Methacrylate

Resins
Contribution from
E. 1. du Pont de Nemours & Company,
Wilmington, Del.

0A
LPHA methyl acrylic acid and some of The earlier work on the hyiithesis of methacrylates was
its derivat,ives have been known for reviewed by Xeher ( I S ) . Methacrylic acid esters can be
many years (6, IS) but only recently has prepared by dehydrohalogenating alpha or beta halogenated
recognition of the unique properties of the methacrylic ester isobutyric esters (1):
polymers stimulated the studies which have led to their (CH3)zCClCOOR---t CH,=CCH&OOR + HC1
commercial development. Although methacrylic acid and
its salts, amide, imide, nitrile, chloride, and anhydride, or from acetone cyanhydrin (3)
have been studied, the esters are of particular interest be-
cause they can be polymerized to thermoplastic resins pos- (CH,)&ORCN + H,SOs + ROH +
CH?=CCHaCOOR + NHaHSOd
sessing unusual clarity and stability.
The synthesis of higher ester methacrylates is conveniently
Properties and Synthesis of Monomeric carried out by alcoholysis with the methyl ester monomer:
Methacrylates CH, = CCH,COOCH, + ROH CH-C(CH3)COOR
+
+ CHIOH
Methyl methacrylate monomer is a volatile liquid of low
viscosity. The physical properties of this compound are Iaard (10) prepared methyl methacrylate by condensing
summarized in Table I, and the boiling point and density methyl chloroformate wibh propylene t o methyl-fi-chloro-
of a number of typical monomeric higher ester methacrylates isobutyrate and by dehydrohalogenating the latter to methyl
are shown in Table 11. methacrylate :
1160
 OCTOBER, 1936 ISDUSTRIAL AND ENGIXEEHING CHEhlISTRY 1161
CHAHCH3 + ClCOOCH3 +ClCH?CH(CH3)COOCH, The results obtained in the absence of oxygen are not
Reid (14) obtained P-chloroisobutyryl chloride from propyl- normally encountered because the monomeric methacrylates as
ene and phosgene. Esters of methacrylic acid yere then prepared contain traces of oxygen and are polymerized in the
prepared by esterification anti dehydrochlorination : presence of air; consequently enough oxygen is always
present to induce polymerization.
+
COCI, CH,=CHCH, +ClCH?CHCHaCOCl
Methyl methacrylate vas obtained in good yields by the
TABLEI. PROPERTIES
OF MOXOMERIC
METHYLMETHACRYLATE
pyrolysis of methyl-a-acetoxy isobutyrate (16):
Sp. gr., 60"/60" F. (15.6O/16.6' C . ) 0.9497
( C H 3 ) 2 C ( O C O C ~ a -+
)~~~~~, Refractive index, n$5.6 1.4168
CH?=C(CHp)COOCH, +
CH,COOH B. p., C.:
760 mm. 100.3
200 mm. 61
100 ryn. 46
Polymerization .\I . C.
p., -48
Relative viscoaity. 29' C. 0.588
Methacrylic acid ester polymerization is autocatalytic; Latent heat of vaporization, cal./grnm:
765 mm. 77
i t is catalyzed by heat, light, ozone, and oxygen. Ozonides 200 mm. 88
Sp. heat, cal./gram/P C. 0.49
and peroxides, such as benzoyl, acetyl, and hydrogen per- Solubility: soluble In typical organic solvents; in-
oxides, are vigorous catalysts. I n the absence of oxygen and soluble in water and formamide; slightly soluble in
glycerol and ethylene glycol.
light a t temperatures u p t o 100" C., the polymerization of
methyl methacrylate practically stops after a small fraction
of the monomer has polymerized. Oxygen appears necessary The methacrylate esters can be cast-polymerized directly
below 100" C. for polymerization to approach completion into solid, glasslike resins in any desired shape in predesigned
under the above conditions. This was demonstrated experi- molds (12) or can 6rst be polymerized in finely divided
mentally: form (4) which can be used as a molding power and molded
Carefully purified methyl methacrylate monomer was fraction- in any manner suitable for a thermoplastic resin. Rapidly
ated at 25 to 30 mm. in an atmosphere of dry, oxygen-free nitro- polymerized preforms can also be used for molding (9).
gen, and the middle fraction transferred to a flask of an all-glass The pure monomeric esters are stable and can be stored
apparatus containing triphenyl methyl to remove traces of per- cool for months without polymerization. Methacrylic acid
oxides. This apparatus had previously been carefully cleaned,
and absorbed gases and water removed by a vacuum bake. After derivative polymerization is inhibited by traces of hydro-
remaining overnight prot,ected from light in contact with tri- quinone, pyrogallol, and antioxidants of this general type.
phenyl methyl, the ester was fractionated. The middle portion For prolonged storage at room temperature, traces of these
was collected in 30-cc. Pyrex glass tubes which were sealed off
directly or after the introduction of a measured pressure of oxygen materials are usually used.
gas. These reaction tubes were then placed in a thermostat for
polymerization in the absence of light. The degree of polymeri- Properties of Polymers
zation at any one time was determined by dissolving the weighed
sample in acetone, precipitating the polymer with methanol, and Methyl methacrylate polymer is a n unusual resin (8).
then drying to constant weight at 90-100" C. in a vacuum oven. Table I V summariges its general properties. I n addition to
It was first shown that 99 per cent of the polymer could be recov- unique clarity, this resin has a high softening temperature,
ered in this manner.
high tensile and impact strengths, good dielectric properties,
The data obtained at 65" C. in the absence of light are low specific gravity, excellent light stability, good ultraviolet
plotted in Figure 1. I n the absence of oxygen only a small transmission; i t is unattached by the usual inorganic
part of the monomer polymerizes even after 620 hours. reagents and some of the more common organic solvents.
Probably the slight polymerization is caused b y traces of These properties make methyl methacrylate an outstanding
unremoved catalytic material, and we can probably assume plastic. Further, the material can be easily molded and
that at 65" C. no polymerization will take place in the com- either the molded or cast form can be readily worked. It can
plete absence of oxygen and light. The addition of as little be sawed, cut, blanked, turned, drilled, formed, swaged,
as 0.01 atmosphere of oxygen definitely catalyzes
the polymerization, and the velocity is markedly
increased by the presence of 0.1 atmosphere of TABLE 11. PROPERTIES OF METHACRYLATE ESTERS
oxygen. Figure 2 gives the data obtained at --Polymer-Molded Disk--
higher temperatures under t h e catalytically pure 7
- Monomer- Softening
7 - B . p.- Densit&. temp.
conditions described. At 100" C. the polymeri- Metbacrylate c. Mna. at 20° C. Description
zation rate is essentially the same as at 65" dur- Methyl 0.945 125 Clear hard, strong
Ethyl 65 Clear' tough
ing approximately 400 hours. At 170" and 210" n-Propyl 0:9Zl 38 Clear' tough flexible
the reaction proceeds relatively rapidly, even Isopropyl 0.888 95 Clear' strong'
?+Butyl 0.894 33 Clear' flexible, strong
without oxygen and light. Isobutyl 0.884 70 Clear: slightly brittle
sec-Butvl 0.890 62 Clear slightly brittle
The catalyzing effect of temperature, oxygen, tert-Amyl 0.887 76 Clear' brittle
and light is summarized in Table 111. These Diisopropyl carbinol 0.878 60 Clear' very brittle
Octyl . .. Room Clear: gel
data were determined from curves similar t o TemD.
those shown in Figures 1and 2. The influence of Lauryl 142 4 . .. < Temn.
Room Clear, viscous liquid
-__r_

light was obtained by arranging several of the Phenyl 83-84 4 1.053 120 Clear very brittle
sealed tubes on the circumference of a circle 40 cm. o-Cresyl 98-103 5 1.031 106 Clear' ver brittle
Cyclohexyl 71-74 5 0.959 105 Clear: sligxtly brittle
in diameter; in the center of the circle was a p-Cyclohexyl phenyl LM.P . 67-68 . . . 145 Haay brittle very hard
Furfuryl 80-82 5 11055 78 Brow;, hard,' brittle
125-watt lamp. Extraneous light was excluded Tetrahydrofurfuryl 81-85 4 1.039 60 Transparent, brittle
by protecting the apparatus with a black cloth. 8-Chloroethyl 61-64 11 1.106 68 Clear colorless tough
The heat emitted from the lamp was sufficient @-Phenylethyl 110-117 5 1.018 40 Clear: slightly brittle
8-Methoxy ethyl 65+7 10 0.990 30 Clear, tough
to maintain the methyl methacrylate at about &Ethoxy ethyl 91-93 35 0.996 , Room Clear, rubbery
Temp.
35" C. Although the effect of light was only de- Ethylene glycol mono- 85-86 5 1.079 70 White, slightly brittle
termined a t 35" C., a definite acceleration of the Ethylene glycol di- 83 2 ... Infusible, insoluble solid
a-.Methyl allyl 57-59 15 0:9il , , Infuaible, insoluble solid
polymerization was observed.
1162 INDUSTKI 4 L I U D EXGIYEEKlUG CHEMISTHI \ O L . '78, uo. 10

0 - --
OF METHYL M E T H A C R Y L A T E .
PEROXIDES REMOVED W I T H FIGURE I . POLYMERIZATION OF METHYL METHACRYLATE 65.C I N DARK
TRIPUENVL VETHYL. PEROXIDES REMOVED W l T U T R I P H E N Y L METHYL. METHYL M f T H A C R Y L A T E D I S
T I L L E D I N ABSENCE OF AIR AND SEALED I N P Y R E X TUBES.

I
I 1

HOURS

I
, R
4
"
0
I . I.,
20 40 M 80 IC0 140 100 220 260 300 340
380
HOURS

ground, polished, sanded, and routed in niuch the same creases the softnes- to the same extent. An ethoxy group
manner as nitrocellulose plastics. Although the resin is gives a soft polymer. K i t h two methacryl groups in one
softer than glass, it is more surface-resistant than iiiost other molecule, as in the case of ethylene glycol dimethacrylate, an
thermoplastics. The original brilliance of a scratched sur- insoluble and infusible polymer results. The same type of
face can readily be restored by a simple and rapid polishing polymer is obtained from methallyl methacrylate.
procedure. The softness of the higher aliphatic methacrylate resiiis
The polymers formed from methacrylic acid esters of the can be decreased by interpolymerization with the harder
higher monohydric alcohols are similar in chemical properties methyl ester. A resin of any degree of plasticity can be pre-
to polyniethyl methacrylate. In the aliphatic series one pared, varying from the hard methyl methacrylate polymer
outstanding difference is the plasticity. -4s the molecular to the viscous liquid polylauryl methacrylate, by co-poly-
weight of the alcohol is increased, the softening point of the merizing the appropriate monomers in the correct proportions
resin decreases. This behavior is illustrated by the examples These resins are compatible with most classes of plasti-
given in Table I1 which describes the properties of some typi- cizers, including phthalates, tartrates, phosphates, adipates,
cal higher esters. The plasticity, as measured by the soften- etc With aliphatic-type softeners of high molecular weight.
ing temperature, increases as the molecular weight of the compatibility is limited. Other resins, such as nitrocellulose,
alcohol increases; lauryl methacrylate polymer, for instance. rosin, ester gum, dammar, cellulosp propionate, certain types
is a viscous liquid The effect of the structure of the alcohol of Bakelite and alkyds, chlorinated rubber, coumarone resins
group is shown by the properties of the butyl methacrylate etc., are highly compatible n i t h the methacrylate plastics.
polymers. The plasticity of the isobutyl and secondary butyl Methacrylate ester polyiiiers are surprisingly heat-stable
ester polyiriers is less than that of the normal butyl. The At 250" C. slight depolymerization can be detected. At
effect of an alcohol coiitaining a carbocyclic or heterocyclic 450" C. approximately 90 per cent of the polymer can be de-
ring is to give a harder, less plastic resin than an aliphatic polymerized to the monomer which can be recovered and
alcohol of approximately the same molecular weight. This purified for re-use (17) This places a definite value on scrap
effect is very pronounced in the case of p-cyclohexyl phenyl polymer.
methacrylate. The influence of four substituents in the beta
position of ethyl methacrylate is shown. Chlorine has no Applications and Uses
effect upon the plasticity. A phenyl arid methoxy group iu- The transparency, strength, high softening temperature,
lorn- specific gravity, and chemical resistance of polymethyl
methacrylate make it an outstanding plastic material ot
TABLE 111. EFFECTO F OXYGEN, TEXPERATURE, AXD 1,IGHT 05
either the cast or molded type. The unusual clarity of this
POLYMERIZATIOK O F METHYL METH.4CRYLhTE
Time for Polymerization, H I . resin permits its fabrication into delicately tinted shades.
Tam$., Oa Pressure, 1st 1st 2nd With the combined use of dyes and pigments, materials of
Atm. 5% 25% 3570
30 0.0 >300 .. varying degrees of color and transparency have been prepared.
0.1 300 The value of this resin is greatly enhanced by the ease with
1 > 300 ..
which it can be worked, as described previously, engraved with
65 0.0 200
0.1 14 35 13 unusual effects, and cemented to itself to give joints which
1 10 22 8
100 0.0 200 .. for all practical purposes are as strong as the resin itself.
0.1 1 2.8 1 8 Methyl methacrylate is readily molded in compression molds
1 0.75 1.2 0 3
170 0.0 13 68 70 under the same conditions used for thermoplastic resins.
210 0.0 6 32 Molding powders suitable for use in injection molding are
Light at 35 0.0
0.1
240
41
450
75 11
being developed.
1 92 10s 12 The glasslike transparency of these resins suggests many
uses as glass substitutes where strength. lightness, ultraviolet
OCTOBER, 1936 ISDUSTRIAL ,4ND EN(3INEERISG CHEMISTRY 1163

transmissibility, and ease of fabrication by molding are

desired. Their substitution for glass in certain fields is facili- Iv.
TABLE PROPERTIES OF UNPLASTICIZED POLYMERIC METHYL
tated by the remarkable chemical inertness of these resins. ;\fETHACRYLATE
General:
Among the many uses which have been evaluated and pat- Density, 25' C.
Hardness, Brinell scale
1 . 1 9 t o 1.20
25 -28
ented in the plastics field are safety glass interlayer (Is), Softening temp. ' C. 80--125
sound-recording records (a), dentures (20),and telephone and Shrinkage of mdlded resin, in./in
Water absorution. %
0 003-0.006
About 0.5 or less
radio transmitter diaphragms (7). Mechanical:
The low viscosity of the monomeric esters of methacrylic Tensile strength lb./sq. in. s,000-11,000
Impact strength' (A.S. T. h.1. ,notched), it./lb. 0.23-0.27
acid together with the ease with which they can be polymerized, Modulus of elasticity, lb./sq. in. 2.3-3.0 X 106
Fiber stress, lb./sq. in. 13,000-18,000
adapt them as impregnating agents which can be polymerized Thermal:
in situ. Various porous, fibrous, and cellular materials, Thermal conductivity, B. t: u./sq. f t . / h r /" F' /in. 1.25
8.2-9.5 x
Coefficient of linear expansion 10-5
w c h as wood, cloth, wallboard, Transite, cork, paper, electri- Optical:
cal coils, stone, tile, etc., have been successfully impregnated Refractive index 1.482-1.521
Light transmission 95%196
in this way to obtain products with increased water, oil, rltraviolet transmission (0.01-in. film). .i. To 2500
Light stability Excellent
alcohol, acid, and alkali resistance. Monomeric methyl Internal reflectability Good
methacrylate has been used to impregnate wood to give Electrical:
a final product containing as much as 60 per cent by weight Volume resistivity, ohms/cc. 2.0-3.0 x 1013
Dielectric constant (60 cycles):
of resin. Catalyzed monomer is readily absorbed b y evacu- 25' C. 3.3-4.5
1000 c. 5.0-6.0
ated wood (pressure facilitates the impregnation, but is not Power factor (60 cycles), %:
necessary) ; then the wood must be heated for several hours a t 25' C. 6.5-8.0
1000 c. 1.0-4.0
elevated temperatures to polymerize the resin. Wood so Dielectric strength (in oil a t 100' '2,):
treated has improved strength, and is resistant to warpage,
Insulation thickness, in. Dielectric strength, volts/mil.
water absorption, and the action of chemicals. 741
0 054
The dielectric properties of methyl methacrylate resin 0 063 687
0.092 615
make it of value in the electrical insulation and instrument 0 245 347
field. Here again the transparency, nontracking qualities, Arc resistance Does not track
Slow burning
Inflammability
inertness to ozone, high softening temperature, strength, Solubility'
water, oil, and chemical resistance, and the decrease of Soluble'in esters. ketones, aromatic hydrocarbons, chlorinated hydrooar-
bons, anhydrous organic acids
power factor with increase in temperature, combine to make Insoluble in water ali hatic alcohols ,lower aliphatic ethers, aliphatio
this material of unusual interest. The monomer can be hydrocarbons, v & e t a h e oils, ~lycold,carbon tetrachloride formamide
phosphoric acid (70%,),hydrochloric acid (30%), sulfuric'acid (60%):
used to impregnate tightly wound electrical coils, following aqua ammonia, sodium hydroxide (30'%)
which the resin can be polymerized to give a thoroughly
resin-filled appliance from which no solvent remains to be
expelled. The fluidity of the monomer permits rapid im- general finishes use. Klein and Pearce (11) included the
pregnation. Solutions of the polymer can be used also for study of polyethyl methacrylate and ethyl methacrylate-
the impregnation of coils, particularly where complete sealing methyl acrylate interpolymer films in their investigation of
is not necessary. Rotors and armatures can be dipped in resin the film-forming properties of acrylic acid resins. The ex-
solutions to bond the vires firmly in place. The toughness tensibility and elasticity of poly-n-propyl and poly-n-butyl
and strength of methyl methacrylate resin give it the ability to methacrylate films, particularly the latter, more closely re-
prevent movement of the wires under the centrifugal force semble polyacrylate than polyethyl methacrylate films used
developed at high rotational speeds. by these investigators. Although the adhesion of meth-
Paper and cloth treated with methacrylate resin have many acrylate polymers is good, it is improved by baking.
uses. Paper, cloth, wire, and other flexible materials can These are but a few of the many uses where the unique
be impregnated with resin monomers, followed by polymeriza- properties of the methacrylate resins can be ernployed to
tion in situ, coated with solutions of the resin polymers, or advantage.
impregnated with aqueous resin emulsions (19).- Paper and Literature Cited
cloth treated in this manner become resistant t o water, oil,
alcohols, inorganic acids, and alkalies, with the result that these (1) Barrett, U. s. Patent 2,013,648 (SePt. 1011935).
materials become of value in the electrical and food-packaging (3) Breni
(2) 1i9979572
Crawford, Ihid., l 6 I lY3')'
2,041,820 (May 26, 1936) and 2,042,458 (June
industries. The treated paper and cloth can be laminated 2, 1936).
to obtain white, translucent sheets which are both strong (4) Crawford and McGrath, British Patent 427,494 (April 25,
and flexible. Because of these qualities and the low specific 1935).
gravity of these resins, laminated stock prepared from them
as well as from the resins themselves are of value to the air-
ti; ~~~~~~~~~~~~~~~~~~~~~~~ ~ e $ ~ ~ , ! ? ~ v2,o l ~ 1080, New
York, Reinhold Publishing C o w , 1935.
craft industry. Paper and cloth laminated with methacrylate (7) Harford, U. s. Patent 2,044,608 (June 16, 1936).
resin can be dyed or pigmented to give colored translucent (8) Hill, Ihid., 1,980483 (Nov. 13, 1934).
sheet stock which can be used with marked success in the (') 2s046p651(June 301 1936)'
(10) Izard, Ibid., 2,020,685 (Nov. 12, 1935).
fabrication of lamp shades, etc. (11) Klein and Pearce, IND. ENQ.CHEM.,28, 635 (1936).
These resins are used in the textile field as sizing and stiffen- (12) Kuettel, U. s. Patents 2,008,719 (July 23, 1935), and 2,044,359
ingagents (18). (June 16, 1936) ; Loder, Ibid., 2,045,660 (June 30, 1936).
(13) Xeher, ISD. E m . CHEX.,28, 268 (1936).
Their clarity, light resistance, water impermeability, re- (14) Reid, u. s. Patent 2,028,012 (Jan. 14, 1936).
sistance to alcohol, oil, alkalies, and acids, and general corn- (15) Renfrew, Ibid., 2,024,389 (Dee. 17, 1935) ; Neher, Ibid., 2,032,-
patibility suggest many applications in the specialty coating 663 (March 3, 1936).
composition field, The polymers dissolved in aromatic hy- (16) Ritchie, Jones, and Burns, British Patent 42'1,885 (%larch 4,
1935).
drocarbons, esters, ketones, or chlorinated hydrocarbons can (17) Strain, U. s. Patent 2,030,901 (Feb, 8 , 1936),
be applied by spraying, brushing, dipping, or roller coating. (18) Ibid., 2,046,885 ( J ~ 7I, 1936).
~
Although any of the methacrylate resins can be used for this (19) Ibid., 2,046,886 (July 7 , 1936).
purpose, n-propyl, n-butyl, isobutyl, or interpolymers of (20) Tidd, Ihid., 2,013,295 ( S a t . 3, 1935).
methyl with the softer resins are more readily adapted to ~~~~~v~~ September 12, 1936.