphatase Formaldehyde, derivatives of 5-arylidene-2, 4-thiazolidinedione, 1,4-butanediol AHphatic alcohols... 

This consists in causing formaldehyde to react with acetylene in the presence of a copper-based catalyst The ethynybtian reaction yields 1,4-butynediol and a few per cent of propargyl alcohol resulting from the condensation of a single molecule of formaldehyde. The 1,4-butynediol is hydrogenated to 1,4-butanediol in a second step. 

Now, THF is produced by selective hydrogenation of maleic anhydride [6, 7] or by dehydration of 1,4 butanediol (resulting from acetylene and formaldehyde, followed by the hydrogenation of the resulting 2-butyne-l,4 diol [23]). The old technology based on furfurol may be reconsidered in the future, because it uses a renewable resource as its raw material. 

The worldwide market for butanediol (EDO) in 2003 was about 800,000 MT, of which more than half of the production used the Reppe process, which uses acetylene and formaldehyde as the raw materials. However, the industry is moving toward the cheaper technology of using maleic anhydride obtained from butane as the raw material [85]. Although other commercial processes are used to synthesize EDO starting from butadiene, dichlorobutene, or propylene oxide, we limit ourselves to processes where carbon-supported catalysts are used the... 

With acid catalysts 1,4-butanediol cyclizes to tetrahydrofuran (toxic) forms 1,4-dichloro-butane with thionyl chloride and 1,4-dibromo-butane with HBr. It forms bis(chloromethyl) ether (toxic) with formaldehyde and HCl. 

The Reppe process is a method that was developed in the 1940s and typical manufacturers include BASF, Ashland, and Invista. Cu-Bi catalyst supported on silica is used to prepare the 1,4-butynediol by reacting formaldehyde and acetylene at 0.5 MPa and 90-110 C (Eq. (10.2)). The copper used in the reaction is converted to copper(I) acetylide, and the copper complex reacts with the additional acetylene to form the active catalyst. The role of bismuth is to inhibit the formation of water-soluble acetylene polymers (i.e., cuprenes) from the oligomeric acetylene complexes on the catalyst [5a]. The hydrogenation of 1,4-butynediol is accom-pUshed through the use of Raney Ni catalyst to produce 1,4-butanediol (Eq. (10.3)). The total yield of 1,4-butanediol production is 91% from acetylene [5b]. Since acetylene is a highly explosive compound, careful process control is necessary. 

Conventional processes for the synthesis of butanediol use petrochemical feedstocks for their starting materials. For example, acetylene is reacted with 2 molecules of formaldehyde in the Reppe... 

Conventional processes for the production of 1,4-butanediol use fossil fuel feedstocks such as acetylene and formaldehyde. The biobased process involves the use of glucose from renewable resources to produce succinic acid followed by a chemical reduction to produce butanediol. PBS is produced by transesterification, direct polymerization, and condensation polymerization reactions. PBS copolymers can be produced by adding a third monomer such as sebacic acid, adipic acid and succinic acid, which is also produced by renewable resources [34]. 

NVP is one of the various products of the acetylene chemistry [477] discovered by Reppe [478-481]. The reaction between acetylene and formaldehyde yields 1,4-butinediol, which is hydrogenated to 1,4-butanediol. After the oxidative cyclization to y-butyrolactone on Cu contact (700 °C), the reaction with ammonia leads to y-hydroxycarbonamide. 

---