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Патент USA US2409345

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Patented 0a. is, 1946
' 2,409,344
UNITED STATES PATENT OFFICE'
2.409.344
msrrcrzmo. cnnoaornnua POLYMERS
Arnold R. Davis, Riverside. Conn., asslgnor to
American Cyanamid Company, New York,
N. ‘2., a corporation of Maine
No Drawing. Application January '1, 1943,
Serial No. 471,605
4
12 Claims‘. (Cl. 260-36)
-
2
1
This invention relates to plasticizing polymers
.
guanidine salts of the disubstituted .dithiophos
phoric acids, the organic base being substituted
of chloroprene (chloro-2-butadiene-1,3) .
It is known that certain products .made by
chloro-2+butadiene-1,3 in the
presence of sulfur may be plasticized by milling
for Y in the above formula:
polymerizing
-
i
To illustrate the effectiveness of the plasticizers
of the present invention, a 400-gram sample of
with diarylguanidines, organic sul?des, disul?des,
Neoprene GN was milled for a total time of 10
aromatic mercaptans, dithiocarbamates, Kan
thates and the like. The unplasticized polymers
minutes on rolls with an initial temperature of
are sometimes referred to under the trade name
temperature. This sample was used as a control. ‘
“Neoprene.”
50° C. and the sample was then cooled to room
10 A similar sample of Neoprene GN was milled with
}
The plasticizlng of Neoprene with chemical
compounds outlined above has certain disad
the gradual addition thereto or a small amount
of one of the plasticizers of the present inven
tion, the rolls having an initial temperature of
of diarylguanidines, a prolonged aging period is
50° C. and the total milling time being 10 minutes,
required for maximum plasticity. Such disad 15 the sample then being cooled to room tempera
vantages are obviously objectionable in the eco
ture as before.
.
‘_
.
The milled samples were tested in 9. Williams
nomical-manufacture of finished products in as
short a time as possible.
plastometer for e?ectivenes's of the compounds
as plasticizers for the Neoprene.‘ A 3-minute “Y"
It is an object of- the present invention to pro-.
vantages such as high cost and, in the case
vide new and improved materials for increasing 20 value in inches at 100° C. was employed‘forthe
the plasticity of polymers of chloro-2-butadiene
tests. The lowest “Y” value indicates the softest
1,3, particularlyg those polymers (or‘ types of
Neoprene) which can be plasticized by the prior
art compounds referred to above. A further ob-
ject is to render the Neoprene highly plastic
without extensive milling.
-
These and other objects are attained by‘ milling
the chloroprene‘ polymers with asmall amount
of organic base salts, of disubstituted dithiophos
phoric acids, said salts having the following
‘ or most plastic stock. The results obtained were
as follows:
-
'
25
Percent
"Y" value
plastlcizer
ininches
Neoprene GN—control ................ ..
p-myrlstoyl ethoxy isothiourea dibutyl
dithioghosphate ..................... ..
30
None
Guenid e d butyl dithiofihos hate"-..
Guanylthioureo dibuty d tliiophos
formula:
.
_
0.100
‘
0.5
l
.070 ‘
0.5
.008
hate ............................... ..
0.5
.061
hospna
0.6
.072 -
D ortho .olyl gusnidine dibutyl dithio
........................... ._
ono pnenyl guanidine dibutyl dithio
ghosphate ........................... ._
0. 6
. 070
dithiophcsphoric acid ............... -_
0.5
.075 ;
35 B (2 cyanoethyl) amine salt of dibutyl
R——0
where R is alkyl, aryl or aralkvl. Y is selected
from the group consisting of aliphatic secondary
Diphenyl gusnldine di~isopropyldithlo- A
amines, aromatic primary amines, cycloaliphatic
p-Phenylene iguanidlne salt of dibutyl
amines, heterocyclic imines and compounds hav
ing the following structural formula:
40 Guanidinedl- opropyldithio hosphste.
Biguanide salt of dlbutyl d thiophos
05
/
,
R1
.070
.053
thiophosphoricacid ................ _.
0.5
.070 s
Aniline dibut ldithiophosphate ....... ..
0.5
.083
hos horlc acid ..................... ..
B s (et oxypropyl) amine salt ofdibutyl
l“
dithiophosphoric acid ............... ..
,
-
-
phosphoric acid ..................... ._
Piperidine salt of dibutyl dithiophos
phoric ac .......................... -.
Phenyl biguanide bis dibutyl dithio—
in which R1 is hydrogen or like Ra, R4 is hydrogen,
an aromatic, thiazyl or an aliphatic radical, X
‘’ ‘
""58
0.5
.072
.
0. 5
. 070
0. 5
. 008
0. 5
.066
—-NH-C-—NH:, -—NH—-(I}—NH| or -Nn-c-Nm
. 074
phosphate ..... -_'. ................... --
0. 5
. 093
phate __________________ .. ........... __
1.0
.OBl
Aniline-dlcryandlamide-dibutyl
hos ho eacidreactionproductdithio
_____ ..
1.5
P eny bigusnide di-isopropyl dithio-
R3 is an aliphatic radical and R4 is an aromatic
radical. These plasticizers include the guanidine, .
biguanide, guanylthiourea, isothiourea and dlaryl
0. 6
50 Pheny biguanide dlbutyl dithiophos-
H
-
phosphate ___________________________ . .
Phony blguanide diamyl tetra thio
‘
.
55
057
‘
phosphate ___________________________ ..
1.5
.050
cyandiamldemction product ....... ..
1.5
052
iline di-isopropyl dithiophoeplmte-di~
v1
.015 l
45 Cyclohexyl amine salt oi‘ dibutyl dithio-
uu= -x
is —SR3, —NH2, --NHR4,
5
l 5
rimmiticmu'‘arias?iazn'"
‘any
guan e‘
o
u y
o-
N
1
‘phosphate ........................... ..
Aniline di-iso ropyl dithiophosphata.-.
-
4
Percent
"Y" value
plasticiur
Bis (oyanoethyl) amine dibutyl dithio
phosphate-d cyandiamlde
reaction
in inches
dibutyl
phosphate-dicyandiamide
. 062
phosphate ___________________________ -.
0.5
. 071
dicyandiamide reaction product _____ . .
1.6
. 058
Phosphoric
acid-aniline-dicyendiam
do reaction product _________________ _.
L5
D lauryi dithiophosphoric acid-aniline
y
,
0.060v
dithio
reaction
1.5
A
such as is obtained with the palmitic acid referred
to in the last compound in the tabulation.
Stearic, oieic, lauric and similar acids may be used
_
1 5
product ....... _'_ .................... ._
Aminobenzothiazoie
471,606, ?led January 7, 1943. These salts may
include various long chain fatty acid radicals
alcohol-methyl hexanoi dithio- .
Suitable modi?cations and ‘changes may be
made in the invention without departing from
the spirit and scope thereof, the foregoing de
10 scription being intended only by way of illus
tration except as de?ned in the following claims.
I claim:
'
dithiophos horic acid react on roduct.
‘Bis (cyanoet yl) amine-dlcyand amide
methyl hexanol dithiophosphoric acid
reaction product ____________________ _.
Diorthotolyl guanidino-methyl heranol
dithio hosphate ..... -_' ______________ __
Phenyl iguanide methyl hexanol dithio
acid reaction product ................ . _
' prene polymer which comprises mixing the poly
mer with a minor proportion of its weight of a
1.5
salt of a dialkyldithiophosphoric acid and a salt
formlng organic base selected from the group
, consisting of the aliphatic secondary amines, the
2
see
I i. 0
. 072
11.0
.060
l. 5
"
mononuclear aromatic primary amines, the cyclo
20
Reaction product of aniiine-dicyandi
amide-dithiophosphoric acid made
from a mixture of amyl alcohol, pai
mitic acid and octadecanol ........... _ _
.
1.5
1.5
phosphate ........................... . _
.
l. A process of softening a rubber-like chloro
Aniiine-dicyandiamida-meth l hexanol
Auiline-dicyandiamida-but l ether of
diethylene glycol dith ophosphoric . .
in the same manner.
aiiphatic amines, piperidine, guanidine, the
mono- and di- mononuclear aryl guanidines, bi
guanide, the mono- mononuclear aryl biguanldes,
guanylthiourea and isothiourea,
2. A process of softening a rubber-like chloro
1The initial roll temperature was 40° C. with these 25
products.
I
mer with about 0.5-5.0 percent of its weight of
a salt of a dialkyldithiophosphoric acid and a
It is apparent from the above tabulation that
the salts of the dialkyl dithiophosphoric acids
are effective plasticizers for chloroprene polymers.
In the tabulation, the amount of plasticizer used
is given in percent by weight based on the weight
of Neoprene used in the formulation.
A portion of each of the plasticized rubber-like
polymers was mixed with light magnesium oxide,
carbon black, zinc oxide and an antioxidant and
vulcanized in the conventional manner. The rub
ber-like flexible vulcanizates had good physical
properties.
salt-forming organic base selected from the group
consisting of the aliphatic secondary amines, the
mononuclear aromatic primary amines, the cyclo
aiiphatic amines, piperidine, guanidine, the
mono- and di_ mononuclear aryl guanidines, bi
guanide, the mono- mononuclear aryl biguanldes,
guanylthiourea and isothiourea.
3. A method of softening a rubber-like chloro
prene polymer which comprises mixing the poly
mer with a minor proportion of a phenyl-bi
guanide salt of a dialkyldithiophosphoric acid.
4. A method of softening a rubber-like chloro
'
Aniline - dicyandiamine - disubstituted
prene polymer which comprises mixing the poly
dithio- <
phosphoric acid reaction products are believed 40 prene polymer which comprises mixing the poly
to be the phenyl biguanide salts of the acids used
mer with a small amount of an organic base salt
and may be represented by the formula:
comprising an aniline-dicyandiamide-dialkyldi- '
thiophosphoric acid reaction product.
5. A method of softening a rubber-like chloro
4.
prene polymer which comprises mixing the poly
mer with a small amount of a phenyl biguanide
where F is alkyl, aryl or aralkyl as before.
As
salt of di(methylhexyl) dithiophosphoric acid.
pointed out in Application 471,606, the di-ortho
tolyl guanidine salt of dixylenol dithiophosphoric
prene polymer which comprises mixing the poly
acid is also suitable as a softening agent,
mer with a small amount of an organic base‘ salt
The amount of softening agent employed may
be varied and in general will be governed by the
particular softening agent selected and the extent
to which softening of the chloroprene polymers is
desired. In general, the amount of plasticizer
may be from about 1/2 % to about 5% based on the
comprising an aniline-dicyandiamide-di(methyl
hexyDdithiophosphoric acid reaction product.
weight of the chloroprene polymers.
Larger
_ amounts of the plasticizers may be used although, '
in general, excessive amounts above 5% do not
give correspondingly increased plasticity.
.
These plasticizers are also valuable fOr use in
reclaiming vulcanized and scrap Neoprene, The
Neoprene is merely ground in a tight cold mill and
then milled with about 21/2% of the plasticizer
on rolls at about 40°-50° C. until a suitable sheet
is formed. The cured reclaim has almost the
6. A method of softening a rubber-like chloro
7. A rubber-like plastic mass comprising a mix
ture of a. chloroprene polymer and a minor pro
portion of its Weight of a salt of a dialkyldithio
phosphoric acid and an organic salt forming base
selected from the group consisting of the aliphatic
secondary amines, the mononuclear aromatic pri
mary amines, the cycloaliphatic amines, piperi
dine, guanidine, the mono- and di- mononuclear
aryl guanidines, biguanide, the mono- mononu
‘.clear aryl biguanides, guanylthiourea and isothio
urea.
8. A rubber-like plastic mass comprising a mix
ture of a chloroprene polymer and about 0.5-5.0
percent of its weight of a salt of a dialkyldithio
phosphoric acid and an organic salt forming base
selected from the gr'oupconsisting of the aliphatic
secondary amines. the mononuclear aromatic pri
same properties as the original product. By mix
ing as much as 25% reclaim with 75% virgin
Neoprene, products are obtaining possessing sub
stantially the same physical properties as ob 70 mary amines, the cycloaliphatic amines, piperi
tained with straight new Neoprene.
dine, guanidine, the mono- and di- mononuclear
The plasticizers of the present invention may
aryl guanidines, biguanide, the mono- mononu
be prepared in any convenient manner but are
preferably formed in accordance with the process
set forth in my copending application Serial No. 75
clear aryl biguanldes, guanylthiourea and isothio
urea.
'
~
9. A rubber-like plastic mass comprising a mix
. 8,409,!“
‘
5
-
.
ture of a chloroprene‘ polymer and a minor pro
portion of its weight of a phenyl bizuanide salt
of a dialkyldithiophosphoric acid.
a
6
mixture oi’ a chloroprene polymer and a minor
‘
proportion of its weight or the phenylbiguanide
salt of di-(methylhexyl)dithiophosphoric acid.
10. A rubber-like plastic mass comprising a
12.‘A rubber-like plastic mass vcomprising a
mixture of a chloroprene polymer and a minor 5 mixture of a chloroprene polymer and a minor
proportion or its weight of .a ‘salt comprising an
proportion of its weight of'a salt comprising an >
aniline - dicyandiamide‘ - dialkyldithiophosphoric
acid reaction product.‘
I
v
11.'A rubber-like plastic mass comprising a
aniline - dicyandiamide - di(methylhexyl)dithio
phosphoric acid reaction product.
i _
‘
ARNOLD R. DAVIS.
Certi?cate of Correction
Patent No. 2,409,344.
October 15, 1946.
ARNOLD R. DAVIS
It is hereby certi?ed that errors appear in the printed speci?cation of the above
numbered patent requiring correction as follows: Column 3, line 47, for the letter “F”
read R; line 69, for the word “obtaining” read obtained; and that the said Letters
Patent should be read with these corrections therein that the same may conform to
the record of the case in the Patent Of?ce.
Signed and sealed this 3rd day of February, A. D. 1948.
[w]
THOMAS F. MURPHY;
Assistant Oommissioner of Patents.
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