A paper presented at the Seventy-fourth Gen-

eral Meeting, held at Rochester, N. Y.,

October 13, 1938, S. O. Morgan presiding.

THE METHACRYLIC ESTER RESINS.'

By H. R. DITTMAR, 2 D. 9. STRAIN 2 AND R. GRIcE KENNELLY. 2

ABSTRACT.

The polymeric esters of methacrylic acid are very stable, water-clear,

thermoplastic resins. Polymeric methyl methacrylate is a hard, rigid
material which softens above 100° C. As the molecular weight of the
esterified alcohol radical increases, the polymers become softer, tougher
and more extensible. These resins are surprisingly resistant to water
and inorganic reagents. They are light-stable and transmit ultraviolet
rays. The polymers are soluble in a wide variety of solvents and are
compatible with a large number of other resinous materials and plasti-
cizers. The properties of these resins render them suitable for general
industrial uses as coating materials and as thermoplastic adhesives appli-
cable in the form of lacquers, solvent-free hot melts or emulsions. Be-
cause of their good electrical properties these resins can be used in wire
enamels, transmission cables, finishes for electrical equipment and as im-
pregnants for electrical coils.

The commercial synthesis of the methacrylate resins 3 makes available

in this country a new series of resinous materials. These are obtained
by the polymerization of alpha-methacrylic acid [CH2=C(CH 3 )COOH]
and its derivatives. The esters are among the more interesting of the
simple derivatives of this acid because they can be polymerized easily
to form a group of resins having a wide range of physical properties.
The most striking characteristic of the polymeric esters of methacrylic
acid is their glass-like transparency. Polymethyl methacrylate is a hard,
rigid, high tensile strength resin which softens above 100° C. As the
molecular weight of the esterified alcohol radical is increased, the poly-
mers become softer and more plastic. The normal butyl methacrylate
polymer is extensible and pliable at room temperature. These variations
i Manuscript received July 6, 1938.
a Ammonia Department, E. I. duPont de Nemours & Company, Wilmington, Delaware.
3 E. I. duPont de Nemours & Co., Ind. Eng. Chem., 28, 1160 (1936).
181

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182 H. R. DITTMAR, D. V. STRAIN AND R. GRICE KENNEr,I,Y.

in properties make possible a series of resinous materials suitable for a

diversity of plastic and industrial applications.
MONOMERIC METHACRYI,ATES.

The monomeric esters of methacrylic acid are colorless liquids of low

viscosity. Table I summarizes the physical properties of the more com-
mon members of the series.
TABLE I.

Properties of Typical Monomeric Methacrylate Esters.

Boiling Specific Refractive
Point Gravity Index Relative
Methacrylate °C. 15.6 C. / 15.6 Viscosity Solubility
760 mm. 15.6° C. aD 25° C.

Methyl ............. 100 0.950 1.417 0.59 Soluble in typical

organic solvents.
Ethyl .............. 117 0.913 1.414 0.70 Soluble in typical
organic solvents.
Normal Propyl..... 141 0.902 1.420 0.84 Soluble in typical
organic solvents.
Isobutyl............ 155 0.889 1.422 0.96 Soluble in typical
organic solvents.
Normal Butyl...... 163 0.889 1.426 1.01 Soluble in typical
organic solvents.

Several syntheses of the methacrylic esters have been discovered

and studied. 3 The alpha- or beta-halogenated isobutyric esters can be
dehydrohalogenated 4
catalyst
(CH 3 ) 2 CCI000R CH2=CCH3000R + HCl
or the esters of alpha-hydroxyisobutyric acid can be dehydrated to
give high conversions of the corresponding methacrylates5
(CH 3 ) 2 COHCOOR > CH 2 aCCH 3 COOR + H 2 O
Acetone cyanhydrin can be reacted with an acid and the desired alcohol.°
(CH 3 2 COHCN + ROH + H 2 SO 4 -> CH 2 =CCH3COOR + NH4HSO4
)

The alcoholysis of a lower boiling ester, such as methyl methacrylate,

provides a very convenient method for the preparation of certain higher
boiling aliphatic, carbocyclic and heterocyclic esters
catalyst
CH 2 =CCH s COOCH 3 + ROH CH2=CCH3COOR + CH8OH
'Loder, U. S. Pat. 2,111,509 (March 15, 1938).
s Crocker, Davies and Hill, U. S. Pat. 2,054,242 (Sept. 15, 1936).
a Crawford, U. S. Pat. 2,101,821 (Dec. 7, 1937).

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 THE METHACRYLIC ESTER RESINS. 183

POLYMERIZATION.

The liquid monomeric esters of methacrylic acid are changed into

tough, transparent, resinous polymers under the influence of heat, light
or oxygen. Ozone and certain oxidizing agents, such as hydrogen per-
oxide, 7 benzoyl peroxide, 7 succinyl peroxide, 8 and the salts of perboric
and persulfuric acids are active catalysts. Sulfur dioxide also markedly
accelerates the conversion of the compounds to their polymeric form."
The polymerization of the methacrylic esters is a strongly exothermic
autocatalytic reaction, the heat of reaction in the case of the methyl
ester being approximately 80 cal./g.
During polymerization the molecules of methacrylic acid and its
derivatives combine through the double bond to form polymeric units
with molecular weights estimated, in some cases, to be as high as several
hundred thousand.
CH3 CH3 CH3
XCH 2 =CCH 3 COOR > —CH 2 C--- CH 2 —C— CH 2 —C-

COOR COOK X-2 COOK

The reaction is assumed to be of the chain type, originating from
activated molecules. The chain growth proceeds rapidly from the
active nucleus until stopped by circumstances not yet clearly understood.
This theory explains the failure to isolate anything but monomer and
fully grown polymer molecules during the polymerization.
Several different methods for conducting these polymerizations have
been studied, including:
(a) Direct Homogeneous Method. The monomeric esters can be
cast-polymerized directly into the glass-like polymers under carefully
controlled conditions in suitable molds to sheets, rods, tubes, etc. 10 Dur-
ing or following polymerization in this manner, the resin can be dis-
integrated into molding powder."
(b) Solution Method. The methacrylate esters are conveniently poly-
merized while dissolved in an inert solvent or solvent mixture containing
ketones, esters, hydrocarbons and alcohols. 12 The polymer, if soluble
7 Marks, U. S. Pat. 2,109,595 (March 1, 1938).
s Crawford, U. S. Pat. 2,097,586 (Nov. 2, 1937).
8 Strain, U. S. Pat. 2,097,263 (Oct. 26, 1937).
10 Loder, U. S. Pat. 2,045,660 (June 30, 1936); Hill, ibid., 2,045,651 (June 30, 1936);
Fields, ibid., 2,057,673 and 2,057,674 (Oct. 20, 1936); Kuettel, ibid., 2,063,315 (Dec. 8, 1936);
Tattersall, ibid., 2,071,907 (Feb. 23, 1937); Rohm, ibid., 2,067,580 (Jan. 12, 1937); Gordon,
ibid., 2,101,061 (Dec. 7, 1937).
U Macht, U. S. Pat. 2,071,932 (Feb. 23, 1937); Macht and Randolph, ibid., 2,056,793 and
2,056,794 (Oct. 6, 1936).
12 Strain, Ind. 1yng. Chem., 30, 345 (1938).

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 184 H. R. DITTMAR, D. E. STRAIN AND R. GRICE Kl~NN1~I I,Y. 4

in the diluent, must be recovered by appropriate methods to obtain the

resin in a form suitable for molding. However, by employing a diluent
in which the polymer is insoluble, the resins precipitate and are easily
recovered.l 3
(c) Emulsion Method. The monomeric methacrylates can be poly-
merized as emulsions in liquids, such as water, which are non-solvents
for both the monomers and polymers. The dispersed resins can be, if
desired, coagulated and obtained in bulk form.
(d) Granulation Method. Under rigidly controlled conditions, it is
possible to convert the methacrylate esters into polymers while tempor-
arily dispersed as droplets in a non-solvent. 14 This avoids emulsifica-
tion. Following the reaction, the resin granules settle rapidly from the
dispersing medium after agitation is stopped. In this comminuted state
the resins can be utilized in general industrial applications without addi-
tional treatment.
(e) Vapor Method. Vapor phase photochemical polymerization has
been studied. 15 Further work will be required, however, before the
commercial possibilities of this method can be fully evaluated.
The molecular weights of the methacrylate ester polymers vary with
the experimental conditions, such as temperature, catalyst, catalyst con-
centration, monomer concentration, and nature of solvent or diluent.
The molecular weight decreases as the temperature and catalyst con-
centration is increased. In general, the resins formed by solution poly-
merization are of lower molecular weight than those obtained by the
other methods at comparable temperatures and catalyst concentrations.
Except for the viscosity of their solutions, the methacrylate resin proper-
ties, such as hardness, strength, and softening temperatures, are little
affected by variations in molecular weight above a critical value lying in
the very low molecular weight range. The commercial resins have
medium molecular weights.
The physical properties of any one methacrylate resin can be varied
by interpolymerization with another ester. By polymerizing a mixture
of the monomers, they react together to form a polymer chain con-
taining both ester units. A series of methyl-normal butyl interpolymers
varying in plasticity between the hard methyl methacrylate polymer and
the soft normal butyl ester polymer is obtained by polymerizing mix-
tures of these esters by the methods outlined above.
]$ Ries, U. S. Pat. 2,072,904 (March 9. 19371.
14 Crawford and McGrath, U. S. Pat. 2,108,044 (Feb. 15, 1938).
15 Melville, Proc. Roy. Soc., 163, 511 (1937).

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 THE METHACRYI,IC ESTER RESINS. 185
POLYMER PROPERTIES.

The most outstanding properties of the polymeric esters of metha-

crylic acid are their unique clarity and stability. Although the plas-
ticity increases with the molecular weight of the monomeric unit, the
impact strength, electrical and chemical properties of the resins ob-
tained from the lower aliphatic esters are relatively constant. Some of
the properties of the available and more common polyesters are sum-
marized in Table II. The pronounced effect of the alcohol radical on
TABLE II.
Properties of Methacrylic Ester Resins.

Property Methyl Normal Normal Isobutyl

Ethyl Propyl Butyl

Density-25° C. ......... 1.19 1.11 1.06 1.05 1.02

Hardness (Pfund) *—g. at
25° C. ..................... 220 141 100 1 210
Thermal yield point—°C. .... 125 65 38 30 70
Tensile strength—lb./sq. in. .. 9,000 5,000 4,000 1,500 3,400
Impact strength (Dynstat)**-
kg. cm./cm.' .............. 10.5 7.1 6.5 11.5 1.6
Refractive index ............. 1.490 1.485 1.484 1.483 1.477
Extensibility-5 mil films (per
cent at break) ............. 4 7 5 230 2
Toughness*** ................ 98 174 76 >1,000 23
Dielectric strength—volts/mil
(thickness, 0.05 in.) at 25° C. 740 ... 650 625 ...
Power factor—per cent at 25°
C. and 60 cycles .......... 6.5 .. 3.8 6.2 ...
• Gardner, "Physical and Chemical Examination of Paints, Varnishes, Lacquers and Colors,"
8th Ed., p. 300.
•• Instruments, 9, 218 (1936).
•*' Area under load-elongation curves, expressed in arbitrary units.

the plasticity (as measured by hardness), softening temperature, tensile

strength and extensibility is apparent.
The dielectric strength of this group of resins is uniformly good. Al-
though the power factors are definitely higher than that of polystyrene,
in the case of polymethyl methacrylate, at least, the 60-cycle value de-
creases to as low as 1.0 per cent as the temperature is increased to 100°
C. Further, the power factor and dielectric constant of this resin de-
crease with frequency.' 6 Its arc resistance is outstanding.
The effect of a branched chain in the alcohol radical of the polyester
is shown by the marked difference in the physical properties, particu-
larly the toughness, extensibility and impact strength of the normal and
8 Elec. Rev., 118, 784 (1936).

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 186 H. R. DITTMAR, -D. E. STRAIN AND R. GRICE KENNELI,Y.

isobutyl ester polymers. The properties of the latter are more compara-
ble to the methyl and ethyl poly-methacrylates.
The solubility characteristics of these materials in a few typical or-
ganic solvents are illustrated in Table III. As a group, they are soluble,
with only a few exceptions, in esters, ketones, ethers, chlorinated
hydrocarbons, organic acids and aromatic-type hydrocarbons. Solubility
TABLE III.
Methacrylate Resin Solubility in Typical Organic Solvents.
10 g. resin added to 100 cc. solvent. S = Soluble. I = Insoluble. PS = Partially
soluble. *= Insoluble cold but soluble hot.
Methacrylate Ester Polymer
Solvent Normal Normal
Methyl Ethyl Propyl Butyl Isobutyl

Methanol ..................... I I I I I
Isobutanol ..................... I* I* S S S
Ethylene Glycol ............... I I I I I
Ethyl Acetate ................. S S S S S
Isobutyl Propionate ........... S S S S S
Acetone.. ........... S S S S S
Methyl Isobutyl Ketone ........ S S S S S
Cyclohexanone ................ S S S S S
Diethyl Ether ................. I S S S S
Dioxane ...................... S S S S S
Carbon Tetrachloride........... I S S S S
Ethylene Dichloride ........... S S S S S
Formic Acid (90%) ........... S I* I I I
Acetic Acid ................... S S S S S
Formamide ................... I I I I I
Toluene ...................... S S S S S
Gasoline ...................... I I I* S S
Turpentine .................... I I* S S S
Castor Oil .................... I I I* PS* PS*
Linseed Oil ................... I I I* S S

of the resins in aliphatic hydrocarbons, terpenes, natural oils and higher

aliphatic alcohols increases progressively from the methyl to the butyl
methacrylate polymers. All of the resins are insoluble in methanol,
ethylene glycol, glycerine and formamide.
The methacrylate resins are surprisingly resistant to water and aque-
ous solutions of inorganic acids, alkalies and salts. Even at 50° C.
sulfuric acid (60 per cent), hydrochloric acid (25 per cent), phosphoric
acid (60 per cent), aqua ammonia or sodium hydroxide (20 per cent)

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 THE METHACRYLIC ESTER RESINS. 187

have little effect. Aqueous salt solutions, including potassium dichro-

mate and sodium hypochlorite, do not attack the resins.
The methacrylate resins are compatible with a large variety of
plasticizers of diverse chemical structure. For certain applications
which require a high degree of pliability, such as in coating composi-
tions for non-rigid materials, the flexibility and plasticity of these poly-
meric esters can be increased by plasticization. Among the common
plasticizers which are suitable for all these resins are the phthalates,
TABLE IV.
Compatibility of Methacrylate Resins with Other Resinous Materials.
Observations made on dried films flowed on glass from solutions which contained
equal weights of the resin mixtures.
C = Compatible. I = Incompatible. SI = Film homogeneous but hazy.
Methacrylate Ester Polymer
Resinous Material Chemical Nature
Methyl l Ethyl I I
Normal Normal
Propyl Butyl I Isobutyl

Cellulose Nitrate C C C C C
(% sec.)
Cellulose Acetate I I I I I
Ethyl Cellulose I I I I I
Manila Copal C SI I I I
Damar I I I I I
Shellac (Orange) I I I I I
Rosin
Ester Gum Esterified rosin
C
I
C
SI C C
C
C
C
Super Beckacite Phenol-formaldehyde C C C C C
2000
Amberol 109 Modified phenol- I I I I I
formaldehyde
Rezyl 110 Modified alkyd SI I I I I
Rezy1408 Modified alkyd SI I I I I
Polyvinyl Acetate C I I I I
Vinylite H Vinyl chloride-acetate C C C C C
interpolymer
Ronilla L Polystyrene I I I I I
Vistanex 6 Aliphatic hydrocarbor. I I I I I
polymer
Asphalt (soft I I C C C
albino)
Cumar V-/ Coumarone-indene I C C C C
polymers
Tornesite Chlorinated rubber Cl CI C C I
Santolite MHP Toluene sulfonamide- C IC I I I
formaldehyde
Aroclor 4465 Chlorinated diphenyl C C C Cl C

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 188 11. R. DITTMAR, D. 1~. STRAIN AND R. GRICE KENNIiLLY.

tartrates, abietates, phosphates, sulfonamides, glycol esters, benzoates,

carbamates and the phthalyl glycolates. Compatibility of the lower
ester polymers with aliphatic-type softeners is limited, but the poly-butyl
methacrylates can be plasticized with butyl stearate and castor oil.
The compatibilities of the methacrylate resins with a number of
natural and synthetic resinous materials have been determined. Table
IV summarizes the results obtained. The methacrylate polymers, with
but a few exceptions, are highly compatible with rosin and cellulose
nitrate, and with certain phenol-formaldehyde, vinyl chloride-acetate,
coumarone-indene, chlorinated rubber and chlorinated diphenyl resins.
The higher ester polymers of this group are more compatible with ester
gum and asphalt, while on the other hand the methyl and/or ethyl
methacrylate polymers blend more readily with Manila copal, vinyl ace-
tate and toluene sulfonamide-formaldehyde resins. Compatibilities of
one or more of these methacrylate resins are limited with damar, shellac,
various alkyds and polyvinyl acetate.
These resins are remarkably heat-stable. When heated above the
softening temperature, the polymers gradually become rubbery but do
not truly melt. Above 200° C., the polymeric esters begin to dissociate
slowly into their monomeric form. At 350-400° C., depolymerization
takes place rapidly with very little charring. Almost quantitative yields
of methyl methacrylate monomer can be recovered from the polymer
in this manner. 17
The rubbery consistency of the propyl and butyl polymers can
be reduced and the fluidity greatly increased at temperatures between
150° and 200° C. by blending with resinous "fluxing agents" such as
ester gum, damar and coumarone-indene polymers. By varying the
methacrylate ester and the nature and concentration of the added "flux",
a number of resinous blends can be prepared, closely resembling the
methacrylate resins in properties except for melting characteristics.
Modification of the methacrylate ester polymers in this manner makes
possible their use in and application from the molten state.
The methacrylate ester polymers are light-stable and transmit ultra-
violet light to wave lengths as low as 2,500 A. Their thermal conduc-
tivity is low, that for methyl methacrylate polymer being 1.25 B.t.u./sq.
ft./hr./1° F./in. (1.55 cal./Cm. 2/hr./1° C./cm.). The stability of the
polymethacrylate esters is demonstrated by the results of a recent
study made by Kline on the weatherability of various transparent plas-
tics, including methyl methacrylate resin. 18
17 Strain, U. S. Pat. 2,030,901 (Feb. 8, 1936).
Kline, Modern Plastics, 15, 47 (April, 1938), and 15, 46 (May, 1938) ; Axilrod and Kline,
J. Research Natl. Bur. Standards, 19, 367 (1937).

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 THE METHACRYI,IC ESTER RESINS. 189
APPLICATIONS AND USES.

Of the methacrylate resins enumerated above, polymethyl methacryl-

ate, because of its high softening temperature, is a unique plastic. 19
The properties and fabrication of this resin in both its cast and molded
forms have been previously described in detail. 20 It can be cast into
sheets, rods or tubes or prepared in comminuted form for molding. In
addition, its striking transparency, high strength, good chemical and
age resistance combine to make this resin a remarkable plastic which is
suitable for many novel applications. For instance, its transparency,
resistance to weathering and the precision attainable in its moldings have
made possible a new type of highway reflecting marker which promises
to greatly reduce the hazards of night driving. 2 '

The methacrylate esters can be utilized in their monomeric state. As

mobile liquids they readily permeate porous materials in which they
can be polymerized to give resin-filled compositions not readily obtain-
able by the more orthodox methods. Wood, marble, tile, electrical coils,
paper, fabrics and anatomical specimens have been impregnated with
the methacrylate resins in this way to improve both strength and chemi-
cal resistance. Biological specimens of many types can be immersed in
the monomeric esters. Following impregnation and polymerization, the
specimens are preserved intact in the transparent, glass-like polymeric
ester. 22 When the softer or plasticized resins are used, the specimen
can be sectioned for microscopical examination. The monomeric
esters can also be used in making anatomical casts. 23 In the case of
rigid metallographic samples, the imbedding can be accomplished by
molding. 24
The methacrylate resins find many applications in the special coating
composition field. 25 Their clarity, low specific gravity, chemical, water
and heat resistance, toughness, extensibility and compatibility with other
finishing ingredients are among the properties which distinguish these
resins for applications of this type. The polymeric esters dissolved in
organic solvents such as toluene, ketones, or esters can be applied by
spraying, dipping, brushing or roller coating. The solubility of the
butyl ester resins in the cheap aliphatic-type hydrocarbon diluents per-
mits the formulation of lacquers with exceedingly low solvent costs.
ID Marketed under the registered trade mark "Lucite" by the Plastics Department, E. I.
duPont de Nemours & Co.
Randolph, Modem Plastics, 15, 28 (Oct., 1937); Plastics, 1, 134 (1937).
21 Modern Plastics, 15, 28 (May, 1938).
22 Hibben, Science, 86, 247 (1937); Knight, ibid., 86, 333 (1937).
23 Schummer, Giessen and Trommstorff, U. S. Pat. 2,108,181 (Feb. 15, 1938).
24 Erdman, Metals & Alloys, 8, 27 (1937).
2 Holl. Farbe u. Lack, 6, 475 (1937).

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 190 H. R. DITTMAR, D. E. STRAIN AND R. GRICZ KENNELLY.

The propyl and butyl ester polymers, because of their flexibility and
adhesion, can be used to advantage in clear metal lacquers, the chemi-
cal resistance of which greatly extends their utility in the field of special
industrial finishes. The application of the methacrylates in coating com-
positions is enhanced by their compatibility with lacquer ingredients. 26
The electrical properties of these resins, including their arc resistance,
inertness to ozone and the oil resistance of the polymethyl and polyethyl
methacrylates, have suggested their use in wire enamels, transmission
cables, finishes for electrical equipment and, as previously mentioned,
as impregnants for electrical coils. 21 The resins can be applied as in-
sulation to wire and cables by hot extrusion.
These resins can be applied to paper, textiles and other fibrous prod-
ucts as lacquers, molten compositions or even in emulsion form. Typi-
cal of the applications in this field may be cited their use as textile stiffen-
ing and sizing agents, 28 oil and waterproofing coatings for paper, the
finishing of leather and the coating of wire screen 29 to produce ultra-
violet permeable window coverings.
The methacrylate resins are exceptionally good thermoplastic adhesives
for paper, textiles, metal, wood, cork, "cellophane", etc. Application
from hot-melt form eliminates the use of solvents and the necessity of a
separate heating step to soften the adhesive before bonding. The ad-
hesive can be applied in this form by roller coating or by extrusion.
Some of the higher ester methacrylate polymers, such as the normal
propyl and normal butyl ester resins, have a remarkable toughening
effect on paraffin and other waxes. The polymers can be dissolved in
the molten wax to give clear, relatively mobile solutions, which on cool-
ing produce tough, flexible wax compositions. These methacrylate-
paraffin wax blends are fluid enough at temperatures above 100° C.
to be applied readily to paper, textiles, leather and other fibrous bases.
In addition to increasing markedly the toughness, flexibility, extensi-
bility and crease resistance of paraffin wax, these methacrylate ester
polymers improve both the water and grease resistance of paraffin wax
This improvement results from the incorporation of at least 25 per
cent resin. As little as 10 per cent resin, however, greatly improves the
seal strength of wax-coated paper or cloth. Application of these resin-
wax blends is not restricted to hot-melt coating, for these compositions
2 Ubben, U. S. Pat. 2,069,983 (Feb. 9, 1937); Barrett, ibid., 2,063,078 (Dec. 8, 1936).
"Miles, U. S. Pat. 2,116,318 (May 3, 1938).
28 Strain, U. S. Pat. 2,046,885 (July 7, 1936); McBurney and Nollau, ibid., 2,083,199
(June 8, 1937).
20 Strain, U. S. Pat. 2,046,886 (July 7, 1936).

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 THE METHACRYI,IC ESTER RESINS. 191

can be prepared in the form of aqueous emulsions which dry to give

tough, continuous films.
The above represent a few of the many applications for which these
resins have been found suitable. 3 °
CONCLUSION.

The methacrylate resins as a group are unique. They possess many

outstanding characteristics and have a range of properties which makes
them of value in a wide variety of plastic and industrial applications.

DISCUSSION.
COLIN G. FINK: Do the methacrylate resins increase the crease resistance
of paraffin wax as well as its water and grease resistance? Or of paper, leather,
etc., to which a wax-resin coating has been applied?
H. R. DITTMAR: They do in both cases, particularly for crease resistance.
J. S. MACKAY: What is the special range of these resins—where do they
transmit and where are they cut off?
H. R. DITTMAR: Thin films of methyl polymethacrylate will transmit light as
low as 2,500 A units. They are not permeable to light in the near infra-red range.
W. W. WINSHIPM: When you speak of a thin film, how thin do you mean?
H. R. DITTMAR: A film 0.001 in. or 0.025 mm. in thickness.
W. W. WINSHIP: Do these methyl methacrylate films retain the ultra-violet
transparency indefinitely or do they suffer eventually and become relatively
opaque?
H. R. DITTMAR: I do not know. If a piece of methyl methacrylate polymer
is placed very close to an intense source of ultra-violet light, some surface
whitening will occur, but not if the film is removed slightly from the light source.
E. J. APPEI,"': Can you employ the resin as a lacquer?
H. R. DITTMAR: Methyl methacrylate polymer is not particularly suited for
lacquers because of its poor adhesion to most surfaces. On the other hand, the
more flexible polymers, such as n-propyl and n-butyl methacrylate resins, are
finding use in film-forming compositions; for instance, they are being used as
finishes for chromium plated automobile parts. One advantage of methyl metha-
crylate polymer as a finish is its resistance to gasoline and aliphatic hydrocarbons.
COLIN G. FINK: Is the inference that these resin lacquers will take the place
of chromium plating?
H. R. DITTMAR: No, but prolong its life.
COLIN G. FINK: That is on these "standard finishes" of a thickness of one
three-hundredths the diameter of your hair.
M. E. FoGI,E ° : Can your wax-resin compound be made clear? And what hap-
pens when you attempt to mold it? Does it retain its composition or does the
wax melt and ooze out?
H. R. DITTMAR: The wax melts out, leaving the resin behind, if heated much
above the melting point of the wax but below the solution temperature of the
two-phase system.
0 Frederick, Chem. & Met. Eng., 44, 468 (1937); Frederick, Modern Plastics,
15, 11
(Oct. 1937); Frederick, ibid., 14 32 (Oct., 1936); Wurth, Chem.-Ztg., 59, 1001 (1935);
Trommsdorff, Kunststoffe, 27, 75 ('1937).
ffi Head, Division of Electrochemistry, Columbia University, New York City.
as Graduate Student, Dept. of Chem. Eng., Columbia University, New York City.
""Thermal Syndicate, Ltd., New York City.
$* Taylor Instrument Co., Rochester, N. Y.
"" Weston .Electrical Instrument Corp., Newark, N. J.

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 192 DISCUSSION.

M. E. Foclg: Could the compound be applied by first melting it?

H. R. DITTMAR: Yes, when heated above the point where the components
become compatible.
M. R. FoGu: And the clarity?
H. R. DITTMAR: All the wax-resin compositions we have made have been
opaque when cooled. The transparency can be improved by rapid cooling as, for
instance, by quenching in ice water, but in the case of paraffin wax the blends
are still somewhat opaque.
R. L. SEABURY°: You mentioned that some of these forms are made by
casting. Do I understand that the sort of optical finish is obtained from the
mold, or is that put on afterward by buffing?
H. R. DITTMAR: This cast rod of methyl methacrylate polymer had mold
marks when removed from the mold and was buffed lightly to remove the marks.
R. L. SEABURY: Is it transparent?
H. R. DITTMAR: Yes, after the surface has been buffed.
R. L. SEABURY: Without buffing?
H. R. DITTMAR: This 2-in. (5-cm.) diameter rod was sawed from a much
larger piece and buffed after removal from the mold. This resin can be molded
under heat and pressure in a good mold to an optical finish.
J. . Rcxzi : Can a paraffin mixture be made by milling; and also, what is
the life of the material?
H. R. DITTMAR: We have not tried to make paraffin wax-resin mixtures by
milling. Melting the components together is convenient. Regarding the life of
these paraffin wax-resin blends, no deterioration in oil or crease resistance of
coated paper has been observed in 4 to 5 months.
J. F. RcKEI,: What about the life of these resins in sunlight? I have been
interested in plastics, in general, from an engineering point of view, as a protec-
tion for metals. If these resins are put in the sunlight, what might be expected
after twenty years?
H. R. DITTMAR: Outdoor exposure tests have been in progress for over three
years. Methyl methacrylate polymer stands up very well. Accelerated tests are
not reliable enough to predict results of 20 years' exposure.
W. W. WINSHIP: I do not know that you said much about the chemical
resistance of these wax compounds. Would a wax-resin composition retain its
flexibility if used as a chemical gasket or something of that kind?
H. R. DITTMAR: I think it would.
W. W. WINSHIP: Would it have good chemical resistance properties?
H. R. DITTMAR: I did not have time to discuss the chemical resistance of
these methcrylic resins. Methyl methacrylate polymer is not affected by 50 per
cent sulfuric acid, 85 per cent phosphoric acid, concentrated hydrochloric acid,
aqua ammonia and sodium or potassium hydroxides in concentrations up to 20-25
per cent at higher than room temperatures. The methacrylic resins do not increase
or greatly reduce the water permeability of the straight wax except at creases
or folds. The resins markedly reduce water permeability at creases.
° Chief Engr., Delco-Remy Corp., Muncie, Ind.
S7 Western Electric Company, Kearny, N. J.

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