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Патент USA US2404268

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Patented July 16, 1946
2,404,268 -
UNITED STATES PATENT OFFICE
2.404.268
METHACRYLIC EIFEERS
AND COPOLYMERS
EREOF
Carl E. Barnes, Belvidere, N. 1., assignor to Polar
old Corporation, Cambridge, Mass., a corpora
tion of Delaware
No Drawing. Application January 10, 1944,
Serial N0. 517,701
5 Claims. H (Cl. 260--83)
1
.
This invention relates to new and improved
synthetic resins and, more particularly, to poly
merizable methacrylic esters of cyclohexyl cyclo
hexanols.
_
'
The present application is a continuation-in
part of my copending application, Serial No.
2
l
method by which all of the methacrylic esters of
the cyclohexyl cyclohexanols may be prepared:
182 grams (1 mol) of 2-cyclohexyl cyclohexanol
are mixed in a suitable ?ask with 154 grams (1
mol) of methacrylic anhydride and 79 grams (1
mol) of pyridine. A small amount of copper cloth
is added to the mixture as an inhibitor of polymer
ization. The mixture is then permitted to stand
esters and copolymers thereof.
at a temperature of approximately 60 degrees C.
An object of the invention is to provide resins
which are polymers of compounds of the char 10 for several hours and is diluted with ether and
extracted several times with dilute sulphuric acid.
acterdescribed and which are useful in the forma
It is then washed several times with dilute sodium
tion of hard, transparent, optical elements pos
hydroxide and finally with water. The ether layer
sessing relatively vhighjndices of refraction.
is then concentrated and distilled under reduced
Further objects of the invention are to provide
431,734, ?led February 20, 1942, for Methacrylic
polymers of compounds of the character described 15 pressure, 2-cyclohexylcyclohexyl ‘methacrylate
being distilled off.
'
_
and to provide copolymers of compounds of the
Monomeric z-cyclohexylcyclohexyl methacryl
character described with polymerizable com
ate is a liquid with a boiling point of approxi
pounds from the class consisting of the unsatu
mately 179-182 degrees C. at 10 mm. pressure,
rated methylene compounds and. more specifi
cally, to provide copolymers of compounds of the 20 or approximately 278 degrees C. at 760 mm. pres
sure. The monomer has a density of .9769 and
character described with other polymeriza-ble
an index of refraction of 1.49. It is clear and
methacrylates.
colorless.
Other objects of the invention will in part be
The monomeric 2-cyclohexylcyclohexyl meth
obvious and will in part appear hereinafter.
There is a pressing demand for- a synthetic 25 acrylate, as well as the monomers of the other es
ters of the invention, may be readily polymerized
by means of heat and/or actinic light, and/or
chemical catalysis. A preferred catalyst is ben
zoyl peroxide, although other catalysts known in
erably be cast or molded to the desired form. A
preferred resin is one which may be cast into the 30 the‘ art, as'for example the organic peroxides and
ozonides, may be employed. The polymerization
desired form by, for example, polymerizing the‘
resin composition’ which may be used in the for
mation of optical elements such for example as
lenses, prisms and the like and which may pref
monomer in a suitable mold or by advancing the
polymerization of the partially polymerized ma
terial in a suitable mold.
This invention con
may be effected 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
templates the provision of new synthetic resins 35 non-solvent for the polymer, or the monomer
or plastics which are particularly useful in the
production of products of the character described.
More speci?cally, this invention contemplates the
provision of synthetic resins which, when poly
may be emulsi?ed and then polymerized. Where
accurately surfaced and shaped elements such as
optical elements are being formed, it is preferable
to ?rst obtain a partial polymer of the ester and
merized, give transparent, hard, colorless prod 40 to complete the. ‘polymerization of the partial
polymer in a suitable mold.
,
‘ucts having relatively high lndices of refraction
One example of a speci?c method whereby the
and which are suitable for use in the production of
monomeric 2-cyclohexylcyclohexyl methacrylate
optical elements of the character described.
which is the product of the above esteri?cation
The compositions of the present invention com
prise compounds from the class consisting of the 45 may be'polymerized is by heating, for example in
a test tube at a temperature of approximately 65°
methacrylic esters of the cyclohexyl cyclohex
C. for approximately twenty-four hours in the
anols, i. e., l-cyclohexylcyclohexyl methacrylate,
Z-cyclohexylcyclohexyl methacrylate, B-cyclo-v presence of roughly .5% by weight of benzoyl per
oxide, and thereafter heating at a temperature of
hexylcyclohexyl methacrylate, and 4-cyclohexyl
cyclohexyl methacrylate, and to copolymers 50 approximately 120° C. for another twenty-four
hours. This polymerization method will insure
thereof with other compounds from the class con
sisting of the polmerizable unsaturated methylene
substantially complete polymerization of the
compounds.
monomer.
‘
I
>_
If it is desired to speed up the polymerization,
The following preparation of 2-cyclohexylcyclo
hexyl methacrylate is given as illustrative of ‘a 65 greater quantities of benzoyl peroxide may be
.
'
.'2,404,268
3
‘.
.
-'
*
added or the polymerization may be effected at
ening agents may be employed in small or'sub;
higher temperatures.
stantial percentages. Any of a vast number'of'
suitable hardening agents may be used. A pre
ferred hardening agent for use with copolymers,
'
-
Polymeric 2'-cyclohexylcyclohexyl methacrylate '
has a density of 1.0746. It has an index of refrac
tion of 1.5219 and a reciprocal dispersion of, 55.
comprising methyl methacryiate is either metha
It is colorless, transparent, brittle and fairly hard,
crylic acid or acrylic acid, although other known
with a softening point of about 80 degrees C.v ‘
hardening agents such as methacrylic anhydride , '
It will-be notedthat the refractive index of
or allyl methacrylate may be used successfully.
While a preferred product is one which is
the_ polymer of 2-cyclohexylcyclohexyl metha
crylate is above 1.5, which is a preferred condi
tion. The. polymer is, however, somewhat
brittle, and where it is to be employed under
10 transparent and which may be molded during >
-
conditions such that it may be subjected to
shock, it may be desirable to copolymerize it
polymerization into a suitable optical element,
it is to be understood that products which are
translucent or even opaque and hence useless
vin the formation of optical elements may be
satisfactorily employed for other purposes where
-wlth polymerizable compounds whose polymers
are somewhat tougher. This is especially true
particularly hard, readily molded, polymerized
where the high refractive index is not required.
plastics are desirable, and such products com
Copolymers having indices of refraction for the
prising the cyclohexylcyclohexyl methacrylates
sodium line, for example greater than 1.5, and
or a copolymer thereof with a polymerizable un
being substantially tougher than the pure poly 20 saturated methylene compound are to be deemed
mers of any the above-described compounds,
to fall within the scope of this invention.
may be readily obtained by copolymerization of
As heretofore described, polymerization of the
the monomers of the above compounds with
products of this invention may be accomplished
such of the following polymerizable compounds
preferably by heating mixtures of monomers or
known to produce tough polymers and whose 25 the slightly polymerized materials at relatively
indices of refraction are not excessively low. In
low temperatures for a predetermined period,
‘this connection it should be noted that the cy
and then carrying the polymerization forward to
clohexylcyclohexyl methacrylates may satisfac
a desired point at substantially increased tem
' '} torily be copolymerized vwith virtually all the
peratures. For best results, it is preferable that
polymerizable unsaturated methylene compounds
to produce products .having diverseand varied
v __
30 the ?rst stage of polymerization, i. e., at the lower '
temperature, be carried out until a hard product
physical and optical properties. Suitable com
is obtained. Higher temperatures of polymeriza
pounds for use‘ in forming copolymers of the
tion generally increase the brittleness of the
type described with cyclohexylcyclohexyl metha
product.
crylates are methyl methacrylate, ethyl metha 35 It is, of course, to be understood that where
crylate, isopropyl methacrylate, ter-butyl metha
molded optical elements are to be produced, the
crylate, cyclohexyl methacrylate and other
surfaces of the mold should be optically smooth
esters -of alpha-methacrylic acid; the vinyl
as the molded product will have substantially the
esters such as vinyl formats, vinyl acetate, vinyl
surface properties of the mold.
proplonate and the vinyl ester of chloracetic 40
Since certain changes may be made in the
acid, etc.; the vinyl ketones- such as methyl vinyl
above article and diiferent embodiments of the
ketone; styrene; and furylethylene (vinyl furan) .
invention could be made without departing from
Other suitable materials for use in the formation
its scope, it is intended that all matter contained
of copolymers falling within the scope of this
in the above description shall be interpreted
invention are the esters of ita‘conic acid, the 45 as illustrative and not in a limiting sense.
esters of ‘acrylic acid, the esters of methylene
It is also to be understood that the following
malonic acid, and conjugated dienes such as 1,3- ~
butadiene, Z-methyI-‘IB-butadiene, and 2-cloro-'
1,3-butadiene.
'
I .
One example of a satisfactory copolymer use
ful for optical purposes is the polymerization
product of a mixture of the monomers of methyl
‘claims are intended to cover all of the generic
and specific features of the invention herein de
scribed and all statements of the scope of the
50 invention which, as a matter of language, might
be said to fall therebetween.
What is claimed is:
methacrylate and z-cyclohexylcyclohexyl metha
1. As a new composition, a cyclohexylcyclo- I ‘Q
hexyl methacrylate.
crylate, the methyl methacrylate monomer con
stituting 5% by weight of the mixture; The 55 2. As a new composition, 2-cyclohexylcyclo
polymerization may. be effected by following the
hexyl methacrylate.
above-described procedure for effecting poly
3. A transparent resin comprising a polymer
of a cyclohexylcyclohexyl methacrylate.
4. A transparent resin comprising a Polymer,
meriz'ation of the monomeric 2-cyclohexylcyclo
hexyl methacrylate.
_
It is to be understood that the list of substances 60 of 2,-cyclohexylcyclohexyl methacrylate.
given is not all inclusive although it is-believed
5. Polymerized z-cyclohexylcyclohexyl metha
that the materials‘mentioned constitute the pre
crylate having a density of 1.0746 and in index
{erred substances for use in the present inven
vof refraction for the sodium line of approxi
on.
It is also be understood that, if desired, hard
mately 1.5219.
65
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I
CARL E.- BARNES.
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