ACRYLIC
RESINS
HARRY T.NEHER
Rohm & Haas Company, Bristol, Pa.
NE of the outstanding chemical develop-
ments of recent years in the industrial field
is the rapid rise of synthetic resins to a
position of considerable importance. Among the more recent
of the commercially available resins are the polymers of the
acrylic acid derivatives, known commercially as Acryloids.’
Their commercial exploitation is another interesting example
of the rather belated realization of the importance and value of
substances knowu for many years. The credit for the recog-
nition and industrial development of these substances belongs,
in large measure, to Otto Rohm of Damstadt, Germany,
one of the early investigators in this field.
Historical Basis
Acrylic acid itself has been known for almost a hundred
years. In 1843 Redtenbacher (19) reported the preparation
of a new acid by the oxidation of acrolein with air and named
it acrylic acid. The silver, sodium, and ba,rium salts of this
new acid were prepared by him. On the basis of later work (8)
it appears likely that he also prepared the ethyl ester in an
8 For the sake of simplicity tire term Acrrioids haa km s p d i e d to the
variow ~ e b i n s made from derivatives of B E I Y ~ ~ Oneid, CH*:CH.COOR.
and methacrylic arid. CHz:C.COOW. They are inanufertured snd sold
CHz
in this country by R6hm 8 Hsse Company.Phiiadelphia. The trade name
Aoryioid ie registered i n the U. S. Patent O f k c .
267
irripure form. A solid modification (polymer) of acrylic acid,
which gradually swelled in water and alcohol and “finally
dissolved to a rubber-lie acid” and formed Salk with metals,
was described by Linnemann in 1872 (15). In 1873 Caspary
and Tollens (7) prepared the methyl, ethyl, and allyl esters
and observed that the allyl ester polymerized a t ordinary
temperatures, especially in the sunlight, to give a “clear hard
transparent mass.” The polymer of methyl acrylate was
iirst described by Kahlbaum in 1880 (14). The perfect
transparency of the polymer and its remarkable physical
properties led him to investigate it further. He established
that its enipirical formula %vas the same as that for methyl
acrylate, and determined the solubility, specific gravity, and
refractive index of methyl acrylate, its polymer, and a liquid
product obtained by destructive distillation of the polymer
in vacuum. Weger (40)reported the preparation of the
methyl, ethyl, and propyl esters of acrylic acid in 1883, and
commented on his ability to obtain only a limited amount of
polymer from the methyl ester after long storage or persistent
heating. The ethyl and propyl esters polymerized readily,
and he described the ethyl ester polymer as being indis-
tinguishable in appearance from the polymer ohtainablc from
styrene. The preparation of acrylic acid chloride, anhydride,
amide, and nitrile was described by Moureu in 1893 (16).
€le observed that the amide and anhydride polymerized
readily.
 268 INDUSTRIAL AXD EXGINEERING CHEMlSTliY
In 1901 Rohm published the results of his researches with
von Pechmann on acrylic acid derivatives (18,20,23). Rohm
subjected methyl and ethyl acrylates to the action of sodium
alcoholate in ether and isolated from the reaction mixtures a
dimeric form, subsequently identified as the ester of a-methyl-
ene glutaric acid, and a trimeric form which was not further
identified. I n every case a considerable amount of solid
polymer was formed, the methyl ester appearing to polymerize
more readily than the ethyl ester. Rohm described the
methyl acrylate polymer (93) as a colorless, transparent,
very elastic mass practically free from any odor of monomer;
insoluble in water, alcohol, and ligroin; but swelling in acetic
acid, phenol, chloroform, acetoacetic ester, acetic anhydride,
ethyl benzoate, and nitrobenzene. Boiling ether swelled the
mass to six to eight times its volume and dissolved a small
portion. Cold mineral acids had little action on the polymer,
which was likewise resistant to the action of aqueous acid
or alkali. Destructive distillation in vacuum gave a liquid
distillate which was shown to contain a-methylene glutarate
and a trimeric form, not identical with that obtained by the
action of sodium alcoholate on methyl acrylate. Its structure
appeared to be COOCH&H : CHCH2CH(COOCH3).CH2.
CHvCOOCHs.
I n his thesis Rohm offered an interesting comment on the
nature of the acrylate polymers. He suggested that these
substances may be considered “higher molecular compounds
but without assuming a carbon linkage between the individual
molecules.” He proposed to call these and similar substances
“pseudopolymers” to distinguish them from higher molecular
substances in which the monomeric molecules are directly
united by carbon linkages. He suggested that reactions such
as the conversion of acetylene to benzene should be designated
as a “polymerization,” whereas the formation of the solid
modification of methyl acrylate from the liquid form should
be called a “pseudopolymerization.” These pseudopolymers
were further compared with the allotropic forms of the ele-
ments, such as phosphorus, sulfur, arsenic. It was suggested
that rosin, rubber, and gutta-percha also belong to this class
of substances. These comments are interesting as an example
of one of the earliest speculations concerning the nature of
these polymeric substances.
The most exhaustive recently published investigation into
the nature of the polyacrylates appears to be that of Staudinger
and his co-workers (34,36,36). There can be little doubt but
that the polyacrylates, in common with polymers of other
compounds containing a vinyl group, are composed of single
molecules of high molecular weight, and that the monomeric
units are joined by direct carbon-to-carbon linkages.
Industrial Development
The remarkable properties of the polymerized acrylates
made a lasting impression on Rohm’s mind. During the early
part of his industrial career, the pressure of other duties
prevented him from taking active steps toward any extensive
commercial exploitation of the acrylate field. However, in
the laboratory he worked indefatigably on a study of the many
interesting properties of the polymers, and he was always on
the lookout for possible uses for them. Eventually in 1912
he secured a German patent (21) in which it was claimed that
bv their vulcanization with sulfur
tge polyacrylates could be used as
m r ym rubber substitutes. In the same
year, work on the preparation of
acrylic acid esters was started as
part of a general program of inves-
tigation in the field of artificial
resins. The war interrupted this
work in 1914, and an opportunity
for its resumption did not present
VOL. 28, NO. 3
itself for a number of years. This early work did serve to
emphasize, however, the possibilities of the polyacrylates,
and R o b became conviuced more than ever of their com-
mercial value. In 1915 he secured a German patent (22) in
which the polyacrylates were recommended as substitutes for
drying oils in paints and lacquers.
The early commercial exploitation of the acrylic acid
derivatives was seriously hampered by the lack of a satis-
factory method of preparing them in quantity. The method
(7, 20, 37) usually employed for their laboratory preparation
consisted in adding bromine to allyl alcohol, oxidizing the
resulting dibromo alcohol to cy, P-dibromopropionic acid,
esterifying the acid with the desired alcohol, and finally
dehalogenating it to the acrylic ester by means of zinc. The
large-scale preparation of acrylates by this method was
obviously out of the question, both because of the number of
reactions involved with a low over-all yield and the cost of
the raw materials. Consequently, the discovery of a cheap
and convenient method of preparing acrylates in quantity
represented an important step in the development of this
field,
The rapid development of chemical warfare and the manu-
facture of large quantities of mustard gas during the war
emphasized the importance of ethylene as a raw material
for the synthesis of many aliphatic substances. An ethylene
derivative became the starting point of a new synthesis of
acrylic acid esters, which made possible their manufacture on
a large scale. This synthesis was worked out by Bauer (30,
31) in Rohm’s laboratory, and by 1927 the work had pro-
gressed to the point where plant production of a limited
quant,ity of methyl acrylate could be commenced. The syn-
thesis is based on the use of ethylene chlorohydrin as a start-
ing material and is effected in essentially two major opera-
tions, although a number of reactions are involved in the
second operation. The reactions involved are as follows:
CH20HCH2Cl NaCN
CHz0H.CHzCN ROH
++ +CH20HCH2CN+ NaCl
+ HzS04 + (1)
CH2:CHCOOR + NHiHSOi (2)
In 1931 the production of acrylic esters was begun in this
country by the Rohm & Haas Company. The methods of
operation were based on the syntheqis discovered by Bauer
but were modified considerably in many details in order to
increase their efficiency.
This method is best suited for the production of the esters
of the lower alcohols. For the manufacture of the acrylates
of the higher alcohols it is sometimes preferable to resort to
direct esterification of the acrylic acid or to a transesterifica-
tion between a lower acrylate and the higher alcohol. The
acrylates can also be prepared from acrylyl chloride and
alcohol (6),or by the catalytic dehydration of hydracrylic
esters (2).
The ease and violence with which the acrylates can polymer-
ize make it generally undesirable either to store or transport
them in the monomeric form. The addition of polymerization
inhibitors increases their stability but cannot be relied upon
always.
Homologs of the Acrylates
Of the homologs of acrylic acid esters, the beta-substituted
ones polymerize slowly, if a t all, and consequently are of
little interest as a source of polymeric materials. Although
esters of the alpha homologs have been known for many years
(6),only those of the methyl homolog can be prepared with
sufficient ease to be of commercial interest. Ethyl a-methyl-
acrylate seems to have been prepared for the first time by
Frankland and Duppa in 1865 (IO). Some years later its
tendency to polymerize was commented upon by Fittig and
Paul ( 9 ) .
MARCII, 1936 INDUSTRIAL AND ENGINEERING CHEMISTRY 269

A number of methods have been reported

for the preparation of methacrylates.% The
method first used and most frequently men-
tioned is that of treating an a-hydroxyiso-
butyric acid ester with phosphorus trichloride
(9,10, 33). Phosphorus oxychloride, which
hes been obsemed to dehydrate hydroxy
esters (38),can be used in place of the tri-
chloride to give good yields of the methacry-
late. Thionyl chloride likewise dehydrates
the hydroxy ester to methacrylate. Both
methyl and ethyl methacrylates have been
formed by the action of sodium nitrite on
a-aminoisobutyrste ( I ) . Dehydrohalogena-
tion of an a-bromoisohutyrate to R methacry-
late bv means of diethvlaniline or auinoline
(11, iZ, 39) has also'been recommended.
@-Chloroisobutyric esters are readily de-
hydrohalogenated by means of hasic ferric
chloride or alcoholic caustic ($6). Estersof
or-hydroxyisobutyric acid are easily and eco-
nomically prepared from acetone cyanohy-
drin. For this reason they are convenient
starting materials for the manufacture of
various methacrylic acid esters. The manu-
facture of methacrylates in quantity offers
no particular difficulties other than the
avoidance of loss through polymerization.
Similar to the acrylates, tlie monomeric
niethacrylates cannot be stored or trans-
ported with safety.
Polymerization and Polymeric
Forms
The esters of both acrylic and methacrylic
acids polymerize readily under the influence
of heat, light, oxygen, and oxygen-yielding
substances such as sodium peroxide, hydro-
gen peroxide, and benzoyl peroxide (25). In
general, the acrylates polymerize much
Eaten of the aoid CWa:C.COOH are ieleried to

CN,
hereafter 81s "msthaerylates" rather than ''a-methyl
a e i y l a t d ' in order t@avoid their conitmion with methyl
aorylatc. the methyl eater of acrylic mid.

Tor: AcRYLoln IIoon FOR A PISSENGEE

PLANE, FOFXED o r ONE PIECEAND BENT
O X THREE SIDEs, PERMITTING AN UNIM-
PAIRED VIEU-
CENTER: VIOLINMADE FROX ACHYLOID
BWmOM: GROW OF OBJECTS LIADE FROM
ACRXLOID
 270 INDUSTRIAL AND ENGINEERING CHEMISTRY
RACINGCAREQUIPPED
WITH ACRYLOID
WINDOWS
its pliability and is a hard,Ftough solid, almost brittle at
ordinary temperatures. The tert-butyl acrylate polymer
seems to be the hardest of all the aliphatic acrylate polymers.
The relationship between the various isomeric polyamyl
acrylates is the same as that of the butyl esters, except that
the corresponding polymer in each case is slightly softer. A
carbon ring increases decidedly the hardness of the polymer.
The polymer of cyclohexyl acrylate is quite hard and tough,
whereas the n-hexyl ester polymer is soft and tacky. Ethylene
glycol diacrylate polymer is extremely hard and practically
insoluble in organic solvents.
The general influence of variations in the structure of the
alcohol group is the same for the polymethacrylates as for the
polyacrylates. However, as a class, the polymethacrylates
are considerably harder than the polyacrylates. Whereas
polymethyl acrylate is a rather soft, elastic, rubber-like
substance, polymethyl methacrylate is a very hard, tough
mass which can be sawed, carved, or worked on a lathe with
ease. It is only when the %-amyl ester is reached that the
softness and pliability of the polymer approach those of
polymethyl acrylate, The higher homologs of acrylic acid,
such as ethacrylic and propacrylic acid, are difficult and
expensive to prepare, and their esters polymerize extremely
slowly to give soft, semi-liquid polymers.
By modifying the conditions under which polymerization
is caused to take place, it is possible to obtain from the same
monomeric ester, polymers which vary from quite tough,
almost insoluble forms to elastic, rather soft, tacky, and highly
soluble varieties. The viscosity of a given polymer may be
influenced a t will by changes in the catalyst, the solvent,
and the temperature used during polymerization. The
presence of impurities has also been shown to have a definite
influence on the properties.8 In general, mixtures of different
polymers do not show the desirable properties to be expected.
However, this difficulty may be entirely overcome and addi-
tional advantages obtained when the monomeric forms are
mixed in desirable proportions before polymerization is
effected (17).
Both acrylic and methacrylic acids are polymerized bg
a Staudinger and Trommadorff [Ann , 502,201-23 (1933)] give an interest-
ina: discussion of the influence of the degree of polymerization on the proper-
ties of polyethyl acrylate.
VOL. 28, NO. 3
much the same agents as are used
for the polymerization of the esters.
The polyacids can be obtained
either as hard, rather brittle, trans-
parent, colorless m a s s e s o r a s
white powders. Polyacrylic acid
gradually swells and dissolves in
water to give highly viscous solu-
tions which are useful as thickeners
for emulsions, as are also the solu-
tions of the alkali salts of the poly-
acid. Acrylonitrile (vinyl cyanide)
and methacrylonitrile polymerize
r a t h e r slowly t o g i v e w h i t e
powders, insoluble in practically all
common organic solvents. The
nitriles are useful, chiefly as com-
ponents of joint polymers with
acrylates or other polymerizable
compounds.
Because of the considerable in-
fluence of the conditions of poly-
merization on the character of the
polymer and of the violence with
which the polymerization can some-
times take place, the polymerization
of large quantities of acrylates and
methacrylates must be carried out under carefully controlled
conditions. With the exception of the lower esters of meth-
acrylic acid, the polymers find their greatest usefulness in the
form of solutions in organic solvents or as aqueous emulsions.
The solutions of the polymers in organic solvents are water-
white and vary in viscosity from thin liquids to semi-solids,
depending on the type and amount of polymer present.
Emulsions of the polyacrylates (13) greatly resemble rubber
latex in appearance and in many of their properties. In
certain processes they can be substituted for rubber latex.
Solid polymers in granular or powder form are obtained by
polymerizing in a liquid which is a solvent for monomer but
in which the polymer is insoluble (98).
Properties and Uses4
The Polymers of the acrylates and methacrylates are
capable of being Produced in a wide Variety of f o m b but
as a class they are distinguishable from other resins by their
colorless transparency, adhesive qualities, great elasticity,
and resistance to many reagents. The brilliant water-white
color of the Polymers makes it Possible to Secure masses of
high light transmission and great optical clarity- Because
of the remarkable stability of the polymers to the action of
heat and light, these Properties are Permanent.
In regard to hardness, toughness, and elasticity, they range
from the very hard, tough Polymers of methyl methacrylate
to the very soft, sticky semi-liquid P o b e r s of the higher
aliphatic acrylates. The water absorption varies from almost
0 UP to 2 O r 3 Per cent, depending on the composition and
type of Polymer. As a class they have good electrical re-
s i s t ~ ~Polymethyl
~ . acrylate, for example, has a dielectric
Constant Of 5-6, a Surface resistivity a t 1000 Volts Of 4-5 x lo6
megohms, and a specific electrical resistance of 4 x
Ohms. The extensibility of the PolYacrYlates is generally
greater than that of the PolPethacrYlates.
The Polymers are generally insoluble in water, alcohoh
and aliphatic hydrocarbons. Most of them are only slightly
swelled by ethers. On the other hand, they are either com-
pletely dissolved or swelled %osoft gels by coal-tar hydrocar-
4 Patent applications for a variety of usee have been made by Rtihm &
Haas Company, Philadelphia, and Rahm & Haas, A.-G., Darmstadt.
MARCH, 1936 INDUSTRIAL AND ENGINEERING CHEMISTRY
bons, chlorinated hydrocarbons, ketones, esters, ether alco-
hols, and ether esters. They show excellent resistance to dilute
acids, and their resistance to dilute alkali is good. The lower
methacrylate polymers appear to be quite resistant to hydro-
fluoric acid fumes. Both the polyacrylates and polymeth-
acrylates are permanently thermoplastic.
The acrylate and methacrylate polymers are characterized
by their excellent adhesion to most surfaces. In the case of
metal surfaces, baking further improves the adhesion.
The properties described make the polyacrylates and poly-
methacrylates especially suitable for a variety of uses. One
of the earliest practical uses for the polyacrylates was as an
intermediate layer in laminated glass (%@. Because of their
optical clarity, stability to light and heat, toughness, and
excellent adhesion, these polymers were particularly suited for
this purpose. Furthermore, they can be readily applied
directly to the glass sheets in the form of their solutions (27).
However, the polyacrylates have the disadvantage, stated
previously and common to most plastics used in laminated
safety glass, of being influenced to a marked degree by tem-
perature changes. This defect has been largely overcome by
using a joint polymer made by polymerizing a mixture of
several different monomeric forms (17). Laminated safety
glass made from this type of polymer is being manufactured
and sold in this country under the trade name of Plexite. In
Europe laminated glass containing polyacrylic acid derivatives
is known as Luglas and Sigla.
The electrical resistance of the polymers is sufficient to
make them of value in electrical insulators. The polyacrylates
are especially useful (24) where a pliable insulating medium is
desired. In cases where tough, rigid insulators are required,
the polymethacrylates, especially polymethyl methacrylate
(32),are recommended. The adhesive nature of the polymers
opens up a wide field of application (3). Their solutions in
organic solvents are well suited for use in clear lacquers and
varnishes, for coatings on metals, wood, paper, etc., and for
undercoatings and finishes on textiles. Their resistance to
mineral oils makes them useful as coatings for gasoline and
lubricating oil storage tanks. By the proper choice of sol-
vents they can be made suitable for application by either
spraying or brushing. The water emulsions offer a convenient
form for their application in certain types of problems-for
example, as undercoatings in leather finishes. Their uses are
increased by adding pigments and fillers. Their compatibility
with other resins and cellulose derivatives varies considerably
with different polymers and even with different types of the
same kind of polymer. In general, the cellulose nitrates
are compatible with more forms than are the cellulose acetates.
The cellulose ethers are compatible in some cases.
Sheets, blocks, rods, and molded, sawed, or turned objects
of methyl or ethyl methacrylate polymers are of a brilliantly
clear, water-white transparency. Their hardness, toughness,
and light weight (specific gravity 1.18)add to their attractive-
ness. These polymers readily lend themselves to use as
substitutes for glass in optical lenses, high ultraviolet-light
transmitting sheets, objets d’art. Many striking and beautiful
effects can be produced by the incorporation of dyes and
pigments. Large quantities of clear sheets of these polymers
are being used in airplane windows in Europe.6
271
Chlorination of the polymers of the acrylic and meth-
acrylic acid esters has a marked influence on their properties
(4). For example, chlorinated polymethyl acrylate is in-
soluble in chloroform, ethyl acetate, and many other solvents
in which it was soluble before chlorination. Chlorination also
increases the hardness and raises the softening point of the
polymers.
It is apparent from this discussion that the acrylic resins
show many unique physical, chemical, and mechanical prop-
erties. I n view of the practically inexhaustible supply of
raw materials and the many and varied uses to which all
of these products have been already put, there is every reason
to believe that in the future we shall see a rapid increase in the
number of fields in which the acrylic resins will be used to
advantage.
Literature Cited
(1) Barker and Skinner, J . Am. Chem. SOC., 46, 406-7 (1924).
(2) Bauer, U. S. Patent 1,890,277 (Dec. 6, 1932).
(3) Zbid., 1,982,946 (Dec. 4, 1934).
(4) Ibid., 2,021,763 (Nov. 19, 1935).
(5) Bauer and Lauth, Ibid., 1,951,782 (March 20, 1934).
(6) Blake and Luttringer, Bull. BOO. chim., [3] 33, 635-52, 760-83
(1905).
(7) Caspary and Tollens, Ann., 167, 247-52 (1873).
( 8 ) Ibid., 167, 250 (1873).
(9) Fittig and Paul, Zbid., 188, 54-5 (1877).
(IO) Frankland and Duppa, Zbid., 136, 12-13 (1865).
(11) Hoae and Perkin. J . Chem. Soc.. 99, 773 (1911).
Hokells, Thorpe, and Udall, Ibid., 77, 947(1900).
I. G. Farbenindustrie, British Patent 358,534 (Oct. 6, 1931).
Kahlbaum, Ber., 13, 2348-51 (1880); 18, 2108 (1885).
Linnemann, Ann., 163, 369-70 (1872).
Moureu, Bull. soc. chim., [3] 9, 386-92, 413-15, 417-19, 424-7
(1893).
Neher and Hollander, U. S. Patent 1,937,323 (Nov. 28, 1933).
Pechmann, von, and Rohm, Ber., 34,427-9 (1901).
Redtenbacher, Ann., 47, 113-48 (1843).
Rohm, Ber., 34, 573-4 (1901).
Rohm, German Patent 262,707 (Jan. 31, 1912); U. S. Patent
1,121,134 (Dec. 15, 1914).
Rohm, German Patent 295,340 (June 5, 1915).
Rohm, “‘ijber Polymerisationsprodukte der Akrylaiiure,”
thesis, Tubingen, 1901.
Rohm and Bauer, U. S. Patent 1,982,831 (Dec. 4 , 1934).
Rohm and Haas, A.-G., British Patent 304,681 (Feb. 3,1930).
Ibid., 316,547 (Jan. 23, 1930); Bauer, U. 8. Patent 1,864,884
(June 28, 1932).
Rohm and Haas, A.-G., British Patent 396,097 (July 31, 1935).
Ibid., 404,504 (Jan. 18, 1934).
Rohm and Haas, A.-G., French Patent 654,357 (May 16, 1928).
Rohm and Haas, A.-G., German Patent 365,530 (Sept. 3. 1919) ;
Bauer, U. S. Patent 1,388,016 (Aug. 16,’1921).
Rohm and Haas, A.-G., German Patent 571,123 (June 18,
1928); Bauer, U. S. Patent 1,829,208 (Oct. 27, 1931).
Rohm and Haas, A.-G., Swiss Patent 146,563 (July 1, 1931).
Schryver, J . Chem. SOC., 73, 69 (1898).
Staudinger and Kohlschutter, Ber., 64, 2091-8 (1931).
Staudinger and Trommsdorff, Ann., 502, 201-23 (1933).
Staudinger and Urech, Helv. C h i m . Acta, 12, 1107-33 (1929).
Vorlander and Knctzsch, Ann., 294, 317 (1897).
Wagner-Jauregg, HeEv. Chim.Acta, 12, 61 (1929).
Walden, 2. phusik. Chem.,20, 574 (1896).
Weger, Ann., 221, 79-82 (1883).
RECEIVED
January 2 , 1936.
6 Manufacturedin Germany by Rohm & Haas, A -G , and sold under the
trade name of Plexiglas.