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Патент USA US2130800

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v‘Patented SephZO,‘ 1938
I
.
' UNITED'STATES- PATENT OFFICE
HYDROGENATED 'RESINS
’Harold S. Holt, Wilmington, Del., assignor to
E.v I. du Pont de Nemours & Company, Wil
' mington, Del., a corporation of Delaware
' No Drawing. >‘pplication November 24,1937,
'
-
.
Serial No. 176,231
13 Claims. (c1. 260-_-2)'
This invention relates to the manufactured the mercury. The temperature of the mercury
resinous materials and more particularly to the
at a point near the end of the‘wire at the instant
preparation of arti?cial resins, both liquid and] the cube appears at the surface, is multiplied by
solid, which are resistant to deterioration by the the arbitrary factor of 1.25 and 2° is added to
5 action of light and heat.-
.
'
‘
U.- S. Patent No. 2,055,708 describes the preparation and properties of certalnjresinous materials which may be made from dihydronaphthaleneand homologues thereof. These resinous
£10 products may be prepared by subjecting, for example;1,2-dihydronaphthalene, 1,4-dihydronaphthalene or a mixture thereof of the action of a
the product to give the apparent melting point
a,
in degrees centigrade. ‘For example, if the mer
cury temperature is 100° C. when the cube -ap
pears on the surface, the apparent melting point
will be (100°><1.25) +2", or 127° C. The melting
points stated herein refer to those obtained by 10
this method. By using as starting material dif
ferent " isomers or mixtures and by producing
solution of the alkali metal addition compound of _ mixtures containing the different polymers, resin
naphthalene or other polycyclic aromatic hydro- ous materials may be obtained from dihydro
l5_ carbon, 'as- described in the above mentioned naphthalene or its homologues, having different 15
patent. The resinous productis recovered by' apparent melting points or di?erent degrees of
distillingo? solvent and unpolymerized material.
These resinous materials described in Patent
No. 2,055,708 are polymers of the hydrocarbons
20 from which they are made; for example, those
hardness~ or viscosity at room temperature.
. The above described'resinous polymersof the
dihydronaphthelenes and their polymers, when
freshly prepared and free from impurities, are 20
made from dihydronaphthalene are polymers of" > clear, transparent and colorless. The solid forms
1,2-dihydronaphthalene or 1,4-dihydronaphtha-~ have the appearance of colorless, crystal glass,
lene or mixtures of these. The polymers are liquid or‘solid, depending on the degree of poly25 merization. ~For example, the dimer of 1,4-dihy- dronaphthalene is a viscous liquid at room tem- .
except for a slight ?uorescence. When impure,
they may have a coloration varying from light
yellow to amber, depending on the degree of 25
impurity._
However, these materials are more
perature, while the tetramer is aybrittlei solid. ' or less subject to actinic e?ects and usually be
These resinous materials,.like resins in general, .- come colored or‘ have their color deepened on '
-> do not have the de?nite, sharp melting points' exposure to heat and vlight, especially ultraviolet
'30 characteristic of crystalline compounds, but grad; light. In a number of uses for which Such resins 30
.
ually' change from the solid state to viscous liquid are well adapted, this lack’ of stability to light
' when suitably heated, the viscosity of the melt
.
is a distinct disadvantage-
'
slowly decreasing as the temperature is ‘raised.
An object of the present inventionis to provide
The'term “melting point" or ‘.‘apparent meltingv
means for stabilizing the above described resin- 1
35 point”, as used herein with reference to these
.resinous materials, and also to the products of
the present invention hereinafter described, refer
. to the temperature at which’ apparent liquefac'tion commences. ’ Such apparent melting point is
40 determined by a standardized procedure known
ous polymers of dihydronaphthalene and their 35
homologues against actinic action- A further
object is to prepare substantially transparent,
colorless or light colored resinous materials which
are stable to light and heat. My invention also
comprises the novel resinous products obtained 40
as the “cube melting point method”, which is
generally applicable to various resinous sub-
by my (process hereinafter‘ described. Further
objects will be apparent from the following de
‘stances.
scription.
In this method a 1/2 inch‘cube of the
.resin' is cast in a, mom on the end- of a, brass
.
The above objects are attained in accordance
-
45 wire 0.1 inch in diameter. The wire is bent at with the-present invention by hydrcgenating the 45
right- angles one inch from the end on‘ which above described resinous polymers of dihydro
the cube is cast, the end of the wireextending ' naphthalene and its homologues. I have found
through the center of the cube. When the cast
that the resulting hydrogenated products are
, cube'has solidi?ed, it is removed from the mold
‘very stable to light. By a proper degree of hy
v50 -and,rwhile stillhot, is suspended one inch below
drogenation, I am able to produce colorless resin- 50
ythe'surface of a body ‘of mercury which has been
ous materials‘which show no trace of color after
‘heated to 6(_)~to .90" vC., the main portion or the
exposure to ultraviolet light of high intensity for
suspending wire being in'avertical position. The '- many hours, whereas the parent material be—
mercury is then heated at the r'ateof 3° C. per comes highly colored by exposure to the sam
56 minuteuntil the cube appears at the surface of
light in a relatively short time.
_
"
'55
2,130,800
2
Although the dihydron'aphthalene polymers are
resinous in character, I have found that they
can be hydrogenated readily unden suitable con
ditions. A method which I have found particu
larly effective consists in dissolving the polymer
in a hydrocarbon solvent, ,e. g. decalin (decahy
dronaphthalene), an ether solvent, e. g. dimethyl
ether of ethylene glycol or other suitable solvent
and applying hydrogen under pressure at 200 to
10 300° C. in the presence of a hydrogenation cata
lyst, e. g., ?nely divided nickel. Attemperatures
below 200° C., the polymers absorb hydrogen rela-_
tively slowly. A preferred temperature range
for rapid ‘hydrogenation is 240 to 275° C. .How
ever,fhydrogenation at temperatures below 200°
vC. may‘ be carriedout effectively if the reaction
‘is continued ‘for a suf?cient ‘length, of time. Hy
drogen pressures of 1000 to 2000 pounds per
square inch have been'found to be suitable for
20
effective and rapid hydrogenation. The various
known hydrogenation catalysts may be used, for
example, finely divided nickel. A‘catalyst con
centration of, for_ example, '7 to 35 grams per
liter of the polymer solution is satisfactory. If
desired, the polymers may be hydrogenated with
out the use of a solvent, by operating at tempera
tures at which they are in the liquid state. How
ever, because of the viscous nature of the poly
mers, I prefer to hydrogenate them in solution,
to 3.25 moles of hydrogen per mole of C1oI-I1o in
the resin.
-
/0n the other hand, the decolorizing effect de
scribed above oftenv may be obtained by a very
light hydrogenation, e. g. the introduction of 0.5v
to 1 mole of hydrogen per mole of CinHm. The
increase in heat stability varie's directly with the
degree of hydrogenation, the heat stability grad
ually increasing as the amount of‘ hydrogen in
troduced is increased. ,
‘
It has further been found that the hydrogena
tion increases the melting points of the polymers
and the increase in melting point varies directly
with. the amount of hydrogen introduced. This
result was surprising and unexpected, since hy 15
drogenation of cyclic organic compounds regular
ly lowers the melting point. For example, naph
thalene is a solid, melting at 80° C., while its hy
drogenation products, dihydronaphthalene, tetra
hydronaphthalene and decahydronaphthalene are 20
,all liquids at 20° C. In general, the melting point
,of the polymer will be increased by my process
about ‘14° C. for each molev of hydrogen intro
duced per mole of CIOHIO. Thus my method en
ables the preparation of resins of different melt 25
ing points, as desired, over a wide range; The hy
drogenated resins made by my process may range
from viscous liquids to solid materials having ap
parent melting points up to about 200° C. A par
30 especially the vpolymers of higher molecular ticularly useful group of products which may 30
thus be prepared are those having apparent melt
' weight. Various modi?cations of the above de
scribed hydrog'enating. process will be apparent ing points of 100 to 200° C. .These are brittle,
glass-like materials which may be utilized in a
to those skilled in hydrogenation of organic com
pounds.
35
_- '
The hydrogenated products made by the pres
ent. invention may contain three or more moles
of added hydrogen (Hz) for each mole of dihy
dronaphthalene _(C10H10)
originally present.
Thus, where a polymer having the empirical‘ for
mula: (CmHw) 1; is hydrogenated, the'product will
have the empirical formula (C10Hl0+$)1|., where
:1: represents a number between zero and 8. Thus,
products have been obtained containing _more
than 3 moles of ‘added hydrogen per mole of
45 (2101110. The degree of hydrogenation may be
variety of resin compositions for imparting hard
ness to the'mass.
v35
.
The hydrogenated products, of the present in
vention exhibit excellent stability toward both
light andheat. For example, a clear, transpar
' ent, colorless, glass-like resin was _made by hy
drogenating the tetramer of 1,4-dihydronaph 40
thalene‘ until hydrogen absorption was substan
tially complete, the amount of hydrogen absorbed
being equivalent to about 3 moles of hydrogen
per mole of CioHm. ,This' resin, after exposure
outdoors in an unshaded location for a period 45
varied .as desired. I prefer to carry on the hydro-' of 18 months was substantially unchanged and
genation until 1 to about 3.25 moles of hydrogen - developed no color. , Samples of the unhydrogen
per mole of CmHm have been absorbed. ,The hy-. _ ated polymer developed a yellow color. - This
drogenated product is generally colorless and, hydrogenated polymer of _ 1,4-dihydronaphthalene
also showed substantially no development of color
50 when sufficiently hydrogenated, is very stable to" ' or other change in properties when exposed to
'light and heat. It has been found thatthe unhy
an intense ultraviolet radiation for four hours.
drogenated polymers which are colored as pro
duced or which have become colored or darkened ‘
. by the action of heat or light are greatly improved
55 irr appearance by ‘my hydrogenation process.
Thus, a colored resin may be changed to‘ a color
less or only very lightly colored, light-stable prod
not by the hydrogenation. Because of this fact,
'my process is of value for reclaiming 'colored,.
In this test the sample was placed 71/2 inches
from the source of ultraviolet‘ light, which con
sisted of a “Uviarc” quartz mercury vapor are 55
lamp (manufactured by the General Electric ‘
Company) operating on ‘a 110 volt D. C. current
of 4 amperes. This lamp was a vertical type,
having a vertical arc tube % in’ch inside diameter
and an arc length of 3 inches. Samples of the
unhydro'genated polymer developed a yellow color '
60 unsalable material.
It has been found that in order tov obtain a. after a few minutes exposure in the same ultra
light-stable _resin by my‘process, it is necessary violet light test. The above hydrogenated resin'
to’ carry the hydrogenation to a relatively high , also suffered no appreciable change when heated
6,5
degree. Thus, the‘ introduction of 1-2 moles of
hydrogen per mole of ClOHlO generally does not
appreciably increase the stability towards actinic
action.
Usually, it is necessary to introduce at
-least_ 2.5 to 3 moles of hydrogen per 'mole of
0101110, the minimum amount depending on the
particular sample. When this minimum point is
' reached, the hydrogenated product is very stable
towards-light. I prefer to hydrogenate the ma
‘ ‘ terial until it will absorb no more hydrogen,‘which
75 corresponds-to the introduction, in general, of 3
to ‘100° c. for 120 hours.
I
‘
-
65
In addition to the vabove described improve
ments caused by the hydrogenation, the ‘hydro
genated' resins differ slightly from the unhydro
genated material in respect to solubilitysin variou‘s
Generally, the hydrogenation 70
increases _the solubility in hydrocarbons but de
. organic solvents.
creases the solubility in oxygenated solvents such
as esters or ethers.
_
’
'
In the appended claims the term “dihydro
naphthalene qhomologue”'is intended to include 75
8,180,800
dihydronaphthalene itself, as the ?rst member
of-the homologous'series. The other ‘homologues
include the.various alkyl derivatives ofdihydro
naphthalene, e. g. methyl dihydronaphthalene,
ethyl dihydronaphthalene, dimethyl dihvdro~
3
7. The process comprising reacting a resinous
polymer of dihydronaphthalene homologue with
hydrogen until at least 2.5 moles of hydrogen per
mole of 'CmHm have been absorbed. ,
-
8. The process comprising reacting a solid,
naphthalene and so on, which may be polymer-' resinous polymer of dihydronaphthalene with
ized to resinous materials according to the method hydrogen until 2.5 to 3.25 moles of hydrogen per
of the above mentioned U. S. patent.
mole of C10H1o have been absorbed.
'Iclaim:
.
.
9. A hydrogenated, resinous polymer of a di
'
1. The process comprising hydrogenating a
resinous polymer of dihydronaphthalene.
2. The process comprising hydrogenating a
resinous polymer of 1,4-dihydronaphthalene.
3. The process comprising hydrogenating a
_resinous polymer of 1,2-dihydronaphthalene.
4. The process. ‘comprising reacting‘ a solid,
‘resinous polymer of. dihydronaphthalene with
hydrogen.
r
,
hydronaphthalene homologue.
10
l0._ A light stable, colorless, hydrogenated, res
inous polymer of dihydronaphthalene.
/
-
11. A light stable, colorless, hydrogenated, res
inous polymer of 1,4-dihydronaphthalene.
12. -A ‘colorless, transparent, hydrogenated, res 15
inous polymer of dihydronaphthalene which is
stable to ultraviolet light radiation.
13. A solid, colorless, transparent, hydrogen
5. The process comprising reacting a solid, . ated, resinous polymer of 1,4-dihydronaphthalene
20
resinous polymer of 1,4-dihydronaphthalene with which remains substantially colorless after being
20
hydrogen.
exposed for four hours to ultraviolet light radi
6. The process comprising reactinga resinous
'polymer. of dihydronaphthalene homologue with
hydrogen.
ated .from a quartz mercury vapor arc lamp.
mom) s. HOLT.
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