CA1258737A - Cyclic monomers derived from trifluoropyruvate esters - Google Patents

Abstract

TITLE
Cyclic Monomers Derived From Trifluoropyruvate Esters ABSTRACT OF THE DISCLOSURE
Perhalogenated dioxoles, halogenated dioxolanes, a process for making the dioxoles and dioxolanes, and polymers of dioxole and dioxolane monomers. The polymers are amorphous with high glass transition temperatures, are moldable and melt extrudable, and may also be cast from solution.
Films and coatings have high clarity and may be used for protective packaging.

Description

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 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.

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` '` ~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 ;

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.

_ X2 X3 X4 x5 Species Code 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 Yl Y2 Y3Species Code 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.

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.

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 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.

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 was 0 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 .

~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.

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.

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 .. . . . . . . . . .. . . . .. . . . . .

~ 7~ 7 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.

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.

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) .

.. , . . . . , .. . , . , . ~

~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.

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.

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.

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 ~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, ;
2-Chloro-2-trifluoromethyl 4,5-difluoro-1,3-dioxole (20) and Polymer 17 Mg > 20 + homopolymer . . . . . .

~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).

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 . .

~ S!37~7 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.

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.

` ' ' ' '' '- ', '-' ' ..

~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 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 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.

Claims (16)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A polymer selected from the group consisting of (a) a polymer of a dioxolane of the formula:

wherein X2, X3, X4 and X5, are independently, are C1 or F, provided that at least two are F; and (b) a polymer of a dioxole of the formula:

wherein Y1, Y2 and Y3, independently, are F or C1 and RF is perfluoroalkyl of 1 to 4 carbon atoms.

2. A polymer of Claim 1 in the form of a copolymer with tetrafluoroethylene.

3. A polymer of the dioxolane of the formula:

wherein X2, X3, X4 and X5, independently, are C1 or F, provided that at least two are F.

4. A copolymer of the dioxolane of the formula:

wherein X2, X3, X4 and X5, independently, are C1 or F, provided that at least two are F, and tetrafluoroethylene.

5. A copolymer according to Claim 4 wherein X2 and X4 are F and X3 and X5 are Cl.

6. A polymer of a dioxole of the formula:

wherein Y1, Y2 and Y3, independently, are F or Cl and RF is perfluoroalkyl of 1 to 4 carbon atoms.

7. A copolymer of a dioxole of the formula:

wherein Y1, Y2 and Y3, independently, are F or Cl and RF is perfluoroalkyl of 1 to 4 carbon atoms, and tetrafluoroethylene.

8. A polymer of Claim 6 in which, in the dioxole, RF is CF3.

9. A copolymer of Claim 7 in which, in the dioxole, RF is CF3.

10. A copolymer according to Claim 9 wherein Y1, Y2 and Y3 are F.

11. A copolymer according to Claim 9 wherein Y1 is Cl and Y2 and Y3 are F.

12. A coating solution comprising a polymer according to Claim 3.

13. A coating solution comprising a polymer according to Claim 6.

14. A coating solution comprising a polymer according to Claim 8.

15. A cellulosic substrate coated with a coating solution according to one of Claim 12, Claim 13 and Claim 14.

16. A film of the polymer according to one of Claim 3, Claim 6 and Claim 8.