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Патент USA US2408610

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Patented Oct. 1', 1946-’ '
2,408,609 }
UNITED. STATES PATENT ‘orrlca
BESINS OF HIGH CHLOBINE CONTENT
Oliver w. can, Niagara Falls, N. ‘2., assignor to
E. L du Pont de Nemours 8: Company, Wil
mington, Del., a corporation of Delaware
No Drawing. Application May 24, 1943, ' ' '
'
Serial No. 488,215
2 Claims.‘
.
-
1
,
‘
(on. zen-ass)
_
This invention relates to the preparation of
certain new and useful chlorine-containing res
inous materials. More particularly,‘it* relates to
-
2
I
invention is tosecure these 'improved'properties -
with resins of the vinyl chloride-trichlorethylene
copolymer type by incorporating additional chlo
the preparation of new and valuable, resins by
introducing chlorine into resins previously pre
pared by copolymerizing vinyl chloride and tri
rine in these resinous products. These and still
further objects will be apparent from the en
suing disclosure of certain preferred embodi
chlorethylene.
ments of my invention.
.
In my copending application, sci-19.1 No. 488,213
illed contemporaneously herewith, I have dis
-
.
In incorporating additional chlorine into the
copolymeric resins prepared by copolymerizing
closed the preparation of new and valuable 10 vinyl chloride
prefer to feed
resins by copolymerizing vinyl chloride and tri
thecopolymer
chlorethylene. As disclosed in that application,
desired, water
' the amount of trichlorethylene presentv in the
and trichlorethylene, ordinarily I
chlorine gas into a suspension of
in anysuitable organic liquid. If
in small amounts may be present
- in the slurry or suspension of the copolymer in
tion should normally range from 1 to 5% by 1.5 the organic liquid, as I have found that a small .
monomeric material subjected to copolymeriza
weight. Copolymeric resins of the most satis
factory character, as described in said copending
application, are ordinarily prepared by copoly
merizing a mixture of vinyl chloride and trichlor
amount of- water under these circumstances
functions as catalyst and renders chlorination
more rapid and veillcient.
'
'
As an illustration, it is possible to suspend the
ethylene wherein the trichlorethylene content» 20 copolymer of trichlorethylene and vinyl chloride
in an organic liquid such as carbon tetrachloride
ranges from 1.5% to 3%.
and supply chlorine gas thereto, actinic radia--'
I have now found that resins prepared by the
copolymerization of trichlorethylene and vinyl
tion being supplied to the reactants by placing‘
chloride as disclosed in said copending applica
tion can be much improved in character, espe
cially as regards their heat stabilities, by chlori
nating the copolymeric resins so that they are
of increased chlorine content. For best results
a light source in contact with the suspension or
slurry. \ From time to time samples of the prod
uct may be withdrawn and tested to ‘determine?
chlorine content. At the beginning it is desir
able to heat the suspension or slurryin order
to initiate the reaction, but as the reaction.pro-‘ '
I have found that the resins prepared by copoly
merizing vinyl chloride and trichlorethylene 80 ceeds exothermically during the latter stages
should be chlorinated to a‘ chlorine content fall
cooling is usually essential in order to maintain
a temperature low enough to prevent excessive
ing within the range 64% to 66% by weight. In
losses of material by vaporization. At thev con- '
addition to improved heat stability, the chlor
clusion of the reaction the reaction mixture may
inated resinous materials are characterized'by
increased solubility in the common lacquer sol 35 be blown with ‘air to free it fromhydrogen chlo
ride and chlorine, and the chlorinated copoly-I
vents such as aromatic hydrocarbons, and by
‘ meric material precipitated by'the addition of
increased softening temperature. The copoly
a precipitating agent such as methanol. It is
mers of vinyl chloride and trichlorethylene, as'
described in my copending application, gen- ' then recovered by ?ltration and dried in the
.
erally have softening temperatures within the 40 usual manner.
As examples of my process for preparing new
range 70 to 80° 0., whereas by the incorpora
and valuable polymeric materials of increased
tion of additional chlorine to yield a resinous
chlorine content, the following are illustrative.
product of 64% or over chlorine content the sof
tening temperature is increased to one in the
Example I
range 109 to 120° 0. Improved heat stability, 45
higher softening temperature, and greater solu
bility in common solvents are all properties of
A copolymer of vinyl chloride and trichlor-‘
ethylene, the trichlorethylene constituting 1.5%
considerable value and importance where the.
of the monomeric material copolymerized, was
heat stability, and increased solubility in the
50° 0., there being-present, as polymerization
prepared by following the procedure described
resin is employed as a coating material.
Accordingly. it is one of the objects of this 60 in Example 1 of my copending application,» Serial
No. 488,213 filed May 24, 1943. 'This involved
invention to prepare resins of the vinyl chloride
trichlorethylene copolymer type which resins will > subjecting the monomeric mixture to copolymer
izatlon at a temperature within the range 40 to
exhibit elevated softening temperature, improved
' common lacquer solvents.‘ Another obiect of this 55
catalyst, ammonium persulfate and sodium bi
2,408,609
4
3
The copolymerization was complete
Example 11
The copolymer of Example 2 of my previously
referred t‘o-copending application was prepared,
after somewhat over three hours, whereupon the
copolymer of vinyl chloride containing 1.5% tri
chlorethylene was recovered from the autoclave
in which the copolymerization was carriedv out.
400 parts of this copolymeric material and
Yutilizing as monomeric material a mixture oi
vinyl chloride and trichlorethylene containing.
3% of trichlorethylene. _ This was copolymerized
5,314 parts by weight of carbontetrachloride
for four- hours and twenty minutes at an elevated
were then placed in a suitable glass-lined vessel
temperature.
.
equipped with a stirrer, a re?ux condenser, a ,
The copolymer thus resulting was chlorinated
thermometer well and thermometer, a light well, 10 after suspension in carbon tetrachloride by the
and an inlet tube for introducing chlorine._ Ac
introduction of chlorine gas, following the proce
tinic radiation was supplied by the light of an
dure described in Example 1, until a chlorinated
ordinary tungsten ?lament lamp placed in the
copolymer containing 64.5% of chlorine was so
light well.
.
v
cured. This material was readily soluble at room
The contents of the reaction vessel were then 16 temperature to the extent of, 33%, without amp,
heated to approximately 60° C. in order to initiate
culty, in mixed solvents such as one comprising
the reaction. Chlorine was introduced into the‘
60% of methyl ethyl ketone and 40% toluene.‘
stirred suspension of copolymer, and chlorination
Films deposited on a‘ steel plate from this solution
continued until a total of 111 parts by weight of
were characterized by the desirable properties
hydrogen chloride has been evolved. The reac 20 enumerated in Example I.
'
tion mixture was then blown with air until sub
The
products
obtained
in
accordance
with this.
stantially free from hydrogen chloride and chlo
invention are useful for many purposes in the
rine.
lacquer industry, and may be generally employed
The chlorinated coplymer was then isolated by
for impregnating and insulating purposes. "they
the addition of methanol as a precipitant to the
may be employed either alone or ‘in combination
reaction mixture. This resulted in the formation
with other resinous products.
‘
of a ?ne, easily ?ltered powder which was recov
As various changes may be made in the pre- '
ered from the methanol-carbon tetrachloride
ferred procedure as described without departing
mixture by ?ltration. In this way there were re
from the scope of my invention, it is intended
covered 485 parts by weight of a chlorinated co 80 that it shall be construed in accordance with the
polymer of vinyl chloride and trichlorethylene,
this chlorinated material analyzing 65.9% chlo
_
appended claims.‘
I claim:
1.
'
_
rine.
.
l, A polymeric product obtained by the chlo
Moldings of this chlorinated copolymeric mate
rination of a copolymer of vinyl chloride and tri
rial were prepared- at 165° C. and compared with 85 chlorethylene prepared by copolymerization of a
moldings of the 'unchlorinated copolymer pre
monomeric mixture containing between 1% and
~ pared at the same temperature. Moldings of the
5% by weight of trichlorethylene and the re
chlorinated polymer containing 65.9% chlorine
mainder of said mixture being vinyl ‘chloride,
were light yellow in color, while moldings of the
said polymeric product, as a result of said chlo
unchlorinated copolymer were jet black in color.
rination, having an increased percentage content
Moreover, in . the latter case, the chromium
of chlorine and an increased resistance to dark
plated surfaces of the molding equipment had
ening at elevated temperatures.
been severely attacked by the copolymer, while
2. A polymeric product obtained by'the chlo
no evidence of attack was noticeable in the case
rination
of a copolymer of vinyl chloride and tri
of the chlorinated resin containing 65.9% chlo 45 chlorethylene prepared by copolymerlzation of a
rine; The solubility and ease of solution of the
monomeric mixture containing between 1% and
chlorinated copolymer in various solvents were
5% by ‘weight of trichlorethylene and the re
clearly superior to those of the unchlorinated co
mainder of said mixture being vinyl chloride,
polymer. Moreover, coatings of the chlorinated
said polymeric product, as a result or said chlo
50
copolymer deposited upon steel strips were of im
rination having a chlorine content of between
- proved character, both as regards flexibility and
64% and 66%, and having an increased resistance
adherence, as well as in regard to resistivity to
to darkening at elevated temperatures. 1 '
the action of moisture. acids and alkalies.
OLIVER W. CASS.
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