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Патент USA US3078299

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United States Patent vO ”
' Patented Feb. '19, 1563
Referring to Formula 1 above, by far the preferred
metallic component “Me” for these compounds is barium,
followed by strontium, calcium, zinc and tin in decreasing
order of preference. With respect to the radical “alky ,”
George P. Rowiand, .ln, Pottstown, and John J. Wolshi,
Spring?eld, Pa, assignors to The Firestone Tire a
Rubber Company, Altron, @hio, a corporation of (this:
No Drawing. @riginal application May 12, 1959, §er. No.
the preferred and most convenient radical is the n-do
decyl radical, the alkyl beta-imino dipropionic acid cor
responding to this value being conveniently available as
812,575, now Patent No. 2,996,4Q0, dated Aug. 15,
1961. Divided and this application Feb. 1%, 1961,
10 “lauryl beta-imino dipropionic acid,” in which the
Ser. No. 3333534}
6 Claims. (El. Zed-429.7)
“lauryl” groups are the mixed radicals containing prin
cipally dodecyl radicals but also some higher (e.g. tetra
This invention relates to the suspension polymeriza
decyl) and lower (e.g. octyl and decyl) radicals, derived
tion of vinyl chloride to yield resins having good dry
by the reduction of coconut oil fatty acids. The com
plasticizer blending properties and good electrical proper
,tyies, and also to certain novel metallic salts of alkyl beta 15 pounds are readily prepared by reacting, in aqueous solu
imino dipropionic acid for use in said process.
tion, the sodium, ammonium, or other water-soluble salt
Vinyl chloride resin compositions are generally made
(2) of an alkyl beta-imino dipropionic acid with a chlo
up by initially mixing the granular resin, liquid plasti
ride or other water-soluble salt of barium, strontium,
calcium, zinc or tin, the following reaction taking place:
cizers, stabilizer, pigments, etc. in a ribbon or blade-type
mixer until a uniform, granular, free»?owing blend re 20
CHrOHz-C 0 ON).
sults. The blend is then transferred to fusing and hot~
+ MeClg ————>
Working machinery such as roll mills, banbury mills, ex
truders, calenders and the like for working up into the
final desired resin products. It is highly desirable that
a resin so processed shall have the property, during the 25
initial mixing stage, of rapidly taking up the liquid plas
Me + 2Na0l
ticizer so that the resin appears macroscopically “dry,”
the liquid plasticizer being completely absorbed into
the pores of the resin granules.
If this state is not
achieved during the preiiminary mixing, considerable 30
The desired insoluble salt is recovered by ?ltration, cen
dif?culties will be encountered in subsequent processing
trifugation and the like. Speci?c exemplary compounds
Any plasticizer not absorbed into the resin lubricates the
under Formula 1 above are barium dodecyl beta-imino
granules so that they are not e?iciently homogenized in
the hot-working machinery, which results in excessive 35 dipropionate, strontium dodecyl bcta-imino dipropionate,
calcium dodecyl beta-imino dipropionate, zinc dodecyl
power consumption and in “?sh-eyes” and other discon
beta-imino dipropionate, stannous dodecyl beta-imino
tinuities in the ?nished products. Very few resins on
dipropionate, barium tetradecyl beta-imino dipropionate,
the market at present have good plasticizer absorption
decyl beta-imino dipropionate, barium Z-ethyl
performance as above outlined.
dipropionate, strontium decyl beta
Accordingly, it is an object of this invention to provide 40
imino dipropionate, stannous tetradecyl beta-imino dipro
a novel process for the production of vinyl chloride
pionate, and the like. It will be understood that mix
resins having excellent plasticizer absorption character
tures of two or more compounds individually coming
Another object is to provide such a process in which
under Formula 1 are also contemplated, for instance,
use is made of the available suspension polymerization 45 mixtures of compounds under the Formula 1 above in
which the alkyl groups are derived from commercial
apparatus and techniques.
of alkylating constituents, for instance the mixed
A further object is to provide new chemical compounds
alkyl radicals contained in the alcohols derived by the re
for use in the process above outlined.
duction of the mixtures of fatty acids occurring in natural
glycerides such as coconut oil, the mixed radicals de
50 rived hy dimerization and trirncrization of propylene and
The above and other objects are secured, in accordance
butylene, oxo process alcohols and so on. Likewise mix
with this invention in a process in which vinyl chloride,
tures of salts of different metals, for instance, mixtures
or a mixture thereof with other unsaturated compounds
of barium and strontium salts, may be used.
copolymerizable therewith, is polymerized in aqueous
suspension in the presence of certain bivalent metal salts 55
of alkyl beta-imino dipropionic acids having the formula
In general, the process of this invention follows the
ordinary suspension polymerization procedure, with the
exception that the compound of Formula 1 is present.
The suspension polymerization process consists in agitat
60 ing the vinyl chloride monomer in an aqueous medium
containing a non-micellesforrning protective colloid sus
pending agent. Suspending agents suitable for this pur
pose are hydrophilic high polymeric materials such as
gelatin, starch, carragheen, albumen, agar-agar, gum
tragacanth, polyvinyl alcohol, polyacrylic acid, poly
alkyl represents an alkyl group of from 8 to 16 carbon
atoms, and
Me represents a metal atom which may be barium, stron
tium, calcium, zinc or tin.
maleic acid, methyl cellulose, and the like. The aqueous
medium constitutes about at least half the entire polym
erization mass. The reaction is promoted by the presence
of free-radical-generating agents soluble in the monomer
phase of the suspension, such as benzoyl peroxide, per
The resins so produced have excellent plasticizer-ab
benzoic acid, lauroyl peroxide, p-chlorobenzoyl peroxide,
" sorption properties.
t-butyl hydroperoxide, and the like. In the practice of
the present invention, there will further be present a salt
in accordance with Formula 1 above. The aqueous phase
A series of runs was made in accordance with the fore
going recipe, using each possible combination of amounts
of gelatin and of barium lauryl beta-imino dipropionate
and the monomer phase are agitated together so as to
in the several runs. In each run, the ingredients, other
suspend the latter in the former without, however, form
ing a permanent emulsion, and the temperature of the 6 than vinyl chloride, were charged into a 12-ounce bev
erage bottle and mixed. The vinyl chloride, slightly in
mass adjusted to values such as to initiate the polym
erization reaction, usually on the order of 30°-100° C.
excess of the recipe amount, was next charged and al
The monomers in the suspended droplets become polym
lowed to vaporize to purge the free space in the bottle
and to reduce the weight of vinyl chloride to the amount
erized, yielding a suspension of granular resin in the
aqueous medium. From this aqueous suspension the 10 in the recipe. The bottle was then capped and tumbled
resin is isolated by ?ltration. The amount of the Com
in a water bath at 25° C. for one hour, after which it
pound 1 used in the polymerization mass will generally be
was tumbled in a water bath at 50° C. for 18 hours.
At the end of this period, the bottle was vented and
upwards of .05%, and preferably upwards of 1.0%,
opened, and the polymer was separated from the suspen~
based on the weight of the monomers in the system. The
upper limit for this concentration is not critical; as high 15 sion medium by ?ltration, washed on the ?lter with dis
tilled water, and dried. The resultant polymer in every
as 10% could be added without adverse effect, so far as.
case had excellent plasticizer-absorbing properties, as ob
the operativeness of the process is concerned. However,
served on a microscope slide. This observation was
amounts in excess of 3% will usually be unnecessary and
wasteful from an economic point of view.
made by placing a small quantity of the resin in a thin
It will be understood that the monomeric compositions 20 layer on a microscope slide, adding a drop of diocty‘!
phthalate, and placing the slide on the microscope stage.
polymerized according to this invention may be either
The resin particles could be seen in the microscope to
unmixed vinyl chloride or mixtures thereof with minor
rapidly imbibe the dioctyl phthalate. The particle size
and shape were very uniform, the particles being pre
saturated compounds copolymerizable with vinyl chlo- 25 dominantly 280 microns in diameter and spherical, and
the resin was free from ?ne and from coarse grains.
ride. Conversely stated, the mixtures should contain at
least 80% vinyl chloride by weight. Ethylenically un
Example 11
saturated compounds copolymerizable with vinyl chloride
proportions, say not over 20%, based on the weight of
said mixtures, of one or more other ethylenically un
are exempli?ed in vinyl esters on the order of vinyl bro
mide, vinyl ?uoride, vinyl acetate, vinyl chloroacetate, 30
vinyl butyrate, other fatty acid vinyl esters, vinyl alkyl
sulfonates and the like; vinyl ethers such as vinyl ethyl
ether, vinyl isopropyl ether, vinyl chloroethyl ether and
Vinyl chloride ______________________________ __
____________________________________ _..
Lauroyl peroxide ___________________________ _.-
Gelatin (100 Bloom) _______________________ __ 0.5
the like; cyclic unsaturated compounds such as styrene,
strontium, stannous or zinc neutral
the mono- and poly-chlorostyrenes, coumarone, indenc,
betaimino dipropionic acid_ 0.11 to 0.18
vinyl naphthalenes, vinyl pyridines, vinyl pyrrole and the
1The “lauryl” substitnent is a mixture of aliryl radicals
like; acrylic acid and its derivatives such as ethyl acrylate,
derived from the alcohols produced by the reduction of
methyl methacrylate, ethyl methacrylate, ethyl chloro
acrylate, acrylonitrile, methacrylonitrile, diethyl maleate,
diethyl fumarate, and the like; vinylidene compounds on
the order of vinylidene chloride, vinylidene bromide,
vinylidene ?uorochloride, and the like; allyl compounds
such as allyl acetate, allyl chloride, allyl ethyl ether and
the like; and conjugated and cross-conjugated ethyleni
mixed fatty acids of coconut oil; predominantly dodecyl
groups and tetradecyl groups.
A series of runs was made in accordance with the fore
going recipe, using the various salts of the imino acid in
amounts over the range indicated.
Each run was con
ducted in accordance with the procedure of Example I.
Good resins from the standpoint of plasticizer-absorption
cally unsaturated compounds such as divinyl ketone and 45 were obtained in all cases. The optimum ranges for the
the like. For a fairly complete list of materials known
amount of the salts used, together with the characteristics
of the products, are tabulated herewith.
to polymerize with vinyl chloride, reference may be had
to Krczil “Kurzes Handbuch der Polymerisations-Tech‘
nik—--II, Mehrstolf Polymerization,” Edwards Bros. Inc.,
1945, pp. 735447, the items under “Vinyl chlorid.”
The resins produced in accordance with' this invention
have the property of rapidly imbibing liquid plasticizers 55
of all conventional types in the preliminary mechanical
Calcium __________ ._
0.13—O. 17
Shagg ' spheres 175;:
mixing. Microscopically examined, the resin granules
Strontium ________ -_
Irregular spheres 310;:
0. 13-0-17
Irregular spheres 140/;
in diameter.
0.11-0. 17
-_--_d0 _______________ .-
will be found to be generally spherical, and of rather nar~
row distribution of particle diameters, usually on the
order of 150-350 microns.
Heat Sta
Range in
Description of
bllity (min
utes, deter
mined) as
in Example
in diameter.
in diameter.
With the foregoing general discussion in mind, there
are given herewith detailed speci?c examples of the prac~
tice of this invention.
Example I
Vinyl chloride _____________ _. 60.
Water ___________________ __
Vinyl chloride _____________________________ .._
Water _____________________________________ _..
Lauroyl peroxide __________________________ __ 0.28
Lauroyl peroxide __________ _- 0.2.
Gelatin (100 Bloom) ______ __ 0.4, 0.5, 0.6 or 0.8.
Example III
Barium lauryl1 beta
imino dipropionate ______ __ 0.11, 0.13, 0.15 or 0.17.
1The “lauryl” substituent is a mixture of alkyl radicals
‘derived from the alcohols produced by the reduction of the
mixed fatty acids of coconut oil; predominantly dodeeyl
groups and tetradecyl groups.
Gelatin (type B-100 Bloom) ________________ _.. 0.50
Barium lauryl beta-imino dipropionate 1 ________ _.. 0.20
1The “lauryl” suhstituent is a mixture of alkyl radicals
derived from‘ the alcohols produced by the reduction of the
mixed fatty acids of coconut oil; predominantly dodccyl
groups and tctradccyl groups.
A. glass-lined steel autoclave provided with an anchor
agitator and with a heating and cooling jacket was pro
vided for the run. All ingredients except the water were
charged ?rst. The reactor was then closed, and the free
ratory press under a pressure of 138 p.s.i. The length of
time in the mixer required before a sample of the resin
space therein purged twice with vinyl chloride vapor fol
lowed by evacuation. The recipe amount of vinyl chlo
ride was then charged, agitation commenced, and the tem
perature raised to 125° F., these conditions being main
produced no stain on the paper was taken as the “Dry
Time,” and is considered to be an inverse measure of de
sirable absorption behavior.
The salts of the lauryl beta-imino dipropionic acids
used in the foregoing experiments were prepared as
tained for 19 hours. At the end of this time the unreacted
vinyl chloride was vented, and the reaction mass cooled
was recovered by ?ltration, washed on the ?lter with 10 Sodiumdauryl beta-imino dipropionate
water, and dried. Following are the properties of the
(“Deriphat 160” a product of Gen
to 25° C. and discharged. The polymerized vinyl chloride
eral Mills Corp.) ______________ __ 373 g. (1 mol).
Table II
Water (dc-ionized) ______________ .._ 1 liter.
Relative viscosity (1% solution in cy
clohexanone at 25° C.) _________ _. 2.52.
Fisheye Rating __________________ __ 2 at 3 min.
Barium chloride _________________ __ 209 g. (1 mol).
Heat stability (peanut oil—180° 0). Failure in 75 min.
Bulking density (gms./cc.) ________ __ 0.44.
Calcium chloride ________________ __ 111 g. (1 mol).
Dry time ______________________ __ 8 min.
Hot ?ow ______________________ __ 3 min.
Strontium chloride _______________ __ 159 g. (1 mol).
Screen analysis (percent retained):
20 mesh ______________________________ __
40 mesh ______________________________ __
60 mesh ______________________________ _..
80 mesh ______________________________ __
100 mesh ______________________________ _.
140 mesh _____________________________ __
200 mesh _
325 mesh
Percent thru 325 mesh _________________ __
Stannous chloride ________________ __ 190 g. (1 mol).
_________________________ __ 500 ml.
A series of preparations was made in accordance with
the above recipe, using the calcium, strontium, barium,
stannous and zinc chlorides individually in the several
30 runs. In each run, the ingredients at “A” were placed in
The properties, other than conventional ones, tabulated
above were determined as follows:
a three-gallon crock provided with a propeller-type agi
tator, and agitated together until complete solution was
achieved. The selected salt and water listed at “B” were
made up into a solution, and slowly added to the solution
Grams 35 of the ingredients “A” with continued stirring. A precipi
Heat stability:
Zinc chloride ___________________ _.- 137 g. (1 mol).
Dioctyl phthalate _______________________ __
tate quickly formed, and the resultant slurry stirred for
an additional ?ve minutes after the last of the ingredients
“A” had been added. The slurry was then ?ltered, and
the recipitate thoroughly washed on the ?lter with water.
40 The precipitate was then sucked as dry as possible on the
The above recipe was sheeted out on a laboratory mill
?lter. The precipitate was then dried in a circulating hot
at 310° F. Test strips were cut from this milled sheet
air oven at 200° F. for 24 hours. Substantially quantita—
and immersed in a peanut oil bath maintained at 180° C.
tive yields were obtained in every case.
Individual strips were removed at predetermined time in
This application is a divisional application of our co
tervals to study color degradation. The time at which a
application Serial No. 812,575 ?led May 12,
specimen removed had changed to dark brown ‘was con 45 1959, now U.S. Patent 2,996,490.
sidered to be the failure time.
What is claimed is:
(Jo-precipitated barium-cadmium laurate _..__..
Dibutyltin dilauryl mercaptide _____________ .. 0.5
‘1. A salt having the formula
Fisheye rating:
Dioctyl phthalate _______________________ __
Dibutyltin dilauryl mercaptide ____________ __
60 50
The above ingredients are milled together at 310° F.
for 3 minutes, and then sheeted out as a ?lm 13-17 mils
C H;- 0 Hr- ff- 0
in thickness. An 8-square inch specimen of the ?lm is cut
out, and the number of ?sheyes counted and taken as an 55 in which formula “alkyl” represents an alkyl group of
inverse measure of the rapidity with which the resin takes
from 8 to 16 carbon atoms, and Me represents a metal
up the dioctyl phthalate plasticizer.
selected from the group consisting of barium, strontium,
calcium, tin and zinc.
2. A salt according to claim 1 wherein “Me” repre
60 sents barium.
Dioctyl phthalate _______________________ __ 200
3. A salt according to claim 1 wherein “Me” repre
Dibutyltin dilauryl mercaptide ____________ _.. 12
sents strontium.
A “Day Mixer,” which is a steam jacketed double-arm
4. A salt according to claim 1 wherein “Me” represents
mixer with a capacity of 0.13 cubic feet with two tan
gential arms rotating at 36 and at 36 and 74 rpm. re 65
5. A salt according to claim 1 wherein “Me” represents
spectively, was employed in the test. Jacket temperature
was adjusted to 330° F., but the temperature drifted
6. A salt according to claim 1 wherein “Me” represents
downwardly during the test, so that the average tempera
ture was about 210° F. The ingredients of the recipe
were added cold to the hot mixer over a period of two 70
References Cited in the ?le of this patent
minutes. Thereafter the progress of the mixing was
watched, and the time at which the mixture fell free from
Gmitter _____________ __ Aug. 17, 1954
the blades taken as the “Hot Flow” time. Likewise, small
Leistner et a1 ___________ __ Feb. 3, 1959
samples were removed at one-minute intervals and spread
Meyer et a1. __________ _- June 16, 1959
and pressed between sheets of paper in an unheated labo 75 2,891,053
Day drier hot ?ow and dry time:
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