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Patented Jan. '7, 1947
2,413,85t
UNITED, STATES PATENT OFFICE
2,413,856
VINYL POLYMER PLASTICIZED WITH
ETHYLENE DIAMINE TETRAACETIC
ACID ESTER
Frederick C. Bersworth, Verona, N. J.
No Drawing. Application July 17, 1943,
Serial No. 495,207
6 Claims. (Cl. 260—-36)
\
2
1 .
This invention relates to the plasticizing and
modifying of certain vinyl compounds of a resin
ous nature, and more particularly to the incor
poration of esters of polyamino-polyacetic acids
as modifying agents in vinyl chloride polymers,
Esters formed from any alcohol containing at
least one esteri?able —OH group attached to a
carbon atom which is not part of a benzene ring
may be used advantageously.v The esteriflcation,
however, is preferably complete as to all the free
carboxylic' acid groups of the amino acid/and
vinyl chloride-vinyl acetate copolymers, vinyl
chloride-vinylidine chloride copolymers, and vvinyl
butyral polymers.
v
must be complete as to at least two of them and
there must, by de?nition, be at least two such
free carboxylic acid groups. The esters used in
.
In the preparation of useful products of these
vinyl polymers and copolymers, it is advisable to 10 the present process will therefore correspond to
add a softening or plasticizing agent. But the
the foregoing formula except for the replacement
addition of such agents generally decreases the
of’ hydrogens of the carboxylic acid groups
tensile strength of the ?nished product to a con
,-COOH byR-s R- being the radical of an alco
siderable degree; furthermore'each such agent
hol ROH.
‘
decreases the tensile strengthto a diiferent de 15
The resinous vinyl compounds with which the
gree. The plasticizing or softening agent must
above de?ned esters have a bene?cial plasticizing
in any event be compatible with the polymer,‘ and "
effect include the polyvinyl chloride polymers and
must not bleed out when the polymer is worked.
‘the polyvinyl chloride copolymers. Speci?cally
It is an object of this invention to set forth a
included are the straight polymers
class of plasticizers for the above-mentioned 20
vinyl polymers and copolymers which have much
less adverse effect than do ordinary plasticizers
~ such ‘as ‘fKoroseaL" the vinyl acetate-vinyl chlo
‘ride copolymers, also called polyvinyl chloride
acetate, the vinyl chloride-vinylidine chloride co
on the tensile strengths of products made of such
polymers and copolymers.
1
‘
Other objects will appear in the following de
tailed explanation of the invention. f
polymers, and polyvinyl butyral.
Brie?y, these objectsmay be accomplished by
the incorporation of an ester of a polyamino poly-‘
acetic acid with the said vinyl polymers and ,co
polymers.
,
_
o
The esters which may be advantageously incor
porated with the said‘ vinyl-polymers and co
polymers ‘to obtain the desired results may be
de?ned in terms of the amino acid and in terms
of the alcohol used for esteri?cation. The method
for preparing these esters is set, forth in detail
in my copending application, Ser. No. 491,670,
?led June 21,1943.
‘
I
'
-
The polyamino polyacetic acid may be broadly
de?ned by the formula: '
nooc-cm
o
I
CHZ'COOH
to
-
The following is a general method for incor
porating the ester of the polyamino polycarbox
ylic acid in the resin. The vinyl resin is ?rst
dissolved in a volatile solvent thereof inert to
both the resin-and the ester and which is pref
erably capable ,of dissolving both substances.
About a 5% solution of the resin has been found
suitable for most practical operations. To this
is added the ester in the desired amount which
is preferably about one third of the'weight of
I
the resin.
'
.
_
.
After thorough incorporation, the resulting.
composition may be sheeted outpand dried by
evaporation of the solvent, or otherwise manipu
lated to form the desired, ?nal product. This
composition, before evaporation of the'solvent,
may be fairly liquid or may be‘jelly-like, depend_
ving principally upon the amount of solvent used.
Itis to be understood that any quantity'of the
Y
Y’ ,
ester will have a softening e?ect and ‘as the quan
wherein Y and Y’ are the same or different and 45 tity of ester added to a given weight of resin is
increased, the softer the resin will become until
are either hydrogen, —OHz-COOH, ‘an alkyl
it ?nally dissolves. The quantity of ester used
group, a cycloalkyl group, or an alkylol group;
will therefore be in accordance with the charac
and Z is an alkylene group,‘ an alkylenesether
teristics of the ?nal product desired for a particu
group; an alkylol group, or a polyalkylene-amine
group in which latter case the amino nitrogen 50 lar purpose, but as ‘stated above, about ‘A; by
weight of the ester based on the weight of resin
atoms intermediate the polyalkylene chain are
will give satisfactory results» for most ordinary
attached either to a hydrogen atom or to a
—CH2'COOH group. Of particular value in the
For evaluation and comparison purposes, the
present invention are the esters of the amino tetra
(or higher) acetic acids, 1. e. of those acids which 55 more or less jelly-like mixture of resin and ester
in solution, prepared as above described, is drawn
correspond to the above formula wherein Y and
to a predetermined thickness on a glass plate,
Y’ are --CH2'COOH, and also wherein Z is an
alkylene or a polyalkylene-amine group (i. e.
thus forming a ?lm which will dry down to about
>N—Z-N< is an alkylene-polyamine radical or
l/éo the thickness originally measured.‘ In the ex
a polyalkylene-polyamine radical).
'
60 amples which follow the ?lms were made .03 inch
'
N——Z—~N\
purposes.
-
I
‘
v
ajiasse
4
3
thick when in solution and were dried down to \.
.001 inch when dry. These dry ?lms were re
moved and part of them were milled on a two roll
Example III
\
resin.
The remainder were then tested for per
resentative samples:
cent elongation and tensile strength at these elon
gations after having been conditioned in a room»
at 65% relative humidity at 70° F. for four hours.
This invention is not limited to the preferred
method of incorporating the ester. For'instance,
the resin and the ester may be added together
and the mixture sheeted on a two-roll mill with-'
out the use of any solvent. Similarly any method
which serves to incorporate the ester in the resin
in a satisfactory manner is included in this inven 15
tion.
'
'
Following the same procedure as in Examples I '
‘and II, but using polyvinyl butyral as the resin,
the following results were obtained in testing rep
mill to ascertain the properties of the treated
‘
A
Percent plasticizer 1 _________ ..
Tests:
B
33
O
33
D
33
.
.
'
E
33
33
3, 700
4, 700
320
100
0
345
100
0
,
1 Based on weight of resin.
Example IV .
.
In order to compare the e?ect of adding the
-
' - Using polyvinyl chloride as the resin and the
esters of polyamino-polycarboxylic acids referred
tetra-isopropyl ester of ethylene diamine tetra
to herein with that of well-known plasticizers,
four of the most widely used plasticizers were se 20 acetic acid as the ester, and following the same
procedure of preparingand testing ?lms as al
lected and incorporated in exactly the same man- ,
ready described, the following results were ob
ner and relative amounts as the said esters. To
tained on testing representative samples:
facilitate comparisons between'the physical prop
erties of the ?nal products, tables are given in
Per cent of plasticizer 1 ___________ __, ____ __
33
Examples I, II, and III in which each of the plas 25
ticizers is designated by a letter as follows:
Tensile _________________ __lb./sq. in__ 4,760
Elongation ______________ ....per cent__ 208
A represents the tetrabutyl ester of ethylene di- ‘
Tests:
amine tetraacetic acid.
-
,
Compatibility. ______________ __do_..__ ' 100
‘
B represents dibutyl sebacate.
C represents tricresyl phosphate.
Spew ____________ -; _____ -i _______ __ None
'30
1 Based on weight of resin. .
D represents triethylene glycol di-2-ethyl butyr
From the foregoing examples, it may readily be
seen that the incorporationof thev herein de?ned
E represents triethylene glycol di-2-ethyl hexate.
esters of polyamino polycarbox'ylic acids-with the
Example I
35 vinyl polymers herein set forth serves not only to
plasticize those polymers but also to yield a prod
To 570 grams. of mesityl oxide were added 30
uct with a tensile strength greater than that en
grams of polyvinyl chloride. To the resulting so
countered when ordinary plasticizers are used.
lution 10 grams of the tetrabutyl ester of ethyl
ate.
ene diamine tetraacetic acid were added.
The
same general procedure of forming ?lms aslout
lined above was then followed. The following is a
table of the results obtained on testing repre
sentative samples: .
A
B
O
D
E
I claim:
40
_
ing of vinyl chloride homopolymer’s, vinyl chlo
ride-vinyl acetate copolymers, vinyl chloride
vinylidene ‘chloride copolymers, and vinyl butyral
45 polymers, and‘a tetra-ester of ethylene diamine
tetraacetic acid.
Percent plasticizer 1 _____ __V._..
33
33
33
33
33
Tens1le-._____-.lb./sq. in__ 6, 930
2, 300
2, 000
l, 700
3, 200
Tests:
_
Elongation: ____ __percent-.
160
170
160
185
290
Compatibility ____ _.do.._-
100
100
100
100
100
Spew ____________________ __
0
0
0
0
0
'
1. A plasticized resinous product comprising a
vinyl compound selected from the group consist
v
'
2. The product of claim 1 wherein said ester is
the tetrabutyl ester of ethylene diamine tetra
acetic acid.
50
'
3. A plasticized resinous product comprising a
vinyl compound selected from the group consist
ing of vinyl chloride homopolymers, vinyl chlo
‘ride-vinyl acetate copolymers, vinyl chloride
1 Based on weight of resin.
vinylidene chloride copolymers, and vinyl butyral
Example II
Following the same procedure as in Example I, '
polyvinyl chloride-acetate (vinyl chloride-vinyl
acetate copolymer) was used as the resin.
Re
sults of tests on representative products thereof
were as follows:
Percent plasticizer 1 _________ -_
B
C 1
'
D
33)
E
33
33
Tonsiie-___-___-lh./sq. in__ 3, 000
370
2, 600
600
l, 400
Elongation .__
(‘ompatibilit
Tests:
33 '
33
'
_.percent._
_._-.do.._.
320
100
320
100
250
100
335
100
265
100
pew ................... -_
0
0
0
0
0
i Based on weight of resin.
,4. ‘The product according to claim 3 wherein
said vinyl compound is a vinyl chloride polymer
—(—CH2-CH Cl-) ii.
’
A
polymers, and an ester of ethylene diamine tetra
acetic acid; said ester being at least a di-ester.
I
.
5. The product according to claim 3 wherein
said vinyl‘ compound is avinyl chloride-vinyl ace- _
tate copolymer.
6. The product according to claim 3 wherein
said vinyl compound is a vinyl butyral polymer.
FREDERICK c. BERSWORTH.
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