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Патент USA US2407414

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I‘ ; 2,4c7,413
Patented Sept. 10,1946 '7 t '
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2,407,413‘v
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. rms'rroizien smash-Mamie RESIN‘
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COMPOSITION
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Howard
"Pittsburgh
L. GerharteMilwaulrec,
:Plate >Glassv, Company,
Wis; assignoritq'
Allegheny
_' County, Pa., acorporation:.otl’cnnsylvania»' v
_
7:' .“No'Drawing'.
'
'~ ‘SerialNo.395,062
Application‘MayM',
,5 1941,"
- i 5
ii‘ Claims. (oi. 204%158)
before’ solidi?cation, withoutobiectionable effects '
The present inventionrelates to-arti?cial resins
and it has particularrelation to such resins as‘
are obtained by reacting ‘substituted or unsub
upon, the reaction. The, resin, under. appropriate
' donditionasetsinto a transparenhhard, bubble
“ jfree,iiand weilplasticized solid, which is" not sub~
stituted ethylenea-wsdicarboxylic acids or an
hydrides thereof». with' a] poly'merizable ole?n. "
One objectfof the- inventionvv is to provide a
vEject toi‘warping- and, cracking and which main»
tains'its properties well upon aging. -
'
I The reaction to form the new resins is typi?ed
clear, hard, toughystable and well, plasticized
by that between'maleic acid or maleic acid an
-' resin or the above type which is relativelyzfree
yhydride' and styrene. The two'com'pounds, along
from bubbles or cavities;
withfanv ester oilevulinic acid, are ,simpiy'ad
A second object of the marinara Mayne» ~10 mixed
directly or are introducedinto a solvent
a resinifying‘?uid material thatYc'an be cast,",or
:suchas triacetin. and are then caused to react
canvb'e employed]as'anl'investment median and’
by .actinic irradiationatq'atemperature within
they range of about 20 to 50°
Irradiationgof
vformedlinto' clear, hard, durable'and tough‘ bodies
at low temperatures andfwith but‘. little ‘distortion.
A third object of the; inventionis'to provide
the reactants may be continued throughout the
period of reaction, but it ‘maybe discontinued
, an; improved method of.‘ incorporating?a,fplas- ticizer with the resin;
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- after the ‘reaction hasl started. It is also‘ pos
sible to introduce a smallamountle-g. 1 tomes)
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vThese and other objects will be apparent from
of preliminarily irradiated reactants into the
'7 consideration of the?following specification; and
the appended claims.
v
a‘
main batch and thus to obviate further irradia- _
.
- It has heretofore beenproposed to heat an un
*ti'on.
or its anhydr’ide and'a: polymerizableole?n such
as styrene to Obtain polymerization products of
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"Reactionimay also be initiated by application
saturated dicarboxylic acidfsuchjas maleic acid
.of-heatandafter it has progressed su?iciently
' far,'heating- isldiscontinued. , .If very hard prod
whitev powdery character, which are soluble‘ in v25 ucts'iare desired the mass‘may ,be,,?nally heat
acetone and dilute alkalies;
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‘treated at a-suitable temperature (e_._ g, 100- -
~
My copending application ,Serial .No. 242,127,
200°? C.) until the desired stage is reached. .The
filedNovember-23, 1938, nowPatent'No. 2,297,351, is based upon the-discovery that unsaturated di
carboxylic acids of the type of jmaleic‘acid, or
maleic anhydride, or fumaric acid, or substituted
hour or less, but byyreduvcing the degree or time
reaction can be brought to completion within an
, of~irradiation it is possible to extend it ofv'er a
period of several days.
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' - The reaction product obtained from maleic an—
‘ ,maleic or fumaricacid and polymerizable .oleflns
of the typelof'styrene will under the in?uence of _ "hydride and styrene may be represented by the
v‘formula.
actinic. radiation react to form clear and hard
resins which are relatively insoluble and substan
‘ tiallyjfree of 'voids} Theseresins are well adapted
for molding, cutting, pressing, or'otherwise form-'‘
'ing into bodies of great beauty. The resin-form
Where :0 represents the number of the foregoing Y
ing reaction may be carried out completely or at
groupsin the molecule and is of ‘variable value.’
‘Since the reaction isgeneral in character and
applies to many unsaturated dicarboxylic acids
or anhydrides; ‘i. e., substituted maieic or fumaric
least in its final stages bycasting the'reacting -
mass in a suitable mold, thus obtaining directly
the ?nally desired object.
_
However, considerable dimculty has been ex
perienced in adequate plasticization of'the resin
in order? to obtain clear, hard and tough, bodies,
that maintain that condition over long periods of
time. Very few plasticizers are adequately com
' acid and to' many of the polymerizable ole?ns, the
3
product may be represented by the type formula:
patibleito admit of'satisfactory use and those
that are compatible usually are too volatile to ad
mit of permanent plasticization.
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where the groups R1, R2, ‘R3, R4, R5, R6, may be
practically any of the possible substituent groups.
The present invention is based upon the dis
covery that methyl‘ levulinate is of outstanding
Ex'amplesof a few. of the possibilities include hy
' merit as a plasticizer for resins of the foregoing
type. It can be incorporated with the reactants
' prior to or during polymerization, but preferably
'drogen and chlorine, carbonyl, carboxyl, alkyl,
'
aromatic and the like groups. Examples of pos
$407,413
4
under heat and pressure, or the comminuted ma
slble ethylene a p dicarboxylic acids or ethylenic
dicarboxylic acids which are transi'ormable to
a 5 form, which may be'employed, include 'maleic
acid (above described), fumaric acid, the mono
terial may be mixed with further polymerizable ‘
' material which by appropriate treatment will be
converted into hard bonding resins. Oil-soluble ' V
UK ' dyes, such as Thodamin B. Victoria Green and
pigments such'as titanium dioxide may be incor- '
alkylated maleic and fumaric ' acids, such as
or di chloro substituted maleicland fumaric acids,
porated into the resins prior to ?nal solidification.
The ‘new resins may be employed in the for
itaconic, citraconic acid, mesaconic acid,'mono
and di phenyl maleic acid, benzyl maleic, dibenzyl
mation of optical lenses, jars, or lids for jars for
maleic, ethyl maleic, or any similar acids con
taining ‘a doublebond in the chain between the 10 cosmetics, drugs,’ foods and the like. They may
be cast or cut to form an in?nite variety of han
two carboxyl groups.
dles, buttons, and objects of similar nature, or
The number of polymerizable ole?nic com-.4
pounds is also very large and of general charac
ter. It includes styrene above described, vinyl
acetate, vinyl chloride, methyl styrene, parahy
cast about specimens or objects of art to effect
an embedment thereof. They may also be used
15 for the formation of panels and coverings for
electrical apparatus of a great variety.
Application of the principles of the invention
droxy styrene, acrylic acid, methyl, ethyl, or other
esters of acrylic acid, acrolein, unsaturated ke
_ is illustrated by the following example:
tones, such as methyl vinyl ketone, indene, cou
marone and the like.
It is to be understood that anyone or‘ more of 20
Example I
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Grams
the dicarboxylic acids can be combined with any
Maleic anhydride __________ ______; _______ __
25
one or more of the ole?nic compounds, to pro
Styrene
35
_____ _~_ ________________________ ..
vide resins in great variety. The ratio of the di
Methyl levulinate _______________________ __ 30
carboxylic acid to the ole?nic compound is sus
In the above example the mixture was Prefer
ceptible of wide variation, but for purposes of 25 ably brought to a temperature sufficient to ob
illustration may be considered as approximately
'tain mutual solution of the components. Poly
molar.
\
merization'was then effected by irradiation with
‘ As previously stated, the reaction can be con-.
The rate of polymerization was
ducted in the absence of solvents. However, in
controlled by increase or decrease of the intensity
some instances it may be preferable to dissolve or 30 of irradiation and/or; the temperature. It can be
admix the reactants and the plasticizer with sol
brought to completion by irradiation with direct
vents such as triacetin, acetone, methyl ethyl ke
‘sunlight for a few minutes (15 or 20), followed
tone, ethyl aceto acetate, diacetone, acetic anhy
by exposure to ‘subdued light for some six hours.
dride, mesityl oxide, or any other solvent for the
These exposures may take place at room tem
reactants.
‘
' actinic rays.
35
oxidizing agents such as benzoyl peroxide‘may .
be employed to speed up reaction of the resins
forming materials. Reducing agents, such as hy
droquinone pyrogallol, tannic acid, etc., maybe
‘ employed to retardreaction.
The solvents in many cases are imbibed in the
resinous reaction product without dissolving the
latter and when so incorporated can not readily
be removed ‘by evaporation. Therefore, they may
perature oi: slightly above, if so desired.
The
product, may also be ‘further hardened by
heating.
But slight distortion takes place during poly
merization. The resin is of exceptional clarity
and is not subject to change of color upon aging.
All of these qualities combine to provide a resin
par excellence for embedding specimens, such as
insects, flowers and biological specimens. An ob
ject, such as a beetle can be introduced into a
be retained as permanent components of the res 45 solution
of styrene and maleic acid or anhydride
inous body. The bodies still retain their clarity,
aplasticizer in a container'of suitablev
hardness and toughness and usually are bubble _ containing
size and shape and. the reaction to form the solid
free. The solvated resins may be hardened by
resin effected, at temperatures sufliciently low to
baking them for a shorttime.
obviate damage to the specimen, merely by mild
As previously stated, the resinous bodies are in 50 irradiation. There is no damage to the specimen,
soluble, but it is possible to cast incipiently poly
due, to shrinkage and distortion of the medium
merized masses into molds in which hardening
during setting. The reaction is sufficiently rapid
to final form is effected. It is also possible to
to be commercially feasible.
I
conduct polymerization in molds formed of soft
Example II
glass, Pyrex, or other material transparent to ac 55
tinic rays. Likewise it is possible to introduce
A sample of a solution from Example I was
reactive mixtures containing at least a portion of
‘placed between two glass plates of soft gloss and
irradiated material into opaque molds of rubber
irradiated for one hour as described. The resin
or plaster and then to complete polymerization. 1 formed as a thin film between the plates which
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It is also possible to heat the resins .to the soft 60 were not easily separated.
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' ening point and then to press them to shape.
A further application of the invention consists ,
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Example III,
A portion of the solution of Example I was
in providing a layer of» polymerizable materials
irradiated for ?ve minutes until it had congealed
and plasticizer between two sheets of glass. By
irradiating this glass, it is possible to form a film 65 to incipient gellation (the mass could still be
poured). This enabled more of the material to
of transparent closely adherent resin between the
be placed between the plates. During the second
glass sheets, thus forming a safety glass. The
15 minutes of irradiation,‘pressure was applied
materials may be partially polymerized prior to
to the plates: The ?nished plates adhered well
application to glass. In a similar manner this
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class of resins maybe employed in the lamina 70 and shattered with difficulty.
In the foregoing examples the vdicar'boxylic
tion of wood, fabrics or other materials.
acids and their anhydrides are to be considered Resinous bodies can be cut to any’ desired
as equivalents, since each anhydride is derived
form and then polished to provide a great variety
from the acid merely by elimination of a mole
of’ articles. . The resins and‘ scraps. of the resin.
may be shredded lor powdered and then molded 75 of water and, the ester. is the. same regardless
2,407,413
5. A method of forming a hard, strong plas
01' whether the acid or the anhydride is employed.
Therefore, the term anhydride in the claims in ' vticized 'styrene-maleic anhydride resin which
comprises conjointly polymerizing about 35 parts
cludes the acids and the term acid includes the
anhydrides.
by weight styrene and about 25 parts by weight
The embodiments of the invention herein de- .
scribed are merely exemplary and numerous mod
i?cations may be madetherein without departure
of maleic anhydride in solution in methyl levu
linate to form a resinous body in which the
methyl levulinate is imbibed as a plasticizer.
6. A process as de?ned in claim 5 in which
, from the spirit of the invention or the scope of
the appended claims.
the methyl levulinate is in a ratio of about 30 -
10 parts by weight.
What I claim is:
1. A method of forming clear; hard and strong
maleic acid and methyl levulinate and then sub-.
7. A process as de?ned in claim~5 in which
the polymerization is‘ effected by irradiating the
solution with light at about 20 to 50° C.
a.v A process as de?ned in claim 5111 which
jecting the styrene and maleic acid to polymer
polymerization is e?'ected by heating the solu- ‘
ization‘to form the-resin in the presence, of dis,
tion to reaction temperature.
plasticized bodies ofv styrene-maleic anhydride
resin, which method comprises admixing styrene,
9. A process as de?ned in claim 5 in which
solved methyl levulinate.
I about 30 parts by weight of methyl levulinate is
2. A process as de?ned in claim 1, ‘in which
polymerization is effected byv irradiation of the
reactants with actinic rays.
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3. A method of fanning clear, hard and strong
rplasticized bodies of styrene-maleic anhydride
employed and the polymerization is effected by
irradiating the ingredients with actinic rays at
a temperature of about 20 to 50° C. ~'
10. A process as de?ned in claim 5 in which
polymerization is effected by heating the mate
, resin, which method comprises mutually dissolv
rials approximately to the range of 100 to 200° C.
' mg heating ‘maleic anhydride, styrene and
11. A process as de?ned in claim 5 in which
, methyl levulinate, then polymerizing the maleic 25
‘the methyl levulinate is in a ratio of about 30
anhydride and styrene in the solution to form
said resin‘.
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4. A process as de?ned in claim 3, in which
the polymerization is effected by irradiation with
actinic rays 'at a temperature 01 about 20 to 30
50° C.
‘
~<
parts by weight and polymerization is effected by
heating the materials up to a temperature within
the approximate range of 100 to 200° C,
HOWARD L. GERHART.
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