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Патент USA US2128136

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2,128,136
Patented’ Aug. 23, 1938
‘UNITED STATES PATENT OFFICE
COATING COMPOSITION
Walter E. Gloor, Parlin, N. J., assignor to Her-l’
cules Powder Company, Wilmington, Del., a
corporation of Delaware
1
‘ No Drawing.
Original ‘application September
23, 1936, Serial No. 102,163. Divided and this
application May 24, 1937, Serial No. 144,538
12 Claims. (Cl. 134-—79)
an esteri?cation
This invention relates to esters of aliphatic suf?ciently reactive to undergo
at a temperature below that at which‘
polyhydric nitro-alcohols with monobasic organic reaction
acids and to compositions in which such organic the aliphatic polyhydric nitro-alcohol is rapidly
a new group of chemical compounds which are
decomposed, such as, for, example, the lower
fatty acids, as, acetic acid, propionic acid, butyrlc
acid, benzoic acid, toluic acid, etc. The tempera—
entirely distinct from the aliphatic nitrates
polyhydric nitro-alcohol is rapidly decomposed,
esters are present as an ingredient.
I
An object of this invention is the ‘provision of
ture at which the rate of decomposition of an
of particular advantage as plasticizers for cellu
lose esters, as nitrocellulose, cellulose acetate, aliphatic polyhydric nitro-alcohol decomposes de
pends upon the particular alcohol and upon the
etc., cellulose ethers, chlorinated rubber, natural condltions'of reaction. It will, however, be found 10
l0 .resins, etc.
A further object of this invention is to provide that the rate of decomposition oi! an aliphatic
compositions of cellulose acetate plasticized with polyhydric nitro-alcohol in an esteriflcation me-'
monobasic organic esters of aliphatic polyhydric dium does not become rapid at a temperature be
nitro-alcohols which are particularly adapted for low 210° C. '
The anhydride of a monobasic organic acid
15 use as molding compositions.
which I may use to esterify the aliphatic poly
The new esters in‘accordance with this inven
hydric nitro-aicohol may be an anhydride of any
tion are esters of an aliphatic polyhydric nitro
alcohol, and are characterized by containing "monobasic ‘organic' acid, which is suiiiciently re
somewhere in their structure an aliphatic active to undergo an esteri?cation reaction at a
20 -—C.--NO2 group. This group of compounds is temperature below that at which the aliphatic
such as, for example, the anhydrides of acetic
acid, propionic acid, butyric acid, benzoic acid, '
toluic acid, etc.
- 25
The'esteri?cation reaction, in accordance with
{Ii/aromatic ring.
‘
’
_
The method in accordance with this invention ~ this invention, will desirably be carried out at a
which contain the group —-'C--O—NO2, and from
- the aromatic nitro compounds which contain the
7N6: group linked to a carbon atom in an
consists of esterifying an aliphatic polyhydric ' temperature below 210° C., and preferably within
nitro-alcohol with a monobasic organic acid or an the range of about 100° C. to about 150° C. The
anhydride of a monobasic organic anhydride. reaction will preferably be carried out in. ‘the 80
3° The aliphatic polyhydric nitro-alcohol which I presence of an esteri?cation catalyst, such as, for
may esterify is characterized by. containing
somewhere in its structure the -—C—~NO2 group
and two or more hydroxyl groups, and may be,
for example, trimethylol nitromethane, di
35 methylol nitroethane, tri-=alpha-ethylol nitro
methane, dimethylol nitropropane, dimethylol
nitrobutane, 1-1 dimethylol-1-nitro-4-hydroxy
butane, etc.
example, zinc chloride, p-toluene sulfonic acid,
benzene sulfonic acid, xylol sulfonic acid, sul
furic acid, pyridine, etc.
In the esteri?cation reaction, in accordance 35
with this invention, the removal of the water pro
duced in the reaction is facilitated by carrying
out the reaction under re?ux in the presence of
'
The aliphatic vpolyhydric nitro-‘alcohols which an azeotrope such as toluene, separating water
40 I may esterify may be conveniently prepared by from the condensate, and returning the azeotrope
the condensation of‘an aldehyde with an aliphatic
compound containing a nitro group, such as, for
, example, a intro-hydrocarbon, a nitro-alcohol,
etc. Thus, for example, dimethylol nitro ethane
- 45 maybe prepared ‘by the alkaline condensation
of formaldehyde with nitroethane._ Triethylol
nitromethane may, be similarly prepared by the
condensation of acetaldehyde with nitromethane.
Similar aliphatic polyhydric nitro-alcohols may,
59 .ior example, be prepared by the condensation of
formaldehyde with l-nitropropane, 2-nitropro
pane, l nitro-2-methyl propane, etc.
‘The monobasic. organic acid which I may use
‘to esterifyi'the aliphatic polyhydric nitro-alcohol
“inlay1bel“any,.monobasic organic acid which is
40
to the reaction. Alternately, the anhydride of
the acid of which the ester is desired, is reacted
with‘ the aliphatic polyhydric nitro-alcohol in
the presence of pyridine with 'or without one of
the other‘esteri?cation catalysts mentioned.
The following examples further illustrate the
method in accordance with this invention.
_
EXAMPLE I
Preparation of dimethylollnitroethane diacetate
50
One mol. (101 grams) ‘of dimethyl nitro
ethane'and 2.4 mols (144 grams) of glacial acetic
acid_were mixed with 75 grams of toluol and 2
grams of p-toluene sulfonic acid. This mixture 65
2
'10
2,128,136
56%, etc., cellulose acetopropionate, cellulose
acetobutyrate, ethyl cellulose, chlorinated rubber,
was boiled beneath a re?ux condenser provided
with a graduated tube for separating the water
given off by the reaction. The reaction was con
tinued until 37 cc. of water had separated out in
the moisture tube. The reaction mixture was
then boiled under vacuum to remove the toluene
etc., and will be found to be valuable plasticizers
in coating compositions and molding'plastics of
and the unreacted acetic acid, after which the
heat and vacuum were increased and the product,
dimethyllolnitroethane diacetate, is distilled over
in admixture with other plasticizers, as plasti
cizers in cellulose acetate plastics. These prod
as a clear colorless oil.
various types.
'
5
are particularly suitable for use either alone or
ucts give good colloiding and non-evaporating 10
1
properties in plastics and will be found to be
_ highly resistant to heat, light, and water, and to
EXAMPLE II
be good solvents for poorly miscible material,
I Preparation of trimethylol nitromethane tripro
such as triphenyl phosphate. }
pionate
15
’
The products in accordance‘ with this invention
' The following table illustrates compositions, 15
made in accordance ‘with this invention, which
One mol. (151 parts by weight) of trimethylol
are suitable for use as ‘molding plastics. .
nitromethane was re?uxed for three hours with
Table II
7.2 mols~ (938 parts by weight) of propionic
'20 anhydride in the presence of one mol. (79 parts
,ExampleNo.
by weight) of pyridine and 2.0 parts by Weight of
‘zinc chloride. This reaction mixtureywas then
cooled, poured into ice water and allowed to stand
until the unreacted propionlc anhydride is de
25 composed.
30
1
2
3
4~
6
G
7
20
8
Cellulose acetate (52% acetic acid) _.~ _ _ .
Dlmethyloi nltroethane dlpropio
mite ___________________ __~~_._-________
Dimethylol nitropropane dlpropio
This mixture was. then extracted
25
natc __________ __; ........... _____-.. .
Trimcthylui nitromethane tnaco
‘with ether, the ether extract neutralized, dried,
and the ether evaporated. The product is then
obtained in puri?ed form by vacuum distillation,
and is trimethylol nitromethane tripropionate.
'i‘rhncthylol nitromethanc tripro
The chemical formulas and properties of rep
resentative products in accordance with this in
'I‘riethyloi nitromethane diacetate-
trite _____________________________ _.
pionatc ............... ____ ........ __
.
Tritmethylol ‘nitromethnne tributyr
a e ______________________________ ._
Dimethylolnitroethanediacetnte.-.
Methyl phthalyl methylglycollate“
T'iphimphi’sphm’ """"""" "
vention are given in the following table:
Table I
85
85
Name
Formula
‘
}
Trimethyiol nitromcthane triacetate ............. -.
83;’:5
~32-21:?‘
332231181:
26 O.
0.
5-10mm.
mcoodcm
.0.
CHLCOOCHF- —N01
-
Hi
000.011,
_
‘o
4 1. 289
1.4585
100-170
1.171
1. 4480
170-185 ‘6
_
mcoo 0.0111011.
45
Trimethylol nitromethane tripropioriate.._'1 ..... ..
CH;.CH1.C00.CHr-C—§N01
H1
,
A
000431110111
7
mcoocomeincm
Trimethylol nltromethane tri-butyrate .......... --
cmomomcooom-c-rro.
’
50
'
H1
H1C.OO(_'J.CH1
Dlmethylol nitroethana diaeetate........
...... -.
CH1. —No,
,
1.115
1.4480
186-116’
DOC-CHl-CHa-CH1
-
I
5o
‘
1.20
1. 4425
152-100
1.142
1.460
160-166
1.152
1.4363
135-168 00
1.4467
6‘
H. .oo'ccm
H|C.OOC.CH1.CH1
55
Dimethyiol nitroethane dipropionata ............ .-
CH1.
.NO,
'
55
H: .0OO.OH|.OH|
, ‘K100000150
60 Dimethylol nitropropane diacetute .............. -'
CH1.CH1. .NO|
H1
ooccm
0H:
65
_
.
cmcnoodcm
Tri-oipha-cthylol nitromethenelrlacetate ........ _. CH1.COOC—- —-NO1.
c1:1—ooo.cm '
(‘1H1 ,
70
The products in accordance with this invention I
Plastics may be prepared from the above com- 70
are soluble in aromatic hydrocarbons, alcohols, positions by colloiding the composition, as, for
esters, and ketones; They are compatible with example, with the ‘aid of a mixture of equal parts
nitrocellulose of various types, as the ester- alcohol and acetone on a differential two-roll mill.
soluble, and the alcohol-soluble type, cellulose The plastic so produced may be sheeted and then
75 acetates of various acetic acid contents, as, 52%, molded‘ into the desired form, and will be‘ found 75
3
8,188,186
to be tough, water-resistant, well bonded and of
good clarity.
.
It will be understood that the details and ex-v
amples hereinbeiore set forth are illustrative only,
and that the invention as herein broadly de-v
scribed and claimed is in no way limited thereby.
This application is a division of my application,
Serial No. 102,163, ?ied September 23, 1936.
What I claim and desire to protect by Letters
10 Patent is:
1. A composition of matter comprising an ester
of an aliphatic polyhydric nitro-alcohol with a
monobasic organic acid and a cellulose deriva
15
tive soluble in organic solvents.
'
2. A composition of matter comprising an ester .
of an aliphatic polyhydric nitro-alcohol with a
-monobasic organic acid and a cellulose ester;
3. A composition of matter comprising an ester
of an aliphatic polyhydric nitro-alcohol with a
20 monobasic organic acid and cellulose acetate.
4. A composition of matter comprising an ester
of an-aiiphatic polyhydric nitro-alcohol with an
6. A composition of matter comprising an ester
or an aliphatic polyhydric nitro-alcohol with
acetic acid and cellulose acetate.
7. A composition 0! matter comprising an ester
0! an aliphatic polyhydric nitro-aicohol with
propicnic acid and cellulose acetate.
8. A composition of matter comprising an ester
oi! an aliphatic polyhydric nitro-alcohol with
butyric acid and cellulose acetate.
9. A composition of matter comprising tri
methylol nitromethane triacetate and cellulose
acetate.
‘10. A composition of matter comprising tri
methylol nitromethane tripropionate and cellu
lose acetate.
-
' lower fatty acid and cellulose acetate.
15
-
11. A composition of matter comprising tri
methylol nitromethane tributyrate and cellulose
acetate.
‘
v
.
.
‘
12. A composition oi- matter comprising an
ester of an aliphatic polyhydric nitro-alcohol with
a monobasic organic acid and a solid ?lm-form
ing material selected from the group consisting
of cellulose esters, cellulose ethers, chlorinated
aliphatic monobasic organic acid and cellulose
rubber and natural resins.
acetate.
5. A composition of matter comprising an ester.
25
of an aliphatic polyhydric nitro-alcohol' with a
'10
‘
WALTER a. moon.
25
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