Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
lX5~7~7
TITLE
Cyclic Monomers Derived From
Trifluoropyruvate Esters
BACKGROUND OF THE INVENTION
Field of the Invention
Halogenated cyclic monomers, i.e., dioxoles
and dioxolanes, preparation thereof and polymers
thereof.
State of the Art
U.S. Patent 2,925,424 discloses cyclic
fluoroketals of the formula
R \ C
~ O / Ry
prepared by reacting fluoroketones with
~-haloethanol. Rx and Ry are perhalohydrocarbyl
radicals of 1 to 7 carbon atoms, and Rz is a
divalent hydrocarbyl or halohydrocarbyl radical of 1
to 12 carbon atoms.
V.S Patents 3,865,845 and 3,978,030
disclose fluorinated dioxoles of the formula
FC O R
FC o/ ~R2
where Rl and R2 are both perhalogenated
hydrocarbyl radicals of 1 to 3 carbon atoms
containing at least one F atom, and preparation of
said dioxoles by reacting the corresponding
dioxolanes with Mg. The dioxolanes are prepared by
fluorination with SbF3-SbC15 at 120C of 2,2-bis-
(perhaloalkyl)-4,4,5,5-tetr2chloro-1,3~dioxolanes,
which in turn are prepared from haloke~ones in
accordance with the method described in U~S.
2,925,424 cited above.
CR-So38
~&
2 ~ ~ 5~7~ 7
V S. Patent 3,555,100 discloses the
decarbonylation of fluorocarboxylic acid fluorides in
the presence of SbF5.
U.S. Patent 3,308,107 discloses perfluoro-2-
5 methylene-4-methyl-1,3-dioxolane, its preparation
from perfluoro-2,4-dimethyl-2-fluoroformyl-1,3-
dioxolane, and polymers thereof.
U.S. Patent 3,532,725 discloses the
photochlorination of alkyl and aralkyl ester groups
of fluorinated esters in the presence of C12, UV
radiation and, optionally, CC14 as solvent.
U.S. Patent 3,557,165 discloses the
conversion to acyl halides, in the presence of Lewis
acids, of fluorinated esters wherein the ester groups
contain polyhalo~enated alkyl or aralkyl groups. The
disclosed Lewis acids include FeC13, SbC15,
ZnC12, ZnC14, BF3, BC13, MoC15, tin
chlorides and metal chlorides, bromides and iodides
such as ZrI4 and antimony bromide.
U.S. Patent 3,316,216 discloses the
preparation of fluorinated dioxolanes of the formula
R'
R~ ¦ \ C/
R C~- O / ~ F2Xl
where R, R' and R" can include H, hydrocarbyl,
haloalkyl and various other carbon-containing groups,
and X and Xl can include H, halogen and
perfluoroalkyl, from fluoroketones and epoxides.
U.S. Patent 3,324,144 discloses
fluorodioxolanes
~C-O~
" ¦ f (RyCYF~(RXCXF)
R~--c~o
prepared from ketones and epoxides.
.. . . . . . .... .. .. .
~L~2S87;~7
U.S. Patent 3,749,791 discloses halogen-
substituted 2j2-bis(trifluoromethyl)-1,3-dioxolanes
XHf-O \ /CF3
X'HC-O CF3
where X is Cl or F and Xi is H, Cl, or F, and their
preparation by hydrogenation of 2,2-bis(trifluoro-
methyl)~l,3-dioxolane.
SUMMARY OF THE INVENTION
This invention concerns halogenated
dioxolanes of the formula-
X2X3C ~ / RF
/c\
X4x5c X
wherein:
Xl is selected from the group consisting
of Cl, F, COF, COC1, CO2CC13, CO2R and CO2M;
R is selected from the group consisting of H
and alkyl of 1 to 4 carbon atoms;
RF is perfluoroalkyl of 1 to 4 carbon
atoms;
M is selected rom the group consisting of
alkali metal ion and ammonium;
X2, X3, X4 and X5, independently~,
are selected from the group consisting of H, Cl and
F; with the proviso that when
X2, X3, X4 and X5 are each H, X
is CO2R or CO2M.
The halogenated dioxolanes described above
can be depicted subgenerically by formulas I and II:
H2C--~ ~RF
H2C - O~ CO2R(M)
and
.. . . .. , . . .. . . ,, .. ...... ,. . . . .. . . ... . . ..... ~
12~3737
4 R
X2X3I \ C/ F II
X4X5C-- \X
wherein:
Xl, R, RF, and M are as defined above;
and
X2~ X3, X4 and X5, independen~ly,
are Cl or F.
This invention also concern.~ dioxolanes of
the formula:
X2X3C - O \ III
x4x5c O
wherein
X2, X3, X4 and X5, independently,
are Cl or F, provided that at least two are F.
This invention also concern-~ perhalogenated
dioxoles of the formula:
Y C-O / RF
Y3C-O \ Yl IV
wherein Yl, Y2 and Y3, independently, are F or
Cl.
This invention also concerns homopolymers
and copolymers of monomers III and IV; a coating
solution comprising one or more polymers derived from
III or IV; one or more polymers derived from III or
IV coated on a cellulosic substrate; films of
polymers derived from III or IV; and a process for
making the cyclic compounds I, II, III and IV.
Hereafter, the term "polymer~s)" is intended
to include homopolymer(s), copolymer(s),
te~polymer(s), etc., depending on the context in
which the term is used.
.. . . . .. . . .. .. . . .
` '` ~L~5~3
Dioxolanes I are prepared by reacting a
1uorinated keto ester of the formula RFCOCO2R
wherein RF and R are as defined above, with ~i) a
compound of formula HORX where X is the nonproton
radical of a hydrogen acid, HX~ and R is a divalent
ethylene radical or haloethylene radical, or (ii)
ethylene oxide, in the presence of a solid basic salt
such as potassium carbonate optionally slurried in an
inert liquid such as n-pentane.
Dioxolanes II, wherein Xl is Cl, COCl or
CO2CC13 and X2 to X5 are each Cl, are
prepared by chlorinating dioxolane I in the presence
of ultraviolet radiation in a chlorinated solvent
such as CC14 below about 80C, or in the absence of
solvent at a temperature above 80C. The former
procedure which is preferred increases the yield of
dioxolane II wherein Xl is CO2CC13.
Although photochlorination also provides
dioxolan2s II wherein Xl is COCl or Cl, the acyl
chloride wherein Xl is COCl is prepared in higher
yield by elimination of phosgene from dioxolane II
wherein Xl is CO2CC13 in the presence of
selected metal chlorides, particularly cesium
chloride.
2~ Fluorine-containing species of dioxolanes II
are prepared by treating the chlorinated species,
prepared as just described, with various fluorinating
agents including, but not limited to, SbF3 in the
presence of SbC15 or SbF5, HF in the presence of
Cr203, or metal fluorides, MF, where M is an
alkali metal or ammonium. Alkali metal fluorides,
particularly KF or NaF, are especially useful or
converting COCl to COF in;f~rmula II dioxolanes
wherein Xl is COCl. Strongér fluorinating agents
such as SbF3-SbC15 or HF-Cr2O3 are necessary
., ., , . , . . , .. , ... . . . ., .. , . ; , .. . .. ..... . , .. . .. . ... .. . . .. ~ .
5 ~ 73 7
.~ to replace Cl in the 4 or 5-ps~$tions with F and/or
to prepare ~pecies whereln Xl i~ Fo
Unsaturated dioxolanes of ~ormula III are
prepared by pyrolysis of formula II dioxolanes
wherein XI is CO2M and at least ~wo of X2 to
X5 are F; the starting dioxolanes are metal salts
and are prepared by treating an approprlate fonmula
II dioxolane wherein Xl is C~Cl or COF with an
alkali 6uch as Na2C03 or Na3P04. When the
reaction is carried out in a high-~oiling aprotic
solvent medium such as tetraglyme, the resulting salt
can be directly pyrolyzed ~o the dioxolanes of
formula III without prior isola~ion, by heating the
dissolved salt at a temperature in the range of about
140 to 200C. Alternatively, the salts can be
isolatsd and separately pyrolyzed in a high-boiling
aprotic solvent such as tetraglyme~ If salt~ of a
formula II dioxolane wherein X2 to X5 contain
less than two fluorines are pyrolyzed under the above
conditions, the principal products are dioxoles of
formula IV wherein Yl and Y2 are Cl and Y3 is
Cl ~r F.
Dioxoles of formula IV oan al50 be prepared
by contacting and reacting a dioxolane of formula II
wherein Xl is Cl or F and a~ least o~e of X2 ta
X5 is Cl, with metallic magnesium in the pre~en e
of a catalytic quantity of iodine t as disclosed in
U.S. 3 865 84S (Example 2), or a ~ombination of
mercuric chloride and iodine. The combination
mercuric chloride/iodine catalyæt i~ des~ri~ed i~
U.S. Paten~ No. 4 393 227 of Edward N. Squire which
i~sued 1983 July 12.
lXS~37~
DETAILS OF T INVENTION
The monomers of formulas III and IV can be
homopolymerized, or copolymerized with one or more
polyhalogenated vinyl monomers of the formula
CZ lz 2=CF2
wherein:
zl is H, F or Cl;
z2 is H, F, Cl or ORF;
RF is perhaloalkyl of 1 to 4 carbon atoms,
~CF2tnCF=CF2, or tCF2C~OtnCF2~F2Z ;
CF3
n is an integer of 0 to 6;
Z3 is SO2F, CO2R or CN; and
R is defined above.
Tetrafluoroethylene, chlorotrifluoroethylene,
perfluoromethylvinyl ether and perfluorodivinyl ether
are preferred comonomers. Polymers of this invention
will usually contain about 0.5 to 100 mol percent of
units derived from monomers of this invention.
The polymers are prepared by well-known
free-radical polymerization techniques, particularly
those employed for copolymerization of tetrafluoro-
ethylene which are described in the literature.
Preferably, polymerization is carried out in
nonagueous media in a perfluorinated or fluorine-
containing perhalogenated solvent such as
per1uorodimethylcyclobutane or 1,1,2-trichlorotri-
fluoroethane and the like/ Useful free-radical
initiators include a perfluorocarbon peroxide such as
perfluoropropionyl peroxide or an azo compound such
as azo-bis(isobutyronitrile) and the like.
Temperatures are in the range of 0 to 200C and
pressures can vary from subatmospheric to about 200
atmospheres.
'
8 ~25~7~7
; The polymers of this invention are amorphous
and have high glass transition temperatures, in the
range of about 90C to about 180C, and low
refractive indices, in the range of about 1.2 to
l.S. They are moldable and melt-extrudable and can
also be cast from solution, providing chemically and
thermally stable molded objects, films, and coatings
for substrates such as wood, paper, glass and metal,
said films and coatings having high clarity suitable
~or protective packaging.
Table 1 lists several representative
halogenated dioxolanes, I and II, which are
illustrated in the Examples. RF is CF3 in each
case.
TABLE 1
_ X2 X3 X4 x5 Species Code
CO2R H H H H 3
CO2~C13 Cl Cl Cl Cl 4
20 Cl Cl Cl Cl Cl 5
COCl Cl Cl Cl Cl 6
COCl Cl F Cl F 7
CO2M Cl F Cl F 7a
F Cl F Cl F 8
25 F Cl Cl Cl F 9
COCl Cl F Cl Cl 13
CQ2M Cl F Cl Cl 14
Cl Cl F Cl Cl 15
CO2M Cl Cl Cl Cl 16
30 Cl Cl F Cl F 17
COF Cl Cl Cl Cl 21
Table 2 lists several representative
perhalogenated dioxoles, IV, which are illustrated in
3S the Examples. RF is CF3 in each case.
.. .. . . . . . . . . . . . . ..
9 125~37~7
TABLE 2
Yl Y2 Y3Species Code
F F F 11
F Cl F 12
S Cl F Cl 18
Cl Cl Cl 19
Cl F F 20
In the following Examples, parts and
percentages are by weight and temperatures are in
degrees Celsius, unless otherwise specified.
Compounds are coded as in Tables 1 and 2.
EXAMPLE 1
2-Carboxymethyl-2-trifluoromethyl-1,3-dioxolane (3)
A S00 ml, 4-necked flask with stirrer,
condenser, dropping funnel, and thermometer were
dried in an oven overnight, assembled while hot and
cooled in a stream of dry nitrogen. The flask was
charged with 31.2 9 of methyl trifluoropyruvate in
100 ml of petroleum ether. To the stirred mixture
was added 25.0 9 of ~-bromoethanol. When the
temperature reached 35C, the mixture was cooled in
an ice bath and stirred for 1/2 hour. It was warmed
to room temperature and 28 9 of anhydrous potassium
carbonate was added and the mixture was stirred
vigorously. The reaction was exothermic; the
reaction mixture was cooled externally and stirring
continued. After 4 hours, 100 ml of anhydrous ether
was added which caused the pasty mixture to become
one liquid phase witb finely dispersed solid
present. The solid was separated by fil~ration and
the solvents were removed from the residue.
Distillatton afforded 28 g or 70% of
2-carboxymethyl-2-trifluoromethyl-1,3-dioxolane,
b.p. 69 to 70.5C at 7 mm, nD5 1.3762. A heart
cut, b.p. 70.5C at 7 mm, was pure.
.. .. - ' -
.
8~7~7
Anal. Calcd. for C6H7F3O4: C, 36.01; H,
3.53; F, 28.48. Found: C, 36.00; H, 3.54; F, 28.50.
The infrared spectrum was consistent with the
structure, and the proton NMR determined on the A-60
with tetramethylsilane as an external standard showed
an unsplit resonance at 6.38 ppm area ratio 3 for a
second unsplit resonance at 5.97 ppm area ratio 4.
EXAMPLE 2
A 500 ml, 3-necked flask fitted with a
water-cooled condenserl thermometer, magnetic stirrer
and pressure-equalizing dropping funnel was flamed
out and charged with 16.1 9 (0.20 mol) of
~-chloroethanol The flask was cooled to 0 and
31.2 g ~0.20 mol) of methyl trifluoropyruvate was
added slowly. The reaction mixture was stirred for
15 min while maintaining temperature below 10 during
the exothermic reaction.
Then, 80 ml of 30 to 60 petroleum ether
was added to the flask and warmed to room
temperature. K2CO3 (27.~ 9) was added in twelve
2.3 9 portions during 1 hour. Stirring was continued
for a furtHer 2 hours and 150 ml of water was added
with stirring to dissolve solids. Three liquid
layers were obtained. The middle (aqueous) layer was
extracted into petroleum ether and the e~tract was
combined with the original upper layer, washed with
25 ml of water, dried over CaC12 and evaporated
using a rotary evaporator. The yellow residue and
the residue obtained by evaporating the original
lower layer, had identical IR spectra consistent with
the structure
~2¦- \ /CF3
H C O/ \CO CH
... , , , . . . .. , . , . .. , ... . , . . .. .. ~ .
~L~5~ 7
11
EXAMPLE 3
To methyl trifluoropyruvate (17Ç g, 1.14 mol)
in a 4-liter beaker was added rapidly 92 g (l.14 mol)
of ethylene chlorohydrin with some cooling by ice
bath to keep below 60. When addition was complete
and after cooling to room temperature, 400 ml of
petroleum ether (b.p. 30 to 60) was added followed
by 153 g ~1.14 mol) of potassium carbonate. The
mixture was stirred occasionally with a metal spatula
to break up the solid. ~hen gas evolu~ion ceased,
the mixture was heated on a steam bath until the
petroleum ether evaporated. Water (500 ml) was then
added to dissolve the solid, the lower layer
containing 2-carboxymethyl-2-trifluoromethyl-1,3-
dioxolane was separated (150 9, 65~); dried and
distilled~ b.p. 66/5 mm.
EXAMPLE 4
2-Carboxytrichloromethyl-2-trifluoromethyl-4,4,5,5-
tetrachloro~l,3-dioxolane (4)
3 > 4, 5, 6
-
chlorination
Chlorination of 144 9 of 3, prepared as in
Example 3, was carried out in pyrex glass next to a
sunlamp; chlorine gas wa~ bubbled in rapidly. No
solvent was used. Hea~ from the sunlamp induced
refluxing. After passing through a water condenser,
off-gas was passed through an ice cooled trap and
then a water scrubber to remove HCl. The reaction
was monitored by gas chromatography. Dioxolane 4 was0 obtained together with dioxolanes 5 and 6.
EX~MPLE S
chlorination
Dioxolane 3 (336.3 9), prepared as in
Example 3, was charged to a 1.5 liter aluminum
11
.
~5~37;:~
foil-wrapped glass reactor, together with 300 ml of
carbon tetrachloride solvent. ~ quartz, water-cooled
cold-finger containing a mercury-vapor lamp was
inserted into the reactor. Chlorine gas was added,
with stirring, the lamp was turned on, and the
progress of the reaction was monitored by gas
chromatography of distilled samples. After 16 h of
reaction, 769.1 g of distillate containing 90~ of 4
(g3~ yield) was obtained.
EXAMPLE 6
2-Trifluoromethyl-2,4,4,~,5-pentachloro-1,3-
dioxolane (5) and 2-Chloroformyl-2-trifluoromethyl-
4,4,5,5-tetrachloro-1,3-dioxolane (6)
3 chlorination- > 5, 6
A solution of 59 9 of 3 in 50 ml of CC14
was irradiated for 30 h with a mercury vapor lamp
while bubbling in C12. During the run, CC14 was
depleted so that higher temperatures were obtained.
From this run there was obtained 22 9 of 5, b.p.
72/22 mm ~nd 14 9 of 6, b.p. 79/15 mm, IR 5.S2
(C=O) .
Anal, Calcd. for C4C15F30~: C,
25 15.28; Cl, 56.40; F, 18.13. Found for 5: C, 15.57;
Cl, 57.23; F, 18.17. Anal. Calcd. for
C5C15F303: C, 17.54; Cl, 51.79; F, 16 65-
Found for 6: C, 17.67: Cl, 50~93; F, 16.77.
EXAMPLE 7
2-Chloroformyl-2-trifluoromethyl-4,4,5,5-
tetrachloro-1,3-dioxolane (6)
Cesium chloride ~10 g~) was added to 572 g of
the perchloroester 4 which was subjected to
distillation at atmospheric pressure. Phosgene
12
.. . . . . . . . . .. . . . .. . . . . .
~ 7~ 7
13
collected in a Dry Ice-acetone cooled trap attached
to the still while 395 g (89~) of acid chloride 6
distilled at 188C~ The product was redistilled at
144/200 mm (356 g) to remove a small amount of
dissol~ed phosgene.
EXAMPLE 8
Fluorination of 2-carboxytrichloromethyl-2-tri-
fluoromethyl-4,4,5,5-tetrachloro-1,3-dioxolane t4)
SbF
4 SbC15 ~ 8 + 9 + 7
Refluxing the perchloroester 4 with
SbF3-SbC15 resulted in loss of phosgene and
decarbonylation to give mainly dioxolanes 8 and 9. A
very small amount of acid chloride survived to give 7.
Antimony trifluoride (162 9) was ground in a
mortar, placed in a two liter 3-neck flask which was
evacuated, and flame heated with shaking to dryness.
After cooling the flask and filling with nitrogen,
100 9 of 4 and 7 ml of SbC15 were added. The
mixtu~e was refluxed (water condensed with Dry Ice
trap attached) for about 4 h when the reflux
temperature had dropped to 80 and phosgene had
collected in the trap. Volatile material from the
flask which distilled under vacuum with steam bath
heating to a liquid nitrogen-oooled trap was
transferred to a still and distilled at a~mospheric
pressure. There was collected 27.5 ~ (46%) of 8,
4,5-dichloro-2,4,5-trifluoro-2-Srifluoromethyl-lD3-
dioxolane, b.p. 68 to 69~.
Anal. Calcd. for C4C12F6O2: C,
18.13; Cl, 26.76; F, 43.03. Found: C, 17093; Cl,
26.80; F, 42.78.
. . , .. ~ , ... . . . ~ . . . . . .. . . . . . .
: ` .
.
~2S~737
In addition, there was distilled 21 9 (33~)
of 9, 4,4,5-trichloro-2,5-difluoro-2-trifluoromethyl-
1,3-dioxolane, b.p. 99 to 100. Anal. Calcd. for
C4C13F5O2: C, 17.07; Cl, 37.80; F, 33.76.
5 Found: C, 16.89; Clt 37.44; F, 33.56.
Finally, there was recovered about 1 g of 7,
2-chloroformyl-2-trifluoromethyl-4,5-dichloro-4,5-
difluoro-1,3-dioxolane, b.p. 126 to 128, IR,
5.5~ ~ (C=O). Anal. Calcd. for C5C13F503:
ld C, 19.41; Cl, 34.38; F, 30.70. Found- C, 19.51; Cl,
35.~7; F, 30.45.
EXAMPLE 9
Fluorination of 2-chloroformyl-2-trifluoro-
methyl-4,4,5,5-tetrachloro-1,3-dioxolane (6)
SbF
SbC15 ~ 13 + 7 + 8 + 9
In the reaction with SbF3-SbC15 the
20 number of chlorine atoms replaced by fluorine depends
on 'che amount of SbF3 used and on the temperature
of reaction. In this Example using only steam bath
heating, an appreciable amount of 13 was isolated.
A mixture of 356 9 (1.04 mol) of 6, 326 g of
25 (1.82 mol) dry 5bF3 and 5 ml of SbC15 was heated
on a steam bath for 5 h and the products isolated for
distillation by vacuum distillation to a liquid
nitrogen-cooled trap as above. Distillation of the
mixture gave about 15 g (4.4%) of 8, b.p. 68; 17 9
30 (4.696) o~ 9, b.p. 100; 148 g (37~) of 7, b.p. 126;
and 101 9 (24%) of 13, 2-chloroformyl-2-trifluoro-
methyl-4,5,5-trichloro-4-fluoro-1,3-dioxolane~ b.p.
153, IR, 5.53 1~ (C=O) .
14
.. , . . . . , .. . , . , . ~
~587;~7
Anal. Calcd. or C5C14F~03: C,
18~43; Cl, 43.52; F, 23.32. Found: C, 18.72; Cl,
42.35; F, 23.76.
EXAMPLE 10
Using higher temperature than in Example 9,
no 13 was isolated: A mixture of 212 9 (0.62 mol) of
6, 166 9 (0.93 mol) of flame and vacuum dried SbF3,
and 10 ml of SbC15 was refluxed for 3 h when the
temperature had dropped to 96. The crude product,
isolated as in Example 9, was distilled to give about
70 9 t43~) of 8, 9 9 (5~) o~ 9 and 47 g (24~) of 7,
with the balance largely high-boiling residue.
EXAMPLE 11
2-Fluoroformyl-2-trifluoromethyl-4,4,5,5-
tetrachloro-1,3-dioxolane (21)
6 tetramethylene ~ 21
sulfone
A mixture of 50 9 (0.15 mol) of the acid
chloride 6, 35 9 (0.60 mol) of flame and vacuum dried
KF and 50 ml of tetramethylene sulfone was stirred
while heating on an 18 inch spinning band still.
There was collected 11 g (22%) of the acid fluoride
21, b.p. 156 to 157, IR 5.33 ~(C=0).
Anal. Calcd. for C5C14F403: C,
18.43; Cl, 43.52; F, 23.3~. Found: C, 18.55; Cl,
43.72; F, 23.28.
EXAMPLE 12
2,4,5-Trifluoro-2-trifluoromethyl-1,3-
dioxole (11~ and 5-Chloro-2,4-difluoro-
2-trifluoromethyl-1,3-dioxole (12) and Polymers
8 _ Mg ~ 12
I2~ HgC12
.. . . . . . . .. . . .. . . . . ..
.
.
16 1 ~ ~ 87 ~7
~ Dioxoles were prepared by dehalogenation of
halodioxolanes according to the Pollowing procedure,
The reae~ion was run in a 250 ml 3-neck flask
aetached to an 18 inch spinning band still and fitted
with a magneti~ stirrer, thermometer and septum for a
50 ml hypodermic syringe driven by a Sage* pump. The
flask was heated by a Glas-Col* mantle. The still
: condenser was cooled by tap water and the 25 ml
receiver by a Dry Ice-acetone bath. A Dry
Ice acetone trap attached to the still collected very
little condensate.
The system was first evacuated to dryness
and filled with nitrogen. Magnesium turnings
(15.0 ~, 0.63 mol) and 0.2 9 each of ~gCl2 and I~
iS were then added and the system was reevacuated and
flushed wath N2. Then, 80 ml of dry
tetrahydrofuran was added, the mixture stirred and
brou~ht to boiling (heat turned off when boiling)
while adding dioxolane 8 through the Sage pump at the
rate of 0.3 ml/min with the still on total reflux,
Addition was stopped after 3 ml had been added if the
reaction h2d not yet started (turning black and very
exothermic - no heat req~ired). When necessary to
start ~he reaction, 35 ~l portions of methyl iodide
were added by hypodermic. During addition of all the
dichloride (37 9, 0.14 mol) no heat was reguired to
maintain reflux,
When addition was complete, heat was applied
and distilla~e was collected until the 25 ml receiver
was about full. Product (b.p. 1~ to 16~) had
already collected in the receiver during the run.
The cold distillate was added to ice water in ~
~eparatory ~unnel, ~haken and the bottom layer stored
cold.
3~ * denotes trade mark
16
~L2~i~37~7
Combined crude products (230 g) from 13 runs
(488.5 g of dichloride 8) on distillation gave 123 9
(34%) of the dioxole 11, b.p. 15 to 16, IR 5.27
(C=C); 41 9 (11%) of the dioxole 12, b.p. 47, IR
S 5.53 ~ (C=C); and 64.5 g of recovered 5 as pot
residue.
Final purification of both 11 and 12
involved passing the vapors through sintered glass
bubblers containing, successively, 2~ K2CO3 and
distilled water to remove traces of tetrahydrofuran
followed by passing the vapors over P2O5O The
condensed materials were stored at -50 in stainless
steel cylinders.
Compound 11 readily formed homopolymer and
15 copolymers with TFE in F-113 (1,1,2-trichlorotri-
fluoromethane) using perfluoropropionyl peroxide as
catalyst at room temperature. Compound 12 formed
copolymers with TFE.
_AMPLE 13
5-Chloro-2~4-difluoro-2-trifluorometh
1,3-dioxole (12)
g Mg ) 12
I2 ~ HgC12
Example 12 was repeated except that
dioxolane 9 was substituted for 8. A sample of 10 9
~48~ yield) of purified dioxole 12 was obtained from
2B.2 9 (0.1 mol) of 9 and 7.3 9 (0.3 mol) of
magnesium,
EXAMPLE 14
;
2-Chloro-2-trifluoromethyl 4,5-difluoro-
1,3-dioxole (20) and Polymer
17 Mg > 20 + homopolymer
17
. . . . . .
~5~37~7
To a stirred mixture of 15 9 (0.63 mol) of
Mg turnings, 0.2 9 each of HgC12 and I2 ~nd 80 ml
of dry tetrahydrofuran was added 25 9 of 17 by Sage
pump at 0.3 ml/min. There was then distilled 50 ml
of a mixture which was washed with ice water to give
16 9 of heavy layer. Distillation gave 2 g of 20,
b.p. 43. This material was carried as vapor by a
stream of nitrogen through fritted discs through 2%
K2CO3 and finally distilled water. The
condensate (Dry Ice-acetone trap) was passed as vapor
over KOH pellets and P2O5 and condensed in a
polymer tube with 30 l~l of 9~ perfluoropropionyl
peroxide catalyst in trichlorotrifluo~oethane. After
standing at room temperature overnight and heating
2 h in a steam bath, there was recovered 2 9 of
polymer (vacuum dried at 100).
EXAMPLE 15
2L4 ,5-Trichloro-2-trifluoromethyl-1,3-dioxole
Na2CO3
6 Tetra9lyme ~ 16 150 to 160~ 19
Dioxoles were prepared by
dehalocarbonylation of chloroformyl dioxolanes
according to the following procedure. The acid
chloride 6 was converted to a carboxylic salt 15
which was decomposed without isolation to the dioxole
19 in a high-boiling, aprotic solvent.
The reaction was carried out in a two liter
3-neck flask fitted with a thermometer, dropping
funnel, large magnet for stirring and Vigreaux still
head. The flask was evacuated, filled with nitrogen
and, then, 32 9 (0.3 mol) of Na2CO3 (dried at
550) was added under nitro~en followed by 50 ml of
dry tetraglyme. Acid chloride 6 (34 g, 0.1 mol) was
then added dropwise with stirring which was
exothermic to about 60. The dropping funnel was
18
. .
~ S!37~7
19
then replaced with a plug and heat applied with a
Glas-Col mantle. A vacuum of about 250 ~m was
applied to the system through Dry Ice and liq~id
nitrogen traps. At about 150 vigorous evolution of
C2 began and distillate was collected at about
80/250 mm. This was washed with water, dried and
distilled at atmospheric pressure to give 20 (16.7 g,
69%) b.p. 110. It was characterized by Raman
absorption ~1692 with 5145 A laser). 13C NMR and
analyse5.
Anal. Calcd. for C4C13F3O2: C,
19.74; Cl, 43.70, F, 23.42. Found: C, 20.00; Cl,
40.72; F, 23.09.
EXAMPLE 16
2,4-Dichloro-5-fluoro-2-trifluoromethyl-1,3-
dloxole (18) and 2,4,4,5-Tetrachloro-5-fluoro-
2 trifluoromethyl-1,3-dioxolane (15)
Na2C
13 tetraglym ~ 14 150-to 15 ~ 18 + 15
The reaction was similar to that of ~xam~le
15. Dioxole 18 was the principal product isolated.
From 55 9 tO.17 mol) of 13 with 55 9
Na2C03 in 75 ml of tetraglyme there was obtained
25.5 g of crude, water-washed product. Distillation
gave 15,5 g (414~ of 18, b.p. 77, IR 5~54 ~ (C=C)
and 3.2 9 (6~) of 15, b.p. 129.
Anal. Calcd. for C4C12F4O2: C,
21.17; Cl, 31.24; F, 33.49. Found for 18: C, 21.30;
Cl, 28.19; F, 27.95. Calcd. for C4C14F402:
C, 16.14; Cl, 47.61; F, 25.51. Found fo~ 15: C,
17~63; Cl, 43.58; F, 27.28.
19
` ' ' ' '' '- ', '-' ' ..
~5~7;~
EXA~5PLE 17
Perfluoro-2-:nethylene-4,5-dichloro-1,3-
dioxolane III, Polymers Thereof, and 2,4,5-Trichloro
4,5-trifluoro-2-trifluoromethyl-1,3~dioxolane (17)
Na2C3
7 tetraglyme 150 to 1603 III ~ 17 + 21
This reaction was carried ou'c as described
in Example 15 excep'c that after formation of salt 7a
by addition of Na2C03 to 7, full vacuum (1 mm)
10was applied to the system through Dry Ice and liquid
nitrogen traps in series.
Each run used about 113 9 (1.1 mol) of dried
Na2C03, 150 ml of dry tetraglyme and 110 9
(0.35 mol) of 4. From five runs using 54~ 9 of 7
15 there was obtained 235.5 9 of crude product.
Distillation gave 79 9 (20%) mostly 21, b.p. 83 to
87; 109 g (22%~ mostly 17, b.p. 93 to 97; 8 g of a
product, b.p. 110 to 117/50 mm and lB g of another
product, b.p. 120/50 mm. All products appeared to
20 be relatively pure by gas chromatography with isomer
separation for 17.
An additional three runs using 340 g of 7
gave 165.5 9 of impure product which was distilled to
give 54 9 (22%) of III, 75 9 (24%) of 17, 15.5 9 of
25 high boilers.
Compound III readily gave homopolymer and
copolymers with TFE in F-113 solvent using
perfluoropropionyl peroxide as catalyst.
Anal. Calcd. for C4C12F4O2: C,
30 21.17; Cl, 31.24; F, 33.49. Found homopolymer of
III: C, 21.04; Cl, 31.35; F, 33.75.
~ 7~ 7
21
EXAMPLE 18
2,4,5-Trifluoro-2-trifluoromethyl-1,3-dioxole(11) and
5-chloro-2,4-difluoro-2-trifluoromethyl-1,3-dioxole(12)
~ g > 11 ~ 12
I2
The same reaction conditions and reactants
were employed as in Example 12 except ~hat no HgC12
was added. Dioxolane 8 (34 grams), 15 9 of Mg
turnings and 0.2 9 of I2 in 80 ml of
tetrahydrofuran were employed. There were obtained
15.5 9 of products which, by gas chromatographic
analysis, were found to comprise dioxole 11 (72%) and
dioxole 12 (9%).
EXAMPLES 19 to 22
Clear, waterproof finishes for wood, paper
and metals were prepared by mixing, with agitation
for 4 to 24 h, various homopolymers and TFE
copolymers of monomers III with solvent consisting
essentially of isomeric trimers of hexafluoropropene.
The mixtures so prepared are summarized below.
Wt of Polymer (g)
Exam- Monomer ~om~- TFE Co- Vol. of HFP
ple III ~olymer polymer Trimers (ml)
19 11 0.1 - 5
11 - 0.2~ 3
21 20 0.3 - 5
22 12 - ~.1 1.9 9
EXAMPLES 23 to 26
The following clear, viscous coating
solution were ob~ained by polymerizing monomers of
formulas III and IV, or mixtures thereof with TFE, in
1,1,2,-trichlorotrifluoroethane (F-113) solvent,
.. . . . .
.,
22 1 ~ 5 ~ ~ 7
using 20 1 of t-butylperacetate (75% in mineral
spirits) as catalyst at 100 for 4 h. In the formula
III monomer used in Examples 25 and 26, X2 and X4
are F, and X3 and X5 are Cl.
Formula III Formula IV Monomer
Exam- Monomer
~le (~) Species Wt (g) TFE (g) F-113 (9)
23 - 20 1.17 0.3 3.4
24 - 20 0.9 - 3.72
2.14 - - 0.66 16.2
26 2.05 - - - 16.3
Each of the eight polymer solutions of
Examples 19 to 26 was applied to filter paper and to
untreated wood and allowed to dry at room
temperature. When water was then applied, it was
rapidly absorbed in untreated areas, whereas it stood
in beads on the treated surfaces until it evaporated.
The polymers adhered very well to the papers
so that they could be folded and bent without
breaking the protective surface. Adhesion to wood
was also very good, with low molecular weight
materials giving a penetrating oil-like finish and
higher molecular weight material giving a semi-gloss
to glossy finish. Coatings that contain polymers of
this invention can be employed on various substrates
including wood and paper to protect the substrates in
caustic and corrosive industrial environments.
Disposable paper gloves coated with polymers of this
invention would be useful in caustic/corrosive work
environments.
This application is a division of copending
Canadian Application Serial No. 412 064 filed 1982
September 23.
