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Патент USA US2129685

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' Patented Sept. 13, 1938
2,129,685 .
George D. Graves, Wilmington, Del., assignor‘ to
E. I. du Pont de Nemours & Company, Wil
mington, Del., a corporation of Delaware
No Drawing. Application July 14, 1934,
:Serial No. 735,281
s Claims. (Cl. 260-2)
parts of methacrylyl chloride used originally and
The present‘ invention relates to new composi
tions of matter, to methods for their preparation heating on the boiling water bath was continued
and more particularly to the methacrylic acid J about 20' minutes longer.
esters of the phenols and more speci?cally-phe
After cooling, the reaction mixture was dis
" 5 nyl methacrylate, ortho cresyl methacrylate and
solved in ether, and extracted with water and 5
then with 5% sodium hydroxide solution until
An object of the present invention is to pro ' free from hydrochloric acid, inhibitor and un
vide new compositions of matter and a p ocess reacted orthocresol. The cold reaction mixture
was neutralized and then washed and dried over
' .' for their preparation. A further 'obj‘ec of the
resorcinyl methacrylates.
, ,
10 invention is to provide a new polymerizable com
i a suitable desiccating medium. The solvents were 10 '
removed from the dried product by fractional dis
tilla'tion, and the ester ?nally separated by frac
vention is to provide a process for the preparation ' tionation under reduced pressure.- A 70% yield
of the methacrylic acid esters of the phenols, of (orthocresyl methacrylate wasobtained, which
.15 which may be obtained by the ester interchange‘~ had a boiling point between 98-103“ 0., at 5 mm., 15
a density of 1.031 at 20° C., and a saponi?cation
method of interacting a lower alkyl ester of-meth
position of matter together with a process for its
polymerization. A still further objectot the in
acrylic acid with the alcohol“ in the presence of a
number of 324 (theoretical 318).
_ suitable catalyst, or by the reaction of the alcohol _
with a methacrylyl halide. Another object of the
20 invention is to provide mixtures or interpolymers
ofthe polymerized resin with other polymerizabl'e
compounds of methacrylic and acrylic acids.
Other objects and advantages of the invention
will hereinafter appear.
There have been prepared in accord with this
which have been found useful as prepared and
, , compounds may be generally described as metha
30 crylie acid esters of the phenols such, for exam
ple, as phenyl methacrylate, orthocresyl metha
peated- with 188 parts (all parts are by weight)‘ of
phenol, and 208 parts 'of methacrylyl chloride. 20
The temperature of the reaction varied from 25°
C. to 100° C., and after 1 hour a 70% yield of
phenyl methacrylate was obtained.
The ester
- I
had a boiling point of 83-851" 0., at4 mm., a den
-sity of 20° 0., of 1.053 and a saponi?cation num-' "a ,
invention valuable esters of methacrylic acid - ber of 339 (theoretical 346). I
even more valuable when polymerized.
ErampleZ-flhe process of Example 1 was re
Example 3.—The process of Example 1 was re
peated with 127 parts of paracyclohexyhphenol
. and, 80 parts of methacrylyl chloride. 1 The tem
perature was maintained between approximately 30
90-95° 0., and after 50 minutes a ‘14% yield of
crylate, resorcinyl methacrylate, .paracyclohexyl
phenyl methacrylate, beta-naphthyl methacryl
ate, alpha naphthyl methacrylate, hydroquinyl
,paracyclohexyl phenol methacrylate was ob
methacrylates and equivalent and homologous
methacrylates, the mono- and poly-methacrylates
'230) and was soluble in hot ether, hot methanol, 35‘
of the mono- and polyhydric phenols such as
Example 4.-104 parts of methacrylyl chloride
resorcinol, catechol, pyrogallol,?phloro-glucinol,
the di- or polyhydroxy naphthols and naph
'40 thalenes; thymol, diphenylol propane; dlpheny'lol
naphthane, and the like.
tained. The ester had a melting point of 67-68° '
C., a saponi?cation number of 242.8 (theoretical
and benzene.
and 55 parts of resorclnol weremixed and the
solution was warmed on a water bath under a
're?ux condenserwat such a rate that hydrogen 40
chloride was liberated vigorously. ‘ After the vig
The following speci?c examples are furnished ' orous liberation of hydrogen chloride had ceased
to illustrate methods of preparing the new c'om- . (usually after the solution had been heated on
positions of matter, but it will be understood that the boiling water bath for about one-half hour)
45 the invention is not limited to the details herein. there was added 10 gramsv of hydroquinone to 45'
‘each-100 grams of methacrylyl chloride used orig-e
inally'and heating on the boiling water bath was ‘
Example 1.—Equimolar quantities of metha
- crylyl chloride and orthocresol were mixed and‘ the
solution was warmed on a water-bath under a\
50 re?ux condenser at such a rate that hydrogen
chloride was liberated vigorously. After the vig
orous liberation of hydrogen chloride had ceased
continued about 20 mi'nutees longer.
’ '
After ‘cooling, the reaction mixture ‘was dis
solved in ether, and extracted with ‘water and 50
then with 5% sodium hydroxide solution until
free from hydrochloric acid, inhibitor. and un
(usually after the solution had been heated on the reacted resorcinol. The cold reaction'mixture 1‘
boiling water bath for about one-half hour) there ' was dried were suitable desiccating medium, the
to was added 10 parts of hydroquinone to each 100
solvents removed byfractional distillation and 555]
monomer 400 parts of acetone and 1 part of hen
zoyl peroxide were mixed and the solution heated
the resulting mixture fractionated under‘ reduced
pressure. A 65% yield of resorcinyl dimetha
under a re?ux condenser at a temperature of ap
crylate was obtained.
The methacrylates as prepared in accord with proximately 75° C. After 4 days the polymeriza
5 the examples are usually mobile liquids, but may. tion was substantially complete. The resin was
sometimes be solids. The esters as thus produced isolated by mixing with gasoline (any suitable
non-solvent for ‘the resin may be used). A 98%
are monomeric and may be polymerized, accord
ing- to the invention, by means of heat, light, yield of the polymer as a coarse powder was ob
and/or a catalyst, e. g., as described for the poly-'4 tained. )‘It is soluble in butyl acetate, acetone 10
and toluene and relatively ‘insoluble in gasoline.
l0 merization of organic vinyl esters in British spec
i?cation 15271/1914. Preferably a catalyst such It has a viscosity of 0.015 poise (5% solution in
toluene at 25° C.) .
as oxygen, ozone, an organic peroxide, an ozonide,
The resin wasplaced in a disk shaped mold in Y
etc. is employed. Other catalysts which maybe
used, include aluminum sulfate, boron ?uoride,
‘which it was subjected to a temperature of 130°
C., and a pressure of approximately 4000 pounds
_ 15 the mineral acids, e. g., hydrochloric, sulfuric
per square inchior approximately 15 minutes. A '
acids, as well as the organic acids and, more par
ticularly acetic and methacrylic acids, etc., as well brittle, molded disk was obtained which softened
as the anhydrides and acid halides of such acids; at a temperature of 120° C.
Example 2.—40 parts of paracyclohexyl phenyl
metal salts of fatty acids and resinic acids, e. g.,"
methacrylate monomer was dissolved in 360 parts
of methanol in- a bottle provided with a stopper,
20 cobalt linoleate and resinate, manganese oleate
and rosin, etc. The polymerization may be ef-fected in the presence or absence of a solvent for
both monomer ‘and polymer, or in the presence of
a solvent for the monomer and a non-solvent for,
25 the polymer, or {the monomer may be emulsi?ed
then‘ 0.4 part of powdered benzoyl peroxide added
to this solution. The gbottlewas securely closed
and then polymerized. rPreferably, polymerizae
> tion is carried out at a moderate temperature, i. e.,
between 60-100° C., altho higher temperatures,
such'as, for example, 130° C., or'higher, may, be
so employed. The polymerization reaction is usually
strongly exothermic and it may be necessary to
control the temperature by cooling devices,
though polymerization may be carried out in an
and set in an oven at approximately 65° C. After
the polymerization was complete in approximately
3 days, the mixture was allowed to cool. The
product was ?ltered,‘washed with a little‘ cold
methanol and dried in a vacuum'pdesiccator. The
polymer'was obtained in a 95% yield as a white 30
powder which gave a turbid solution in toluene.
It is relatively insoluble ~‘in butyl acetate, ace
tone and gasoline. A 5% turbid solution in tolu
ene gave a viscosity at 25° C., of 1.25 poises.
The resin was placed in a disk shaped mold in
which it was subjected to a temperature of 160°
' C.,' and a pressure of approximately 6000 pounds
As indicated various methods may be employed . per square inch for approximately 15 minutes. ' A
paratus which may or may not be provided with
,35 condensing devices, or in suitable pressure equip
for polymerizing the monomeric esters of metha
brittle, very hard, slightly hazy, molded disk was
crylic acid and it has been found that the prop
obtained which softened at a temperature of
40 erties of the resins, the physical properties to a
large extent and the chemical properties to a
145° C.
. Example 8.--Resorcinyl dimethacrylate poly
lesser extent, are altered considerably by the type
merizes readily without the aid of a catalystegiii
of polymerizing process utilized. ‘ The process
at a temperature of 100° C., the monomer is con
described in the copending applications of D. E. verted 100% to-the polymer which is a amber
45 Strain Serial No. 668,080 ?led April 26, 1933 and colored, ?int like, brittle material which burns
704,753 ?led Dec. 30, 1933 may be‘used if- desired. without softening. It is relatively insoluble in
Methods illustrating the polymerization of the common organic solvents.
esters will now be described but it will be under
' Valuable products may be obtained by utiliz~
stood that other suitable polymerizing processes
ing the (polymers of the esters described herein
50 may be employed.
together with equivalents or-homologues thereof 50
admixed with other'polymeric acrylic or metha-_
crylic esters or other derivatives. Especially valu
able products result if themonomeric esters are
mixed and then polymerized, by this method in
Example 5.—40 parts (parts are given by
.weight) of or’thocresyl methacrylate monomer
was dissolved in 310 parts of methanol in a bottle
provided with a stopper, then 0.4 part of pow,
55', dered benzoyl peroxide added to this solution. terpolymers having a wide range of character4 '
After the- benzoyl-peroxide was all dissolved, 50 'istics are made. Due to the unique character~
parts of water insufficient to cause'permanent istics of methyl methacrylate polymer which is
turbidity was ad$rl “The bottle was securely a hard resin having a high melting point, its ad
' closed and setinan oven at approximately 55° C‘. mixture with the polymeric esters of methacrylic
complete in'approx
acids herein timmlbedor interpolymers thereof 7
wes'aiiewed to seal.
d with a little
' -
are particulariy well adapted for many uses,
oi methacrylic acid as
or lnterpolymers thereof with
le corn-pounds are particularly
no?water, -
rela= .
tnermoplastic molding.
The men
other may he polymerlmd and! or preformed prior
in "
accord ‘w
mold and then may be molded
-..,-. usual procedural stepsem
ployed partumsriy in the molding of methyl
the Rowland Hill
pounds per methacrylate as described
approximately 15 minutes. A. Patent 1,980,483 of November 13, 1934. The 'moid
I prderabiy is hot, prior to the introduction of the.
.moided disk was obtained
which softened at a temperature of ‘106° C’.
as 7 Example 61-100 parts 01’ phenyl methaorylate
product, is ‘then closed and the
materialso con?nedheated and pressed. the tem
peratures ranging from approximately 80-150° C.,
and pressures from 200 pounds per square inch,
upward, are usually suflicient to give a suitably
3 .
substance such as wood, paper, textile fabric,
arti?cial stone, or the like be coated with the
said syrupy solution or be impregnated therewith,
molded. product. The presence or absence of .' very resistant coating and impregnations are‘ ob
plasticizers will, of course, alter considerably the tained on completing the polymerization of the
molding conditions and it is usually advantageous ,_ coating, painting,‘ or impregnation, for instance,
to have present plasticizers to alter the physical _ by exposing the‘article to arti?cial or natural
characteristics of the resulting product to ?t the light or by heating it, or by employing both light
particular need for which the molded article is
to be used.‘
and heat. In this case a portion of the un
changed methacrylic acid ester‘ in the syrupy
solution may or may not ‘be evaporated while
another portion may be converted into the solid
polymerization product. The articles thus treat
ed have imparted to them a very high resistance
to external in?uences, e. g., resistance to water, 15
The masses resulting from polymerization can
immediately (1. e., in- the state they have been
obtained) be made into useful articles. It is pos
sible to obtain the required articles if; for in
stance,-the polymerization be carried out ,while
the initial material is in a suitable mold, for in , acids, alkalisand‘atmo'spheric changes.
The said syrupy mass can be mixed with com
- stance one of steel or glass, so that the articles,
for example, umbrella handles, fountain pen bar , minuted-matter, such, for instance, as ground
rels, buttons and the like, are obtained directly ‘ cork, or ground wood, ?brous substances, mineral
20 from the mold. Orif desired the masses may be
?llers, or the like‘ and the mixture be made into 20
worked to the required shape by softening vwith ' the proper shape and the unchanged methacrylic
. suitable softeners or plasticizers in the presence
of volatile solvents and, after shaping, evaporat
. ing the solvent.
acid esters in the articles be converted, by suit
able polymerization, into the solid ?nal product.
It is also possible to start from solid, semi
The polymerization ‘products may be worked _ I solid, or plastic, polymerization products of the 25
into the required shapes in various ways, for ex
ample, they can be softened and kneaded, rolled,
methacrylic acid esters, these' being softened by
heating them ‘by themselves, or with suitable
compressed, drawn into wires, threads or the like, . ' solvents, and using them in- their softened state.
On cooling, or on the evaporation‘ vof‘the diluent,
or the niasses can be/inixed with additional sub
so stance, and rolled ‘into plates, or ?lms, or they that may still be present, the product is'con 30.
may be pressed into the required shapes such as > 'verted into the solid, lacquer-form.
buttons, combs and the like.
. It is obvious that mixtures'of various poly
' The so d masses can be worked by. cutting,
merized methacrylic acid esters can be, used for
sawing, ?ling, or the like, whether they be ob
tained directly by polymerization, or after special
treatment of. the polymerized masses. These
ance with this invention. It ‘is likewise obvious 35
‘that the wholly, or partly polymerized esters can
' shaped articles may be polished, and parts con
nected together by smearing the faces to be con-'
nected with a suitable solvent, suchyas acetone, v
epichlorhydrin, or the corresponding methacrylic
acid ‘ester.
The polymerization product dissolved in a suit-'
~ able solvent which may or may not be the mono- , mer may be transformed into a useful article, "
.45 e. ;g., ?lms by casting and then evaporating the
lacquering, painting, or impregnating in accord
be mixed with suitable additional substances to
modify the properties of the lacquering, painting, .
orjvmpre‘gnating materials in'any desired manner.
As additions of this kind oils?'should be men 40
tioned (such, for instance, as 'castor oil), dyes, .
powdered substances, (such as zinc oxide) cam
phor, camphor substitutes, and the like.
In accordance with this invention it is possible
to obtain valuable products if the said polymers _
be dissolved, or softened, in suitable solvents and
then be converted again to the solid state. The
products thus obtained 'may be used for purposes
- The polymer may be recovered from such solu
tions by precipitation with a suitable non-solvent‘ ‘for which cellulose esters have hitherto been used,
‘ _ _ solvent, or by extruding through a suitable ori?ce
into a precipitating bath or drying atmosphere.
for the polymer.
' The properties of the resulting masses may be
widely‘ varie'd‘by modi?cation with plasticizers,
e. g., dibutyl phthalate. tricre'syl phosphate, etc.‘,
drying, semi-drying and “none-drying oils, syn
thetic and natural resins, waxes, bitumens, cellu
lose derivatives, e.,g., cellulose nitrate and ethyl
cellulose, etc., pigments, ?llers, and dyes, etc.
,Thus it is possible to produ‘ce?instead of hard,
‘glassllke masses, also soft and ?exible ‘masses.
Likewise, by the addition of suitable coloring
means, it is possible to produce masses,‘ or ob
jects, having any v‘desired color effects.‘ The in
_ corporation of the additions can be effected either
namely a‘s substitutes for horn, amber,‘ arti?cial
resins, lacquers, for impregnation purposes and
‘also for the production of ?lms, interlayer for ‘
safety glass, pressure adhesives, arti?cial threads, ‘
and the like.
The products thus formed have the advantage i"
over products made from nitrocellulose in being
less, in?ammable. By the addition of suitable
agents, the strength and hardness of the products ‘
may be modi?ed within wide limits so that it is
possible to manufacture, both hard, horn-like 60
substances and softand more pliable products.
The products may also be modi?ed by varying
the conditions ‘of the polymerization.
before, or during, the polymerizing process, or ‘ _ The monomer may be polymerized in the pres
05 the additions can be made to the already formed
polymerization products ina suitable condition.
If‘ the polymerizationof an organic metha
crylic acid ester, be carried out in an incomplete
ence of a solventand the, solution used as such 65
or‘ the polymer recovered; from the solution by
evaporation or precipitation, methods. In many
cases, however, it ‘is more pro?table to use an
mannen-a syrupy solution of the polymerization , amount of solvent insu?icient to produce a freely
70 product containing some unchanged-methacrylic
?owing solution, so that soft plastic masses are
‘ acid ester is obtained. This product can be obtained which can be pressed, kneaded, rolled
utilized either directly, or along with other’ sol-v . or drawn into shape, or formed into blocks, plates, _
vents, or diluents, for the production of. sub
stances to be used for coating, painting, or im
Plasticizers or other modifying agents may be I
75 pregnating purposes. If, for instance, apnrous ‘ added to the monomer prior to polymerization or; 75
directly to the polymerized product, it being gen
erally desirable to employ a plasticizer which is
soluble in the polymer and the monomer, altho
it is not essential that the dual solubility char
in acteristics be present. Thus,‘ plasticizers or softlening agents, such as for example, camphor;
phthalates, such as ethyl, propyl, isopropyl, butyl,
isobutyl, cyclohexyl, methyl cyclohexyl, or benzyl
phthalate or phthalates of the mixed type such
as cyclohexyl butyl, benzyl butyl or butyl lauryl
phthalate; esters of other dibasic acids, such as
the ethyl, propyl, isopropyl, butyl, isobutyl, cyclo
hexyl, methyl cyclohexyl or benzyl esters of suc
cinic, fumaric, tartaric, adipic and sebacic acids;
esters of monobasic acids, such as the butyl, iso
butyl, cyclohexyl, methyl cyclohexyl, benzyl or
lauryl esters of lauric, laevulinic, benzoic, benzoyl
propionic and benzoyl benzoic acids; esters of
polyhydric alcohols, e.\g., glycol and glycerol, such
as glycol benzoate, glycol laevulinate, triacetin,
tripropionin and tributyrin; substituted toluene
sulphonamides, such as ethyl paratoluene sul
partially polymerized compositions, the polymer
ization may be effected by subjecting the sand
wich of glass and compound to suitable applica
tion of light and/or heat.
>When the term “poly” is employed in the
speci?cation or in the claims it refers only to the
number of methacrylate groups attached to the
designated alcohol, in contradistinction to the
“polymerized” ester which is the union of two
_ or more molecules of the ester.
From a consideration of the above speci?ca
tion it will be realized that various changes may
be made in the process or product without de
parting from the invention or sacri?cing any of
its advantages.
I claim:
1. The polymeric methacrylic acid ester of a
phenol prepared by polymerizing the monomeric
ester by heating to a temperature of approxi
mately 65° C. in the presence oi benzoyl peroxide. 20
2. The polymeric phenyl methacrylate pre
pared by polymerizing the monomeric ester by
phonamide; substituted amides, such as tetra» heating ‘to a temperature of approximately 65° C‘.
ethyl phthalamide, tetrabutyl succinamide, tetra~ in the presence of benzoyl peroxide.
butyl adipamide, tetraethyl phthalamide; hydro
3. The polymeric paracyclohexyl phenyl'meth
carbons, such as dixylyl ethane; halogenated hy-v acrylate prepared by polymerizing the monomeric
drocarbons, such as chlorinated diphenyls and di .ester by heating to a temperature of approxi
chlordibenzyl; ether compounds such as dicresoxy mately 65° C. in the presence of benzoyl peroxide.
4. The polymeric resorcinol dimethacrylate
ethyl ether; and drying, non-drying or semi-dry
by polymerizing the monomeric ester by 30
30 ing oils, such as castor oil, cotton seed oil, linseed
oil and the like. These additions also facilitate heating to a temperature of approximately 65° C.
later mechanical treatment, as cutting, sawing, in the presence of benzoyl peroxide. '
and polishing.
The polymerized esters, mixtures‘of the poly
merized esters with dissimilar polymerizable es-'
tersor' other polymerizable compounds of meth
acrylic or acrylic acids, or vinyl compounds; or
interpolymers of the esters with such other com
pounds, may be used advantageously as safety
glass interlayers. These polymerized esters, mix
tures thereof, or interpolymers thereoi may be
plasticized or otherwise modified as desired. The
5. The polymeric polymethacrylate of a phenol
prepared by polymerizing the monomeric ester
by. heating .to a temperature ‘of approximately 36
65° C. in the presence of benzoyl peroxide.
6. The interpolymer of a methacrylic acid ‘ester
of a phenol and a polymerizable derivative of an
acid selected from the group consisting of acrylic
acid and methacrylic acid, which interpolymer is 40
prepared by polymerizing a mixture of the
monomeric compounds by heating the mixture to
compositions may be compounded with glass in
a temperature oi approximately 65° C. in the v '
an unpolymerized, partially polymerized, or com
presence of benzoyl peroxide. '
pletely polymerized condition. When compound
ing the safety glass with the 'unpolymerized or
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