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Патент USA US2396261

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Patented Mar. 12, 1946
Jesse Harmon, Wilmington, Del, assignor to E. 1.
(iii ll’ont de Nemours & Company, Wilmington,
Del., a corporation of Delaware
No Drawing. Application February 22, 19%,
Serial No. 523,466
5 Claims. (Cl. 260—488)
merization.” The designation “telomer" is de
This invention relates to new halogen-contain
rived from the Greek “te1os" meaning “end” and
ing organic chemical products and to a process
the Greek "mer” meaning “part.” “Telomers”
for their preparation. More paticularly, this in
differ from simple compounds or polymers in that
vention relates to the reaction of vinyl acetate
the end groups vof the chain formed from the
with carbon tetrachloride and to the products
vinyl compound are characteristic. They di?er
obtained therefrom.
from polymers or interpolymers in that they have
It ‘is known that when an unsaturated com
a lower molecular weight and in chemical and
pound such as vinyl acetate is treated with‘a
physical properties. They are usually liquids or
peroxygen catalyst, polymers are obtained. Fur
thermore, when a mixture of two or more un 10 semi-liquids. The broader aspect of telomeriza—
tion is more completely described in pending ap
saturated compounds, such as vinyl acetate and
plication Serial No. 438,466 ?led April 10, 19%2.
vinyl chloride is subjected to polymerizing con
The reaction between carbon tetrachloride and
ditions in the presence of a peroxygen catalyst,
vinyl acetate can be carried out at any tempera
interpolymers are formed. The macromolecules
thus produced have physical properties which
are of greater interest than their chemical prop
erties. For example,‘such solid polymers or in
terpolymers can be formed into ?bres and ?lms
while the chemical properties are characteristic
ture between room temperature (25° C.) and ap
proximately 150° C. to produce the 1:1 addition
product and liquid products having a plurality
of vinyl acetate units and ends from one mole
cule of carbon tetrachloride. A ratio of vinyl
of the multiplicity of repeating groups present 20 acetate to carbon tetrachloride of between 10
to 3 and 1 to 10 parts by weight is employed in
rather than reactivity of the molecule as a unit.
this reaction. The reaction is preferably carried
However, it has not previously been discovered
out in the presence of from 0.01 to 5% (based
that vinyl acetate can‘ be converted into liquid
on the weight of vinyl acetate) of a polymeriza
products of relatively low molecular weight by
treatment under suitable conditions with carbon 25 tion catalyst, such as benzoyl peroxide, which is
e?ective for the polymerization of vinyl acetate
and ineffective as a Friedel-Crafts catalyst. By
An object of this invention is the production
Friedel-Crafts catalysts are meant such com
of compounds which are represented by the gen
pounds as aluminum chloride or boron tri?uoride
eral formula
30 as used in alkylation or acetylation reactions as
0 ClzF-CHzCH-J-Cl
described in Chemical Reviews 17, 327-392 (1935) .
The catalysts operable in the present invention
have been designated “telomerization catalysts”
in which n is an‘ integer. Further objects will
in Hanford and Joyce copending application,
appear from the description given hereinafter.
These objects are accomplished by the follow 35 Serial No. 438,466, ?led April 10, 1942. The time
for the reaction of carbon tetrachloride with
ing invention which‘ comprises reacting vinyl
vinyl acetate is not critical, being dependent
acetate with carbon tetrachloride preferably in
upon temperature, catalyst and the presence of
the presence of a compound which is a cata
an inert diluent such as benzene or isooctane.
lyst for the polymerization of vinyl acetate and
a non-catalyst for the 'Friedel-Crafts reaction.
40 When temperatures of approximately ‘70° to 80° ,
C. are employed, the reaction readily takes place
The novel reaction products obtained by this
at atmospheric pressure. When higher tempera
invention can be represented by the general for
tures are employed, the reactants are placed in
a sealed container capable of withstanding the
45 autogenous pressure developed, or even higher
pressures that may be employed.
where n is an integer and in general has a value
In the preferred procedure, the reaction is
of from 1 to approximately 8. When n in the
stopped when the major part of the low boiling
above formula is unity, the compound is a simple
‘ vinyl acetate and carbon tetrachloride reactants
addition product of carbon tetrachloride to vinyl 50 have been used and the products are concentrated
acetate. However, where the value of n is greater
by vaporization of the volatile unreadted carbon
than unity, the compounds are not simple ad
dition products. For simplicity, these latter com
pounds have been called "telomers" and the proc
ess for their production has been termed “telo
tetrachloride and vinyl acetate.
reaction ,
product is not a single molecular species but is
a mixture of structurallyhomologous compounds
differing from one another by the number of vinyl
acetate units which comprise the chain between
the chlorine and CCl: groups. For many appli
cations, the mixture can be employed per se in
corrected) when heated at a rate of 10° C. per
minute. The analysis for this hydrazone was:
I\_l:l6.4% (Dumas); calculated for
asmuch as it is a mixture of functionally similar
compounds of varying chain length.
The reaction products obtained from carbon
more, where the average number of vinyl acetate
tetrachloride and vinyl acetate have chlorine
which is capable of replacement or further reac
tion by chemical ragents, for example, halogen
can be removed by treatment with a methanolic
solution'of hydrogen chloride followed by treat
ever, the addition product of carbon tetrachlo
ment withconcentrated aqueous alkali.
ride to vinyl acetate and the lower molecular
As catalysts which are useful in the promotion
weight products, such as those having two or
of this reaction, there can be used any catalyst
three vinyl acetate units can be distilled at, re
duced pressure.‘ Products having more than 15 effective for the polymerization of vinyl acetate
eight vinyl acetate units tend to be solid.
and ineffective in the Friedel-Crafts reaction.
Useful catalysts include compounds having di
This invention is further illustrated but not
units present is large, for example, three to eight,
the compounds are subject to decomposition
when heated and it is, therefore, undesirable to
subject such a mixture to distillation. How 10
limited by the following example in which the
parts given are by weight.
pounds such as diacyl peroxides such as benzoyl
Into a reaction vessel equipped with a re?ux
condenser were placed 172 parts of vinyl acetate
~ and -769 parts of carbon tetrachloride.
rectly linked oxygen atoms, e. g., peroxygen com
After re
peroxide, propionyl peroxide, lauroyl peroxide;
dialkyl peroxides such as diethyl peroxide; other
peroxides such as ascaridol, cyclohexanone per
oxide, diethyl perdicarbonate hydrogen peroxide.
tertiary butyl hydroperoxide, ozone, ozonides,
?uxing for a few minutes, 0.3 part of benzoyl per 25 etc. Other catalysts include amine oxides such ,
oxide was added, after which the temperature of
as trimethylamine oxide; ultra-violet light in the
the boiling mixture gradually rose from 73° to 84°
presence of photo sensitizers such as diacetyl.
C. over a period of ten hours. No additional rise
mercury, alkyl iodides and acetone; and metal
in temperature 'was noted when a similar addi
alkyls. Especially useful when the reaction is
tional amount of catalyst was added. After dis 30 carried out in an aqueous emulsion are water sol‘
tillation of unreactedvinyl acetate and carbon
uble persulfates, perborates, and percarbonates,
tetrachloride by heating on a water bath at a
for example, sodium, potassium, or ammonium
pressure of 20 centimeters of mercury (absolute),
persulfate, perborate, or percarbonate. Emulsi
a total ‘of 336 parts of a colorless, oily liquid refying agents and/or a buffer may be employed
mained; When this liquid was subjected to vac .85 with a persulfate or a similar catalyst when an
uum distillation, two principal fractions 'were
aqueous system is used. Furthermore, oxidizable
obtained. The ?rst fraction boiled at 62.5° C. at
sulfoxy compounds such as bisul?te may be ad
0.9 millimeter and underwent no decomposition
vantageously employed in conjunction with a
upon standingfor several weeks. This material
persulfate or similar catalyst in aqueous systems.
was found to contain 59.3% chlorine. The cal 40 It is to be understood that carbon tetrachloride
culated value for the chlorine content of the 1
and vinyl acetate can react to form the addition
to 1 addition product of vinyl acetate to car
product and products of low molecular weight
bon tetrachloride, (CC13(CH2CHOCOCH3)CD is
when no catalyst is present, however, the reac
tion requires a longer period of time. For this
The higher boiling product, which had a boil 45 reason, the addition of small amounts of a cat
ing point of 107°. C. at 1.5 mm. pressure, had a
alyst of the type hereinbefore mentioned is ad
chlorine content of 43.0%. The calculated chlo
rine content of a compound having two vinyl ace- '
The compounds obtained by the process of this
tate units combined with one carbon tetrachlo
invention are useful as plasticizers, solvents, and
50 in other applications. Forv many such uses, sep
ride unit
aration of the individual compounds is unneces
sary in view. of the fact that the compounds all
is 42.2%. Attempted distillation of higher boil
have the same functional groups and differ only
ing products present in the reaction product, even
in the number of'vinyl acetate units present. By
under diminished pressure, is accompanied by 55 virtue of the presence of active halogen in the 1:1
some decomposition.
, addition product and products having a plurality
The 1:1 addition compounds and the products
of vinyl acetate units and ends from one molecule
having a plurality of vinyl acetate units and ends
of carbon tetrachloride produced in this reaction,
from one molecule of carbon tetrachloride which
hydrolysis or other chemical reactions convert
are obtained from vinyl acetate and carbon tetra 60 these compounds to other materials having fur
chloride by therpresent novel reaction react with
ther utility for special applications. Thus, hy
aldehyde reagents such as phenylhydrazine and
drolysis gives rise to polyhydroxy compounds use
semicarbazide hydrochloride, indicating that
ful in resin or coating compositions.
the products formed are alpha-chloroesters of
The above description and examples are in
acetic acid. For example, the semibarbazone of
tended to be illustrative only. Any modi?cation
the 1 to 1 addition product of vinyl acetate and
of, or variation therefrom, which conforms to
carbon tetrachloride was found to darken at 160°
the spirit of the invention, is intended to be in
C. and melt with decomposition at 192° C. (un
cluded within the scope of the claims.
corrected); it contained 19.3% nitrogen as de
What is claimed is:
termined by the Dumas method. The calculated 70
1. A liquid mixture of compounds of the for
nitrogen content of the compound
19.3%. , A
2,4-dinitrophenylhydrazone i was
readily prepared and found to melt at 173° C. (un
75 wherein n is an integer from one to eight.
2. A liquid having the general formula -
of obtaining Ipolychlorinated
compounds which comprises reacting at 25450”
' C. vinyl acetate with from 0.3 to 10 parts, per part
of vinyl acetate, of carbon tetrachloride.
wherein n is an integer from one to eight.
3. A liquid of the formula.
4. A process
I 5. Process of claim 4 wherein a. peroxy poly
merlzatlon catalyst is employed.
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