Page 11 - Academic Press Encyclopedia of Physical Science and Technology 3rd Organic Chemistry

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Acetylene 63

TABLE VII Applications of Vinyl Ethers and Polymers a
Product Composition Applications
Methyl vinyl ether CH 3 O CH CH 2 Specialty monomer; intermediate; Gantrez resins
Ethyl, n-butyl, isobutyl, CH 2 H 2 + alcohol → RO CH CH 2 Specialty monomers; copolymers (adhesives); lacquers, paints,
decyl vinyl ethers plasticizers, pour-point depressants; reaction intermediates
Gantrez M Polyvinyl methyl ether grades M-55, Adhesive formulations with high wet tack; adhesion
M-154 (50% H 2 O) M-574 to plastic and metal surfaces; uses: adhesives, coatings,
(70% solids in toluene) printing inks, textiles
Gantrez AN Copolymer of methyl vinyl ether and Polyelectrolyte in aqueous media; uses: hair sprays, shampoors,
maleic anhydride grades AN-139, detergents, leather, paper coating, pigment grinding,
AN-149, AN-169 nonwoven fabrics, topical remedies, tablet coating,
photoreproduction
Gantrez VC Copolymers of alkyl vinyl ethers Traffic, marine, and maintenance surface coatings; foundation
(e.g., isobutyl vinyl ether) and sealants; corrosion-resistant paints; flame retardancy for vinyl
vinyl chloride substrates; primer coat for metals, paper coating
a Reprinted from Tedeschi, R. J. (1982). “Acetylene-Based Chemicals from Coal and Other Natural Resources,” p. 142, courtesy of
Dekker, New York.

summarizes typical uses of polymers and copolymers de- copolymers have various uses as adhesives, particularly in
rived from N-vinylpyrrolidone. high-tack formulations.
Propargyl alcohol is used extensively in the United Vinyl ether monomers are prepared by the base-
States as a corrosion inhibitor in acid media for such appli- catalyzed reaction of alcohols with acetylene. With reac-
cations as oil-well acidizing and acid pickling of steel and tive alcohols such as methanol, ethanol, and isopropanol,
electroplating and as an intermediate for vitamin A and the reaction can be carried out at atmospheric pressure:
pesticides. These combined uses are estimated to com-
prise about 3–5 million pounds annually. C 2 H 2 + ROH → RO CH CH 2 .
Other Reppe derivatives such as γ -butyrolactone,
The original Reppe process involved heating the
pyrrolidone, N-methylpyrrolidone, and N-vinylpyrroli
alcohol–acetylene charge at 150–180 C using 1–2% KOH
◦
done are used mainly as intermediates in the manu-
or sodium as catalyst under pressure, with a partial ni-
facture of PVP. However, butyrolactone and N-methyl-
trogen atmosphere. GAF has produced a variety of alkyl
pyrrolidone are used extensively as solvents for polymers
vinyl ethers, but the most important is methyl vinyl ether,
and acetylene. Butynediol has minor uses in metal treat-
probably due to the commercial success of its copolymer
ment and as a pesticide intermediate (Barban). However, it
series with maleic anhydride. The vinyl ethers polymer-
is very important as a starting point in the manufacture of
ize readily via free-radical catalysts to yield both homo-
THF and butanediol, the two largest volume Reppe prod-
and copolymers. They are reactive molecules and can
ucts. Both of these products have large-volume uses in
also be used as intermediates to make a large variety of
the manufacture of engineering plastics and polyurethane
products.
polymers (see Table V and Sections VI.C and VI.D). PVP
has important uses in the clarification of beer, wine, and
fruit juices, in pharmaceutical tablet manufacture, and
B. Butane-1,4-Diol and Tetrahydrofuran:
in cosmetic manufacture. Its high degree of solubility
Large-Volume Polymer Uses
and compatibility makes it useful in numerous adhesive
applications. Butanediol has evolved into the most important chemical
Vinyl ethers and derived polymers are summarized in in the Reppe line on the basis of its uses in the manufac-

formu-
in
useful

VII
.

Table VII. These products are particularly useful in formu- ture of polybutylene terephthalate (PBT) and THF. It is
T
able
are
particularly

These

products
lating adhesives and coating additives. The copolymer of also important as a chain extender for polyurethanes. If
methyl vinyl ether and maleic anhydride is sold by General total acetylene usage for acetylenic chemicals in 1984 is
Aniline and Film Corporation (GAF) under the name estimated to be 115 million pounds and butanediol pro-
GantrezANseries.Thesecopolymersareimportantinhair duction is estimated conservatively to be 75% of this total,
sprays and shampoos and compete with the PVP polymers then at least 270 million pounds of butanediol were then
asversatilespecialtypolymers.Polyvinylmethyletherand produced.