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Патент USA US3025282

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3,025,272
Patented Mar. ‘13, 1952
ice
2
hydroxy carboxylic acid with vinyl chloride. Such im
proved vinyl chloride interpolymers contain 0003-030
3,025,272
weight percent of the allyl ether-allyl ester of the hydroxy
COPULYMERS
Richard H. Martin, .lr., Spring?eld, Mass, assignor t0
Monsanto Chemical (Iornpany, 'St. Louis, Mo., a cor
5
carboxylic acid with the balance of the interpolymer
being vinyl chloride. The vinyl chloride interpolymers
of improved physical properties are obtained at rates of
polymerization which are fully equivalent to those ob
tained in the homopolymerization of vinyl chloride.
As noted earlier herein, it is known that the physical
The present invention relates to novel vinyl chloride
properties
of vinyl chloride polymers such as tensile
10
interpolymers and to methods for preparing same.
strength, 100% modulus and crush-resistance are im
Vinyl chloride homopolymers are widely employed as
poration of Delaware
No Drawing. Filed July 31, 1959, Ser. No. 830,705
8 Claims. (Cl. zen-7m)
a surface coating resin, as a wire insulation resin, and
proved as the molecular weight of the vinyl chloride poly
mer is increased. This is true not only for vinyl chloride
for diverse other purposes. A relatively recent develop
polymers per se, but also for formulated vinyl chloride
ment in the art has been the employment of vinyl chloride
polymer compositions containing plasticizers, pigments,
polymer insulated wires as underground electrical cables. 15 ?llers and other conventional polymer compounding in
The insulation on such underground cables must be able
gredients. Since the precision of molecular weight de
terminations is much higher than the precision of determi
nations of tensile strength, 100% modulus and crush
cal properties superior to those of many of the presently
resistance,
the comparison of polymer properties in the
20
commercially available vinyl chloride homopolymers. In
subsequent examples is based primarily upon polymer
particular, this development requires vinyl chloride poly
molecular weights, such molecular Weights being ex~
mers having a high tensile strength, a high 100% modulus
pressed in terms of the speci?c viscosities of the poly
and a high crush-resistance.
mers. All of the speci?c viscosities reported herein are
It is known that the physical properties of vinyl chlo
determined on 0.4 weight percent solutions of the poly
to withstand severe physical punishment and for maxi
mum utility requires vinyl chloride polymers having physi
ride homopolymers such as tensile strength, 100% modu 25 mer in cyclohexanone at 25 :0.050 C. The precision of
Ins and crush~resistance can be improved by preparing the
the reported values is 10.002. The formula employed
polymer under such conditions that higher molecular
for calculating speci?c viscosities is set forth below:
weights are obtained. To obtain‘such higher molecular
weights it has heretofore been necessary to lower the
Speci?c Viscosity
polymerization temperature or to reduce the concentra 30
__Soluti0n Viscosity-Solvent. Viscosity
tion of free radical generating polymerization initiator
_
Solvent Viscosity
employed or both. Such modi?cations of the polymeriza
tion process increase the cost of preparing vinyl chloride
The following examples are set forth to illustrate more
homopolymers in that they lower the rate of polymeriza 35 clearly the principle and practice of this invention to those
tion and concomitantly the productive capacity of the
skilled in the art. All parts are by weight.
equipment in which the polymer is prepared.
A method sometimes proposed for increasing the mo
EXAMPLE I
lecular weight of polymers is to incorporate a small quan
tity of a cross-linking monomer, i.e., a monomer con
Part A
taining two or more non-conjugated terminal ethylenic
groups, in the monomer charge. This method has been
used successfully with some polymer systems, but ‘it is
_A vinyl chloride homopolymer is prepared in a stirred
autoclave employing the suspension polymerization system
not generally applicable to the preparation of vinyl, chlo
ride polymers of high molecular weight. In particular, it
set forth below:
'
Component:
is di?icult to ?nd cross~linking monomers which will in
Parts by weight
Monomer _____________________________ __
Water ________________________________ __
terpolymerize with vinyl chloride at satisfactory rates.
Moreover, where interpolymers can be formed, they tend
to be quite heterogeneous in composition and in most
cases the interpolymer contains a highly gelled fraction
which is insoluble in most solvents for the vinyl chloride
interpolymer. Such interpolymers, ‘because of their
heterogeneity and insoluble gel fraction, can not be em
100
150
Suspending agent1 ______________________ __ 0.15
Lauroyl peroxide _______________________ __ 0.25
1Equimolar interpolymer of vinyl acetate and malelc an
hydride.
The polymerization is carried out at 51° C. and is com
pleted in about 16 hours. The vinyl chloride homopoly
ployed in surface coating compositions.
It is an object of this invention to provide vinyl chloride 55 mer has a speci?c viscosity of 0.51.
polymers having improved physical properties.
Part B
Another object of this invention is to provide a process
for preparing vinyl chloride polymers of improved physi
cal properties, which process can be carried out in con
ventional polymerization equipment.
An interpolymer consisting of 99.98 weight percent of
vinyl chloride ‘and 0.02 weight percent of allyl-beta-allyl
60 oxypropionate is prepared by the procedure of Part A
A further object of this invention is to provide a vinyl
chloride polymerization process which, with no sacri?ce
in the rate of polymerization, yields vinyl chloride poly
mers ‘of improved physical properties.
Other objects and advantages of this invention will be 65
apparent from the following detailed description thereof.
It has been discovered that vinyl chloride polymers of
improved physical properties, as compared with vinyl
chloride homopolymers prepared under otherwise identical 70
conditions, can be obtained by interpolymerizing minute
but critical quantities of an allyl ether-allyl ester of a
above and has a speci?c viscosity of about 0.55.
In
comparing this speci?c viscosity value with the speci?c
viscosity of the vinyl chloride homopolymer prepared in
Part A above, it will be noted that, although the inter
p’olymer contains only 0.02 weight percent of allyl-beta
allyloxypropionate, the speci?c viscosity of the resulting
interpolymer is about 8% higher than the value obtained
with the vinyl chloride homopolymer.
Part C
The vinyl chloride-allyl-beta-allyloxypropionate poly
3,025,272
3
4
mer of Part B is compounded into the wire coating for
mulation set forth below:
Component:
R
OH2=(IJ—CHZ—O~
Parts by weight
Secondary plasticizer 1 ___________________ __
22
where R is selected from the group conssiting of a hy
drogen atom and a methyl radical, (2) containing at
least one carballyloxy group of the formula:
Clay _________________________________ __
Calcium carbonate ______________________ .._
Stabilizer ______________________________ __
20
15
8
CHFé-OHr-O-J‘i
Lubricant _____________________________ __
1
Resin _________________________________ __ 100
Di(2-ethylhexyl)phthalate _______________ __ 42
1 Hydrocarbon type.
The resulting formulation has a tensile strength of
about 2600 p.s.i. and 100% modulus of about 1800
p.s.i. By way of contrast, when the vinyl chloride homo
polymer of Example I, Part A is substituted for the
vinyl chloride-allyl-beta-allyloxypropionate interpolymer,
the resulting formulation has a tensile strength and 100%
R!
10 where R’ is selected from the group consisting of a
hydrogen atom and a methyl radical, (3) the number
of allyloxy and carballyloxy groups from ( 1) and (2)
totaling not more than three, and -(4) containing no poly
merizable terminal ethylenic groups other than those
speci?ed in (1) and (2).
Typical examples of suitable polyallyl compounds in
culde allyl (or methallyl) ether-allyl (or methallyl)
esters of monohydroxy monocarboxylic acids, e.g., hy
modulus approximately 100 points lower.
droxyacetic acid, hydroxyisobutyric acid, 2-hydroxynico_
EXAMPLES I*I—V
20 tinic acid, etc.; polyhydroxy monocarboxylic acids, e.g.,
gallic acid, etc.; and monohydroxy polycarboxylic acids,
Example ‘I, Part B, is repeated except that the allyl
e.g., 3-hydroxyadipic acid, etc. Such polyallyl com~
beta-allyloxypropionate contained in the polymerization
pounds can be prepared by classical methods and certain
system is replaced with, respectively, allyl-allyloxyace
of these compounds are commercially available.
tate, allyl-o-allyloxybenzoate (the allyl ether-allyl ester
The proportions of vinyl chloride and polyallyl com
25
of salicylic acid), allyl-p-allyloxybenzoate and allyl
pound included in the interpolymers will depend upon
gamma-allyloxybutanoate. The physical properties of
the number of allyl (or methallyl) groups included in
the resulting interpolymers correspond to those of the
the polyallyl compound. When the polyallyl compound
interpolymer obtained in Example I , Part B.
contains 2 allyl (or methallyl) groups, the interpolymer
EXAMPLE VI
30 will consist of 99.70—99.99 and preferably 99.85-99.98
weight percent of vinyl chloride and, correspondingly,
An interpolymer consisting of 99.97 weight percent
0.30-0.01 and preferably 0.15-0.02 weight percent of
of vinyl chloride and 0.03 weight percent of allyl-3,4
the polyallyl compound. When the polyallyl compound
diallyloxybenzoate is prepared by the procedure of Ex
contains 3 allyl (or methallyl) groups, the interpolymer
ample I, Part B and has a speci?c viscosity of about 0.60.
35 will consist of 99.95»99.997 and preferably 99.96-99.995
EXAMPLES VII-XI
weight percent of vinyl chloride and, correspondingly,
0.05-0.003 and preferably 0.04—0.005 weight percent of
the polyallyl compound.
Five vinyl chloride-allyl~beta-allyloxypropionate poly
mers containing varying quantites of allyl-beta-allyloxy
The interpolymers of the invention are preferably pre
propionate are prepared under identical polymerization
conditions following the procedure of Example I, Part 40 pared by the Well-known suspension polymerization proc
ess in which the monomers are dispersed as small drop
B. The composition of the interpolymers and the speci?c
lets in water and polymerized therein. Although a water
viscosities thereof are set forth in Table I.
soluble interpolymer of vinyl acetate and maleic anhy
dride has been employed as the suspending agent in the
45 examples herein presented, other known suspending
agents such as gelatin, protective colloids, etc. may be
employed if desired. The polymerizations are carried
TABLE I
Wt. percent
allyl-beta-
Polymer
allyloxyinterpolymers
Speci?c
Viscosity
propionate in
out at temperatures in the range of 30—70° C. in the
Control-Vinyl Chloride Homopolymer..__
0
0.51
Example VII ____________________________ __
0.01
0.53
Example VIII-
____
0.03
0.57
Example IX__
0.05
0. 61
Example X_ __
0.08
O. 65
Example XL-
0.10
0. 69
presence of free radical generating polymerization ini
50 tiators such as lauroyl peroxide, benzoyl peroxide, etc.
The interpolymers of this invention have higher molec
ular weights and better physical properties than corre
sponding vinyl chloride homopolymers prepared under
identical polymerization conditions. Thus, the process of
55 this invention makes possible the attainment of a su
As seen from the above table, each of the interpoly
mers containing allyl-beta-allyloxypropionate has a higher
perior product at no increase in cost. Alternatively, in
terpolymers of this invention having equivalent physical
speci?c viscosity than the control vinyl chloride homo
properties to vinyl chloride homopolymers can be pre
polymer. Each of the allyl-beta-allyloxypropionate con
pared at higher polymerization temperatures. Polymeriz
taining interpolymers also has a higher tensile strength 60 ing the interpolymers at higher temperatures increases
and 100% modulus than the control vinyl chloride homo
polymer. In addition, each of the interpolymers is free
the rate of polymerization and raises the productive ca
pacity of the polymerization vessel in which the reaction
of gels and is completely soluble in such solvents as
is carried out. Thus, the interpolymers of this invention
cyclohexanone and nitrobenzene. Accordingly, the inter
make possible the attainment of a higher productive ca
polymers are well suited for use in paints and other sur 65 pacity per unit of capital investment. In general, the
face coating compositions.
productive capacity of a polymerization vessel for the
The interpolymers of this invention are binary inter
interpolymers of this invention is approximately 30%
polymers consisting of vinyl chloride and an allyl ether
higher than the productive capacity of the same vessel for
allyl ester of a hydroxy carboxylic acid, which for the
a vinyl chloride homopolymer, both of said polymers be
sake of brevity will sometimes be referred to simply as 70 ing polymerized under conditions which give identical
the polyallyl compound.
The polyallyl compounds
which can be employed in the practice of this inven
tion can be aliphatic, aromatic or heterocyclic in nature
and are characterized by (1) containing at least one
allyloxy group of the formula:
molecular weights.
The interpolymers of this invention may be used inter
changeably with vinyl chloride homopolymers in virtually
all industrial applications. The interpolymers are partic
75 ularly suitable for use in the insulation of electric wire
3,025,272
6
carboxylic acid of the group consisting of aliphatic, aro
matic and heterocyclic hydroxy carboxylic acids which
compound contains (1), as the ether moiety, at least one
allyloxy group of the formula:
and particularly for electric wire that is to be employed
as underground cable.
The above descriptions and particularly the examples
are set forth by way of illustration only. Many other
variations and modi?cations thereof will be obvious to
R
OI-IF('J~CH2——O—
those skilled in the art and can be made without depart
ing from the spirit and scope of the invention herein
disclosed.
where R is selected from the group consisting of a hy
drogen atom and a methyl group, (2), as the ester moiety,
What is claimed is:
at least one carballyloxy group of the ‘formula:
l. A resinous interpolymer selected from the group
consisting of (a) a binary interpolymer of 99.70-99.99
'
0.30-0.01 weight percent of a polyallyl compound which is
an allyl ether-allyl ester of a hydroxy carboxylic acid of the
group consisting of aliphatic, aromatic and heterocyclic
hydroxy carboxylic acids which compound contains (1),
0
CH2=(l3-—CHz—O—-(|%—
weight percent of vinyl chloride and, correspondingly,
where R’ is selected from the group consisting of a hy
drogen atom and a methl radical, (3) the number of al
lyloxy and carballyloxy groups from (1) and (2) totaling
three, and (4) no polymerizable terminal ethylenic groups
other than those speci?ed in (1) and (2).
3. A suspension polymerization process for preparing
15
as the ether moiety, one allyloxy group of the formula:
l‘
a resinous interpolymer of a monomer mixture consisting
CH2=C-—CH2—O—
20 of vinyl chloride and a polyallyl compound, which process
where R is selected from the group consisting of a hy
comprises dispersing the monomers as droplets in an
drogen atom and a methyl group, (2), as the ester moiety,
aqueous medium containing therein a suspending agent
one carballyloxy group of the formula:
and polymerizing the monomers at a temperature of
30—70° C. in the presence of a free radical generating
25 initiator; said monomer mixture being selected from the
group consisting of (a) a binary mixture of 99.70~99.99
where R’ is selected from the group consisting of a hy
drogen atom and a methyl radical, and (3) no poly~
Weight percent of vinyl chloride and, correspondingly,
0.30-0.01 weight percent of a polyallyl compound which
merizable terminal ethylenic groups other than those speci
is an allyl ether-allyl ester of a hydroxy carboxylic acid
?ed in (1) and (2), and (b) a binary interpolymer of 30 of the group consisting of aliphatic, aromatic and hetero
99.95-99.997 weight percent of vinyl chloride and, cor
cyclic hydroxy carboxylic acids which compound contains
respondingly, 0.05-0.003 weight percent of 'a polyallyl
(1), as the ether moiety, one allyloxy group of the
compound which is an allyl ether-allyl ester of a hydroxy
carboxylic acid of the group consisting of aliphatic, aro
matic' and heterocyclic hydroxy carboxylic ‘acids which
“compound contains (1), as the ether moiety, at least one
allyloxy group of the formula:
'
formula: _
35
R
CH2=(\]-—CH2—O——
where R is selected from the group consisting of a
hydrogen atom and a methyl group, (2), as the ester
moiety, one carballyloxy group of the formula:
where R is selected from the group consisting of a hy 40
drogen atom and a methyl group, (2), as the ester moiety,
at least one carballyloxy group of the formula:
RI
CHFCll-—CH2—O—(%—
where R’ is selected from the group consisting of a
hydrogen atom and a methyl radical, and (3) no poly
I
ll
45 merizable terminal ethylenic groups other than those
speci?ed in (l) and (2), and (b) a binary mixture of
where R’ is selected from the group consisting of a hy
99.95-99.997 weight percent of vinyl chloride and, cor
respondingly, 0.05—0.003 weight percent of a polyallyl
drogen atom and a methyl radical, (3) the number of
allyloxy and carballyloxy groups from (1) and (2) total
ing three, and (4) no polymerizable terminal ethylenic
compound which is an allyl ether-allyl ester of a hydroxy
carboxylic acid of the group consisting of aliphatic,
groups other than those specified in (l) and (2).
2. A resinous interpolymer selected from the group
consisting of (a) a binary interpolymer of 99.85-99.98
aromatic and heterocyclic hydroxy carboxylic acids
Which compound contains (1), as the ether moiety, at
least one allyloxy group of the formula:
weight percent of vinyl chloride and, correspondingly,
0.l5—0.02 weight percentof a polyallyl compound which
is an allyl ether-allyl ester of a ‘hydroxy carboxylic acid 55
of the group consisting of aliphatic, aromatic and hetero
cyclic hydroxy carboxylic acids which compound contains
(1), as the ether moiety, one allyloxy group of the for
mula:
60
l‘
CH2=C——OH2—O—
where R is selected from the group consisting of a
hydrogen atom and a methyl group, (2), as the ester
moiety, at least one carballyloxy group of the formula:
I
l‘
CH2=C~CH2~O——
where R is selected from the group consisting of a hy
drogen atom and a methyl group, (2), as the ester moiety,
one carballyloxy group of the formula:
where R’ is selected from the group consisting of a
hydrogen atom and a methyl radical, (3) the number of
65 allyloxy and carballyloxy groups from (1) and (2) total
ing three, and (4) no polymerizable terminal ethylenic
groups other than those speci?ed in (l) and (2).
Ill,
l
4. A suspension polymerization process for preparing
CHn=C-—CHa—-O-—-C——
a resinous interpolymer of a monomer mixture consisting
where R’ is selected from the group consisting of a hy
drogen atom and a methyl radical, and (3) no poly 70 of vinyl chloride and a polyallyl compound, which proc
ess comprises dispersing the monomers as droplets in
merizable terminal ethylenic groups other than those
an aqueous medium containing therein a suspending agent
speci?ed in (1) and (2), and (b) a binary interpolymer
and polymerizing the monomers at a temperature of
of 99.96-99.995 weight percent of vinyl chloride, and,
30-70“ C. in the presence of a free radical generating
correspondingly, 0.04-0.005 weight percent of a polyallyl
compound which is an allyl ether-allyl ester of a hydroxy 75 initiator; said monomer mixture being selected from the
3,025,272
group consisting of (a) a binary mixture of 99.85-99.98
weight percent of vinyl chloride and, correspondingly,
0.15-0.02 weight percent of a polyallyl compound which
is an allyl ether-allyl ester of a hydroxy carboxylic acid
of the group consisting of aliphatic, aromatic and hetero
Where R is selected from the group consisting of a hydro
gen atom and a methyl group, (2), as the ester moiety,
one carballyloxy group of the formula:
cyclic hydroxy carboxylic acids which compound contains
(1), as the ether moiety, one allyloxy group of the
formula:
R’
0
CH:=(|]-CH2—O—(l;|‘-—
R
where R’ is selected from the group consisting of a
hydrogen atom and a methyl radical, and (3) no poly
where R is selected from the group consisting of a
merizable terminal ‘ethylenic groups other than those
hydrogen atom and a methyl group, (2), as the ester
speci?ed in ( 1) and (2), and (b) a binary interpolymer
moiety, one carballyloxy group of the formula:
of 99.95-99.997 weight percent of vinyl chloride and,
15 correspondingly, 0.05-0.003 weight percent of a polyallyl
compound which is an allyl ether-allyl ester of a hydroxy
carboxylic acid of the group consisting of aliphatic,
aromatic and heterocyclic hydroxy carboxylic acids which
where R’ is selected from the group consisting of a
compound contains (1), as the ether moiety, at least one
hydrogen atom and a methyl radical, and (3) no poly
merizabie terminal ethylenic groups other than those 20 allyloxy group of the formula:
speci?ed in (1) and (2), and (b) a binary mixture of
R
99.96-99.995 weight percent of vinyl chloride and, cor
respondingly, 0.04-0.005 weight percent of a polyallyl
where R is selected from the group consisting of a hydro
compound which is an allyl ether-allyl ester of a hydroxy
CH:=é1—CHz-O—
carboxylic acid of the group consisting of aliphatic, 25 gen atom and a methyl group, (2), as the ester moiety,
at least one carballyloxy group of the formula:
aromatic and heterocyclic hydroxy carboxylic acids which
compound contains (1), as the ether moiety, at least one
R’
_"
allyloxy group of the formula:
CH7—C—CH2—O—
0
'4.
—
30 where R’ is selected from the group consisting of a
hydrogen atom and a methyl radical, (3) the number of
allyloxy and carballyloxy groups from (1) and (2) total
ing three, and (4) no polymerizable terminal ethylenic
where R is selected from the group consisting of a hydro
groups other than those speci?ed in ( 1) and (2).
gen atom and a methyl group, (2), as the ester moiety,
6. A resinous interpolymer of monomers consisting of
35
at least one carballyloxy group of the formula:
99.85-9998 weight percent of vinyl chloride and, corre
spondingly, 0.15-0.02 weight percent of allyl-beta
allyloxypropionate.
7. A resinous interpolymer of monomers consisting of
where R’ is selected from the group consisting of a 40 9985-9998 weight percent of vinyl chloride and, corre
hydrogen atom and a methyl radical, (3) the number
spondingly, 0,15—0.02 weight percent of allyl-gamma
of allyloxy and carballyloxy groups from (1) and (2)
totaling three, and (4) no polymerizable terminal ethylenic
groups other than those speci?ed in (1) and (2).
allyloxybutanoate.
8. A resinous interpolymer of monomers consisting of
99.85-9998 Weight percent of vinyl chloride and, corre
5. An insulated electric wire comprising an electrical 45 spondingly, 0.15-0.02 weight percent of allyl-o-allyloxy
benzoate.
wire carrying an insulating coating of a resinous inter
polymer selected from the group consisting of (a) a binary
interpolymer of 99.70-99.99 weight percent of vinyl
chloride and, correspondingly, 0.30-0.01 weight percent
of a polyallyl compound which is an allyl ether-allyl 50
ester of a hydroXy carboxylic acid of the group consist
ing of aliphatic, aromatic and heterocyclic hydroxy car
boxylic acids which compound contains (1), as the ether
moiety, one allyloxy group of the formula:
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,202,846
Garvey ______________ __ June 4, 1940
2,437,508
2,448,246
D’Alelio ______________ __ Mar. 9, 1948
Barker et al. _______ __ Aug. 31, 1948
2,515,132
2,898,244
Milone ______________ __ July 11, 1950
Martin ______________ __ Aug. 4, 1959
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