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Патент USA US2404780

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4
2,404,780
Patented July so, me '
UNITED STATES“, PATENT OFFICE
\ W380
PROCESS FOR m 00mom cor. romaine
'l'ION OF VINYL crmonmn WITH
ES‘I'EBS
Harold W. Arnold.
em:
ELdul'ontdeNemom-a 0! Delaware’
mlngtomnolsa
~tionJanuas723JM2.
No Drawing. Ashlin
in
SerlI-l No. when
‘I clllll'il- (Cl. 260-78]
1
2
v
This invention relates to valuable compositions
of
More
matter
particularly,
and to a process
it relates
fortotheir
a new and im
proved process for the conioint polymerization
of vinyl chloride with fumaric esters.
- r
'
Products resulting from the conjoint poh'mer
ization of vinyl chloride with fumarlc esters pos
sess many valuable properties which make them
very attractive for use in such applications as
,
isadiustedtoapll ofaboutl-dbytheaddition
ofacidsoracidreaetingsalts. 'l‘hlsmediumis
then placedinasuitablepressurevessel, which
is provided with a means of agitation such as
stirring or shaking, followed by about one-half
its weightof the mixture tobepolymerized. The
vesseliscooledbelowtheboilingpointofthe
spaceofthevesselisdisplacedbyaninertgas
’ monomeric vinyl chloride and the air in the free
'l'hevesselisthenclosedand
plastics, coating compositions, ?lms and fibers. 10 suchasnitrogen.
heated thereafter at a constant temperature in
The lack of an economical process for the pro
the range of 20-80‘ C. with constant or inter
duction of these interesting compositions in high
mittent agitation until polymerization has pro
state 0! quality has restricted wider utilisation
of these products in the synthetic resin ?eld.
ceeded to the desired extent.
The following examples, in which the parts
15
This invention has as its object to provide a
' are given by weight, further illustrate the prac
practical and eilicient process {01' the (501110!!!‘ ' tice of the invention.
polymerization of vinyl chloride with a lunatic
ester. Another object is to provide a new and
Exam-I l
improved process for the conloint
A
The
following
solution
is prepared:
tion of vinyl chloride with a fumaric ester that 20
Parts
is practicable for large scale operation. Still
Water
..
484
new
and
improved
‘another object is to produce
sodium salt of sulfonatcd paramn oil
synthetic conjoint polymers of vinyl chloride The
(a commercial dispersing agent con
Other
objects
will
be
appar
with fumaric esters.
taining about 52% of active ingredient
ent from the following description of the inven
which is essentially identical to that
tion.
’
described in Example 111 of U. 8. Patent
These objects are accomplished by the follow
ing invention which comprises polymerizing the
polymerizable components of an emulsion of
vinyl chloride in admixture with, at least. one 30
No. 2,197,800) __.._....___..._.___-____..___
Ammonium perdisulfate ______________ __
31.2
1.25
The pH of this solution is adjusted to 2.5 by
fumaric ester in an aqueous medium containing
a dissolved salt of perdisuli'uric acid, and a dis
adding a suitable amount of 89% formic acid.
Fifty parts of this solution is placed in a glass
parsing agent selected from the group consist
pressure vessel capable of withstanding elevated
pressures and the mixture is then cooled below
ing of
O
0
the boiling point of vinyl chloride. A mixture
/
/
consisting of 22 parts of vinyl chloride and 3
aoséo and sage
parts of diethyl fumarate is then added and the
OM
OM
vessel sealed. After the contents of the pressure
wherein R is an acyclic hydrocarbon of 12 to 18
vessel have become completely lique?ed, the ves
carbon atoms and M is an alkali metal, said 40 sel is agitated in a bath maintained at 40“ C. for
emulsion during said polymerization having a
24 hours. The resulting milky dispersion is
substantially oxygen-free gas thereover.
frozen to coagulate the polymer, which is then
The exact manner of practicing this invention
?ltered and washed repeatedly with warm water
will vary depending upon the ration of the com
until substantially all residual dispersing agent
pounds~polymerized, the catalyst and dispersing 45 has been removed. The polymer, after treat
agent selected; however, the following will illus
ment with a 0.5% horas solution, is washed with
trate its application.
methanol to facilitate drying and is thereafter
of a dispersing agent oil the type defined above
line. white granular powder obtained represents
An aqueous medium. containing about 0.1 to
2.0% of a perdisuli'ate salt and about 1 to 5%
air dried to constant weight. The 22 parts of
3
2,404,7eo
' a yield of 88 per cent. Chlorine analysis showed
the product to contain 87.8 per cent vinyl chlo
while polymerization takes place.v During this
time an additional 540 parts of diethyl fumarate
is forced into the autoclave at such a rate that
the total number of parts of ester added is re
lated to the density 01' the polymer dispersion as
ride. The polymer can be molded into strong,
tough, light-colored ?lms and bars which have
a softening point of 78° C. and a speci?c gravity
of 1.36.
For purposes of comparison in these examples,
the softening point of the resin is de?ned as that
shown in the following table:
temperature :1" C. at which a molded bar of
7
,
Dispersion density, gJcc. (23° C.)
the material, 2.5x0.5x0.05" rigidly clamped at 10
present
one end and loaded with a 27.5 gram weight
applied 2" from the point of support and in the
plane of the 0.5" dimension, deforms 0.06" when
the bar is heated in a liquid bath at the rate of
2° 0. per minute.
Exsuru: 11
.
is
Totgl
8S
1‘ pagsho!
W be
C
should
_
1.0147.
1.041.
1.047.
129
234
288
323
428
118652.
482
1.073.
610
.
_
550
Five hundred parts of the aqueous solution de
scribed in Example I is adjusted to a pH of 2.5
The mixture is heated for one hour after all
by the addition of a suitable amount of 89% 20
the diethyl fumarate has been added. The poly
formic acid and placed in a glass pressure vessel.
mer dispersion is then removed from the auto
The contents are cooled below the boiling point
clave, diluted with 25,000 parts of water, heated
of vinyl chloride and then is added a mixture con
to 70° C. with stirring, and 500 parts of 10%
sisting of 200 parts of vinyl chloride and 50 parts
of dimethyl i'umarate. The vessel is then swept 25 aluminum sulfate solution added. The coagulated
polymer is washed by decantation four times with
with nitrogen to remove air and sealed. It is
distilled water, once with 0.25% sodium hydroxide
then agitated at 40" C. for 40 hours. The polymer
solution, and once with methanol. The polymer
dispersion so obtained is frozen to coagulate the
is sucked as dry as possible on a ?lter and spread
product which is washed with water, borax solu
tion, and methanol as in Example I. The yield 30 to dry completely on trays in a current of air.
The polymer, obtained in an 80% yield, is a fine
of dry polymer is 103 parts or 41%. The prop
white powder containing 19.2% of combined di
erties of this product are shown in the" table
ethyl fumarate and is easily soluble in acetone to
below:
1.080 ............................................... . .
Vinyl chloride ______________ __per cent...
Softening point __________________ __°C__
660
give viscous solutions from which ?bers and clear,
54.’!
brilliant ?lms can be prepared. The polymer can
80 35 also be hot-pressed ‘into tough, colorless .sheets or
Tensile strength __________ __lbs./sq. in__ 9,040
Flexural strength _________ __lbs./sq, in__ 16,300
molded, either by the compression or injection
process, into tough, strong, light-colored objects.
Other physical properties are outlined in the table
When molded into ?lms and bars this polymer
is exceptionally clear and shows little of the dis 40 below:
coloration usually in evidence when chlorine-con
Softening point _______________ __°C__
75
taining resins are subjected to high tempera
Impact strength--ft. lbs/in. of notch__
0.60
tures. In addition to good solubility in toluene,
Bell ?ow (AB'I'M 1940 preprint #108) __ 22.3/136“
tri-chlorethylene, methylene chloride, methyl
Viscosity, poises (10% solution in cy
ethyl ketone, and mesityl oxide the polymer is 45
clohexanone)
1.3
compatible with nitrocellulose.
This invention is generic to the conjoint poly
Exam“: 111
merization of vinyl chloride with fumaric esters.
In addition to dimethyl, diethyl, and diisobutyl
When 238 parts of vinyl chloride and 13 parts
‘of di-isobutyl fumarate are substituted for the 50 esters of i'umaric acid disclosed in the foregoing
examples, the following esters of fumaric acid are
amounts of vinyl chloride and dimethyl rumarate
also suitable; di-n-butyl, di-cyciohexyl, di-benzyl
specified in Example II and polymerization and
or di-(chloroethyl) esters or the esters of fumaric
isolation carried out in the same manner, there is
obtained 238 parts of dry polymer-a yield of
95%. This product has the properties tabulated
below:
acid with methyl, ethyl or butyl glycol others.
The diethyl and dimethyl esters are preferred
since they yield higher softening and tougher
variety of uses. If desired, the copolymerization
Vinyl chloride ______________ _ _per cent-..
94.2
Softening point"--- _____________ __°C__
78.5
Tensile strength__________ -_lbs./sq_ in__
8,010
Fiexural strength__________ __lbsJsq, in__‘ 13,750
Exmru: IV
products which are of great interest for a wide
may be carried out in the presence of other com
pounds capable of polymerization under the same
conditions. For example, such compounds as
vinylyesters, acrylates, methacrylates, acryloni
trile, methacrylonitrile, styrene, asymmetrical di
A mixture of 505 Parts of a commercial dis
chloroethylene or methyl vinyl ketone may be
present.
persing agent containing as its active ingredient
30 to 35% or a sulfonated para?in oil, 23.8 parts 65
The present invention is not restricted as re—
of ammonium perdisulfate, and 8500 parts of
gards the proportion 01' vinyl chloride and fu
distilled water is brought to a pH of 2.5 by the
maric esters which- may be employed. It is within
addition of formic acid and placed in a nickel
the scopeof this invention to polymerize vinyl
lined pressure vessel fitted with a stirrer. After
chloride with i'umaric esters in weight ratios
sweeping the vessel free space with nitrogen, 3865
ranging from about 1:19 to about 19:1. It is
parts of vinyl chloride and 129 parts of diethyl
_realized, of course, that the relative proportions
fumarate are forced into the autoclave under
of the two monomers employed has an important
nitrogen pressure. The resulting mixture is
in?uence on the properties of the polymerization
heated with stirring to 40° C. and maintained at
products. A preferred embodiment of this inven
this temperature for approximately 24 hours 75 tion is directed to the brenaratinn m mmim-..
2,404,?!»
materials, are usually not produced in high state
oi purity and contain minor constituents which
in?uence the effectiveness oi.’ the active ingre
having ester contents ranging from 1% up to 25
percent. It has been found that the products
within this range are characterlzed' by desirable
dientj Polymerization systems containing such
softening points, toughness, impact strengths and 5 ancillary ingredients, which are present adven
other properties which make them very attrac
tive for use in such applications as moldings,
coating compositions and ?bers. This is more
clearly illustrated in Table I which shows the
titiously or added deliberately, are recognized as
part of this invention. These ingredients, which
are useful only when an operable dispersant is
also present, may include inorganic salts, long
variation in physical properties with increasing 10 chain primary alcohols, carbohydrate derivatives,
ester content tor several series of vinyl chloride
polyvinyl alcohol, etc.
fumaric ester copoiymers.
Using the rate of polymerization as a criterion,
Table I
the invention encompasses the use of dispersing
-
agent active ingredients in concentrations of 0.2
15 to 5% based on the weight of the aqueous
pm
Content '
pawl
'
BoitsnPH
.
point,
5
11
0”-..“ '
Do_-__.--
1mm
strength '
it.
of lbt?n.
notch
83- 5
79. 0,
0- B28
0 603
ill
I
am
strength
lbs'rsq in’
14:, 200
'14, B00
31
79. 5
............ - _
15, B00
45
a9. 0 ............ ..
16. 3“)
5
1D
15
20
25
83- o
81. D
an. 0
76. o
T2. 0
13, 669
13, 700
11,000
i2, 500
10, 509
30
67.0
a. 50
0. B2
0. at
o. 61
0. 54
.
0. 5D
0. B13
i]. 575
,medium used in the copolymerization of vinyl
chloride and iumaric esters. Within this range
the preferred concentration will in general de
pend upon the proportion or monomer present,
20 but is usually irom 0.5 to 4%. From the stand
point of economy and to facilitate removing the
____________ _
s
12. 5
is. 5
77. 0
36
62. 5
............ _.
13, 760
13, 150
12, 300
47
at. o ............ -_
11, 000
dispersing agent from the polymerized product.
it is customary to use the least amount of dis
persing agent necessary to bring about the de
25 sired rate of polymerization. It is to be under
stood that when reference is made to the use of
de?nite precentages of dispersing agents, these
values are calculated on the basis of the known
active ingredient concentration in the commer
It can be seen from the data in Table I that 30
the products within the preferred range of ester
content possess the most attractive properties
requisite of a good plastic and that products of in
creased ester content are less attractive for such 35
cial dispersants.
It may also be pointed out that the effective
ness of the dispersing agent, especially if small
concentrations are employed, is enhanced by agi
tation of the mixture. Any method of agitation
The polymerization catalysts encompassed by
emulsions. The most commonly employed meth
od of mixing is stirring, preferably in vessels
purposes as noted above;
this invention include the water-soluble salts of
perdisuliuric acid, In addition to the ammonium
may be used in producing and maintaining the
containing suitable ba?les. Other methods in
clude shaking, tumbling and the use of turbo
salt disclosed in the examples, there may also be 40 mixers. The dispersing agents operable in this
used the sodium, potassium, lithium, barium, and
invention are in general useful in forming stable
calcium perdisulfates. It is observed that the
emulsions, which after they are once formed,
sulfate ion appears in aqueous solutions of per
require little or no agitation thereafter. It has
disulfates. For this reason, while the water-solu
found, however, that polymerization occurs
ble alkaline earth metals salts are operable, they 45 been
more rapidly in certain emulsions while they are
are not usually used because of their tendency
being agitated. It is, accordingly, preferred to
to form a precipitate of the corresponding alka
assist the dispersing agent in producing and
line earth sulfate, The preferred salts are the
maintaining the emulsion by mechanical means
ammonium and alkali metal salts. Ammonium - which may or may not be continuous. It should
perdisuliate is especially suited for economic con 59 be emphasized that the dependence of the ef
siderations.
ficiency or the dispersing agents upon the active
The concentration of perdisulfate salt employed
ingredient concentration and agitation in no way
may be varied within wide limits. For instance,
repudiates the sharp distinction previously noted
amounts of perdlsulfates varying from 0.1% to
between the dispersing agents operable in this
10% of the quantity of monomer employedL are 55 invention and those which are not. Thus, with
operable. In respect to economy of catalyst,
most of the inoperable or impractical dispersing
quality of product and rapidity of polymerization,
the preferred proportion of perdisulfate salts lies
in the range of 0.1% to 4% based on weight of
monomer.
.
_
agents, it is impossible to obtain the rapid rate
characteristic of the operable agents either by
most vigorous agitation or by the use of con
60 centrations as high as the solubility of the ma
As operable dispersing agents in addition to
those disclosed in the foregoing examples, there
~may be mentioned the alkali metal salts of the
following long chain =alkyl sulfates and suito
natcs: dodecyl-l acid sulfate, tetradecyl-l acid 65
sulfate, octadecyl-l acid sulfate. dodecane-l-sul
ionic acid, tetradecane-l-sulfonic acid, hexa
terial will permit. Even in instances where such
modi?cations of systems involving impractical
dispersing agents permit su?icient acceleration
of the polymerization rate, the process is not
practicable because of the expense and operating
diillculties entailed by the use of very high pro
portions oi‘ such dispersing agents.
The process of this invention may be carried
acid. The salts of long chain sulionated paraihn
out in alkaline, acid or neutral media. However,
oil hydrocarbons are especially effective dispers_ 70 it is preferred to carry out the polymerization
ants, and need be employed only in small propor
in an aqueous medium whose pH may vary from
decane-l-sulfonic acid and octadecane-l-sulfonic
tions to achieve the desired results. It will be un
about 1 to about 5 since this this range appears
derstood that the dispersants to which reference
to enhance the polymerization rates of vinyl
is made above are commercial materials which,
chloride and fumaric esters. It is realized, how
because of the methods used in their manufac 75 ever, the pH 0! the aqueous media used will de
ture and because oi’ the sources oi the starting
7
8,404,780
pend on the nature of the monomers copolymer
lzed with vinyl chloride. For example, when
vinyl esters of carboxylic acids are employed,
care must be taken to prevent the hydrolysis
of the ester. Since the polymerization, in gen
eral, proceeds more slowly in environments of
8
this invention may vary to a considerable extent,
and it may also be found in copolymerizing vinyl
chloride with fumaric esters that one of the
monomeric materials polymerizes more rapidly
than the other, thus giving rise to products char
acterized by non-homogeneity and other inferior
low acidity and since high acidity may cause
physical properties. These effects are avoided to
excessive corrosion of the polymerization vessel,
a great extent by using the present invention.
it is preferred that the polymerization be carried
However, if additional improvement is desired,
out at a pH of about 2 to about 4. If it is 10 the polymerization procedure may be modi?ed by
desired to avoid changes in pH during the course
mixing initially all Of the vinyl chloride and 8‘
of polymerization, bull’er mixtures may be added
small proportion of the fumaric ester with the
to the aqueous medium.
aqueous medium. and thereafter adding small
The operability of the invention is not con?ned
portions of the fumaric ester at about the rate
to any particular proportion of polymerizable
at which the ester is used up. The emulsion
monomer or monomers relative to the amount
process of this invention is also adapted to be
of aqueous media present. Thus, the ratio of
carried out in a continuous manner.
the aqueous to the non-aqueous phase may vary
At the conclusion of polymerization the prod
between approximately 10:1 and 1:1. In gen
ucts of this invention may be isolated as ?nely
eral, it is preferred that the, aqueous/non 20 divided powders by a variety of methods. For
aqueous ratio shall be approximately 4:1 to 1:1
example, the dispersion may be sprayed into a
since for a given reaction vessel the time-space
heated and/or evacuated chamber whereby the
yield is greatly reduced by the use of higher
water is removed as vapor and the polymer falls
ratios. It can be further said that higher
to the bottom of the chamber. The polymer may
aqueous/non-aquecus ratios usually tend to favor 25 also be isolated by cooling the dispersion below
the production of lower molecular weight prod
the freezing point of the aqueous medium or by
ucts. It is also helpful in maintaining anemul
the addition of a large volume of a lower ali
sion if the proportion by weight of non-aqueous
phatic alcohol such as methanol or ethanol. The
to aqueous phases is not greater than 1:1. As is
most satisfactory method consists in adding an
well known, the dependence of the rate of vinyl 30 appropriate amount of an electrolyte solution to
polymerization upon the temperature is very im
the dilute aqueous dispersion with rapid agitation
portant, and low temperatures cannot be gen
at a. temperature just below the point at which
erally used because the corresponding rate of
the precipitated particles tend to cohere. This
reaction is impracticably low. The present in
procedure yields a Polymer in the form of dense
vention can be operated at any temperature 35 granular particles which are readily ?ltered and
above the freezing point of the aqueous phase
washed. Suitable electrolytes include sodium
which is somewhat below 0'‘ C. up to about 80° 0.,
chloride, sodium sulfate, hydrochloric acid, phos
above which the product may be adversely af
phoric acid, calcium chloride, magnesium sulfate.
fected by the aqueous medium. It is preferred
lead nitrate, lead acetate, stannous chloride, and
to employ temperatures in the range of 20° C. 40 aluminum sulfate. After precipitation of the ‘
to 60° C.
polymer it is ?ltered and washed repeatedly with
It is realized that the presence of oxygen in
water to remove traces of‘ electrolyte and dis
th polymerization vessel, while not appearing to
persing agent which may adhere to the particles.
have a deleterious effect on the properties“ of the
Washing with dilute solutions (0.1 to 1%) of
polymers of this invention, may adversely affect 46 caustic soda or ammonium hydroxide assists in
the rate of polymerization in certain cases. In
removing the last traces of dispersing agent and
these cases it is, therefore, preferable to displace
at the same time yields polymers of improved
the air from the polymerization vessel by means
heat stability. In order to facilitate low temper
of a gas which does not reduce the rate of poly
ature drying of the polymers, it is beneficial to
merization. Suitable gases are nitrogen, carbon
employ a ?nal wash with a lower aliphatic alco
dioxide, methane and helium. These gases may
hol such as methanol or ethanol. Before pre
be passed through the free space of the polymer
cipitation it may be advantageous to add to the
ization vessel until the air has been completely
dispersion small amounts of heat and light sta
displaced or may be introduced under suillciently
bilizers such as epichlorohydrin, 1-phenoxy-2, 3
high pressure that the oxygen originally present
epoxypropane, l-p-tolyloxy-Z, 3-epoxy ro ne,
alpha, alpha-dimethyl glycide and ethyl gpl‘yci
is so greatly diluted as to have little effect on
the rate of polymerization.
date; cadmium, copper, lead and manganese salts
of oleic, llnoleic, stearic, ricinoleic, palmitic, lauric
and fatty oil acids generally; eugenol, butyl sali
cylate and guaiacol; glycine, leucine, alanine and
the m-octyl ester of C-dimethyl glycine ; and 4
cyclohexyl morpholine. In general, monocarbox
ylic acid amides, preferably of the secondary or
‘The process is not limited to any particular
apparatus, but it is important that the reaction
vessel shall be constructed of material which has
no effect on the rate of polymerization or on the
quality of the products and is not affected by
the aqueous medium used in carrying out the
polymerization. Suitable vessels may be con
structed of stainless steel, nickel, silver or lead.
Vessels equipped with glass or enamel liners_may
also be used.
N-monosubstituted type, having heavy hydrocar
bon residues, preferably in the form of long open
chains, may be used advantageously as stabi
lizers. Speci?c compounds of this type include:
It is within the scope of this invention to em
N-(2-methyl-3-hydroxylpropyl)amide of IO-un
ploy any of the known procedures for carrying
decenoic acid, N-isobutylamide o1’ naphthenic ac
out the polymerization. The entire amounts of 70 ids, N-lsobutyl lauramide, N-allylamide of IO-un
the vinyl chloride and fumaric ester may be ini
decenoic acid, N-(p-ethoxyphenyi) amide of 10
tially added to the aqueous medium followed by
undecenoic acid, amides of castor oil acids, N-iso
subsequent emulsiilcation and polymerization of
the aqueous dispersion. It is well known that the
polymerization rate of the monomers operable in
a
butylamide of IO-undecenoic acid, N-isobutyl;
amide of oleic acid. N-isobutylamide of coconut
oil acids, and the mixture of N-alkylamides of
“ca-rec
9
.
10
components 01' an aqueous emulsion consisting 01'
vinyl chloride in admixture with an amount of
about 5%, based on the total polymerizable com
ponents, of a i‘umaric acid diester of a saturated,
carbamic acid in which the alkyl groups corre
spond in sine and proportion to those present in
the higher alcohols obtained by catalytic hy
drogenation oi’ carbon oxides. It may also be 01 5 aliphatic, single monohydric alcohol containing
advantage to add small amounts oi plasticizers
not more than 2 carbon atoms, said emulsion be
such as dibutyl-phthalate, tricresyl phosphate,
ing in an aqueous medium wherein the ratio oi
and dibutyl sebacate.
aqueous to non-aqueous phase, is between 10:1
The products prepared according to this inven
and 1:1 having a pH ranging from about 1-5 and
tion may be used for the preparation of plastics,
containing from about .l% to 10%, based on the'
10
coatings, ?bers, ?lms, foils and adhesives. For
weight of monomer present, oi’ a dissolved salt of
any 01' these purposes. the polymers may be com
perdisuliuric acid, and from about .2%—5%, based
bined with or prepared in the presence of plas
onthe weight of said aqueous medium, of a dis
ticizers, stabilizers, ?llers, pigments. dyes, soften
persing agent selected from the group consisting
ers. natural resins or other synthetic resins.
I In cases in which the products are to be used 15
oi’
‘
o
as coating or impregnating agents for porous ma
/
o
/
terials, it is‘ possible to apply the emulsion di
rectly to the material to be coated without the
on
Oh!
intermediate isolation of the polymer.
wherein
R
is
an
acyclic
hydrocarbon
01’ 12-18 car
20
As many apparently widely di?erent embodi
aoséo and nséo
‘ bon atoms and M is an alkali metal.
ments oi this invention may be made without
4. A process for obtaining a resinous material
departing from the spirit and scope thereof, it is
which comprises polymerizing at a temperature
to be understood that this invention is not lim
ranging from 20° (2-60’ 0. the polymerizable
ited to the speci?c embodiments shown and de
25 components of an emulsion consisting of vinyl
scribed.
chloride in admixture with from 1%-25% by
I claim:
weight of a fumaric diester derived from the
1. The process for obtaining a resinous material
esteri?cation oi fumaric acid with a saturated,
which comprises polymerizing at a temperature
single monohydric alcohol containing not more
ranging from about 0° C.-80° C. the polymeriz?ble
components of an emulsion consisting of vinyl 30 than 2 carbon atoms, said emulsion being in an
aqueous medium wherein the ratio or aqueous to
chloride in admixture with from 1-25% by weight
non-aqueous phase is between 10:1 and 1:1 hav
of said polymerizable components of a tumaric di
ing a pH ranging from about 2-4 and containing
ester or a saturated, single monohydric alcohol
containing not more than 2 carbon atoms in an
from about 0.1 %-4%, based on the weight or the
aqueous medium wherein the ratio 0! aqueous to 35 monomer‘ present, oi’ a dissolved salt of perdisul
non-aqueous phase ranges from 10:1 to 1:1, and
iuric acid and from about 0.5%—4%. based on the
having a pH ranging from about 1 to 5 and con
weight of the aqueous medium, of a dispersing
taining a catalytic amount or a dissolved salt 01’
agent from the group consisting or
perdisulfuric acid and from .2% to 5%, based on
o
/
/
'
the weight of said aqueous medium, oi a dispers 40
noséo
ing agent selected from the group consisting oi’
OH
o
/
and R520
.
on
/
noséo and- aséo
OM
wherein R is an acyclic hydrocarbon of 12-18 car
45 bon atoms and M is an alkali metal, said emulsion
OM
during said polymerization having a substantially
inert, oxygen-free gas thereover.
wherein R is an acyclic hydrocarbon 0! 12-18 car
bon atoms and M is an alkali metal.
'
5. The process for obtaining a resinous mate
2. The process for obtaining a resinous mate
‘ rial which comprises polymerizing at a tempera
rial which comprises polymerizing at a tempera
ranging from 20° C.- 60° C. the polymerizable
ture ranging from about 0° C.-80" C. the polymer 50 ture
components of an emulsion consisting of vinyl
izable components of an emulsion consisting of
chloride in admixture with from 1%-25% by
vinyl chloride in admixture with from 1-25% by ,
weight of the diethyl ester or fumario acid, said
weight 01 said polymerizable components oi! a fu
emulsion being in an aqeuous medium having a
maric diester of a saturated, single monohydric
oi aqueous to non-aqueous phase of from 4: 1
alcohol containing not more than 2 carbon atoms 55 ratio
to
1:1
and having a pH ranging from 2-4 and con
in an aqueous medium wherein the ratio of aque
taining from about 0.1%-4%, based on the weight
ous to non-aqueous phase ranges between 10:1
of monomer present, of ammonium perdisulfate,
and 1:1 having a pH ranging from about 1 to 5
and from about 0.5%-4%, based on the weight of
and containing from .1% to 10%, based on the
the aqueous medium, of the sodium salt of sul
weight or the monomer present. of a dissolved sal; 60 ionated
paraihn oil, said emulsion during said
" oi perdisuliuric acid and from 2% to 5%, base
polymerization ‘being in contact with an atmos
on the weight or said aqueous medium, of a dis
parsing agent selected from the groupgconsisting
phere of nitrogen.
6. A process for obtaining a resinous material
which comprises polymerizing at a temperature
O
ranging from about 20° C. to 60° C. the polymeriz
able components of an emulsion consisting 01'
vinyl chloride in admixture with from 1-25% by
OM
OM
weight of said polymerizable components 0! the
wherein R is an acyclic hydrocarbon or 12-18 car
diethyl ester 01’ fumaric acid, said emulsion being
70
bon atoms and M is an alkali metal, said emulsion
in
an aqueous medium at a pH 0! from about 2-4,
during said polymerization having a substantially
having a ratio 01' aqueous to non-aqueous phase ‘
inert. onsen-i'ree gas thereover.
- ranging between 10:1 and 1:1, and containing
3. The process tor obtaining a resinous mate
from .1% to 4%, based on the weight oi’ monomer,
rial which comprises polymerizing at a tempera
ture ranging from 0° (‘L-80° C. the polymerizable' 78 or a dissolved salt oi perdisulruric acid and irom
of
V65
308%0 and 38:0
8,404,780
11
.2% to 5%, based on the weight or the aqueous
medium, of a dispersing agent selected from the
group consisting oi’
12
being in an aqueous medium wherein the ratio of
aqueous to non-aqueous phase ranges from 4:1 to ‘
1:1. having a pH of from about 2-4 and contain
O
ing iromyabout 0.1% to 4%, based on the weight
120520 and R850
of monomer present. or a dissolved salt oi.’ perdi
sulfuric acid and from 0.5% to 4%. based on the
weight of the aqueous’ medium of a dispersing
agent selected from the group consisting of
/
on
wherein R is an acyclic hydrocarbono! 12-18 car-.
bon atoms and M is an alkali metal, said‘emulsion
during said polymerization having a substantially 10
inert. oxygen-free sas thereover. ‘
7. The process for obtaining -a resinous mate
{o
/o
nos==o and nséo
ON
on
rial which comprises polymerizing at a tempera
wherein R‘is an acyclic hydrocarbon oi 12-18 car
ture ranging from about‘ 20'' 0.160’ C. the poly
bon atoms and M is an alkalimetal, said emulsion
merizsble components or an emulsion consisting 15 duringisaid polymerisation having a substantial
of vinyl chloride in admixture with from 145%
ly inert oxygen-‘tree gas thereover.
by weight oi’ said polymerisabie components oi
the dimethyl ester or rumaric acid, said emulsion
m'mom w. mom.
Certi?cate of Correction
Patent No. 2,404,780.
July so, 1946.
HAROLD W. ARNOLD
“
It is hereby certi?ed that errors appear in the printed speci?cation of the above
numbered Jxatent requiring correction as follows: Column 9, line 39, claim 1, for
“ .5%” tea 5%; column
V
10 line 54, claim 5, for "aqeuous" read aqueous; and that the
said Letters Patent should lie read with these corrections therein that the same may
conform to the record of the case in the Patent O?ce.
Signed and sealed this 29th day of October, A. D. 1946.
[ml
LESLIE FRAZER,
e
‘ First Assistmvt Oonmcim'amr of Patents.
8,404,780
11
.2% to 5%, based on the weight or the aqueous
medium, of a dispersing agent selected from the
group consisting oi’
12
being in an aqueous medium wherein the ratio of
aqueous to non-aqueous phase ranges from 4:1 to ‘
1:1. having a pH of from about 2-4 and contain
O
ing iromyabout 0.1% to 4%, based on the weight
120520 and R850
of monomer present. or a dissolved salt oi.’ perdi
sulfuric acid and from 0.5% to 4%. based on the
weight of the aqueous’ medium of a dispersing
agent selected from the group consisting of
/
on
wherein R is an acyclic hydrocarbono! 12-18 car-.
bon atoms and M is an alkali metal, said‘emulsion
during said polymerization having a substantially 10
inert. oxygen-free sas thereover. ‘
7. The process for obtaining -a resinous mate
{o
/o
nos==o and nséo
ON
on
rial which comprises polymerizing at a tempera
wherein R‘is an acyclic hydrocarbon oi 12-18 car
ture ranging from about‘ 20'' 0.160’ C. the poly
bon atoms and M is an alkalimetal, said emulsion
merizsble components or an emulsion consisting 15 duringisaid polymerisation having a substantial
of vinyl chloride in admixture with from 145%
ly inert oxygen-‘tree gas thereover.
by weight oi’ said polymerisabie components oi
the dimethyl ester or rumaric acid, said emulsion
m'mom w. mom.
Certi?cate of Correction
Patent No. 2,404,780.
July so, 1946.
HAROLD W. ARNOLD
“
It is hereby certi?ed that errors appear in the printed speci?cation of the above
numbered Jxatent requiring correction as follows: Column 9, line 39, claim 1, for
“ .5%” tea 5%; column
V
10 line 54, claim 5, for "aqeuous" read aqueous; and that the
said Letters Patent should lie read with these corrections therein that the same may
conform to the record of the case in the Patent O?ce.
Signed and sealed this 29th day of October, A. D. 1946.
[ml
LESLIE FRAZER,
e
‘ First Assistmvt Oonmcim'amr of Patents.
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