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Патент USA US3084154

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United States Patent O? ice
1
2
3,084,144
cient process 'for the production of ?uorine-containing
elastomérs from fluorine-containing vinyl type com
PROCESS FDR POLYMERIZATION 0F. FLUORINE
CONTAINING ORGANIC CONIPOUNDS
George H. Crawford, Jr., Rahway, N.J., assignor, by
mesne assignments, to Minnesota Mining and Manu
facturing Company, St. Paul, Minn., a corporation of
Delaware
.
.
No Drawing. Filed July 2, 1956, Ser, No. 595,085
33 Claims. (Cl. 260—87.7)
The present invention relates to an improved process
for the polymerization of ?uorine~containing organic
compounds.
3,084,144
Patented Apr. 2, 1963
In one aspect this invention relates to an
improved process for the polymerization of ?uorine-con
taining ole?ns including both monoole?ns and polyole
?ns to yield polymer products in good yields. In another
aspect this invention relates to an improved process for
polymerizing tri?uorochloroethylene to high molecular
weight and essentially pure white thermoplastic 'homo—
polymer.
Fluorine-containing polymers including both homo
polymers and copolymers have been found to possess
pounds.
Various other objects and advantages of the present
invention Will become obvious to those skilled in the art
from the accompanying description and. disclosure.
Accordingly, the above objects are accomplished by the
process which comprises reacting a ?uorine-containing
organic compound having at least one ethylenic carbon
10 to-carb'on double bond in the presence of a catalyst com
position ‘comprising a chlorine-containing organic com
pound, an organic compound of a metal of group lllA,
and a halide of‘a transition heavy metal to produce a
polymer. The presently described process is carried out
at _' a ‘temperature __from about —-l00° C. to about
—|-'200° C.,’ and usually at a temperature between about
-20° C; and about 100° C. The process of this inven—
tion is particularly advantageous for polymerizing ?uo
?ne-containing monoole?ns and polyole?ns including
both partially halogenated and perhalogenated ?uorine
containing compounds to normally solid polymer prod
ucts.
many useful applications by virtue of their relative ‘chem
‘The preferred organic metallo compounds which are
ical inertness and high physical strength and solvent re
used to prepare the catalysts which are used in accord
25
sistance. Because of these properties, such ?uorine-con
arice with this invention‘ are the compounds of aluminum,
taining polymers can be fabricated into a wide variety of
indium and gallium in which the metal is bonded to at
useful articles having improved chemical and physical
least one alkyl ‘group such as, for example, in the alkyl
stability. One of the most useful polymers in this ?eld
aluminum halides, alkyl aluminum hydrides and tri
is the high molecular weight thermoplastic homopolymer
alkyl aluminum compounds. Of the halides of a transi
of tri?uorochloroethylene which possess excellent chem 30 tion heavy 'metal to be used as a starting material in
ical inertness, ?exibility 'and resilience, and is an efficient
the: preparation of the above catalyst composition, the
insulating material. Polymers derived from ?uoro-l,3
halides, and particularly the chlorides, of metals of
themes such as 2-?uorobutadiene—l,3 also are useful com
groups IVB and VIII are preferred. The chlorine~con
positions. In certain instances, the industrial applica
tairiing organic compound used as a starting material in
tion of such ?uorine-containing polymers may be limited; 35 the preparation of the presently employed catalyst com
however, due to the‘dif?culty in polymerizing ?uorine
positions include aliphatic and aromatic chlorine~con~
containing ole?ns.
taining compounds, preferably having only chlorine or a
There has been a demand in the ?eld of polymeriza
combination of chlorine and hydrogen bonded to carbon.
tion of ?uorine-containing ole?ns for a generally simpli 40 The
presently employed catalyst compositions are pre
?ed and improved process for the polymerization of such
pared by independently adding the organic metallo com
ole?ns to solid polymers which process also leads to good
pound and themetal'halide to the chlorine-containing or
conversions of monomer to polymer product which is es
ganic compound to produce a liquid composition having
sentially free of occluded catalyst contaminants. Often
a characteristic red color, the red color being attributed
times the polymerization system contains ingredients
to vthe formation of a complex between the organic
which are only di?icultly removed, or cannot be com
metallo compound, the metal halides and the chlorine
pletely removed from the polymer product. ‘Such con
containing organic compound. When carbon tetrachlo
taminants may have a detrimental effect on the desirable
ride is employed as the‘ chlorine-containing organic com‘
properties of the polymer, and will cause discoloration,
pound starting ‘material, the liquid catalyst composition
clouding and bubbling of the polymer when the polymer 50 thereby obtained ‘is stable, that is, no precipitation of
is subjected to elevated temperatures such as, for ex
ample, during molding of the polymer.
It is an object of the present invention to provide an
solid material is observed after prolonged storage or dur
ing its use to ‘e?ect polymerization of the ?uorine—con
taining ole?ns hereindescribed. When the other chlo
tine-containing organic compounds used in accordance
with this invention, such as chloroform, for example,
improved process for the polymerization of ?uorine-con
taining ole?ns to polymer products.
55
Another object is to provide an improved process for
are used to prepare, the catalyst compositions of this in
the homopolymerization and interpolymerization of ?uo
vention some precipitation of solid material occurs upon
rine-containing ole?ns to produce normally solid poly
mers in good yields and which are essentially free of
entrained contaminants derived from the polymerization
catalyst system.
prolonged standing, which precipitation can be avoided
to yield stable liquid catalysts by the addition of n-hex
ane, for example, to the chloroform before or at the
same time that either the organic metallo compound or
Another object is to provide an improved process for
metal halide are added thereto.
polymerizing ?uorine‘containing monoole?ns and espe
The advantages obtained by using the hereindescribed
cially per?uoro- and perfluorochloro-monoole?ns to high
liquid catalyst compositions to effect polymerization of
polymer products.
_
65 ?uorine-containing vinyl type compounds are numerous,
A further object is to provide an improved process for
one very important advantage being that polymerization
polymerizing ?uorine-containing polyole?ns such as
is capable of being effected in a homogeneous medium,
fluoro-l,3-dienes to normally solid polymer products.
i.e., in a medium in which the monomer to be polymerized
A further object is to provide an improved processv for
and the catalyst are present in the same phase. This
the homopolymerization of tri?uorochloroethylene to 70 homogeneity is realized not only at the beginning of the
high molecular weight thermoplastic polymer.
polymerization reaction but also throughout the entire re
A further object is to provide an improved highly e?i
action since the catalyst remains in a completely liquid
8,084,144
3
and dissolved state from the beginning to the conclusion
of any one polymerization reaction. Due to the homo
suitable compounds of this type which may be employed
are as follows: titanium tetrachloride, zirconium tetra
geneity of the reaction medium, the polymerization proc
chloride, ferric chloride, ferrous chloride, nickel chloride,
palladium dichloride, manganese dichloride, chromium
ess of this invention is easily controlled and represents
a generally simpli?ed process which is capable of being
dichloride, and tungsten hexachloride.
Of these com
conducted in simple equipment and is readily adapted to
pounds the inorganic chlorides of metals of groups IVB
continuous operation. Since the active catalyst species is
and VIII such as titanium tetrachloride, zirconium tetra
in a stable liquid state, the handling of the catalyst
chloride and ferric chloride are preferred, the titanium
is facilitated. A further advantage of the present stable
tetrachloride being particularly preferred. These com.
liquid catalyst compositions is that when they are used 10 pounds may be used singly or in admixture without de
to effect polymerization of various ?uorine-containing
parting from the scope of this invention.
vinyl type compounds such as tritluorochloroethylene, for
The various groups of metals above-referred to, are
example, the polymer product which forms cannot become
those set-forth in Dcming’s Periodic Table used in his
occluded within the catalyst and the catalyst in turn, which
book entitled General Chemistry (John Wiley and Sons,
remains in the liquid state, does not become occluded with
Inc., 5th edition) and in the Handbook of Chemistry and
in the polymer to any appreciable or serious degree. The
Physics, 29th edition (1945), page 314.
work-up of the polymer product is thereby facilitated and
As indicated above, a chlorine-containing organic com
the e?iciency of the process is at a maximum. The poly
pound also is employed as a starting material to prepare
mer product is freed of substantially all color by a simple
the catalyst compositions of this invention. This starting
washing procedure with carbon tetrachloride, for ex 20 material may contain from 1 to 15 carbon atoms and
ample.
Further, by using the novel catalyst compositions of
preferably contains not more than 8 carbon atom per
molecule. The chlorine-containing organic compound
this invention which enable the polymerization to be car
may be chlorine-containing aliphatic compound or a chlo
ried out in a homogeneous medium, the conversions of
rine-containing aromatic compound including both par
monomer employed to polymer product are signi?cantly 25a tially chlorinated and wholly chlorinated compounds. The
higher than the conversions obtained under the same re
chlorine-containing aliphatic compounds to be used include
action conditions of time, pressure, and temperature when
both the saturated and unsaturated compounds and are
the polymerization is effected in the presence of the solid
preferably the straight chain alkanes and alkenes having at
catalyst obtained by contacting the organic metallo com
least as many chlorine atoms as carbon atoms. Of these
pound and metal halide in the absence of the chlorine 30 aliphatic compounds those having not more than four car
containing organic compound such as carbon tetrachloride.
bon atoms per molecule are particularly preferred. The
As indicated above, one starting material which is used
preferred alkenes to be used are the nonpolymerizable
to produce the novel catalyst compositions of this inven
chlorine-containing alkenes or the :alkenes having at least
tion is an organic compound of a group IIIA metal such
three chlorine atoms bonded to the carbon atoms of an
as aluminum, indium, and gallium, and is a compound 35 ethylenic double bond. Typical examples of suitable chlo
in which the metal is bonded to at least‘ one alkyl or
rine-containing organic compounds to be used are methyl
aryl group. The organic radical which is common to
ene dichloride, chloroform, carbon tetrachloride, trichloro
each of the organic metallo compounds may contain
ethylene, tetrachloroethylene, tetrachloroethane, penta
from 1 to about 20 carbon atoms and preferably has not
more than 6 carbon atoms per radical. Of the organic
metallo compounds to be used as a starting material for
chloroethane, 1,2,3-trichloropropane, polychloro- and per
chloropropanes, -propenes, -butanes, »butenes, and higher
molecular weight homologues, and chlorobenzene.
the preparation of the present catalyst composition, those
The novel catalyst compositions of this invention are
that are preferred are compounds of aluminum in which
prepared by independently adding the organic metallo
aluminum is bonded to an alkyl radical and is additionally
compound and the inorganic metal halide to the chlorine
bonded to a member of the group consisting of an alkyl 45 containing organic compound such as carbon tetrachlo
radical, a halogen atom, a hydrogen atom, and any com~
ride, for example, in the substantial absence of air and
bination thereof and are, for example, the trialkyl alumi
moisture. It ‘is preferred to ?rst add the organic me
num compounds, alkyl aluminum halides and alkyl alumi
tallic to the carbon tetrachloride, for example, fol-lowed
num hydrides. Of the organic metallo starting materials,
by the addition thereto of the metal halide component,
which may be used in accordance with this invention, the 50 although the reverse order or independent simultaneous
alkyl aluminum halides such as dialkyl aluminum chlo
addition may be used without departing from the scope
rides and bromides are particularly preferred since these
of this invention. The mol ratio of the inorganic metal
compounds lead to the most active catalyst compositions
halide starting material to the organic metallo compound
of this invention. Typical examples of suitable organic
may vary over relatively wide limits and generally ranges
metallo compounds to be employed in the preparation of 55 between about 0.05:1 and about 2:1 and preferably
the catalyst composition of this invention are as follows:
ranges from about 0.111 and about 08:1. The num
trimethyl aluminum; triethyl aluminum; tripropyl alumi
ber of moles of chlorine-containing organic compound
num; triisobutyl aluminum; aluminum tri-n~hexyl; tri
methyl indium; triethyl indium; triphenyl aluminum; tri
phenyl gallium; diethyl aluminum ?uoride; dimethyl alu
minum bromide; diethyl aluminum bromide; diisobutyl
to the total number of moles of organic metallo com
pound plus the inorganic halide similarly may vary over
60 a relatively wide range such as from about 0.8:1 to
aluminum chloride; dimethyl aluminum hydride and ethyl
about 200:1, the number of moles of the chlorine-con
taming organic compound such as carbon tetrachloride,
preferably being at ‘least equal to the combined num
aluminum dihydride. It is to be understood that the
organic metallo compounds may be employed singly or in
ber of moles of the other two starting materials. For
admixture without departing from the scope of this in 65 practical purposes the carbon tetrachloride, for example,
vention.
generally is not employed in more than a 100 molar ex
As stated above, a second type of starting material for
cess and usually in not more than a 50 molar excess.
the production of the present catalyst compositions is a
In order to obtain stable liquid catalyst compositions
metal halide derivative of a transition heavy metal, viz. a
from chlorine-containing organic compounds other than
metal of ‘groups IVB, VB, VIB, VIIB and VIII of the peri 70 carbon tetrachloride, i.e. stable liquid catalysts from
odic system. Thus, various halide derivatives such as chlo
which solid material does not precipitate upon prolonged
rides, bromides and oxychlorides of titanium, zirconium,
hafnium, thorium, vanadium, co‘lumbium, tantalum, chro
mium, molybdenum, tungsten, manganese, iron, cobalt,
nickel, and palladium may be used. Typical examples of 75
standing or during use, a hydrocarbon compound such
as n-hexane is necessarily employed in addition to the
chlorine-containing organic compound. When a hydro
carbon compound is used in conjunction with chlorine-'
5
3,084,144
containing compounds other than CCl4, the mol ratio of
this compound to chlorine-containing organic compound
invention are those having at least one carbon to carbon
ethylenic double bond and include the partially halogen
such as chloroform, is preferably at least 1:1, although this
ated and perhalogenated ?uorine-containing mono-un
saturated and poly-unsaturated- compounds having from
mol ratio may be as low as 0.5:1 or as high‘ as 100:1 or
higher without departing from the scope of this inven-. C21 2 to about 20' carbon atoms and preferably not more
tion. In addition to n-hexane other-hydrocarbon type
than ‘12 carbon atoms per molecule. Ofthe fluorine
compounds maybe used to prepare the stable liquid cata
containing monooleiins to be employed, those that are
lyst composition when chloroform, pentachloroethane or
preferred are compounds having at least as many ?uorine
tetrachloroethylene, for example, are employed as a start
atoms as there are carbon atoms and in which any ad~
ing material, their use and effect‘ being essentially the 10 ditional halogen substitution is chlorine. The preferred
same as that of n-hexane in preventing solid material
polyolefins to be employed are the fluoro-1,3-butadienes
from precipitating from the liquid catalyst composition.
having ?uorine as the only halogen substitution and in
Typical examples of such compounds are thevaliphatic
clude the alkyl substituted butadienes and the tri?uoro
hydrocarbons or hydroaromatic compounds such aspen
methyl substituted butadienes. The ‘ole?ns to be em
tane, isopentane, cyclohexane, kerosene, tetrahydronaph 15 ployed may contain in addition to ?uorine ‘other sub
thalene, and aromatic ‘hydrocarbons such as benzene,
stituents such as, for example, alkoxy, chlorine, bromine
toluene, and xylene. Thus, for'example, stable liquid
and aryl groups.
catalyst compositions ‘which possess outstanding reac
Typical examples of the monoole?ns to be employed
tivity for initiating polymerization of fluorine-containing
are the partially halogenated ?uoroethylenes such as
ole?ns may be prepared as‘ described‘ herein ‘by the in 20
dependent addition of diethyl aluminum bromide‘and
titanium tetrachloride, for example, to arnixture of chloro~
form and pentane or benzene.
It is to be understood
that these hydrocarbon type compounds may be used in
admixture without departing from the scope of this in
vention. When it is necessary to employ‘ n-hexane, for
example, to prepare the stable ‘liquid catalyst composi~
tions of this invention, it is again important‘ that the
organic metallo compound and the metal halide be'added
vinyl ?uoride, Ivinylidene fluoride, 1,1-di?uoro-2-chloro
ethylene, 1,1-chloro?uoroethylene, and tri-iluoroethylene;
partially halogenated ?uoropropenes such as 3,3,3-tri
r?uoropropene, '2-chloro-3,3,3-tri?uoropropene, 1,1-di?uo
ropropene, 1,1,3,3,3~penta?uoropropene, and 2,3,3i,3-tetra
25, ?uoropropene; partially halogenated butenes such as
3,3,3 ~ triiluoroisobutenes, 1,1,1 - trifluoro - 3r - tri?uoro
methylbutene-Z, and hexa?uoroisobutene; perfluorohalo
monoole?ns such as 'tritluorochloroethylene, trifluoro
bromoethylene, tetra?uoroethylene, dichlorodifluoroethyb
to the chlorine-containing organic compound independ 30 ene, hexa?uoropropene, 2~chloropenta?uoropropene, 4,4
ently of each other.
When carbon tetrachloride is used as at‘starting ma
terial, stable liquid catalysts are prepared as described
above by the independent addition of the organic 'rnetallo
compound and the inorganic metal halide, and n-liexane
may be‘added at any stage during the preparation of the
liquid catalyst, if desired, since n-hexane is not neces
sary to obtain the liquid catalyst from which solid ma
terial does not precipitate when carbon ‘tetrachloride is
employed. Thus when CCL; is'employed, n-‘hexane may
dichloroper?uorocyclobutene, per?uoroisobutene, and per
?uorocyclobutene.
Typical examples of ‘?uorine-containing polyole?ns to
be used ‘are: Z-?uorobutad-iene; 2-tritluoromethyl-buta—
diene; 1,1 - di?uorobutadiene; 1,1,2 - tri?uorobutadiene;
1,1,3 -tri?uorobutadiene;
butadiene;
1,1 - ‘di?uoro - 2 - methyl
1,1 - di?uoro -‘ 3 - methyl - butadiene;
tri?uoro - 2 - methyl - butadiene;
1,1,3
1,1,2,4,4 - penta?uoro~
butadiene; 1,1,2,2~tetrafluorobutadiene; 1, l ,2,4,4-penta
fluoro-3-methylebutadiene and hexa?uorobutadiene.
be added to the stable liquid catalyst after it“has=been
Additional examples of monomers which are polym
prepared as described above, or the n-hexane may be
erized in the presence of the above-described catalyst
admixed with the carbon tetrachloride before one or
compositions are as follows: phenyltri?uoroethylene;
both of the other two components are added, or the
alpha-di?uorornethyl styrene; alpha-tri?uoromethyl sty
n-hexane may be added after or at the same time that 45 rene; 1,1,2,2—tetra?uoroethyl vinyl ether; 1,1»dihydro
‘ ?uoroalliyl vinyl ethers; and tri?uoroacrylonitrile.
either the organic metallo compound or metal halide are
added to the carbon tetrachloride.
It is to be understood that the process of this invention
is suitable not only for the homopolymerization of any
On the other hand, when one of the above-described
chlorine-containing organic compounds other than carbon
‘one 'of the above-mentioned monomers but also for the
interpolymeriza-tion of these monomers to produce co
tetrachloride is used as a starting material it is important
that the n-hexane, for example, be present when the or
ganic metallo compound and the metal halide are brought
into contact in the chlorine-containing organic compound
The polymerization process also may be used
to successfully copolymerize any of the above-mentioned
?uorine-containing ole?ns with other types of vinyl type
’ polymers.
compounds such as hydrocarbon mono- and poly-ole?ns.
such as chloroform in order to obtain a liquid catalyst
from which no solid material precipitates upon stand 55 Thus the following monomer mixtures may be polymer
ing or‘during use. Thus, for example, the organic metallo
ized in the presence of the above-described catalyst com
compound and metal halide may be independently added
positions to‘yield valuable interpolymers: butadiene and
tri?uorochloroethylene; butadiene and tetra?uoroethylene;
to an admixture of chloroform and n-hexane; or the metal
halide may be added to the n-hexane ‘followed by the
addition thereto either simultaneously or in sequence‘ of
ethylene ‘and tetra?uoroethylene; tri?uorochloroethylene
and vinylidene ?uoride; te-trafluoroethylene and (vinyl
idene ?uoride; hexa?uoropropene and vinylidene ?uo
ride; hexa?uoropropene and tetra?uoroethylene; 1,1,2,2~
the chloroform and organic metallo compound.
The independent addition of the organic metallo com
tetra?uoroethyl vinyl ether and 1,1,2~tri?uorobutadiene;
pound and the metal halide to the carbon tetrachloride,
1,1,2 - tri?uorobutadiene and 1,1,3 - tri?uorobu-tadiene;
for example, is a very important aspect of the process
for making the highly reactive liquid catalyst of this in 65 phenyltri?uoroethylene ‘and 1,l,3-tri?uorobutadiene; ‘2
"tri?uorornethyl-butadiene and 2-chloro-3,3,3-tri?uoropro
vention, since if one contacts diethyl aluminum bromide
pene; Z-?uorobutadiene and 2-chloro-3,3,3-tri?uoropro
and titanium tetrachloride, for example, both of which
pene; tri?uorochloroethylene, vinylidene ?uoride and
are liquids at room temperature,“ in the absence of car
vinyl chloride.
bon tetrachloride, for example, a solid material precipi
The number of moles of monomers to be polymerized
tates which solid cannot be dissolved in n-hexane, carbon
“with respect to the total number of moles of liquid cat
tetrachloride, chloroform, methylene dichloride, ‘and‘the
alyst may vary over relatively wide limit-s without depart
like.
ing from the scope of this invention. For example, this
The ?uorine-containing unsaturated compounds which
mole ratio may vary between ‘about 1:1 and ‘about 5000: 1,
are polymerized to advantage in accordance with‘this 75 and preferably is between about 100:1 and about 1800zl.
3,084,144
7
8
The polymerization process of this invention is carried
out at a temperature between about —l00° C. and about:
200° ‘C. and preferably is effected between about —-20°‘
C. and about 100° C. The particularly preferred temperature is between about 0° C. and about 65° C. The
pressure to be employed also may vary over relatively’
wide limits such as from substantially atmospheric pres»
sure to about 1,000 atmospheres, although lower and‘.
higher pressures may be used without departing from;
the scope of this invention. The process is conveniently‘ 10
conducted under autogenous pressure in a suitable pressure vessel. The rate of reaction varies and depends, in‘.
general, upon the particular monomer or mixture of menomers used. Generally, the time of reaction varies from;
about 10 minutes to about 7 days. The longer reaction. j
times, i.e. more than ‘about 1 hour are usually employed!
when polymerizing a per?uorohalomonoole?n.
,
ane, the polymer product possesses a brown to block color
due to the occlusion of solid catalyst contaminants whic
contaminants are only removed with di?iculty.
The chlorine-containing organic compounds above-de
scribed are unique in their ability to form a stable liquid
catalyst from which no solid material precipitate-s and
that of these compounds carbon tetrachloride is further
unique in that it leads to the formation of a liquid cata
lyst which remains as a stable liquid upon prolonged
storage or use to e?ect polymerization reactions without
the necessity of using n-hexane to obtain stable liquid
catalysts therefrom. Attempts to prepare similar liquid
catalyst from various other types of organic compounds
either with or without the use of n-hexane were unsuc
cessful. For example, when diethyl aluminum bromide
and titanium tetrachloride are independently added to
n-hcxane' alone; bromobenzene; a mixture of n-hexane
and bromobenzene; and Fluorochemical N-4-3 and Fluoro
The exact nature of the active species of the stable
chemical O-75 supplied by Minnesota Mining and Manu
liquid catalysts employed in this invention is not com‘
pletely understood or known. However, there is evidence: :20 facturing Company, a solid precipitate forms which can
not be dissolved in carbon tetrachloride, a mixture of
which indicates that the active species obtained by the in»
chloroform and hexane or any other common organic
solvent.
The following examples are offered as a better under
standing of the present invention and are not to be con
dependent addition of the organic metallo compound and
the metal halide to the chlorine-containing organic compound such as carbon tetrachloride is a complex of these
three starting materials, any excess of the carbon tetrachloride, for example, which may not enter into the for-t
m‘ation of the complex serving as a solvent for the active:
strued as unnecessarily limiting thereto. In the following
examples, the organic metallo compounds were prepared
by procedures known to those skilled in the art.
catalyst species. Substantiating evidence for the forma—v
tion of a complex between the organic metallo compound
For
example, the diethyl aluminum bromide (boiling point
such as diethyl aluminum bromide, and the metal halide I30 56° C. at 0.3 mm. mercury pressure) was prepared by
reaction of magnalium alloy (2:1 by weight of alumi
such as titanium tetrachloride, and the chlorine-contain
numrmagnesium) with ethyl bromide in the presence of
ing organic compound such as carbon tetrachloride, is
a catalytic amount of a magnesium Grignard reagent at
the following:
a temperature of about 56° C. In each of the following
(1) The liquid catalysts possess ‘a characteristic lasting;
examples normal precautions were taken to exclude air
red color indicative of the formation of a complex be-l .
and moisture, i.e. the chlorine-containing organic com
tween the organic metallo compound, the metal halide
pounds and n-hexane were dried over sodium prior to
and the chlorine-containing aliphatic compound. This;
characteristic color is not observed until both of the
metal-containing compounds are added to the chlorine-
containing organic compound.
use; the preparation of the catalysts and the polymeriza
tion reactions were conducted in a nitrogen atmosphere;
40 and the reaction vessels were dried and flushed with nitro
gen prior to introduction of the starting materials.
EXAMPLE 1
This example is intended to illustrate the preparation
(2) The above~described chlorine-containing organic:
compounds are speci?c in their ability to produce a liquid
catalyst having the characteristic lasting red coloration
and which possesses sufficient reactivity to cause polym
erization of the above-described monomers.
(3) When the stable liquid catalysts employed in the:
process of this invention are diluted with a very large ex»
cess of a hydrocarbon compound such as n-hexane no‘
precipitation of solid material occurs.
The fact that
45
of the liquid catalyst compositions used in accordance
with the present invention.
To a 200 ml. glass ?ask there were added 100‘ ml. of
anhydrous carbon tetrachloride followed by the inde
pendent addition thereto of 2 ml. (0.016 mole) of diethyl
aluminum bromide and 0.1 ml. (0.0009 mole) of titani
no precipitation occurs upon dilution with n-hexane is 50
um tetrachloride at room temperature (25° C.), the
unexpected since when diethyl aluminum bromide and
material precipitates which solid is insoluble in n-hex-ane,
addition of the titanium tetrachloride being accompanied
by stirring. A clear wine-red liquid resulted which was
in the absence of the chlorine-containing organic com
standing for many days.
titanium tetrachloride, for example, are admixed a solid
?ltered in order to remove any trace amounts of small
carbon tetrachloride and other common organic solvents.
The fact that no precipitation occurs when the stable 55 particles. The ?ltering was accomplished by transferring
the solution to a ?ltering apparatus in a nitrogen atmos
liquid catalysts of this invention are diluted with exces
phere. The liquid was then passed through a sintered
sive amounts of n-hexane ‘indicates that the diethyl alu
glass ?ne grade ?lter disc into a glass container, and
minum bromide and the titanium tetrachloride are bound
the red colored mother liquor was stored under nitrogen
in some manner to the chlorine-containing organic com
pound and that they are in a dilierent form as compared 60 until ready for use. No precipitation of solid material
from this liquid catalyst was observed after prolonged
to the form that they may be in when they are contacted
EXAMPLES 2-4
It has been found that if one carries out the polymeriza
These examples illustrate the polymerization of tri
tion of tri?uorochloroethylene, for example, in the pres 65 fluorochloroethylene in the presence of the liquid catalyst
ence of the solid precipitate which forms when diethyl
composition of this invention.
aluminum bromide and titanium tetrachloride are ad
A series of experiments was conducted in which various
mixed, and subsequently ‘injects carbon tetrachloride into
aliquots of the stable liquid catalyst prepared as de
the reaction medium, a homogenous catalyst and me
scribed in accordance with Example 1 above were added
dium are not obtained but instead the catalyst and the 70 to 300 ml. glass polymerization tubes which had previ
reaction medium remain heterogenous. it is further
ously been ?ushed with nitrogen. The contents of each
pointed out that the polymer product obtained by polym
tube were then frozen at liquid nitrogen temperature and
erization of a ?uorine-containing vinyl type compound in
100 grams of tri?uorochloroethylene were condensed into
the presence of the combination of diethyl aluminum
each of the tubes. In each case the tube was sealed and
bromide and titanium tetrachloride suspended in hex 75 the tubes were allowed to stand at 25° C. for a period
pounds.
10
to, of 300 gramsof freshly distilled tri?uorochloroethylene.
The tube was thensealed and allowed to stand at 25° C.
for ,arperiod of 7 days. The tube was then opened to
of 7 days. At the end of this time, solid polymer particles
were observed in each tube and the tubes were vented
to atmospheric pressure to allow unreacted monomer to
.allow unreacted monomer to escape, and the contents of
the tube were agitated with ‘.200 ml. of carbon tetrachlo
ride. This reaction mixture was then ?ltered, and the
solid polymerproduct was dried at 190? C. An 80 per
cent conversion of monomer employed to essentially
escape. In each case carbon tetrachloride (200 _ml.) was
added to the contents of the tubes with agitation. The re
action mixture was then ?lteredandthe solid .polymer
was again washed with carbon tetrachloride until essen
tially all of the red color was removed from the polymer
product. In each experiment ‘the solidgwhite polymer
pure white high molecular- weight polytri?uorochloro~
was dried for 8 hours at 190° C. The amount of liquid 10 ethylene homopolymer wasobtained, said polymer having
catalyst employed in each experimentas well asv the physi
cal properties of the white resinous polytri?uorochloro
a ZST of 547 seconds, and a dilute solution viscosity of
Table 1
0.68. gram’ of diethyl aluminum bromide. The contents
of the tube werefrozen at liquid nitrogen temperature
followed by the addition thereto of 0.28 gram of titanium
1.35 centistokesasdetermined in a 0.75 percent solution
ethylene homopolymer product are, indicated in the fol
of dichlorobenzotri?uoridc at 266° F.
lowing Table I. In each run the conversion vof monomer
"‘ EXAMPLE 10
employed to polymer product was good, e.g.. in Ex 15
After
?ushing
a
300
ml. glass polymerization tube with
ample 2 a 45 percent conversion was obtained.
nitrogen, the tube was evacuated and was charged with
Volume of
Liquid
Example
Dilute
Solution
Catalyst
Viscosity
(ml .) '
(centi
2 ............................... __
ZST
tetrachloride. After refreezing the contents ,of the tube,
_(Secouds)
100 grams of tri?uorochloroethylene were condensed into
stokes)\>
40
the tube in the absence of hair and moisture; The tube
--
_
a ............................... --
2
1.812
818
4 _______________________________ --
10
1.204
312
was thensealed and’ was allowed to stand at 25 ° C. for 5
25 days yielding" a 10 percent ‘conversion ‘of total monomer
employed _to polytrilluorochloroethylene homopolymer
having a ZST of v95 seconds and a dilute solution viscosity
1 Liquid catalyst prepared as described in Example 1, i.e., in which the
volume ratio of CCl4:(C2H5)2A1Br:TiCl4 is'l00:2:0.l.
b As determined
of 0.40 centistoke as determined in a 0.75 percent solu
'
0.75%.so1ution of dichlorobenzotritiuorlde at 266° F.
EXAMPLES 5-8
Various stable liquid catalysts were‘prepared by inde
pendently. adding 2" .X.111- Pf 'diéthylaluhiinum .bmmide
tion of dichlorobenzotri?uoride‘at 266° _F.
By comparing the results obtained by the procedure of
so'Example
10 with Examples 2~9 above, it is‘ apparent that
the liquid catalyst compositions of this invention lead to
improved conversions of tri?uorochloroethylene to poly
mervp'roduct, and that a ‘higher molecular weight product
and various amounts oftit'anium tetrachloride to 25 ml.
portions of anhydrous carbon‘ tetrachloride. The‘ amount
of titanium tetrachloride ‘added "to the 25 ml. of carbon
35 is obtained as‘compared to that of the product obtained
when the catalyst consistsessentially of titanium tetra
tetrachloride and 2 ml. of diethyl‘ aluminum bromide
are indicated in the following Table II. These stable
chloride and diethyl‘ aluminum bromide.
. EXAMPLE l1
liquid catalysts were prepared following the same general
procedure of Example 1 above. Two milliliter aliquots
' To. 0.5 ml..of carbon tetrachloride there were inde
of each of these catalyst preparations were then added to
pendently added at room temperature 0.02 ml. of diethyl
aluminumbromide and 0.002 ml. of titanium tetrachlo
ride. The resultant red liquid was charged to a 10 ml.
each'of four‘300 ml. glass polymerization tubes, the
tubes‘ having been previously ?ushed with nitrogen. Into
each tube there were then condensed 100 grams of tri
polymerization tube. The’ tube was then cooled in a
?uorochloroethylene. In each example, the tube was sealed
liquidnitrogenbath followed by the addition thereto of
and allowed to stand at 25° :C. for a period of 5 days, after 45 l0_grams.of. 1,1,3-tri?uorobutadiene. The tube was then
which time the tubes were vented to atmospheric pres
sealedand .the polymerization reaction was allowed to
sure to allow any ,unreacted monomer to escape. The
contents of each tube weregthen treated with carbon
tetrachloride and the polymer product was worked up fol
proceed for a period of 30 minutes at 25 ° C. under auto
above. In each example essentially pure white high
molecular weight polytri?uorochloroethylene was obtained
in good yields. The physical properties of the polymer
obtained in each case are given in 'the following Table
tion andwaswashed with n-hexane and dried in a vacuum
genouspressure.
The tube was then transferred to a
liquid nitrogen bath and was vented to atmospheric pres
lowing the same procedure vas described in Examples 2-4 50 sure. ,The solid. polymer product was collected by ?ltra
oven at 80°, C. _A white tough rubbery homopolymer of
l,l-,3-tri?uorobutadiene. was obtained .in a quantitative
55
conversion ,of rnonomeremployed.
EXAMPLE 12.
Table II
Example
Prepara-
Catalyst
tion'l 0014
TiCli (ml.)
’ (ml.)
'
‘
Amount of
Dilute
Liquid
S_olut_1on
Catalyst
Viscosity b
Used (ml.)
To 0.5 .ml. of carbontetrachloride there. were inde
pendently added at room temperature 0.2 ml. of diethyl
aluminum bromide and 0.002 ml. of titanium tetrachlo
60 ride. The resultant red liquid was charged to a 10 ml.
polymerization,.,tube.
0. 02
0.05
0. 1
0. 25
25
25
25
25
2
2
2
2
1. 505
1.279
1. 486
*1 1. 345
“ Each catalyst preparation contained 2.0 ml. of diethly aluminum
bromide per 25 ml. of C014 and the indicated amount of T1Cl4.
_
b As determined in a 0.75% solution of d1chlorobenzotn?uonde at
266° F.
‘1 ZST=373 seconds.
'
EXAMPLE 9
.The tube was then cooled in a
liquid vnitrogen bath followed by the addition thereto of
1.0_ ‘grams oil-?uorobutadiene. The tube was then sealed
and thepolymerizationreaction was allowed to proceed
65 for a period of 5 minutes at 25°-C. under autogenous
pressure. The, tubewas then transferred to a liquid nitro
gen bath and was vented to atmospheric pressure. The
solid polymer product was collected by ?ltration and was
washed?with n-hexane and dried in a vacuum oven at 80°
70 C. A white rubbery-homopolymer of 2-?uorobutadicne
A liquid catalyst was prepared by independently adding
was obtained in good yield.
1 ml. of diethyl aluminum bromide and.0.25 ml. of titani
EXAMPLE 13
um tetrachloride to '25 ml. of substantially anhydrous
carbon tetrachloride. Of this red liquid 2 ml. were added
To 0.5 ml. of carbon tetrachloride there were inde
to a polymerization tube followedby the addition there 75 pendently added at room temperature 0.02 ml. of diethyl
3,084,144
11
12
aluminum bromide and 0.002 ml. of titanium tetrachlo
ride. The resultant red liquid was charged to a 10 ml.
EXAMPLE 1?
To 0.5 ml. of carbon tetrachloride there were inde
pendently added at room temperature 0.02 ml. of diethyl
aluminum bromide and 0.002 ml. of titanium tetrachlo
polymerization tube.
The tube was then cooled in a
liquid nitrogen bath followed by the addition thereto of
10 grams of 1,1-di?uorobutadiene. The tube was then
sealed and the polymerization reaction was allowed to
proceed for a period of 5 days at 25° C. under autoge
nous pressure while rotating the tube end-over-end. The
tube was then transferred to a liquid nitrogen bath and
ride. The resultant red liquid was charged to a 10 ml.
polymerization tube. The tube was then cooled in a
liquid nitrogen bath followed by the addition thereto of
10 grams of 1,1,2-tri?uorobutadiene. The tube was then
was vented to atmospheric pressure. The solid polymer 10 sealed and the polymerization reaction was allowed to
proceed for a period of 5 minutes at 25 ° C. under autog
product was collected by ?ltration and was washed with u
enous pressure. The tube was then transferred to a liquid
hexane and dried in a vacuum oven at 80° C. A white
nitrogen bath and was vented to atmospheric pressure.
The solid polymer product was collected by ?ltration
tough rubbery homopolymer of 1,1-di?uorobutadiene was
obtained in good yield.
and was washed with n-hexane and dried in a vacuum
EXAMPLE 14
oven at 80° C. A white rubbery powdery homopolymer
of 1,1,2-tri?uorobutadiene was obtained in a 90 percent
To 0.5 ml. of carbon tetrachloride there were inde
conversion of monomer employed.
pendently added at room temperature 0.02 ml. of diethyl
aluminum bromide and 0.002 ml. of titanium tetrachlo
EXAMPLE l8
ride. The resultant red liquid was charged to a 10 ml. 20
To 0.5 ml. of carbon tetrachloride there were inde
polymerization tube. The tube was then cooled in a
pendently added at room temperature 0.02 ml. of di
liquid nitrogen bath followed by the addition thereto of a
ethyl aluminum bromide and 0.002 ml. of titanium tetra
monomer mixture containing 5 grams each of 1,1,3-tri
chloride.
The resultant red liquid was charged to a 10
?uorobutadiene and ‘1,1,2-tri?uorobutadiene. The tube
ml.
polymerization
tube. The tube was then cooled in a
was then sealed and the copolymerization reaction was 25
liquid nitrogen bath followed by the addition thereto
carried out for about 10 minutes at 25° C. under autoge
of 10 grams of l,=l-di?uorobutadiene. The tube was then
nous pressure while the tube was rotated end-over-end.
sealed and the polymerization reaction was allowed to
The tube was then transferred to a liquid nitrogen bath
proceed for a period of 2 minutes .at 25 ° C. under autog~
and vented to atmospheric pressure. The solid copolymer
product was collected by ?ltration and was washed with 30 enous pressure. The tube was then transferred to a
liquid nitrogen bath and was vented to atmospheric pres
n-hexane and dried in vacuo at about 80° C. A snappy
‘sure. The solid polymer product was collected by ?ltra
white rubbery copolyrner of 1,1,3-tri?uorobutadiene and
tion and was washed with n-hexane and dried in a
l,l,2-trifluorobutadiene was obtained in an 86 percent con
version of total monomer charged to polymer product.
vacuum oven at 80° C. A white rubbery powder of poly
end-over-end. The tube was then transferred to a liquid
polyvinylidene ?uoride in good yield.
1,1-di?uorobutadiene was obtained in a 95 percent con
35
version of monomer charged.
EXAMPLE 15
To 0.5 ml. of carbon tetrachloride there were inde~
EXAMPLE 19
pendently added at room temperature 0.02 ml. of di
After ?ushing a 300 ml. glass polymerization tube with
ethyl aluminum bromide and 0.002 ml. of titanium tetra
nitrogen, the vessel is charged with 10 ml. of carbon
chloride. The resultant red liquid was charged to a 10 40 tetrachloride followed by the independent addition there
ml. polymerization tube. The tube was then cooled in a
to of 1 ml. (0.00825 mole) of diethyl aluminum bromide
liquid nitrogen bath followed by the addition thereto of
and 0.5 ml. (0.0045 mole) of titanium tetrachloride.
a monomer mixture containing 5 grams each of 2-tri~
The contents of the tube are then frozen at liquid nitro
?uorornethyl - butadiene and 1,1,2 - tri?uorobutadiene.
gen temperature and about 50 grams of vinylidene ?uo
The tube was then sealed and the copolymerization re 45 ride are condensed into the tube, after which the tube is
action was carried out for about 10 minutes at 25° C.
sealed. The reaction mixture is allowed to stand at about
under autogenous pressure while the tube was rotated
30° C. for a period of about 3 days to produce solid
nitrogen bath and vented to atmospheric pressure. The
solid copolymer product was collected by ?ltration and 50
EXAMPLE 20
To 200 ml. of carbon tetrachloride there are independ
80° C. A copolymer of Z-trifluOrOmethyl-butadiene and
ently added at room temperature 4 ml. of triisobutyl
1,1,2-trifluorobutadiene was obtained in a 96 percent con
aluminum and 1 ml. of titanium tetrachloride. A clear
version of total monomer charged to polymer product.
red liquid is obtained from which no solid precipitates.
55 A 20 ml. aliquot of this liquid preparation is then trans
EXAMPLE 16
ferred to a 300 ml. glass polymerization tube. After
To 0.5 ml. of carbon tetrachloride there were inde
freezing the contents of the tube at'liquid nitrogen tem
pendently added at room temperature 0.02 ml. of di
perature, about 100 grams of tri?uorochloroethylene are
ethyl aluminum bromide and 0.002 ml. of titanium tetra
condensed into the tube. The polymerization reaction is
chloride. The resultant red liquid was charged to a 10 60 allowed to proceed at about 35° }C. for a period of 24
ml. polymerization tube. .-....The tube was‘ then cooled in a
hours under autogenous pressure to yield white high
was washed with n-hexane and dried in vacuo at about
liquid nitrogen bath followed by the addition thereto of
molecular weight polytrifluorochloroethylene in good
a monomer mixture containing 5 grams each of 1,1,3
yield.
Vtriiluorobutadiene and 2-tri?uoromethyl-butadiene. The
EXAMPLE 21
tube was then sealed and the copolymerization reaction
was carried out for about 10 minutes at 25° C. under
After ?ushing a glass polymerization tube having a
autogenous pressure while the tube was rotated end-over
volume capacity of 300 ml. with nitrogen there are added
end. The tube was then transferred to a liquid nitrogen
25 ml. of anhydrous n-hexane and 25 ml. of anhydrous
bath and vented to atmospheric pressure. The solid co
chloroform followed by the independent addition thereto
polymer product was collected by ?ltration and was 70 of 1 ml. of diethyl aluminum bromide and 0.2 ml. of
washed with n-hexane and dried in vacuo at about 80°
titanium tetrachloride. A clear wine-red liquid is ob
C. A white rubbery copolymer of 1,1,3-tri?uorobutadi
tained from which no solid material precipitates upon
ene and Z-tri?uoromethyl-butadiene was obtained in a
good- conversion of total monomers charged to polymer
product.
prolonged standing at room temperature. About 25
grams of triiluorochloroethylene are condensed into the
75 tube at liquid nitrogen temperature and the tube is sealed.
15
3,084,144
-'strued as unnecessarily limiting thereto. Various altera
1tions and modi?cations of the reaction conditions, re
actants and techniques described herein may become
apparent to those skilled in the art without departing from
the scope of this invention.
Having described my invention, I claim:
1. A process which comprises polymerizing a ?uorine
containing ethylenically unsaturated compound having at
16
containing from 2 to about 12 carbon atoms per mole
cule in admixture with a liquid catalyst composition com
prising pentachloroethane, an alkyl aluminum compound,
and a halide of a transition heavy metal.
12. A process which comprises polymerizing a ?uorine
containing ethylenically unsaturated compound having at
least one carbon to carbon ethylenic. double bond and
containing from 2 to about 1-2 carbon atoms per mole
cule in admixture with a liquid catalyst composition com
least one carbon to carbon ethylenic double bond and
containing from 2 to about 12 carbon atoms per mole 10 prising tetrachloroethylene, an alkyl aluminum compound,
cule in admixture with a catalyst composition compris
and a halide of a transition heavy metal.
ing a liquid organic solution of a chlorine-containing
13. A process which comprises polymerizing a ?uorine
aliphatic compound possessing l to .15 carbon atoms and
containing ethylenically unsaturated compound having at
having at least as many chlorine atoms as carbon atoms,
least one carbon to carbon ethylenic double bond and
to which solution has been independently added an alkyl 15 containing from 2 to about 12 carbon atoms per mole
aluminum compound, and a halide of a metal of group
cule in admixture with a catalyst composition compris
IVB, thereby producing a polymer.
ing a liquid organic solution of a chlorine-containing
2. A process which comprises polymerizing a ?uorine
aliphatic compound possessing l to .15 carbon atoms and
containing ethylenically unsaturated compound having at
having at least as many chlorine atoms as carbon atoms,
least one carbon to carbon ethylenic double bond and
to which solution has been independently added an alkyl
containing from 2 to about 12 carbon atoms per mole
aluminum compound, and titanium tetrachloride, thereby
cule in admixture with a catalyst composition compris
producing a polymer.
ing a liquid organic solution of a chlorine-containing
14. A process which comprises polymerizing a fluorine
aliphatic compound possessing l to 15 carbon atoms and
containing ethylenically unsaturated compound having at
having at least as many.ichlorine atoms as carbon atoms, 25 least one carbon to carbon ethylenic double bond and
to which solution has been independently added an alkyl
containing from 2 to about 12 carbon atoms per mole
aluminum halide, and a halide of a metal of group IVB,
cule in admixture with a catalyst composition compris
thereby producing a polymer.
ing a liquid organic solution of a chlorine-containing
The process of claim 2 in which said alkyl alumi
aliphatic compound possessing 1 to ‘15 carbon atoms and
compound is diethyl aluminum bromide.
30 having at least ‘as many chlorine atoms as carbon atoms,
The process of claim 2 in which said alkyl alumi
to which solution has been independently added an alkyl
compound is diethyl aluminum chloride.
aluminum compound, and a halide of a metal of group
A process which comprises polymerizing a ?uorine
VIII, thereby producing a polymer.
containing ethylenically unsaturated compound having at
15. The process of claim 14 in which said halide of a
Eleast one carbon to carbon ethylenic double bond and
metal of group VIII is ferric chloride.
‘containing from 2 to about 12 carbon atoms per mole~
16. A process which comprises polymerizing a ?uoro
'cule in admixture with a catalyst composition compris
monoole?n in admixture with a catalyst composition com
ing a liquid organic solution of a chlorine-containing
prising a liquid chlorine-containing organic solvent, to
aliphatic compound possessing 1 to 15 carbon atoms and
which liquid has been added independently an alkyl alumi
'having at least as many chlorine atoms as carbon atoms, 40 num compound, and a chloride of a. transition heavy
T to which solution has been independently added a trialkyl
metal, to produce a polymer of the ?uoromonoole?n.
'a’l'u‘tninum compound, and a halide of a metal of group
17. A process which comprises polymerizing a per
IVE, thereby producing a polymer.
3.
num
4.
num
'5.
halogenated ?uorine-containing monooleiin in admixture
6. The process of claim 5 in which said trialkyl alumi
with a catalyst composition comprising a liquid organic
:num compound is triisobutyl aluminum.
45 solution of a chlorine-containing aliphatic compound
7. A process which comprises polymerizing a ?uorine
possessing l to 15 carbon atoms and having at least as
'containing ethylenically unsaturated compound having at
.least one carbon to carbon ethylenic double bond and
‘containing from 2 to about 12 carbon atoms per mole
'cule in admixture with a catalyst composition compris
.'ing a liquid organic solution of a chlorine-containing
‘aliphatic compound possessing 1 to 15 carbon atoms and
having at least as many chlorine atoms as carbon atoms,
ito which solution has been independently added an alkyl
many chlorine atoms as carbon atoms, to which solution
has been independently added an alkyl aluminum com
pound and a chloride of a metal of group IVB, thereby
producing a polymer of said ?uorine-containing mono
ole?n.
18. A process which comprises polymerizing tri?uoro
chloroethylene at a temperature between about ~100° C.
and about +200“ C. in admixture with a liquid catalyst
aluminum hydride, and a halide of a metal of group IVB, 55 composition comprising a chlorine-containing aliphatic
thereby producing a polymer.
8. The process of claim 7 in which said alkyl alumi
num hydride is diisobutyl aluminum hydride.
9. A process which comprises polymerizing a ?uorine
containing ethylenically unsaturated compound having at 60
compound possessing -1 to 15 carbon atoms and having at
least as many chlorine atoms as carbon atoms, an alkyl
aluminum compound, and a chloride of a metal of group
IVB, to produce a polymer of tri?-uorochloroethylene.
19. A process which comprises homopolymerizing .tri
least one carbon to carbon ethylenic double bond and
containing from 2 to about 12 carbon atoms per mole
cule in admixture with a liquid catalyst composition com
prising carbon tetrachloride, an alkyl alumintu'n com—
pound, and a halide of a transition heavy metal.
65
10. A process which comprises polymerizing a ?uorine
catalyst composition comprising diethyl aluminum bro
containing ethylenically unsaturated compound having at
?uorochloroethylene at a temperature between about
?uorochloroethylene at a temperature between about
—-20° C. and about.100° C. in admixture with a liquid
mide, titanium tetrachloride and carbon tetrachloride, to
produce a solid homopolymer of tri?uorochloroethylene.
20. A process which comprises homopolymerizing tri
least one carbon to carbon ethylenic double bond and
—20° C. and about 100° C. in admixture with a liquid
containing from 2 to about 12 carbon atoms per mole—
catalyst
composition comprising triisobutyl aluminum,
cule in admixture with a liquid catalyst composition com 70 titanium tetrachloride and carbon tetrachloride, to pro
prising chloroform, an alkyl aluminum compound, and
duce a solid homopolymer of tri?uorochloroethylene.
a halide of a transition heavy metal.
21. A process which comprises homopolymerizing tri
11. A process which comprises polymerizing a ?uorine
?uorochloroethylene at a temperature between about
containing ethylenically unsaturated compound having at
least one carbon to carbon ethylenic double bond and 75
—20° C. and about 100° C. in admixture with a liquid
catalyst composition comprising diethyl aluminum bro
3,084, 144
17
18
mide, titanium tetrachloride, chloroform and n-hexane, to
produce a solid homopolymer of tri?uorochloroethylene.
carbon tetrachloride; diethyl aluminum bromide and ti
tanium tetrachloride, to produce a copolymer of 1,1,2
22. A process which comprises homopolymerizing tri—
tri?uorobutadiene and .1,l,3~tri?uorobutadiene.
30. A process which comprises copolymerizing 1,1,2
?uorochloroethylene at a temperature between about
~20“ C. and about 100° C. in admixture with a liquid
catalyst composition comprising diisobutyl aluminum
hydride, titanium tetrachloride, pentachloroethane and
n-hexane, to produce a solid homopolymer of tri?uoro
chloroethylene.
tri?uorobutadiene and 1,1,3-tri?uorobutadiene at a tem
perature between about ~20" C. and about 100° C. in
admixture with a liquid catalyst composition comprising
carbon tetrachloride; triisobutyl aluminum and titanium
tetrachloride, to produce a copolymer of 1,1,2-tri?uoro
23. A process which comprises copolymerizing tri 10 butadiene and 1,1,3-tri?uorobutadiene.
?uorochloroethylene and vinylidene ?uoride at a tem
31. A process which comprises copolymerizing 1,1,2
perature between about —20° C. and about 100° C. in
-tri?uorobutadiene and 2-tri?uoromethyl-butadiene at a
admixture with a liquid catalyst composition comprising
temperature between about —20° C. and about 100° C.
carbon tetrachloride, diethyl aluminum bromide and ti
in admixture with a liquid catalyst composition com
tanium tetrachloride, to produce a copolymer of tri?uoro 15 prising carbon tetrachloride, diethyl aluminum bromide
chloroethylene and vinylidene fluoride.
and titanium tetrachloride, to produce a copolymer of
‘24. A process which comprises polymerizing a par
1,1,2-Iri?uor0butadiene and 2-tri?uoromethyl-butadiene.
tially halogenated ?uorine~containing monoole?n in ad~
32. A process which comprises polymerizing 2-?uoro~
mixture with a catalyst composition comprising a liquid
butadiene at a temperature between about —‘20° C. and
organic solution of a chlorine-containing aliphatic com 20 about 100° C. in admixture with a liquid catalyst com
pound possessing from 1 to 15 carbon atoms and having
position comprising carbon tetrachloride, diethyl alumi
at least as many chlorine atoms as carbon atoms, to
num bromide, and titanium tetrachloride, to produce a
which solution has been independently added an alkyl
polymer of Z-?uorobutadiene.
33. A process which comprises polymerizing 1,1-di
aluminum compound and a chloride of a metal of group
IVB, to produce a polymer of said ?uorine-containing 25 ?uoro-butadiene at a temperature between about --20° C.
monoole?n.
and about 100° C. in admixture with a liquid catalyst
.25. A process which comprises homopolymerizing
composition comprising carbon tetrachloride, diethyl alu
vinylidene ?uoride at a temperature between about
minum bromide, and titanium tetrachloride, to produce
~20° C. and about 100° C. in admixture with a liquid
a polymer of 1,l-di?uorobutadiene.
catalyst composition comprising diethyl aluminum bro 30
mide, titanium tetrachloride and carbon tetrachloride, to
produce a ‘solid homopolymer of vinylidene ?uoride.
26. A process which comprises polymerizing a ?uoro
1,3-diene in admixture with a catalyst composition com
prising a chlorinecontaining organic compound, an alkyl 35
aluminum compound, and a chloride of a transition heavy
metal, to produce a polymer of the ?uoro-1,3-diene.
27. A process which comprises homopolymerizing
1,1,2-tri?uorobutadiene at a temperature between about
-20° C. and about 100° C. in admixture with a liquid 40
catalyst composition comprising diethyl aluminum bro
mide, titanium tetrachloride and carbon tetrachloride, to
produce a ‘solid homopolymer of 1,1,2-tri?uorobutadiene.
28. A process which comprises homopolymerizing
1,1,3-tri?uorobutadiene at a temperature between about 45
—-20° C. and about 100° C. in admixture with a liquid
References Cited in the ?le of this patent
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‘2,781,410
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1960
catalyst composition comprising diethyl aluminum bro
mide, titanium tetrachloride and carbon tetrachloride, to
produce a solid homopolymer of 1,1,3-tri?uorobutadiene.
29. A process which comprises copolymerizing 1,1,2 50
trifluorobutadiene and 1,1,3-tri?uorobutadiene at a tem
perature between about —-20° C. and about 100° C. in
admixture with a liquid catalyst composition comprising
FOREIGN PATENTS
533,362
534,792
Belgium _____________ __ May 16, 1955
Belgium _____________ _.. Ian. 31, 1955
OTHER REFERENCES
Mueller, “Inorganic Chemistry” (1952), page 405.
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