CA1199645A - Fluorodioxoles and fluorodioxole polymers - Google Patents
Fluorodioxoles and fluorodioxole polymersInfo
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- CA1199645A CA1199645A CA000451912A CA451912A CA1199645A CA 1199645 A CA1199645 A CA 1199645A CA 000451912 A CA000451912 A CA 000451912A CA 451912 A CA451912 A CA 451912A CA 1199645 A CA1199645 A CA 1199645A
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Abstract
TITLE
NOVEL FLUORODIOXOLES AND FLUORODIOXOLE POLYMERS
ABSTRACT OF THE DISCLOSURE
Novel fluorodioxoles which may have Cl or F
substituents in the 4 or 5 positions and have two F
or CF3 substituents in the 2 position are useful monomers for the preparation of homopolymers and copolymers with tetrafluoroethylene and terpolymers with tetrafluoroethylene and vinylidene fluoride.
The homopolymers are suitable for glazing materials, while copolymers are useful, among others, for corrosion-resistant seals, gaskets, and linings.
NOVEL FLUORODIOXOLES AND FLUORODIOXOLE POLYMERS
ABSTRACT OF THE DISCLOSURE
Novel fluorodioxoles which may have Cl or F
substituents in the 4 or 5 positions and have two F
or CF3 substituents in the 2 position are useful monomers for the preparation of homopolymers and copolymers with tetrafluoroethylene and terpolymers with tetrafluoroethylene and vinylidene fluoride.
The homopolymers are suitable for glazing materials, while copolymers are useful, among others, for corrosion-resistant seals, gaskets, and linings.
Description
TITT.~
NOVEL FLUORODIOXOLES AND FLUORODIOXOLE POLYMERS
BACKGROUND OF T~E I~VENTION
This invention relates to certain novel fluorodioxoles, their polymers, and processes for making the fluorodioxoles.
Various dioxolanes having the following formula 1 are known from ~erman Patent 2,604,350 to Stanford Research Institute:
CHX - CHY
O ~ c~ ~ 1 ) F F
where each of X and Y may be F or C1.
Dioxolanes corresponding to formula (2), - 15 below, are reported in U.S~ Patent 3,749,791 to Terrell et al.:
CHX - CHX' ~ C~ (2) - where X is Cl or F, and X' is H, Cl, or F.
The intermediate 2,2-bis(trifluoromethyl)-1,3-dioxolane is known from U.S. Patent 2,925,424 to Simmons.
Dechlorination of
NOVEL FLUORODIOXOLES AND FLUORODIOXOLE POLYMERS
BACKGROUND OF T~E I~VENTION
This invention relates to certain novel fluorodioxoles, their polymers, and processes for making the fluorodioxoles.
Various dioxolanes having the following formula 1 are known from ~erman Patent 2,604,350 to Stanford Research Institute:
CHX - CHY
O ~ c~ ~ 1 ) F F
where each of X and Y may be F or C1.
Dioxolanes corresponding to formula (2), - 15 below, are reported in U.S~ Patent 3,749,791 to Terrell et al.:
CHX - CHX' ~ C~ (2) - where X is Cl or F, and X' is H, Cl, or F.
The intermediate 2,2-bis(trifluoromethyl)-1,3-dioxolane is known from U.S. Patent 2,925,424 to Simmons.
Dechlorination of
2,2-bis(trifluoromethyl)-4,5-dichloro-4,5-difluoro-1,3-dioxolane to the corresponding perfluorodioxole has been reported by Resnick ln U~S. Patents 3,865,845 and 3,978,030.
; That perfluorodioxole has been found to form - 30 both homopolymers and copolymers (especially with tetrafluoroethylene) which have interesting chemical and physical properties (e.g., chemical inertness to hydrogen fluoride, optical clarity, ability to form films). It ean be speculated that simpler and/or cheaper fluorodioxoles al50 would be capable of forming useful homopolymsrs and copolvmers.
SI~M~ARY OF THE ~'~VENTIO~
According to the present invention, there is provided a class of fluorodioxoles having the following formula (3):
CY C%
` C~ (3) R R
in which Y is hydrogen or chlorine; Z is hydrogen, fluorine, or chlorine; and R is fluorine or the trifluoromethyl group; with the proviso that when R
is trifluoromethyl, only one of Y and Z can be hydrogen or chlorineO
These fluorodioxoles are useful monomers for the preparation of homopolymers and copolymers having a wide range of potential applications. This , invention also includes such polymers as well as certain novel polymers of known dioxoles. Generally, the monomers from which the novel polymers of the ~resent invention are made can be represented by the same formula (3) in which Y, Z and R have the same meaning as above, but the above proviso no longer - applies.
DETAIL~D DESCRIPTIO~ OF THE I~VE~TIO~i The fl~loro~ioxoles of the present invention can be conveniently made by dechlorination o~ the corresponding 4,5-dichlorodioxolanes with magnesium in the ~resence of a catalytic amount of iodine and of a water-soluble mercury salt or metallic mercury, as shown in the following equation.
CCl~ - CClz C ~ ~9, I2 (3) ~ MgCl2 , R R Hg or Ha (4) Where R, Y, and Z have the same meaning as ~! 35 in Formula (3), above.
i Ltj This dechlorination reaction preferably is carried out in solution in tetrahydrofuran. For maximum production rate, an excess of magnesium is employed in this reaction, the preferred amount heing 1.1 to 8 gram-atoms of magnesium per t~70 gram-atoms of vicinal chlorine to be removed. Ho~ever, for maximum yield of dioxole, less than stoichiometric - amounts may be desirable to minimize side reactions.
Mercury salts suita~le in this reaction include, for example, mercuric-chloride, acetate, and nitrate.
~etallic mercury, when used, forms in situ an amalgam with magnesium. However, an amalgam can be prepared separately in advance. The amount of mercury need not be large. For example, a weight of mercuric - 15 chloride about equal to the weight of iodine, in turn equal to about 1~ of the weight of magnesium usually is sufficient. A slightly larger amount o metallic mercury may be advisable to permit more effective agitation and thus easier amalgam formation.
Although some 4,5-dioxolanes represented hy . the above formula (4) are known, as discussed earlier, those represented by formula (5), below are believed to be novel:
CYCl-CFCl `C~
R R (5) in which R is fluorine or trifluoromethyl, and Y is hydrogen or chlorine.
All the fluorodioxoles of this invention copolymerize with tetrafluoroethylene (TFE) to tough, crystalline copolymers suitable for use as a dielectric in electrical and electronic equipment.
In these crystalline copolymers the fluorodioxole usually is present in an amount of ahout 12 ~ole 3S percent oe less. r~hen the fluoroaio~ole content ~P~396~5 increases beyond 12 mole percent, the copolymers become amorphous. ~at~rally, the 12 mole percent level is not a sharp line of demarcation, since copolymers having some crystallinity may exist above it, and significantl~ amorphous copolymer ~ay exist below it. However/ one can expect that a large majority of copolymers having less than 12 mole % of a fluorodioxole (3) will be crystalline, an~ a large majority of those containing more than 12 mole % of such a fluorodioxole will be amorphous. The - amorphous copolymers are tough and at moderate molecul~r weight soluble in various organic liquids, such as 1,1,2-trichloro-1,2,2-trifluoroethane and Fluorinert* Electronic Liquid FC-75 (3~ Company) and are particularly suitable for finishes and coatings - that are chemically inert and are stain and weather - resistant. Fluorodioxoles (3) in which each of Y and Z is chlorine could not be incorporated into a copolymer with TFE at a high enough level to result ~ 20 in an amorphous copolymer. Those copolymers that were made were crystalline.
- Fluorodioxoles (3) form with vinylidene fluoride (~2) and TFE strong, plastic and elastomeric terpolymers suitable for ~: 25 corrosion-resistant seals, gaskets, and linings.
_ Finally, the fluorodioxoles corresponding to ~~ formula (3) in which Y is hydrogen and Z is hydrogen or fluorine ~orm homopolymersl which are tough~
amorphous resins suitable for transparent glazing ~ 30 materials, especially as sight glasses in chemically corrosive uses employing hydrogen fluoride.
In addition to the novel dioxoles of Formula
; That perfluorodioxole has been found to form - 30 both homopolymers and copolymers (especially with tetrafluoroethylene) which have interesting chemical and physical properties (e.g., chemical inertness to hydrogen fluoride, optical clarity, ability to form films). It ean be speculated that simpler and/or cheaper fluorodioxoles al50 would be capable of forming useful homopolymsrs and copolvmers.
SI~M~ARY OF THE ~'~VENTIO~
According to the present invention, there is provided a class of fluorodioxoles having the following formula (3):
CY C%
` C~ (3) R R
in which Y is hydrogen or chlorine; Z is hydrogen, fluorine, or chlorine; and R is fluorine or the trifluoromethyl group; with the proviso that when R
is trifluoromethyl, only one of Y and Z can be hydrogen or chlorineO
These fluorodioxoles are useful monomers for the preparation of homopolymers and copolymers having a wide range of potential applications. This , invention also includes such polymers as well as certain novel polymers of known dioxoles. Generally, the monomers from which the novel polymers of the ~resent invention are made can be represented by the same formula (3) in which Y, Z and R have the same meaning as above, but the above proviso no longer - applies.
DETAIL~D DESCRIPTIO~ OF THE I~VE~TIO~i The fl~loro~ioxoles of the present invention can be conveniently made by dechlorination o~ the corresponding 4,5-dichlorodioxolanes with magnesium in the ~resence of a catalytic amount of iodine and of a water-soluble mercury salt or metallic mercury, as shown in the following equation.
CCl~ - CClz C ~ ~9, I2 (3) ~ MgCl2 , R R Hg or Ha (4) Where R, Y, and Z have the same meaning as ~! 35 in Formula (3), above.
i Ltj This dechlorination reaction preferably is carried out in solution in tetrahydrofuran. For maximum production rate, an excess of magnesium is employed in this reaction, the preferred amount heing 1.1 to 8 gram-atoms of magnesium per t~70 gram-atoms of vicinal chlorine to be removed. Ho~ever, for maximum yield of dioxole, less than stoichiometric - amounts may be desirable to minimize side reactions.
Mercury salts suita~le in this reaction include, for example, mercuric-chloride, acetate, and nitrate.
~etallic mercury, when used, forms in situ an amalgam with magnesium. However, an amalgam can be prepared separately in advance. The amount of mercury need not be large. For example, a weight of mercuric - 15 chloride about equal to the weight of iodine, in turn equal to about 1~ of the weight of magnesium usually is sufficient. A slightly larger amount o metallic mercury may be advisable to permit more effective agitation and thus easier amalgam formation.
Although some 4,5-dioxolanes represented hy . the above formula (4) are known, as discussed earlier, those represented by formula (5), below are believed to be novel:
CYCl-CFCl `C~
R R (5) in which R is fluorine or trifluoromethyl, and Y is hydrogen or chlorine.
All the fluorodioxoles of this invention copolymerize with tetrafluoroethylene (TFE) to tough, crystalline copolymers suitable for use as a dielectric in electrical and electronic equipment.
In these crystalline copolymers the fluorodioxole usually is present in an amount of ahout 12 ~ole 3S percent oe less. r~hen the fluoroaio~ole content ~P~396~5 increases beyond 12 mole percent, the copolymers become amorphous. ~at~rally, the 12 mole percent level is not a sharp line of demarcation, since copolymers having some crystallinity may exist above it, and significantl~ amorphous copolymer ~ay exist below it. However/ one can expect that a large majority of copolymers having less than 12 mole % of a fluorodioxole (3) will be crystalline, an~ a large majority of those containing more than 12 mole % of such a fluorodioxole will be amorphous. The - amorphous copolymers are tough and at moderate molecul~r weight soluble in various organic liquids, such as 1,1,2-trichloro-1,2,2-trifluoroethane and Fluorinert* Electronic Liquid FC-75 (3~ Company) and are particularly suitable for finishes and coatings - that are chemically inert and are stain and weather - resistant. Fluorodioxoles (3) in which each of Y and Z is chlorine could not be incorporated into a copolymer with TFE at a high enough level to result ~ 20 in an amorphous copolymer. Those copolymers that were made were crystalline.
- Fluorodioxoles (3) form with vinylidene fluoride (~2) and TFE strong, plastic and elastomeric terpolymers suitable for ~: 25 corrosion-resistant seals, gaskets, and linings.
_ Finally, the fluorodioxoles corresponding to ~~ formula (3) in which Y is hydrogen and Z is hydrogen or fluorine ~orm homopolymersl which are tough~
amorphous resins suitable for transparent glazing ~ 30 materials, especially as sight glasses in chemically corrosive uses employing hydrogen fluoride.
In addition to the novel dioxoles of Formula
3 as defined ~herein, ~ioxoles in which both X and Y
`- are hydrogen or chlorine~ and R is trifluoromethyl can be made by the same general techniques but are *denotes trade mark .
~ 4 , _, ;.
not believed to be novel. Those dioxoles also form novel and valuable copolymers; the dioxoles in which X is hydrogen, and Y is hydrogen or fluorine also form homopolymers.
3roadlyr this invention includes, thereforer homopolymers of the novel dioxoles of this invention as well as copolymers of the dioxoles represented by formula (3) in which Y is hydrogen or chlorine; Z is hydrogenr fluoriner or chlorine; and R is fluorine or trifluoromethyl with tetrafluoroethylene and terpolymers with tetrafluoroethylene and vinylidene fluoride.
This invention is now illustrated by representative examples of certain preferred embodiments thereof, wherein all parts, proportions~
! and percentages are by weight unless otherwise indicated. Further, unless shown otherwise, all reactions, separations, distillations, and storage were carried out in a nitrogen atmosphere.
~ABLE I
SUM~ARY OF PREPARATION OF DIOXOLES OF
FORMULA l3) AND DIOXOLAN~S OF FOR.~ULA (4) Example Compo~nd Com~ound Substituents ~o. No. Y Z R
PreP. of:
lA (4a) Cl F CF3 lB (3a) Cl F CF3 .lB (3b) F H CF3 lB (4b) F H CF3 lC (3a) Cl F CF3 lD (3b) F H CF3 8A (4c) ~ H CF3 8A ~d) Cl H CF3 8A (4e) Cl Cl CF3 8B (3c) H H CF3 8B (3d) Cl R CF3 8B (3e) Cl Cl CF3 8C (3d) Cl H CF3 t 15 . 15A ~4f) Cl F . F
15B (3f) Cl F F
15B ~3g) F H F
15B (4g) F H F
16A/B (4g) F H F
17 (39) F H F
22 (4h) H H F
22 (3h) H H F
(4i) Cl H F
(3i) Cl H F
28 (3i) Cl Cl F
28 ~4j) Cl Cl F
/
~ 35 - TABLE II
SUMMARY OF EXA~PLES --POLYMERIZATION
Example Monomer Polymer Properties ~o. Com~ound No. Comonomer ~ol ~ ~ioxole, Tm,* Tg**
2 (3~) - 100%, Tg~300C
3 (3b) TFE 5.2~, Tm=266 & 320C
`- are hydrogen or chlorine~ and R is trifluoromethyl can be made by the same general techniques but are *denotes trade mark .
~ 4 , _, ;.
not believed to be novel. Those dioxoles also form novel and valuable copolymers; the dioxoles in which X is hydrogen, and Y is hydrogen or fluorine also form homopolymers.
3roadlyr this invention includes, thereforer homopolymers of the novel dioxoles of this invention as well as copolymers of the dioxoles represented by formula (3) in which Y is hydrogen or chlorine; Z is hydrogenr fluoriner or chlorine; and R is fluorine or trifluoromethyl with tetrafluoroethylene and terpolymers with tetrafluoroethylene and vinylidene fluoride.
This invention is now illustrated by representative examples of certain preferred embodiments thereof, wherein all parts, proportions~
! and percentages are by weight unless otherwise indicated. Further, unless shown otherwise, all reactions, separations, distillations, and storage were carried out in a nitrogen atmosphere.
~ABLE I
SUM~ARY OF PREPARATION OF DIOXOLES OF
FORMULA l3) AND DIOXOLAN~S OF FOR.~ULA (4) Example Compo~nd Com~ound Substituents ~o. No. Y Z R
PreP. of:
lA (4a) Cl F CF3 lB (3a) Cl F CF3 .lB (3b) F H CF3 lB (4b) F H CF3 lC (3a) Cl F CF3 lD (3b) F H CF3 8A (4c) ~ H CF3 8A ~d) Cl H CF3 8A (4e) Cl Cl CF3 8B (3c) H H CF3 8B (3d) Cl R CF3 8B (3e) Cl Cl CF3 8C (3d) Cl H CF3 t 15 . 15A ~4f) Cl F . F
15B (3f) Cl F F
15B ~3g) F H F
15B (4g) F H F
16A/B (4g) F H F
17 (39) F H F
22 (4h) H H F
22 (3h) H H F
(4i) Cl H F
(3i) Cl H F
28 (3i) Cl Cl F
28 ~4j) Cl Cl F
/
~ 35 - TABLE II
SUMMARY OF EXA~PLES --POLYMERIZATION
Example Monomer Polymer Properties ~o. Com~ound No. Comonomer ~ol ~ ~ioxole, Tm,* Tg**
2 (3~) - 100%, Tg~300C
3 (3b) TFE 5.2~, Tm=266 & 320C
4 (3b) TFE 28.8~, Tg-58C
(3b) TFE 2.4~, Tm=307C
6 (3a) TFE 3.1%, Tm=295C
- 7 (3a) TFE/VF2 5.3~,14.3~ TFE; Tm-131C
9 (3c) TFE 6.9%, Tm=253C
(3c) TFE 46.3%, Tg=61C
11 (3c) TFE/VF2 7.9%, 36.4% TFE; Elast., Tm=114C
12 (3c) - 100%
15 13 (3d) TFE 5.9%, Tm=269C
14 (3c)/(3d) TFE 8.6~ (3c)/6.2~ (3d), Tg=54C
~- 18 (3~) TFE 4.0%, Tm=274C
19 (3g) - 100%
20 20 (3f) TFE 10.5~, Tg=61C
21 ~3f) TFE~VF2 g.9~, 27.7% TFE; no Tm 23 (3h~ - 100 24 (3h) TFE 7 26 (3i) TFE 6%
25 27 (3e) TF~ 0.6~, Tm=312C
29 (3j) TFE 1.4~, Tm=310, 297C
;` * melt temperature (indicates that the polymer has crystallite regions) ** glass transition temperature (indicates that the polymer is amorphous) ExamPle 1 Preparation of 2,2 bis(trifluoromethyl)-4-chloro-5-fluoro-1,3-dioxole, (3a), 2,~-bis(trifluoromethyl)-4-1uoro-1,3~dioxole, (3b), and the corresponding dioxolanes (4a) and ~4b).
9Çi~5 A. 2,2-Bis(trifluoromethyl)-4,4,5-trichloro-
(3b) TFE 2.4~, Tm=307C
6 (3a) TFE 3.1%, Tm=295C
- 7 (3a) TFE/VF2 5.3~,14.3~ TFE; Tm-131C
9 (3c) TFE 6.9%, Tm=253C
(3c) TFE 46.3%, Tg=61C
11 (3c) TFE/VF2 7.9%, 36.4% TFE; Elast., Tm=114C
12 (3c) - 100%
15 13 (3d) TFE 5.9%, Tm=269C
14 (3c)/(3d) TFE 8.6~ (3c)/6.2~ (3d), Tg=54C
~- 18 (3~) TFE 4.0%, Tm=274C
19 (3g) - 100%
20 20 (3f) TFE 10.5~, Tg=61C
21 ~3f) TFE~VF2 g.9~, 27.7% TFE; no Tm 23 (3h~ - 100 24 (3h) TFE 7 26 (3i) TFE 6%
25 27 (3e) TF~ 0.6~, Tm=312C
29 (3j) TFE 1.4~, Tm=310, 297C
;` * melt temperature (indicates that the polymer has crystallite regions) ** glass transition temperature (indicates that the polymer is amorphous) ExamPle 1 Preparation of 2,2 bis(trifluoromethyl)-4-chloro-5-fluoro-1,3-dioxole, (3a), 2,~-bis(trifluoromethyl)-4-1uoro-1,3~dioxole, (3b), and the corresponding dioxolanes (4a) and ~4b).
9Çi~5 A. 2,2-Bis(trifluoromethyl)-4,4,5-trichloro-
5-fluoro-1,3-dioxolane, (4a).
A 330 mL Hastelloy* C lined shaker tube was ch~rged under anhydrous conditions with 100 g (0.285 mole) of 2,2-bis(trifluoromethyl)-4,4,5,5-tetrachloro-1,3-dioxolane (4e) and 8.6 g (0.0432 mole) of antimony pentachloride; the tube ~las then chilled to about -50C, and 20 g (1 mole) of hydrogen fluoride was introduced into it. The tube was mounted in a horizontal shaker, agitated for 5 hours at 70C, then chilled in wet ice, slowly vented, and opened. The tube contents were dumped into wet ice. The liquid product was separated from the ice water, washed twice with 50 mL portions of cold water, then with 20 mL of a 10% aqueous sodium carbonate solution. There was obtained 83.5 g of a clear, colorless liquid product of which approximately 93% was the desired 2,2 bis(trifluoromethyl)-4,4,5-trichloro-5-fluoro-1,3-dioxolane, (4a).
The product was distilled at atmospheric pressure on a 0.76 m spinning band column; a small amount of 2,2-bis(trifluoromethyl)-4,5-dichloro-4,5-difluoro-1,3-dioxolane (about 2% of the product) boiling at 85-86C distilled first, followed by the 2,2-bis(trifluoromethyl)-4,4J5-trichloro-5-fluoro-1,3-dioxolane, b.p. 115C, which was obtained as a colorless, clear liquid in purity exceeding 9~%.
Both infrared spectroscopy and Fluorine-19 nuclear magnetic resonance spectroscopy were consistent with this chemical structure.
The pot residue was largely starting material, approximately 5~ of the total mixture from the shaker tube run.
B. Dechlorination of 2,2-bis(tri1uoro-methyl)-4,4,5-trichloro-5-fluoro-1,3-dioxolane, (4a).
*denotes trade mark 3~
A 300 mL, 3-neck glass flask equipped with magnetic stirrer, thermometer, Vigreux column, still head to a 100 mL receiver, and dry ice trap under 100 kPa of nitro~en was charged with 165 mL of l-propanol, 42.6 g (0.651 mole~ of zinc dust, and 1.
9 (0.0109 mole) of zinc chloride. The mixture was stirred while being heated to 98C over a 21 minute period; when this temperature was reached, 2,2-bis(trifluoromethyl)-4,4,5-trichloro-5-fluoro-1,3-dioxolane, 72.0 g (0.217 mole~, was introduced intothe refluxing mixture via a svringe pump at 0.33 mL/minute. Thirty-five minutes later the head temperature fell to 59C, and distillation of the product was started. Total addition time was 127 minutes. Total ~istillation time was 268 minutes, during which time the head temperature decreased to a minimum of 55C. The distillate, 60 mL, contained some l-propanol which was extracted with water, leaving 47.7 g of a clear, colorless liquid containing about 52% of 2,2-bis(trifluoro-methvl)-4-chloro-S-fluoro-1,3-dioxole, (3a), 25~ of 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b), and 22~ of 2,2,-bis(trifluoromethyl)-4,5-dichloro-4-fluoro-1,3-dioxolane (4b) 3S a mixture of 30% cis and 70~ trans isomers.
The crude reaction product was fractionated at atmospheric pressure on a 0.51 m spinning band column. 2,2-Bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b), b.p. 44-45C, polymerizes spontaneously at room temperature when pure. It was therefore collected in a receiver maintained at -80C
and stored in a dry ice chest. 2,2-Bis(trifluoro-methyl)-4-chloro-5-~luoro-1,3-dioxole, (3a), distilled at 56C; this monomer did not polymerize spontaneously ~t room temperature~ The cls/trans mixture of 2,2-bis(tri-fluoromethyl)-4,5-dichloro-4-fluoro-1,3-dioxolane, (4b), distilled within the range of 82-90C.
The IR, F-l9 and proton N~IR spectra, and mass spectrometry support the above chemical structures.
C. Alternate dechlorination of 2,2-bis(trifluoromethyl)-4,4,5-trichloro-5-fluoro~
dioxolane, (9a).
The equipment described in the above section B was charged with 80 mL of tetrahydrofuran, 10.8 g (0.444 mole) of magnesium turnings, 0.2 g of mercuric chloride, and 0.2 g of iodine and heated to 66C
(iodine color disappears). 2,2-Bis(trifluoro-methyl)-4,4,5-trichloro-5-fluoro-1,3-dioxolane, 33.1 g (0.1 mole), was added by means of a syringe pump at the rate of 0.16 mL/minute over a period of 110 minutes. Distillation was started 41 minutes after the addition; the head temperature remained at 54~55C during the remainder of the addition. The distillation was stopped after 2.5 hours, and the distillate was extracted with water to remove some tetrahydrofuran. The extracted clear, colorless liquid was found by ~as chromatography to contain about 95~ of 2,2-bi~s(trifluoromethyl)-4-chloro-S-fluoro-1,3-dioxole, (3a); the 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b), amounted to only 1~.
D. Alternate preparation of 2,2-bis(tri-fluoromethyl)-4-fluoro-1,3-dioxole, (3b)o Using the same equipment, except for a smaller, 100 mL flask, a mixture of 30 mL of tetrahydrofuran, 3.6 g of magnesium turnings, 0.2 g of mercuric chloride, and Ool y of iodine was heated to reflux. 2,2-Bisttrifluoromethyl)-4,5-dichloro-4-fluoro-1,3-dioxolane, (4b3, 10 g, (prepared as described in Section B, above) was then introduced into the flask at approximately 0.19 mL/minute over a 34 minute period. Distillation was started 21 minutes after the a~dition was completed and continued until 20 mL of cold distillate was recovered. This was extra~ted with ice water to remove tetrahydrofuran. The remaining product was 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b).
Example 2 Homopolymerization of 2,2-bis(tri-fluoromethyl)-4-fluoro-1,3-dioxole, (3b).
T~is monomer, 4.6 g, (99.88~ pure by gas chromatography) was placed at 25C in a small, tightly ca~ped vial under room lighting conditions.
;~ Within a few hours the viscosity of the clear liquid increased to that of a light syrup, and overnight a solid, clear, colorless plug of polymer formed on the bottom of the vial.
A small sample of the monomer-polymer syrup was evaporated on a salt plate to remove the residual monomer and form a film of the homopolymer. The infrared absorbance spectrum of this film was consistent ~ith the molecular structure of a homopolymer of 2,2-bis(trifluoromethyl)-4~fluoro-1,3-dioxole, (3b).
The plug was placed in a vacuum oven at 110-120C to remove residual monomer, and then a sample was examined by Differential Scanning Calorimetry between room temperature and 300Co There were no second order transitions or melting points in this re~ion, indicating that the homopolymer was amorphous and that its Tg was above - 300C.
3~
Example 3 Crystalline copoly~er of 2,2-bis(trifluoro-methyl)-4-fluoro-1,3-dioxolc, (3b), and TFE.
A 110 mL stainless steel shaker tube ~as charged with a cold solution containing 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 1.0 g of the dioxole, and 0.03 ~ of bis~4-t-butylcyclohexYl) peroxydicarbonate; the tube was chilled to -50C and alternately evac~ated and flushed with nitro~en three times. The evacuated tube was then charged with lO g of tetrafluoroethylene and agitated in a horizontal shaker. The tem~erature was held at 55C for two hours and then at 65C for two hours. After cooling the tube and venting, the resulting suspension of ; 15 copolymer in 1,1,2-trichloro-1,2,2-trifluoroethane ; was recovered. The solvent was distilled off, and the polymer was dried to give ~.7 g of white, solid granules. A portion of these was pressed at 300C
into a tough, self-supporting filmO The infrared spectrum of the film showed absorbancies characteristic of a tetrafluoroethylene/2,2-bis(tri-fluorome~hyl)-4-fluoro-1,3-dioxole copolymer.
Differential Scanning Calorimetry showed a major, broad, crystalline melting point at 266C; there also 25 was a minor melting point at 320C. Infrared and F-l9 NMR s~ectra support the copolymer struGture containing 94.8 mole ~ of tetrafluoroe~hylene and 5.2 mole % OL 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b).
Example 4 - Amorphous copolymer of 2,2-bis(trifl~oro-methyl)-4 fluoro~1,3-dioxole, (3b), and TFE.
A snaker tube was charged with 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.03 g of bis(4-t-hutylcyclohexyl) peroxydicarbonate~ 5.0 g (0.022 mole) of the dioxole, and 5.0 g (0.05 mole) of TFE. Polymerization was carried out at 55 and 65C. ~fter sep~rating and drying the product, 4.5 a of a white solid polymeric product was obtained. A
portion oE the product was pressed at 230C into thin, tough, clear, colorless, self-supporting films. ~he infrared and F-l9 N~IR spectra established the product to be a copolymer containing 71.2 mole %
of TFE and 28.8 mole ~ of the dioxole. Differential Scanning Calorimetry showed a Tg at 58C but no melting ~oint, thereby indicating that the copolymer was amorphous.
Example 5 A high melting crystalline copolymer of ,3 15 2,2-bisttrifluoromethyl)-4-fluoro-1,3-dioxole, (3b) ;- and TFE.
A shaker tube was charged with 100 9 of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.03 g of bis(4-t-butylcyclohexyl) peroxydicarbonate, 0.5 g t0.0022 mole) of the dioxole, and 10 g (0.1 mole) of TFE. Polymerization was carried out at 55 and 65C. After se~arating and drying the product, 9.4 g of a white, solid polymer was obtained. A portion of the polymer was pressed at 330C into thin, tough, colorless, transparent, self-supporting films. The infrared and F-l9 NMR spectra were consistent with a copolymer of 97.6 mole ~ TFE and 2.4 mole ~ of 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole.
Differential Scanning Calorimetry showed a relatively sharp melting point at 307C, thus indicating the crystalline nature of the polymer.
ExamPle 6 A crystalline copolymer of 2,2-bis-(trifluoromethyl)-4-chloro-5-fluoro-1,3-dioxole, (3a), and TFE.
A shaker tube was charged with 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.03 g of bis(4-t~butylcyclohexyl) peroxydicarbonate, 1.5 g (0.0058 mole) of the dioxole and 10 g of 1'FE, and polymerization was carried out at 55 and 65C.
After se~arating and drying the ~roduct, 4.3 g of a white, solid polymer was obtained. A portion of the polymer was pressed at 300C to give tough, thin, colorless, clear, self-supporting films. Infrare~
and F-19 NMR spectra support the structure of a copolymer containing 96.9 mole % of TFE and 3.1 mole % of 2,2-bis(trifluoromethyl)-4-chloro-5-fluoro-1,3-dioxole, (3a). Differential Scannin~
Calorimetry showed a melting point at 295C, indicating the crystalline nature of the polymer.
Example 7 .
A terpolymer of 2,2-bis(trifluoromethyl)-4-chloro-S fluoro-1,3-dioxole, (3a), vinylidene fluoride, and TFE.
A shaker tube was charged with lOQ ~ of 1,1,2-trichloro-1,2,2-trifluoroethane, 3.0 g of the dioxole, 0.03 g of bis(4-t-butylcyclohexyl~
peroxydicarbonate, 6.0 g of vinylidene fluoride, and
A 330 mL Hastelloy* C lined shaker tube was ch~rged under anhydrous conditions with 100 g (0.285 mole) of 2,2-bis(trifluoromethyl)-4,4,5,5-tetrachloro-1,3-dioxolane (4e) and 8.6 g (0.0432 mole) of antimony pentachloride; the tube ~las then chilled to about -50C, and 20 g (1 mole) of hydrogen fluoride was introduced into it. The tube was mounted in a horizontal shaker, agitated for 5 hours at 70C, then chilled in wet ice, slowly vented, and opened. The tube contents were dumped into wet ice. The liquid product was separated from the ice water, washed twice with 50 mL portions of cold water, then with 20 mL of a 10% aqueous sodium carbonate solution. There was obtained 83.5 g of a clear, colorless liquid product of which approximately 93% was the desired 2,2 bis(trifluoromethyl)-4,4,5-trichloro-5-fluoro-1,3-dioxolane, (4a).
The product was distilled at atmospheric pressure on a 0.76 m spinning band column; a small amount of 2,2-bis(trifluoromethyl)-4,5-dichloro-4,5-difluoro-1,3-dioxolane (about 2% of the product) boiling at 85-86C distilled first, followed by the 2,2-bis(trifluoromethyl)-4,4J5-trichloro-5-fluoro-1,3-dioxolane, b.p. 115C, which was obtained as a colorless, clear liquid in purity exceeding 9~%.
Both infrared spectroscopy and Fluorine-19 nuclear magnetic resonance spectroscopy were consistent with this chemical structure.
The pot residue was largely starting material, approximately 5~ of the total mixture from the shaker tube run.
B. Dechlorination of 2,2-bis(tri1uoro-methyl)-4,4,5-trichloro-5-fluoro-1,3-dioxolane, (4a).
*denotes trade mark 3~
A 300 mL, 3-neck glass flask equipped with magnetic stirrer, thermometer, Vigreux column, still head to a 100 mL receiver, and dry ice trap under 100 kPa of nitro~en was charged with 165 mL of l-propanol, 42.6 g (0.651 mole~ of zinc dust, and 1.
9 (0.0109 mole) of zinc chloride. The mixture was stirred while being heated to 98C over a 21 minute period; when this temperature was reached, 2,2-bis(trifluoromethyl)-4,4,5-trichloro-5-fluoro-1,3-dioxolane, 72.0 g (0.217 mole~, was introduced intothe refluxing mixture via a svringe pump at 0.33 mL/minute. Thirty-five minutes later the head temperature fell to 59C, and distillation of the product was started. Total addition time was 127 minutes. Total ~istillation time was 268 minutes, during which time the head temperature decreased to a minimum of 55C. The distillate, 60 mL, contained some l-propanol which was extracted with water, leaving 47.7 g of a clear, colorless liquid containing about 52% of 2,2-bis(trifluoro-methvl)-4-chloro-S-fluoro-1,3-dioxole, (3a), 25~ of 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b), and 22~ of 2,2,-bis(trifluoromethyl)-4,5-dichloro-4-fluoro-1,3-dioxolane (4b) 3S a mixture of 30% cis and 70~ trans isomers.
The crude reaction product was fractionated at atmospheric pressure on a 0.51 m spinning band column. 2,2-Bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b), b.p. 44-45C, polymerizes spontaneously at room temperature when pure. It was therefore collected in a receiver maintained at -80C
and stored in a dry ice chest. 2,2-Bis(trifluoro-methyl)-4-chloro-5-~luoro-1,3-dioxole, (3a), distilled at 56C; this monomer did not polymerize spontaneously ~t room temperature~ The cls/trans mixture of 2,2-bis(tri-fluoromethyl)-4,5-dichloro-4-fluoro-1,3-dioxolane, (4b), distilled within the range of 82-90C.
The IR, F-l9 and proton N~IR spectra, and mass spectrometry support the above chemical structures.
C. Alternate dechlorination of 2,2-bis(trifluoromethyl)-4,4,5-trichloro-5-fluoro~
dioxolane, (9a).
The equipment described in the above section B was charged with 80 mL of tetrahydrofuran, 10.8 g (0.444 mole) of magnesium turnings, 0.2 g of mercuric chloride, and 0.2 g of iodine and heated to 66C
(iodine color disappears). 2,2-Bis(trifluoro-methyl)-4,4,5-trichloro-5-fluoro-1,3-dioxolane, 33.1 g (0.1 mole), was added by means of a syringe pump at the rate of 0.16 mL/minute over a period of 110 minutes. Distillation was started 41 minutes after the addition; the head temperature remained at 54~55C during the remainder of the addition. The distillation was stopped after 2.5 hours, and the distillate was extracted with water to remove some tetrahydrofuran. The extracted clear, colorless liquid was found by ~as chromatography to contain about 95~ of 2,2-bi~s(trifluoromethyl)-4-chloro-S-fluoro-1,3-dioxole, (3a); the 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b), amounted to only 1~.
D. Alternate preparation of 2,2-bis(tri-fluoromethyl)-4-fluoro-1,3-dioxole, (3b)o Using the same equipment, except for a smaller, 100 mL flask, a mixture of 30 mL of tetrahydrofuran, 3.6 g of magnesium turnings, 0.2 g of mercuric chloride, and Ool y of iodine was heated to reflux. 2,2-Bisttrifluoromethyl)-4,5-dichloro-4-fluoro-1,3-dioxolane, (4b3, 10 g, (prepared as described in Section B, above) was then introduced into the flask at approximately 0.19 mL/minute over a 34 minute period. Distillation was started 21 minutes after the a~dition was completed and continued until 20 mL of cold distillate was recovered. This was extra~ted with ice water to remove tetrahydrofuran. The remaining product was 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b).
Example 2 Homopolymerization of 2,2-bis(tri-fluoromethyl)-4-fluoro-1,3-dioxole, (3b).
T~is monomer, 4.6 g, (99.88~ pure by gas chromatography) was placed at 25C in a small, tightly ca~ped vial under room lighting conditions.
;~ Within a few hours the viscosity of the clear liquid increased to that of a light syrup, and overnight a solid, clear, colorless plug of polymer formed on the bottom of the vial.
A small sample of the monomer-polymer syrup was evaporated on a salt plate to remove the residual monomer and form a film of the homopolymer. The infrared absorbance spectrum of this film was consistent ~ith the molecular structure of a homopolymer of 2,2-bis(trifluoromethyl)-4~fluoro-1,3-dioxole, (3b).
The plug was placed in a vacuum oven at 110-120C to remove residual monomer, and then a sample was examined by Differential Scanning Calorimetry between room temperature and 300Co There were no second order transitions or melting points in this re~ion, indicating that the homopolymer was amorphous and that its Tg was above - 300C.
3~
Example 3 Crystalline copoly~er of 2,2-bis(trifluoro-methyl)-4-fluoro-1,3-dioxolc, (3b), and TFE.
A 110 mL stainless steel shaker tube ~as charged with a cold solution containing 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 1.0 g of the dioxole, and 0.03 ~ of bis~4-t-butylcyclohexYl) peroxydicarbonate; the tube was chilled to -50C and alternately evac~ated and flushed with nitro~en three times. The evacuated tube was then charged with lO g of tetrafluoroethylene and agitated in a horizontal shaker. The tem~erature was held at 55C for two hours and then at 65C for two hours. After cooling the tube and venting, the resulting suspension of ; 15 copolymer in 1,1,2-trichloro-1,2,2-trifluoroethane ; was recovered. The solvent was distilled off, and the polymer was dried to give ~.7 g of white, solid granules. A portion of these was pressed at 300C
into a tough, self-supporting filmO The infrared spectrum of the film showed absorbancies characteristic of a tetrafluoroethylene/2,2-bis(tri-fluorome~hyl)-4-fluoro-1,3-dioxole copolymer.
Differential Scanning Calorimetry showed a major, broad, crystalline melting point at 266C; there also 25 was a minor melting point at 320C. Infrared and F-l9 NMR s~ectra support the copolymer struGture containing 94.8 mole ~ of tetrafluoroe~hylene and 5.2 mole % OL 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole, (3b).
Example 4 - Amorphous copolymer of 2,2-bis(trifl~oro-methyl)-4 fluoro~1,3-dioxole, (3b), and TFE.
A snaker tube was charged with 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.03 g of bis(4-t-hutylcyclohexyl) peroxydicarbonate~ 5.0 g (0.022 mole) of the dioxole, and 5.0 g (0.05 mole) of TFE. Polymerization was carried out at 55 and 65C. ~fter sep~rating and drying the product, 4.5 a of a white solid polymeric product was obtained. A
portion oE the product was pressed at 230C into thin, tough, clear, colorless, self-supporting films. ~he infrared and F-l9 N~IR spectra established the product to be a copolymer containing 71.2 mole %
of TFE and 28.8 mole ~ of the dioxole. Differential Scanning Calorimetry showed a Tg at 58C but no melting ~oint, thereby indicating that the copolymer was amorphous.
Example 5 A high melting crystalline copolymer of ,3 15 2,2-bisttrifluoromethyl)-4-fluoro-1,3-dioxole, (3b) ;- and TFE.
A shaker tube was charged with 100 9 of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.03 g of bis(4-t-butylcyclohexyl) peroxydicarbonate, 0.5 g t0.0022 mole) of the dioxole, and 10 g (0.1 mole) of TFE. Polymerization was carried out at 55 and 65C. After se~arating and drying the product, 9.4 g of a white, solid polymer was obtained. A portion of the polymer was pressed at 330C into thin, tough, colorless, transparent, self-supporting films. The infrared and F-l9 NMR spectra were consistent with a copolymer of 97.6 mole ~ TFE and 2.4 mole ~ of 2,2-bis(trifluoromethyl)-4-fluoro-1,3-dioxole.
Differential Scanning Calorimetry showed a relatively sharp melting point at 307C, thus indicating the crystalline nature of the polymer.
ExamPle 6 A crystalline copolymer of 2,2-bis-(trifluoromethyl)-4-chloro-5-fluoro-1,3-dioxole, (3a), and TFE.
A shaker tube was charged with 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.03 g of bis(4-t~butylcyclohexyl) peroxydicarbonate, 1.5 g (0.0058 mole) of the dioxole and 10 g of 1'FE, and polymerization was carried out at 55 and 65C.
After se~arating and drying the ~roduct, 4.3 g of a white, solid polymer was obtained. A portion of the polymer was pressed at 300C to give tough, thin, colorless, clear, self-supporting films. Infrare~
and F-19 NMR spectra support the structure of a copolymer containing 96.9 mole % of TFE and 3.1 mole % of 2,2-bis(trifluoromethyl)-4-chloro-5-fluoro-1,3-dioxole, (3a). Differential Scannin~
Calorimetry showed a melting point at 295C, indicating the crystalline nature of the polymer.
Example 7 .
A terpolymer of 2,2-bis(trifluoromethyl)-4-chloro-S fluoro-1,3-dioxole, (3a), vinylidene fluoride, and TFE.
A shaker tube was charged with lOQ ~ of 1,1,2-trichloro-1,2,2-trifluoroethane, 3.0 g of the dioxole, 0.03 g of bis(4-t-butylcyclohexyl~
peroxydicarbonate, 6.0 g of vinylidene fluoride, and
6.Q g of TFE. Polymerization was carried out at 55 and 65C for 4 hours under autogenous pressure.
After separating and drying the product, 3.6 g of a white, solid polymer was obtained. A portion of this polymer was pressed at 230C into thin, tough, clear, self-supporting films. Infrared and F-19 NMR spectra identified the polymer as a terpolymer containing 14~3 mole % of TFE, 80.4 mole % of vinylidene fluoride, and 5.3 mole ~ of the dioxole.
Differential Scanning Calorimetry showed a ~elting point at 131C, thus demonstrating the crystalline character of the polymer Example 8 Preparation of 2,~-bis(trifluoromethyl)-1,3-dioxole, (3c), 2,2-bis(trifluoromethyl)-4-chloro-1,3-dioxole, (3d), and 2,2-bis(trifluoro-5 methyl)-4,5-dichloro-1,3-dioxole, (3e).
A. Synthesis of 2,2-bis(trifl~oromethyl)-4,5-dichloro-1,3-dioxolane, (4c), 2,2-bis(tri fluoromethyl)-4,4,5-trichloro-1,3-dioxolane, (4d), and ~,2-bis(trifluoromethyl)-4,4,5,5~tetrachloro-1,3-dioxolane, (4e).
A 300 mL, 3-neck round bottom ~lask equipped with a magnetic stirrer, chlorine gas inlet, thermometer, and a water condenser topped by a dry ice condenser communicating with a drying tower and then with a water scrubber was charged with 210 9 (1.0 mole) of 2,2-bis(trifluoromethyl)-1,3-dioxolane.
After purging the system with nitrogen, chlorine was I passed into the solution at such a rate as to ; maintain a yellow coloration of the solution. The stirred mixture was irradiated with a 275 watt General Electric sun lamp so as to maintain a reaction temperature for the most part in the range ~- of 46-72C for 4.5 hours. The concentration of the starting dioxolane in the reaction mixture had dropped by then to approximately 0.1~, and the reaction was terminated. Residual chlorine and hydrogen chloride were removed with a water aspirator, leaving a colorless, clear liquid weighing 28~ g and containing the di-, tri-, and tetrachloro-derivatives (4c), (4d~, and (4e), as confirmed byN~, mass spectrometry, and gas chromatographic analyses.
B. Dechlorination of the di-, ~ri-, and tetrachlorodioxolanes obtained in step A, above.
~5 s~
A 500 mL, 3-neck, round bottom flask equipped with a magnetic stirrer, a syringe pump inlet, a ther~ometer, a 15-cm still leading to a 100 mL recei~er and then to a nitrogen tee and a bubbler was charged with 98.1 ~ ~1.5 moles) of zinc dust, 3.0 g (0.022 mole) of ~inc chloride, and 300 mL of _-butyl alcohol. A syringe pump was charged ~ith 139.5 g of the chlorinated dioxolanes from step A.
After the flask contents were brought to 115C, the chlorinated dioxolanes were pumped into the flask at 0.33 mL/minute. The addition was completed in 224 minutes. Twenty minutes after the start of the addition, distillation began at a rate of about 15-20 mL/hour. The head temperature then was 79-80C but during the distillation decreased to 75C and at the end was 116C; 119.8 g of product containing hutyl alcohol was distilled. The produc~ distribution was about 21% of 2,2-bis(trifluoromethyl)-1,3-dioxole, (3c), 47~ of 2,2-bis(trifluoromethyl)-4-chloro-1,3-dioxolel (3d), and 30~ of 2,2-his(trifluoromethyl)-4,5-dichloro-1,3-dioxole, (3e). The crude product was fractionated at - atmospheric pressure on a 0O76 m spinning band column to provide each dioxole as a clear, colorless liquid having a ~urity of at least 99%:
2,2-bis(trifluoromethyl)-1,3-dioxole, (3c), b.p~
67C; 2,2-bis(trifluoromethyl)4-chloro-1,3-dioxole, ~3d), b.p. 76C; and 2,2-bis(trifluoromethyl)-4,5 dichloro-1,3-dioxole (3e), b.p. 85C. The infrared, F-l9 and proton N.~R, and masq spectrometry data ~or these dioxoles support their molecular structures.
C. Alternate synthesis of 2,2-bis(trifluoro-methyl)-4-chloro-1~3-dioxole~ (3d).
~3~
A 100 mL, 2-neck, round-bottom glass flask equipped with magnetic stirrer, thermometer, Vigreux - column, still head, and receiver was charged under a nitrogen blanket with 40 mL of di(ethylene glycol) dimethyl et`ner, 9.8 g of crude 2,2-bis(trifluoromethyl)-4,5-dichloro-1,3-dioxolane, (4c), and 6.7 g of solid potassium hydroxide. The flask contents were heated at 1~1C for 2 hours during which time the 2,2-bis(trifluoro-methyl)-4-chloro-1,3-dioxole, (3d), distilled overO
Purified by gas chromatography, the product had the same retention time and infrared spectrum as an authentic sample of 2,2-bis(trifluoromethyl)-; 4-chloro-1,3-dioxole, (3d).
Exam~le 9 i A crystalline copolymer of 2,2-bis(tri-fluoromethyl)-1,3-dioxole, (3c) and TFE.
A shaker tube was charged with 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.03 g of bis(4-t-butylcyclohexyl) peroxydicarbonate, 1.5 g ~ (0.0072 mole) of the dioxole, and 10 9 (0.1 mole) of TFE. Polymerization was carried out at 55 and 65C. After separating and drying the product, 10.5 `~` g of a white, solid polymer was obtained. A portion 25 of the polymer was pressed at 300C into tough, clear, colorless, self-supporting films. Infrared and F-19 N~R spectra established a copolymer structure of 93.1 mole ~ of TFE and 6.9 mole % of 2,2-bis(trifluoromethyl)-1,3-dioxole, (3c).
30 Differential Scanning Calorimetry showed a melting point at 253C, thereby establishing the crystalline character of this polymer.
Exam~le 10 A An amorphous copolymer of 2,2-bi~(tri-35 fluoromethyl)-1,3-dioxole, (3c) and TFEo A shaker tube was charge~ with 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 4.2 g (0.02 mole) of the dioxole, 0.03 g of bis(4-t-butyl-cyclohexyl) peroxydicarbonate, ar.d 10 g of TFE.
Polymerization was carried out at 55 and 65C under autogeno~s pressure or 4 hours. ~fter separation and drying, a white, solid polymer, 1.4 g, ~as obtained. It was soluble in the trichlorotrifluoro-ethane solvent; a clear, transparent, ~elf-supporting film was cast from this solution. Infrared and F-l9 and proton NMR spectra identified the copolymer as containing 46.3 mole % of the dioxole and 53.7 mole %
of TFE Differential Scanning C~lorimetry showed a Tq at 61C and other transitions at 113C and 246C;
there was no melting point, and the polymer was therefore amorphous.
Exa~ole 11 An elastomeric terpolymer of 2,2-bis~tri-fluoromethyl)-1,3-dioxole, (3c), vinylidene fluoride, 20 a~d TFE.
A shaker tube was charged with 100 g of 1,1,2-trichloro-1-~,2,-trifluoroethane, 3.0 g (0.0144 mole) of the dioxole, O.G3 g of bis(4-t-butyl-cvclonexvl) peroxydicarbonate, 6.0 g (0.094 mole) of 25 vinylidene fluoride, and 6.0 q (0.06 mole) of TFE.
Polymerization was carried out under a-1togenous pressure at 55 and 65C. After separation and drying, a white, solid poly~er, ~.4 q, was obtained.
It was not soluble in the trichlorotrifluoroethane.
30 A portion of the ~olymer was pressed at 230~C to give thin, tough, elastomeric, clear, self-supporting films. Infrared and F-19 NMR spectra identified the i terpolymer as contain ng 36.4 mole % of TFE~ 55.7 mole ~ of vinylidene fl~oride, and 7~9 mole % of 35 dioxole. ~iferential Scanning Calorimetry showed a s melting point at 114C, indicating the crystalline nature of the polymer~
Exam?le l2 Homopolymer of 2,2-bis(trifluoromethyl)-1,3 dioxolQ, (3c)-The dioxole, 3.0 g, which had been kept in adry ice chest, was placed in a 10 mL closely capped, clear, glass vial and allowed to stand at room temoerature under laboratory fluorescent lighting conditions. After two weeks, ~ portion of the liquid was pl~ced on a salt plate and allowed to ev~porate, leaving a thin, transparent, clear, colorless solid film~ In~r~red analysis of this film was consistent with the homopolymer structure.
Exam~le 13 crystalline copolymer of TFE and 2,2-bis-(trifluoromethyl)-4-chloro-1,3-dioxole, (3d).
A shaker tube was charqed with 100 g of 1,1,2-trichloro,1,2,2-trifluoroethane, 0.03 g of bis (4-t-butylcyclohexyl) peroxydicarbonate, 1.5 g (0.00613 mole) of the dioxole, and 10 g (0.1 mole) of TFE. Polymerization was carried out under autogenous pressure at 55 and 65Co After separation and drying, a white solid polymer, 5.0 g, was obtained.
A portion of the polymer was pressed at 300C into thir, tough, clear, self-supporting films. Infrared and F-l9 N~IR s~ectra showed the copolymer to contain 94.1 mole ~ of TFE and 5.9 mole % of the dioxole.
Differential Scanning Calorimetry showed a melting 3~ ~oint at 269~C, thus indicating the polymer to be crystalline.
! Example 14 An amorphous terpolymer of TEE with ~,2-bis-(trifluoromethyl)-1,3-dioxole, (3c) and ~,2 bis(trifluoromethyl~-4-chloro-1,3-dioxole, ~3d)o 2~
A shaker tube was charged with 100 g of 1,1~2-trichloro-1/2,2-trifluoroethane, 1.0 g of 2,2-~is(trifluoromethyl)-1,3-dioxole, (3c), 2.0 g of 2,2-bis(trifluoromethyl)-4-chloro-1,3-dioxole, ~3d) 0.03 g of bis(4-t-butylcyclohexyl) peroxydicar~onate, and 10 g TFE. Polymerization was carried out under autogenous pressure at 55 and 65C. After separation and drying, 3 g of white, solid, ~olymer granules were obtained. A portion of tne ~olymer was pressed at 300C to give thin, tough, self-supporting, colorless, clear films. The infrared and F-l9 NMR spectra were consistent with a terpolymer structure consisting of 85.2 mole ~ of TFE, 8 . 6% of 2,2-bis(trifluoromethyl)-1,3-dioxole, (3c), and 6.2 mole % of 2,2-bis(trifluoromethyl)-4-chloro-1,3-dioxole~ (3d). The Differential Scanning Calorimetry analysis showed a Tg at 54C but no melting point, thereby indicating the polymer to be amorphous.
~xample 15 Preparation of 2,2,4-trifluoro-5-chloro-1,3-dioxoler (3f) 2,2,4-trifluoro-1,3-dioxole, (3g), and the corresponding dioxolanes (4f) and (4g).
A. 2,2,4-trifluoro-4,5f5-trichloro-1,3-dioxolane (4f) A dry, 360 mL "Hastelloy~ C lined shaker tube was charged with 81.8 g (0.33 mole) of 2,2-difluoro-4,4,5,5-tetrachloro-1,3-dioxolane, ~4j), containing 9.0 g (0.03 ~ole) of antimony pentachloride. The tube was cooled, alternately evacuated and purged with nitrogen three times, and charged with 22 g (1~1 mole) of hydrogen fluoride~
The ~ube was agitated and warmed to 40C over a period of 1 hour, heated under autogenous pressure for 4 hours at 40C, then cooled to 0C, 510wly 2~
s vented, and opened. The contents were poured into ice; the organic phase was se~arated from the aqueous phase, extracted twice with distilled water and once with an aqueous 10~ sodium carbonate solution; 63.3 g of crurle product was obtained which contained about 3 . 9% of 2, 2, 4, 5-tetrafluoro-4,5-dichloro-1,3-dioxolan~, 85.8% 2,2,4~trifluoro-4,5,5-tri-chloro-1,3-dioxolane, (4f), and 8.1~ of the starting material. This product mixture was combined with those of three other similar runs and separated by distillation on a 0.76 m spinning band column;
2,2,4,5-tetrafluoro-4,5-dichloro-1,3-dioxolane boiled at 45-46~C; 2,2,4-trifluoro-4,5,5-trichloro-1,3-dioxolane, ~4f), at 84C; and the starting 5. 15 material, 2,2-difluoro-4,4,5,5-tetrachloro-1,3-dioxolane (4j), at 115C. Their purities were greater than 99%. Both infrared and ~-19 NMR
spectroscopy confirmed their structures.
B. ~echlorination of 2,2,4-trifluoro-4,5,5-trichloro-1,3-dioxolane, (4f).
A 300 mL 3-neck glass flask equipped with magnetic stirrer, thermometer, Vigreux column with a dry ice-cooled still head leading to a cold receiver, trap, a nitro~en tee, and bubbler was charged with 76.7 g ~1.17 gram-atom~) of zinc, 2.6 g (0.019 mole) of zinc chloridet and 175 mL of propanol. ~he stirred mixtuxe was heated to 9~C; then 89.6 g (0.387 mole) of 2,2,4-trifluoro-4,5,5-trichloro-1,3-dioxolane, (4f), was introduced from a syringe pump at a rate of 0.~3 mL/minute during 172 minutes. Distillation at a rate of about 15 mL/hour began 33 minutes after the start of the addition and continued for 270 minutes; 65 mL of clear, colorless distillate weighing 84.5 g and con,aining some propanol was obtained. It was redistilled through a 0.76 m spinning band column with a dry ice-cooled head. The product distribution was approximately 3 9~ of 2,2,4-trifluoro-1,3-dioxole, (3g), b.p, 10C;
71.7% of 2,2,4-trifluoro-5-chloro-1,3-dioxole, (3f), b.p. 25-27C; and 24.3% of 2,2,4-trifluoro-4,5-dichloro-1,3-dioxolane, (4g), b.p. 73C. The infrared, F-l9 and proton NMR spectra of these compounds were consistent with the assigned structures.
Example 16 Alternate synthesis of 2,2,4-trifluoro-4,5-dichloro-1,3-dioxolane, (4g).
A~ 4,4,5-trichloro-1,3-dioxolan-2-one.
- A creased 3-neck, 300 mL, round bottom flask equipped with magnetic stirrer, gas inlet tube, thermometer, and water condenser topped by a dry ice condenser leading to a trap and scrub~er was charged with a8. 1 g of ethylene carbonate. The system was purged with nitrogen and then dry chlorine gas was introduced while irradiating the reaction vessel with a 275 watt General ~lectric*Sun Lamp; the amount of chlorine was sufficient to maintain a yellow color in the solution. The temperature ranged from 35C
during the initial part of the chlorination and up to 115C during the later part of the 6-hour reac'ion.
The reaction mixture was analyzed by gas chromatography techniques and, when all of the 4-chloro-1,3-dioxolan-2-one had been consumed, the reaction was terminated. The product was principally 4,4,5-trichloro-1,3-dioxolan-2-one wi~h lesser amounts of 4,5-dichloro- and 4,4,5,5-tetrachloro-derivatives. Two similar runs were made and the products combined.
Bo Fluorination of 4,4,5-trichloro-1,3-35 dioxolan-2-one.
*denotes trade mark ~ ~2~
A shaker tube was charged with 113 g of crude 4,4,5-trichloro-1,3-dioxolan-2-one, 18 g of HF, and 194 g of SF4. After agitating 10 hours at 200C, the tube was cooled to 0C, and the product was mixed with ice. The organic phase was separated ; and neutralized by sha~ing witn an aqueous potassium carbonate solution and then distilled vn a 0.76 m spinning band column; the first fraction, 2,2,4,5-tetrafluoro-4,5-dichloro-1,3-dioxolane, b.p.
47-48C, was followed by the desired 2,2,4-trifluoro-4,5 dichloro-1,3-dioxolane, (4g), b.~. ~9-73C. Infrared and F-l9 NMR spectra were consistent with this structure.
~x~m~le 17 ~ 15 Preparation of 2,2,4-trifluoro-1,3-dioxGle, ; ~3g), by dechlorination of 2,2,4-triEluoro-4,5-dichloro-1,3-dloxolane, (4g).
A 100 mL, 3-neck, round bottom flask equipped with m~gnetic stirrer, thermometer, Vigreux still leading to a dry ice-cooled head, cold receiver and trap, was charged under a nitrogen blanket with 3.6 g of magnesium turnings, 0.2 g of mercuric chloride, 0.1 g of iodiner and 30 mL of ! tetrahydrofuran. The mixture was stirred and heate~
to 67C; 8~8 g of 2,2,4-trifluoro~4,5-dichloro-1,3-dioxolane, (4g), was then added at a rate of 0.092 mL/minute. After 2~ mL had been added the distillation began and continued for 3 hours until 5 mL of distillate was obtained. The cold distillate was extracted with ice water to remove some tetrahydrofuran and there remained 4.7 g of prcduct which was largely 2,2,4~trifluoro-1,3-dioxole, (3g), b.p. 10C.
This dioxole was purified by gas chroma~ography; ~he infrared absorbance spectra, and 2~
especially the absorbance in the region of 5.6 ~m, as well as its subsequent polymerization substantiated the assigned molecular str~cture.
~xamPle l8 A crystalline copolymer of tetrafluoro-ethylene with 2,2,4-trifluoro-1,3-dioxole, (3y).
A shaker tube was charged ~ith 100 9 of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.8 g of the dioxole, 0.03 g of bis(4-t-butylcyclohexyl) peroxydicarbonate, and 10 g of TFE and heated at 55 and 6$C for 4 hours. After separation of the produc~ and drying, 4.7 q of a whi~e solid polymer was obtained. A portion of this was pressed at 330C
to give thin, tough, self-supporting, colorless filmsO The infrared an2 F-l9 NMR spectra showed the copolymer composition to be 96.0 mole % TFE and 4.0 mole ~ dioxole. Differential Scanning Calorimetry showed a crystall;ne melting point at 274C.
Exam~le 19 Homopolymer of 2,2,4-trifluoro-1,3-dioxole, (3~)-A 10 mL clear, glass vial was charged with 5.7 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.001 g of bis(4-t-butylcyclohexyl) peroxydi-carbonate, and G.5 g of the dioxole, capped securely and allowed to stand two days on the bench top at about 25~C exposed to the normal fluorescent light of the laboratory. A portion of the solution was then evaporated on a micro salt plate to give a clear, colorless, self supporting film which was identified by its infrared spectrum to be the dioxole homopolymer.
Example 20 An amorphous copolymer of TFE and 2,2,4-tri fluoro 5-chloro-1,3-dioxole, (3f)O
A shaker tube was charged with 100 g of 1,1,2-trifluoro-1,2,2-trichloroethane, 1.7 g of the dioxole, 0.03 g of bis(4-t-butylcyclohexyl) peroxy-dicarbonate, and 10 9 of TFE. Polymerization ~as carried out at 55 and 65C under autogenous pressure for 4 hours. After separation and drying of the - product, 1~8 g of a white, solid polymer was obtained. A portion of this ~as pressed at 300C to ~ive thin, tough, self-supporting, colorless clear films. The infrared and F-l9 N~R spectra of this polymer showed it to contain 10.5 mole ~ of the dioxole and ~9.5 mole ~ of ~FE. Differential Scannin~ Calorimetry showed a Tg of 61C, there ~as no melting point.
! 15 Example 21 An amorphous, elastomeric terpolymer of TFE, 2,2,4 trifluoro-5-chloro-1,3-dioxole, (3f), and vinylidene fluoride.
~ shaker tube was charged with 100 9 of 1,1,2-trichloro-1,2,2-trifluoroethane, 2.1 g of the dioxole, 0.03 g of his(4-t-butylcyclohexyl) peroxydi-carbonate, 6 g of vinylidene fluoride, and 6 g of TFE. Polymerization was carried out at 55 and 65C
over a 4 hour period under autogenous pressure.
After separating and drying, there was obtained ~.5 g o white, solid polymer granules. A portion of this polymer was pressed at 200C to give thin, elastic, tough, self supporting, clear, colorless films.
Infrared and F-l9 ~MR spectra showed the terpolymer to consist of 27.7 mole % of TFE, 9.9 mole ~ of the dioxole and 6204 mole ~ of vinylidene fluoride.
- Differential Scanning Calorimetry showed no meltin~
point~ thus indicating an amorphous polymerO
~5 ~t3~
Example 22 Synthesis of 2,2-difluoro-1,3-dioxole, (3h).
A. 4,5-Dichloro-1,3-dioxolan-2-one A 500 mL, 3-neck round-bottom flask equipped with a nitrogen purge line, magnetic stirrer, thermometer, and reflux condenser leading to a trap and drying tower was charged with 88 g of ethylene carbonate, 297 g of sulfuryl chloride, and la 0 g of azobisisobutyronitrlle. After purging the assembly with nitrogen, the stirred mixture was irradiat2d with a Hanovia mercury vapor lamp at a temperature of 34-47C during the first 3 hours of the reactionO
During the next 7 hours, the temperature was increased rrorn 51 to 103C. During the final 3 hours of the reaction, the temperature was held in the 95-107C range.
After cooling to room temperature, the flask was evacuated on a water aspirator to remove small amounts of HCl. The flask contents were then flash-distilled at a pressure of about 266 Pa and a pot temperature of up to 150C; 85.7 q of distillate was collected. GC analysis of the distillate showed it to contain a~proximately 86.3~ of 4,5-dichloro-1,3-dioxolan-2-one, 8.8% of ~-chloro-1,3-d-oxolan-2-one, and 3.1~ of 4,4,S-trichloro--1,3-dioxolan-2-one.
8. 2,2-Difluoro-4,5-dichloro~1,3~dioxolane (4h) A 300 mL "Hastelloy'l C shaker tube was char~ed ~ith 136.2 g o~ 4,5-dichloro~1,3-dioxolan-2-one, 16.2 g of HF, and 19~.4 g of SF4. The tube was then heated to 150~C and agitated for 300 hours.
After ~he tube was cooled to 0C, it was slowly vented and then its contents were dumped into ice.
The organic layer was separated and extracted twlce 3,C~ 5 with 50 mL of distilled water. The product weighed 93.0 g and contained about 69~ of 2,2,4-trifluoro-5-chloro-1,3-dioxolane and abollt 7%
of 2,2-difl~loro-4~5-dichloro-5 1,3-dioxolane, (4h).
C. Dechlorination of 2,2-difluoro-4,5-di-chloro-1,3-dioxolane (4h) Equipment like that of Example 15B, except that a 100 mL flask was used~ was charged with 7.8 g 10 of zinc dust, 0.2 g of zinc chloride, and 40 m~ of butyl alcohol. The stirred mixture was heated to 114C; 6.5 ~ of crude 2,2-difluoro-4,5-dichloro-1,3-di~xolane (4h) was -then adde~ ~y a syringe pump at 0.092 mL/minute over a 52-minute lS period. Distillation be~an 20 minutes after the beginning of the addition and continued for 94 min~tes until 4.5 mL of distillate containing some butyl alcohol was obtained. The distillate was purified by gas chromatography. The infrared 20 absorbance spectrum, especially the absorbance in ~he region of 6.05 ~m, was consistent with the 2,2-difluoro-1,3-dioxole structure (3h).
E.Yample 23 Homooolymer of 2t2-difluoro-1,3-dioxole ~3h).
A shaker tube is charged with 3 g of 2,2-difluoro-1,3-dioxole in 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, and 0.005 q of bis(4-t-butylcyclohexyl) peroxydicarbonate.
30 Polymerization is carried out at 55 and 65C for 4 hours. Af~er seParating and drying the solid, white polymer, 0.6 g, a portion of it is pressed at 250C
to give a tough, clear, transparent, self supporting, thin film, of the ho~opolymer, which is amorpho~s.
r ' ~a~
Example 24 A crystalline copolymer of tetrafluoroethylene and 2,2-difluoro-1,3-dioxole, (3h).
A shaker tube is charged with 1 g of the dioxole in 100 g of 1,1,2-trichloro-1,2,2-trifluoro-ethane, 0.03 g of bis(4-t-butylcyclohexyl) peroxy~icarbonate, and 10 g of TFE. Polymerization is carried out at 55 and 65C. ~fter separating and drying the product, 9.9 g of white, granular, solid, crystalline polymer is obtained. It contains approximately 93 mole % TFE and 7 mole ~ of the dioxole.
Exa~Dle 25 ` 15 Synthesis of 2,2-difluoro-4-chloro-1,3-! dioxole, (3i).
This synthesis is carried out in the same manner as that of Example 22, except that 106.7 9 ~0.5 mole) of 2,2-difluoro~4,4,5-trichloro-lt3-dioxolane, (4i), prepared from 4,4,5-trichloro-1,3-dioxolan-2-one (Example 16A) is the starting material. Rectification of the product mix through a 0.76 m spinning band column gives 47~1 9 of 2,2-difluoro-4-chloro-1,3-dioxole, t3i).
~xampl~ 26 A crystalline copolymer of TFE with 2,2~difluoro-4-chloro-1,3-dioxole, (3i).
~ shaker tube is charged with 100 g o 1,1,~-trichloro-1,2,2-trifluoroethane containing 1 g of 2,2-difluoro-4-chloro-1,3-dioxole, (3i), 0.03 g of bis(4-t-bwtylcyclohexyl) peroxydicarbonate, and 10 g of TFE. Polymerization is carried out at 55 and 65C. After separating and drying the product, 5.2 g of a white solid granular polymer i5 obtained. ~his is pressed at 300C into a tough, self-supporting, , r ~
L~
2g clear film. The polymer is crystalline and contains approximately 94 mole % TFE and 6 mole % of the dioxole.
Exa~ple 27 A Crystalline TFE/2,2-bis(trifl~oromethyl)-4,5-dichloro-1,3-dioxole, (3e), copolymer A 110 mL shaker tube was charged with 100 g of 1,1,2-trichloro-1,~,2-trifluoroethane, 3.0 g of the dioxole, 0.04 g bis(4-t-butylcyclohexyl) peroxydicarbonate, 10 g of TFE and heated 3.5 hours at 55 and &5C under autogenous pressure. After separation and drying the product, ~.3 g of a white solid polymer was obtained. Differential thermal analysis showed a crystalline melting point at 312C;
the infrared spectrum of a film possessed the , absorbancies characteristic of the TFE/2,2-bis(trifluoromethyl)-4,$~dichloro-1,3-dioxole copolymer/ By elemental analysis, the copolymer contained 0.44~ chlorine which corresponds to 0.6 mole percent of dioxole.
Exa~ple 28 Synthesis of 2,2-difluoro~4,5-dichloro-1,3-dioxole, (3j) A. Tetrachloroethylene Carbonate 2~ A 1000 mL creased flask equipped with a stirrer, thermometer and gas inlet tube, and topped by water and dry ice condensers, was charged with 352.4 g (4 moles) of melted ethylene carbonate. The system was purged with nitrogen while ethylene carbonate was stirred and heated to 50~C. After turning off the nitrogen, chlorine was introduced at a rapid rate and when the solution turned yellow~ a sunlamp was lit. The flow of chlorine and the intensity of the light were adjusted so that the solution remained yellow and the temperature did not e~ceed 80C during the first few hours of the cnlorination. Later on, the temperature was increased to lQ0 120C.
The chlorination was continued until intermediates were no longer present in the product, as evidenced by periodic gas chromatographic analysis. When the product was free of the mono-, di-, and trichloro intermediates, it was distilled at a reduced pressure on a water aspirator. After the removal of chlorine and hydrogen chloride, the 1 distillation was continued using a high vacuum pump.
B. 2,2-difluoro-4,4,5,5-tetrachloro-1,3-dioxola~e t4j) ~ 360 mL "Hastelloy" C shaker tube was charged with 113 g (0.5 mole) of tetrachloroethylene carbonate, closed under nitrogen, cooled in ~ry ice/acetone, evacuated, flushed with nitrogen, reevacuated and then charged with 18 g (0.9 ~ole) of HF and 194 g tl.8 mole) of SF4. The tube was then agitated for 10 hours at 200C. Following ~his, the 2 ~ube ~as chilled in an ice-water bath and then slowly vented to remove the excess of SF4 and HF. The product was dumped from the tube into we. ice and allowed to stand a day. The water-product mixture was placed in a polvethylene separatory runnel, and the dioxolane (4j) was withdrawn into a polyethylene Erlenrneyer flask, weighed~ and stirred one hour with 10 mL of a 30~ ~2CO3 solution in water (the pH of the aqueous phase must be alkaline). The dioxolane (4j) was then separated and bottled. The 2,2-difluoro 4,4,5,S-tetrachloro-1,3-dioxolane (4j) was dried over X2CO3 and distilled at a reduced pressure priox to use (b.p. 126~C at 101 KPa). Fl9 NMR and IR analyses supported the molecular structure.
C. ~echlorination of 2,2-difluoro 4,4,5,5-tetrachloro-1,3-dioxolane, (4j).
A 300 mL, 3-neck glass 1ask eq~ipped with magnetic stirrer, thermometer, Vigreux column with a water condenser to receiver, trap to a nitrogen tee and bubbler was charged with l-propanol, 175 ml.; zinc dust, 59.3 g; ~inc chloride, 2.0 g. After heating to reflux, the 2,2-difluoro-4,4,i,5-tetrachloro-1,3-dioxolane (4j), 74.3 g, was added by syringe pump at 0-33 mL/minute. The addition was complete in 148 minutes. Distillation was begun 40 minutes after the start of the addition and continued for 6 hours until 72 mL of distillate was collecte~. The prod~ct was 98.7% pure desired dioxole, (3j), at 100% conversion of the dioxolane; the distillate which containe~ some propanol was redistilled through a 0.51 m spinning band column to separate the dioxole, (3j), b.p.
64-65C, at a purity of 98.6~. A 3.66 m x .0064 m diameter 30% Krytox* perfluoroether (Du Pont Co.) column at 6~C was used in the analysis. The infrared spectrum was consistent with the structure.
Example 29 A crystalline TFE/2,2-difluoro 4,5-dichloro-lt3-dioxole, (3j), copolymer.
A 110 mL shaker tube was charged with 100 g of l,1,2-trichloro-1,2,2-trifluoroethane, 1.8 g of the dioxole, 0 04 g of bis(4-t-butylcyclohexyl) peroxydicarbonate, and 10 g of tetrafluoroethylene and heated 4 hours at 60-~5C. After separation of the insoluble product and drying, 2.4 g of a~ite solid polymer ~as ob~ned. Differential Scanning Calorimetry shawed a major cryst~ll;n~ melting point at 310C and a ~unor one at 297C. F-l9 ~ysis sh~ed the copolymer to contain 1.4 m~le ~ of the ~;~xnle (3~). Both the infrared and F-l9 ~ s ectra agreed with the copolym~r ~u~L~
This application is a division of copending application Serial;~o. 427 320, filed 1983~av 03.
*denotes trade mark
After separating and drying the product, 3.6 g of a white, solid polymer was obtained. A portion of this polymer was pressed at 230C into thin, tough, clear, self-supporting films. Infrared and F-19 NMR spectra identified the polymer as a terpolymer containing 14~3 mole % of TFE, 80.4 mole % of vinylidene fluoride, and 5.3 mole ~ of the dioxole.
Differential Scanning Calorimetry showed a ~elting point at 131C, thus demonstrating the crystalline character of the polymer Example 8 Preparation of 2,~-bis(trifluoromethyl)-1,3-dioxole, (3c), 2,2-bis(trifluoromethyl)-4-chloro-1,3-dioxole, (3d), and 2,2-bis(trifluoro-5 methyl)-4,5-dichloro-1,3-dioxole, (3e).
A. Synthesis of 2,2-bis(trifl~oromethyl)-4,5-dichloro-1,3-dioxolane, (4c), 2,2-bis(tri fluoromethyl)-4,4,5-trichloro-1,3-dioxolane, (4d), and ~,2-bis(trifluoromethyl)-4,4,5,5~tetrachloro-1,3-dioxolane, (4e).
A 300 mL, 3-neck round bottom ~lask equipped with a magnetic stirrer, chlorine gas inlet, thermometer, and a water condenser topped by a dry ice condenser communicating with a drying tower and then with a water scrubber was charged with 210 9 (1.0 mole) of 2,2-bis(trifluoromethyl)-1,3-dioxolane.
After purging the system with nitrogen, chlorine was I passed into the solution at such a rate as to ; maintain a yellow coloration of the solution. The stirred mixture was irradiated with a 275 watt General Electric sun lamp so as to maintain a reaction temperature for the most part in the range ~- of 46-72C for 4.5 hours. The concentration of the starting dioxolane in the reaction mixture had dropped by then to approximately 0.1~, and the reaction was terminated. Residual chlorine and hydrogen chloride were removed with a water aspirator, leaving a colorless, clear liquid weighing 28~ g and containing the di-, tri-, and tetrachloro-derivatives (4c), (4d~, and (4e), as confirmed byN~, mass spectrometry, and gas chromatographic analyses.
B. Dechlorination of the di-, ~ri-, and tetrachlorodioxolanes obtained in step A, above.
~5 s~
A 500 mL, 3-neck, round bottom flask equipped with a magnetic stirrer, a syringe pump inlet, a ther~ometer, a 15-cm still leading to a 100 mL recei~er and then to a nitrogen tee and a bubbler was charged with 98.1 ~ ~1.5 moles) of zinc dust, 3.0 g (0.022 mole) of ~inc chloride, and 300 mL of _-butyl alcohol. A syringe pump was charged ~ith 139.5 g of the chlorinated dioxolanes from step A.
After the flask contents were brought to 115C, the chlorinated dioxolanes were pumped into the flask at 0.33 mL/minute. The addition was completed in 224 minutes. Twenty minutes after the start of the addition, distillation began at a rate of about 15-20 mL/hour. The head temperature then was 79-80C but during the distillation decreased to 75C and at the end was 116C; 119.8 g of product containing hutyl alcohol was distilled. The produc~ distribution was about 21% of 2,2-bis(trifluoromethyl)-1,3-dioxole, (3c), 47~ of 2,2-bis(trifluoromethyl)-4-chloro-1,3-dioxolel (3d), and 30~ of 2,2-his(trifluoromethyl)-4,5-dichloro-1,3-dioxole, (3e). The crude product was fractionated at - atmospheric pressure on a 0O76 m spinning band column to provide each dioxole as a clear, colorless liquid having a ~urity of at least 99%:
2,2-bis(trifluoromethyl)-1,3-dioxole, (3c), b.p~
67C; 2,2-bis(trifluoromethyl)4-chloro-1,3-dioxole, ~3d), b.p. 76C; and 2,2-bis(trifluoromethyl)-4,5 dichloro-1,3-dioxole (3e), b.p. 85C. The infrared, F-l9 and proton N.~R, and masq spectrometry data ~or these dioxoles support their molecular structures.
C. Alternate synthesis of 2,2-bis(trifluoro-methyl)-4-chloro-1~3-dioxole~ (3d).
~3~
A 100 mL, 2-neck, round-bottom glass flask equipped with magnetic stirrer, thermometer, Vigreux - column, still head, and receiver was charged under a nitrogen blanket with 40 mL of di(ethylene glycol) dimethyl et`ner, 9.8 g of crude 2,2-bis(trifluoromethyl)-4,5-dichloro-1,3-dioxolane, (4c), and 6.7 g of solid potassium hydroxide. The flask contents were heated at 1~1C for 2 hours during which time the 2,2-bis(trifluoro-methyl)-4-chloro-1,3-dioxole, (3d), distilled overO
Purified by gas chromatography, the product had the same retention time and infrared spectrum as an authentic sample of 2,2-bis(trifluoromethyl)-; 4-chloro-1,3-dioxole, (3d).
Exam~le 9 i A crystalline copolymer of 2,2-bis(tri-fluoromethyl)-1,3-dioxole, (3c) and TFE.
A shaker tube was charged with 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.03 g of bis(4-t-butylcyclohexyl) peroxydicarbonate, 1.5 g ~ (0.0072 mole) of the dioxole, and 10 9 (0.1 mole) of TFE. Polymerization was carried out at 55 and 65C. After separating and drying the product, 10.5 `~` g of a white, solid polymer was obtained. A portion 25 of the polymer was pressed at 300C into tough, clear, colorless, self-supporting films. Infrared and F-19 N~R spectra established a copolymer structure of 93.1 mole ~ of TFE and 6.9 mole % of 2,2-bis(trifluoromethyl)-1,3-dioxole, (3c).
30 Differential Scanning Calorimetry showed a melting point at 253C, thereby establishing the crystalline character of this polymer.
Exam~le 10 A An amorphous copolymer of 2,2-bi~(tri-35 fluoromethyl)-1,3-dioxole, (3c) and TFEo A shaker tube was charge~ with 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 4.2 g (0.02 mole) of the dioxole, 0.03 g of bis(4-t-butyl-cyclohexyl) peroxydicarbonate, ar.d 10 g of TFE.
Polymerization was carried out at 55 and 65C under autogeno~s pressure or 4 hours. ~fter separation and drying, a white, solid polymer, 1.4 g, ~as obtained. It was soluble in the trichlorotrifluoro-ethane solvent; a clear, transparent, ~elf-supporting film was cast from this solution. Infrared and F-l9 and proton NMR spectra identified the copolymer as containing 46.3 mole % of the dioxole and 53.7 mole %
of TFE Differential Scanning C~lorimetry showed a Tq at 61C and other transitions at 113C and 246C;
there was no melting point, and the polymer was therefore amorphous.
Exa~ole 11 An elastomeric terpolymer of 2,2-bis~tri-fluoromethyl)-1,3-dioxole, (3c), vinylidene fluoride, 20 a~d TFE.
A shaker tube was charged with 100 g of 1,1,2-trichloro-1-~,2,-trifluoroethane, 3.0 g (0.0144 mole) of the dioxole, O.G3 g of bis(4-t-butyl-cvclonexvl) peroxydicarbonate, 6.0 g (0.094 mole) of 25 vinylidene fluoride, and 6.0 q (0.06 mole) of TFE.
Polymerization was carried out under a-1togenous pressure at 55 and 65C. After separation and drying, a white, solid poly~er, ~.4 q, was obtained.
It was not soluble in the trichlorotrifluoroethane.
30 A portion of the ~olymer was pressed at 230~C to give thin, tough, elastomeric, clear, self-supporting films. Infrared and F-19 NMR spectra identified the i terpolymer as contain ng 36.4 mole % of TFE~ 55.7 mole ~ of vinylidene fl~oride, and 7~9 mole % of 35 dioxole. ~iferential Scanning Calorimetry showed a s melting point at 114C, indicating the crystalline nature of the polymer~
Exam?le l2 Homopolymer of 2,2-bis(trifluoromethyl)-1,3 dioxolQ, (3c)-The dioxole, 3.0 g, which had been kept in adry ice chest, was placed in a 10 mL closely capped, clear, glass vial and allowed to stand at room temoerature under laboratory fluorescent lighting conditions. After two weeks, ~ portion of the liquid was pl~ced on a salt plate and allowed to ev~porate, leaving a thin, transparent, clear, colorless solid film~ In~r~red analysis of this film was consistent with the homopolymer structure.
Exam~le 13 crystalline copolymer of TFE and 2,2-bis-(trifluoromethyl)-4-chloro-1,3-dioxole, (3d).
A shaker tube was charqed with 100 g of 1,1,2-trichloro,1,2,2-trifluoroethane, 0.03 g of bis (4-t-butylcyclohexyl) peroxydicarbonate, 1.5 g (0.00613 mole) of the dioxole, and 10 g (0.1 mole) of TFE. Polymerization was carried out under autogenous pressure at 55 and 65Co After separation and drying, a white solid polymer, 5.0 g, was obtained.
A portion of the polymer was pressed at 300C into thir, tough, clear, self-supporting films. Infrared and F-l9 N~IR s~ectra showed the copolymer to contain 94.1 mole ~ of TFE and 5.9 mole % of the dioxole.
Differential Scanning Calorimetry showed a melting 3~ ~oint at 269~C, thus indicating the polymer to be crystalline.
! Example 14 An amorphous terpolymer of TEE with ~,2-bis-(trifluoromethyl)-1,3-dioxole, (3c) and ~,2 bis(trifluoromethyl~-4-chloro-1,3-dioxole, ~3d)o 2~
A shaker tube was charged with 100 g of 1,1~2-trichloro-1/2,2-trifluoroethane, 1.0 g of 2,2-~is(trifluoromethyl)-1,3-dioxole, (3c), 2.0 g of 2,2-bis(trifluoromethyl)-4-chloro-1,3-dioxole, ~3d) 0.03 g of bis(4-t-butylcyclohexyl) peroxydicar~onate, and 10 g TFE. Polymerization was carried out under autogenous pressure at 55 and 65C. After separation and drying, 3 g of white, solid, ~olymer granules were obtained. A portion of tne ~olymer was pressed at 300C to give thin, tough, self-supporting, colorless, clear films. The infrared and F-l9 NMR spectra were consistent with a terpolymer structure consisting of 85.2 mole ~ of TFE, 8 . 6% of 2,2-bis(trifluoromethyl)-1,3-dioxole, (3c), and 6.2 mole % of 2,2-bis(trifluoromethyl)-4-chloro-1,3-dioxole~ (3d). The Differential Scanning Calorimetry analysis showed a Tg at 54C but no melting point, thereby indicating the polymer to be amorphous.
~xample 15 Preparation of 2,2,4-trifluoro-5-chloro-1,3-dioxoler (3f) 2,2,4-trifluoro-1,3-dioxole, (3g), and the corresponding dioxolanes (4f) and (4g).
A. 2,2,4-trifluoro-4,5f5-trichloro-1,3-dioxolane (4f) A dry, 360 mL "Hastelloy~ C lined shaker tube was charged with 81.8 g (0.33 mole) of 2,2-difluoro-4,4,5,5-tetrachloro-1,3-dioxolane, ~4j), containing 9.0 g (0.03 ~ole) of antimony pentachloride. The tube was cooled, alternately evacuated and purged with nitrogen three times, and charged with 22 g (1~1 mole) of hydrogen fluoride~
The ~ube was agitated and warmed to 40C over a period of 1 hour, heated under autogenous pressure for 4 hours at 40C, then cooled to 0C, 510wly 2~
s vented, and opened. The contents were poured into ice; the organic phase was se~arated from the aqueous phase, extracted twice with distilled water and once with an aqueous 10~ sodium carbonate solution; 63.3 g of crurle product was obtained which contained about 3 . 9% of 2, 2, 4, 5-tetrafluoro-4,5-dichloro-1,3-dioxolan~, 85.8% 2,2,4~trifluoro-4,5,5-tri-chloro-1,3-dioxolane, (4f), and 8.1~ of the starting material. This product mixture was combined with those of three other similar runs and separated by distillation on a 0.76 m spinning band column;
2,2,4,5-tetrafluoro-4,5-dichloro-1,3-dioxolane boiled at 45-46~C; 2,2,4-trifluoro-4,5,5-trichloro-1,3-dioxolane, ~4f), at 84C; and the starting 5. 15 material, 2,2-difluoro-4,4,5,5-tetrachloro-1,3-dioxolane (4j), at 115C. Their purities were greater than 99%. Both infrared and ~-19 NMR
spectroscopy confirmed their structures.
B. ~echlorination of 2,2,4-trifluoro-4,5,5-trichloro-1,3-dioxolane, (4f).
A 300 mL 3-neck glass flask equipped with magnetic stirrer, thermometer, Vigreux column with a dry ice-cooled still head leading to a cold receiver, trap, a nitro~en tee, and bubbler was charged with 76.7 g ~1.17 gram-atom~) of zinc, 2.6 g (0.019 mole) of zinc chloridet and 175 mL of propanol. ~he stirred mixtuxe was heated to 9~C; then 89.6 g (0.387 mole) of 2,2,4-trifluoro-4,5,5-trichloro-1,3-dioxolane, (4f), was introduced from a syringe pump at a rate of 0.~3 mL/minute during 172 minutes. Distillation at a rate of about 15 mL/hour began 33 minutes after the start of the addition and continued for 270 minutes; 65 mL of clear, colorless distillate weighing 84.5 g and con,aining some propanol was obtained. It was redistilled through a 0.76 m spinning band column with a dry ice-cooled head. The product distribution was approximately 3 9~ of 2,2,4-trifluoro-1,3-dioxole, (3g), b.p, 10C;
71.7% of 2,2,4-trifluoro-5-chloro-1,3-dioxole, (3f), b.p. 25-27C; and 24.3% of 2,2,4-trifluoro-4,5-dichloro-1,3-dioxolane, (4g), b.p. 73C. The infrared, F-l9 and proton NMR spectra of these compounds were consistent with the assigned structures.
Example 16 Alternate synthesis of 2,2,4-trifluoro-4,5-dichloro-1,3-dioxolane, (4g).
A~ 4,4,5-trichloro-1,3-dioxolan-2-one.
- A creased 3-neck, 300 mL, round bottom flask equipped with magnetic stirrer, gas inlet tube, thermometer, and water condenser topped by a dry ice condenser leading to a trap and scrub~er was charged with a8. 1 g of ethylene carbonate. The system was purged with nitrogen and then dry chlorine gas was introduced while irradiating the reaction vessel with a 275 watt General ~lectric*Sun Lamp; the amount of chlorine was sufficient to maintain a yellow color in the solution. The temperature ranged from 35C
during the initial part of the chlorination and up to 115C during the later part of the 6-hour reac'ion.
The reaction mixture was analyzed by gas chromatography techniques and, when all of the 4-chloro-1,3-dioxolan-2-one had been consumed, the reaction was terminated. The product was principally 4,4,5-trichloro-1,3-dioxolan-2-one wi~h lesser amounts of 4,5-dichloro- and 4,4,5,5-tetrachloro-derivatives. Two similar runs were made and the products combined.
Bo Fluorination of 4,4,5-trichloro-1,3-35 dioxolan-2-one.
*denotes trade mark ~ ~2~
A shaker tube was charged with 113 g of crude 4,4,5-trichloro-1,3-dioxolan-2-one, 18 g of HF, and 194 g of SF4. After agitating 10 hours at 200C, the tube was cooled to 0C, and the product was mixed with ice. The organic phase was separated ; and neutralized by sha~ing witn an aqueous potassium carbonate solution and then distilled vn a 0.76 m spinning band column; the first fraction, 2,2,4,5-tetrafluoro-4,5-dichloro-1,3-dioxolane, b.p.
47-48C, was followed by the desired 2,2,4-trifluoro-4,5 dichloro-1,3-dioxolane, (4g), b.~. ~9-73C. Infrared and F-l9 NMR spectra were consistent with this structure.
~x~m~le 17 ~ 15 Preparation of 2,2,4-trifluoro-1,3-dioxGle, ; ~3g), by dechlorination of 2,2,4-triEluoro-4,5-dichloro-1,3-dloxolane, (4g).
A 100 mL, 3-neck, round bottom flask equipped with m~gnetic stirrer, thermometer, Vigreux still leading to a dry ice-cooled head, cold receiver and trap, was charged under a nitrogen blanket with 3.6 g of magnesium turnings, 0.2 g of mercuric chloride, 0.1 g of iodiner and 30 mL of ! tetrahydrofuran. The mixture was stirred and heate~
to 67C; 8~8 g of 2,2,4-trifluoro~4,5-dichloro-1,3-dioxolane, (4g), was then added at a rate of 0.092 mL/minute. After 2~ mL had been added the distillation began and continued for 3 hours until 5 mL of distillate was obtained. The cold distillate was extracted with ice water to remove some tetrahydrofuran and there remained 4.7 g of prcduct which was largely 2,2,4~trifluoro-1,3-dioxole, (3g), b.p. 10C.
This dioxole was purified by gas chroma~ography; ~he infrared absorbance spectra, and 2~
especially the absorbance in the region of 5.6 ~m, as well as its subsequent polymerization substantiated the assigned molecular str~cture.
~xamPle l8 A crystalline copolymer of tetrafluoro-ethylene with 2,2,4-trifluoro-1,3-dioxole, (3y).
A shaker tube was charged ~ith 100 9 of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.8 g of the dioxole, 0.03 g of bis(4-t-butylcyclohexyl) peroxydicarbonate, and 10 g of TFE and heated at 55 and 6$C for 4 hours. After separation of the produc~ and drying, 4.7 q of a whi~e solid polymer was obtained. A portion of this was pressed at 330C
to give thin, tough, self-supporting, colorless filmsO The infrared an2 F-l9 NMR spectra showed the copolymer composition to be 96.0 mole % TFE and 4.0 mole ~ dioxole. Differential Scanning Calorimetry showed a crystall;ne melting point at 274C.
Exam~le 19 Homopolymer of 2,2,4-trifluoro-1,3-dioxole, (3~)-A 10 mL clear, glass vial was charged with 5.7 g of 1,1,2-trichloro-1,2,2-trifluoroethane, 0.001 g of bis(4-t-butylcyclohexyl) peroxydi-carbonate, and G.5 g of the dioxole, capped securely and allowed to stand two days on the bench top at about 25~C exposed to the normal fluorescent light of the laboratory. A portion of the solution was then evaporated on a micro salt plate to give a clear, colorless, self supporting film which was identified by its infrared spectrum to be the dioxole homopolymer.
Example 20 An amorphous copolymer of TFE and 2,2,4-tri fluoro 5-chloro-1,3-dioxole, (3f)O
A shaker tube was charged with 100 g of 1,1,2-trifluoro-1,2,2-trichloroethane, 1.7 g of the dioxole, 0.03 g of bis(4-t-butylcyclohexyl) peroxy-dicarbonate, and 10 9 of TFE. Polymerization ~as carried out at 55 and 65C under autogenous pressure for 4 hours. After separation and drying of the - product, 1~8 g of a white, solid polymer was obtained. A portion of this ~as pressed at 300C to ~ive thin, tough, self-supporting, colorless clear films. The infrared and F-l9 N~R spectra of this polymer showed it to contain 10.5 mole ~ of the dioxole and ~9.5 mole ~ of ~FE. Differential Scannin~ Calorimetry showed a Tg of 61C, there ~as no melting point.
! 15 Example 21 An amorphous, elastomeric terpolymer of TFE, 2,2,4 trifluoro-5-chloro-1,3-dioxole, (3f), and vinylidene fluoride.
~ shaker tube was charged with 100 9 of 1,1,2-trichloro-1,2,2-trifluoroethane, 2.1 g of the dioxole, 0.03 g of his(4-t-butylcyclohexyl) peroxydi-carbonate, 6 g of vinylidene fluoride, and 6 g of TFE. Polymerization was carried out at 55 and 65C
over a 4 hour period under autogenous pressure.
After separating and drying, there was obtained ~.5 g o white, solid polymer granules. A portion of this polymer was pressed at 200C to give thin, elastic, tough, self supporting, clear, colorless films.
Infrared and F-l9 ~MR spectra showed the terpolymer to consist of 27.7 mole % of TFE, 9.9 mole ~ of the dioxole and 6204 mole ~ of vinylidene fluoride.
- Differential Scanning Calorimetry showed no meltin~
point~ thus indicating an amorphous polymerO
~5 ~t3~
Example 22 Synthesis of 2,2-difluoro-1,3-dioxole, (3h).
A. 4,5-Dichloro-1,3-dioxolan-2-one A 500 mL, 3-neck round-bottom flask equipped with a nitrogen purge line, magnetic stirrer, thermometer, and reflux condenser leading to a trap and drying tower was charged with 88 g of ethylene carbonate, 297 g of sulfuryl chloride, and la 0 g of azobisisobutyronitrlle. After purging the assembly with nitrogen, the stirred mixture was irradiat2d with a Hanovia mercury vapor lamp at a temperature of 34-47C during the first 3 hours of the reactionO
During the next 7 hours, the temperature was increased rrorn 51 to 103C. During the final 3 hours of the reaction, the temperature was held in the 95-107C range.
After cooling to room temperature, the flask was evacuated on a water aspirator to remove small amounts of HCl. The flask contents were then flash-distilled at a pressure of about 266 Pa and a pot temperature of up to 150C; 85.7 q of distillate was collected. GC analysis of the distillate showed it to contain a~proximately 86.3~ of 4,5-dichloro-1,3-dioxolan-2-one, 8.8% of ~-chloro-1,3-d-oxolan-2-one, and 3.1~ of 4,4,S-trichloro--1,3-dioxolan-2-one.
8. 2,2-Difluoro-4,5-dichloro~1,3~dioxolane (4h) A 300 mL "Hastelloy'l C shaker tube was char~ed ~ith 136.2 g o~ 4,5-dichloro~1,3-dioxolan-2-one, 16.2 g of HF, and 19~.4 g of SF4. The tube was then heated to 150~C and agitated for 300 hours.
After ~he tube was cooled to 0C, it was slowly vented and then its contents were dumped into ice.
The organic layer was separated and extracted twlce 3,C~ 5 with 50 mL of distilled water. The product weighed 93.0 g and contained about 69~ of 2,2,4-trifluoro-5-chloro-1,3-dioxolane and abollt 7%
of 2,2-difl~loro-4~5-dichloro-5 1,3-dioxolane, (4h).
C. Dechlorination of 2,2-difluoro-4,5-di-chloro-1,3-dioxolane (4h) Equipment like that of Example 15B, except that a 100 mL flask was used~ was charged with 7.8 g 10 of zinc dust, 0.2 g of zinc chloride, and 40 m~ of butyl alcohol. The stirred mixture was heated to 114C; 6.5 ~ of crude 2,2-difluoro-4,5-dichloro-1,3-di~xolane (4h) was -then adde~ ~y a syringe pump at 0.092 mL/minute over a 52-minute lS period. Distillation be~an 20 minutes after the beginning of the addition and continued for 94 min~tes until 4.5 mL of distillate containing some butyl alcohol was obtained. The distillate was purified by gas chromatography. The infrared 20 absorbance spectrum, especially the absorbance in ~he region of 6.05 ~m, was consistent with the 2,2-difluoro-1,3-dioxole structure (3h).
E.Yample 23 Homooolymer of 2t2-difluoro-1,3-dioxole ~3h).
A shaker tube is charged with 3 g of 2,2-difluoro-1,3-dioxole in 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane, and 0.005 q of bis(4-t-butylcyclohexyl) peroxydicarbonate.
30 Polymerization is carried out at 55 and 65C for 4 hours. Af~er seParating and drying the solid, white polymer, 0.6 g, a portion of it is pressed at 250C
to give a tough, clear, transparent, self supporting, thin film, of the ho~opolymer, which is amorpho~s.
r ' ~a~
Example 24 A crystalline copolymer of tetrafluoroethylene and 2,2-difluoro-1,3-dioxole, (3h).
A shaker tube is charged with 1 g of the dioxole in 100 g of 1,1,2-trichloro-1,2,2-trifluoro-ethane, 0.03 g of bis(4-t-butylcyclohexyl) peroxy~icarbonate, and 10 g of TFE. Polymerization is carried out at 55 and 65C. ~fter separating and drying the product, 9.9 g of white, granular, solid, crystalline polymer is obtained. It contains approximately 93 mole % TFE and 7 mole ~ of the dioxole.
Exa~Dle 25 ` 15 Synthesis of 2,2-difluoro-4-chloro-1,3-! dioxole, (3i).
This synthesis is carried out in the same manner as that of Example 22, except that 106.7 9 ~0.5 mole) of 2,2-difluoro~4,4,5-trichloro-lt3-dioxolane, (4i), prepared from 4,4,5-trichloro-1,3-dioxolan-2-one (Example 16A) is the starting material. Rectification of the product mix through a 0.76 m spinning band column gives 47~1 9 of 2,2-difluoro-4-chloro-1,3-dioxole, t3i).
~xampl~ 26 A crystalline copolymer of TFE with 2,2~difluoro-4-chloro-1,3-dioxole, (3i).
~ shaker tube is charged with 100 g o 1,1,~-trichloro-1,2,2-trifluoroethane containing 1 g of 2,2-difluoro-4-chloro-1,3-dioxole, (3i), 0.03 g of bis(4-t-bwtylcyclohexyl) peroxydicarbonate, and 10 g of TFE. Polymerization is carried out at 55 and 65C. After separating and drying the product, 5.2 g of a white solid granular polymer i5 obtained. ~his is pressed at 300C into a tough, self-supporting, , r ~
L~
2g clear film. The polymer is crystalline and contains approximately 94 mole % TFE and 6 mole % of the dioxole.
Exa~ple 27 A Crystalline TFE/2,2-bis(trifl~oromethyl)-4,5-dichloro-1,3-dioxole, (3e), copolymer A 110 mL shaker tube was charged with 100 g of 1,1,2-trichloro-1,~,2-trifluoroethane, 3.0 g of the dioxole, 0.04 g bis(4-t-butylcyclohexyl) peroxydicarbonate, 10 g of TFE and heated 3.5 hours at 55 and &5C under autogenous pressure. After separation and drying the product, ~.3 g of a white solid polymer was obtained. Differential thermal analysis showed a crystalline melting point at 312C;
the infrared spectrum of a film possessed the , absorbancies characteristic of the TFE/2,2-bis(trifluoromethyl)-4,$~dichloro-1,3-dioxole copolymer/ By elemental analysis, the copolymer contained 0.44~ chlorine which corresponds to 0.6 mole percent of dioxole.
Exa~ple 28 Synthesis of 2,2-difluoro~4,5-dichloro-1,3-dioxole, (3j) A. Tetrachloroethylene Carbonate 2~ A 1000 mL creased flask equipped with a stirrer, thermometer and gas inlet tube, and topped by water and dry ice condensers, was charged with 352.4 g (4 moles) of melted ethylene carbonate. The system was purged with nitrogen while ethylene carbonate was stirred and heated to 50~C. After turning off the nitrogen, chlorine was introduced at a rapid rate and when the solution turned yellow~ a sunlamp was lit. The flow of chlorine and the intensity of the light were adjusted so that the solution remained yellow and the temperature did not e~ceed 80C during the first few hours of the cnlorination. Later on, the temperature was increased to lQ0 120C.
The chlorination was continued until intermediates were no longer present in the product, as evidenced by periodic gas chromatographic analysis. When the product was free of the mono-, di-, and trichloro intermediates, it was distilled at a reduced pressure on a water aspirator. After the removal of chlorine and hydrogen chloride, the 1 distillation was continued using a high vacuum pump.
B. 2,2-difluoro-4,4,5,5-tetrachloro-1,3-dioxola~e t4j) ~ 360 mL "Hastelloy" C shaker tube was charged with 113 g (0.5 mole) of tetrachloroethylene carbonate, closed under nitrogen, cooled in ~ry ice/acetone, evacuated, flushed with nitrogen, reevacuated and then charged with 18 g (0.9 ~ole) of HF and 194 g tl.8 mole) of SF4. The tube was then agitated for 10 hours at 200C. Following ~his, the 2 ~ube ~as chilled in an ice-water bath and then slowly vented to remove the excess of SF4 and HF. The product was dumped from the tube into we. ice and allowed to stand a day. The water-product mixture was placed in a polvethylene separatory runnel, and the dioxolane (4j) was withdrawn into a polyethylene Erlenrneyer flask, weighed~ and stirred one hour with 10 mL of a 30~ ~2CO3 solution in water (the pH of the aqueous phase must be alkaline). The dioxolane (4j) was then separated and bottled. The 2,2-difluoro 4,4,5,S-tetrachloro-1,3-dioxolane (4j) was dried over X2CO3 and distilled at a reduced pressure priox to use (b.p. 126~C at 101 KPa). Fl9 NMR and IR analyses supported the molecular structure.
C. ~echlorination of 2,2-difluoro 4,4,5,5-tetrachloro-1,3-dioxolane, (4j).
A 300 mL, 3-neck glass 1ask eq~ipped with magnetic stirrer, thermometer, Vigreux column with a water condenser to receiver, trap to a nitrogen tee and bubbler was charged with l-propanol, 175 ml.; zinc dust, 59.3 g; ~inc chloride, 2.0 g. After heating to reflux, the 2,2-difluoro-4,4,i,5-tetrachloro-1,3-dioxolane (4j), 74.3 g, was added by syringe pump at 0-33 mL/minute. The addition was complete in 148 minutes. Distillation was begun 40 minutes after the start of the addition and continued for 6 hours until 72 mL of distillate was collecte~. The prod~ct was 98.7% pure desired dioxole, (3j), at 100% conversion of the dioxolane; the distillate which containe~ some propanol was redistilled through a 0.51 m spinning band column to separate the dioxole, (3j), b.p.
64-65C, at a purity of 98.6~. A 3.66 m x .0064 m diameter 30% Krytox* perfluoroether (Du Pont Co.) column at 6~C was used in the analysis. The infrared spectrum was consistent with the structure.
Example 29 A crystalline TFE/2,2-difluoro 4,5-dichloro-lt3-dioxole, (3j), copolymer.
A 110 mL shaker tube was charged with 100 g of l,1,2-trichloro-1,2,2-trifluoroethane, 1.8 g of the dioxole, 0 04 g of bis(4-t-butylcyclohexyl) peroxydicarbonate, and 10 g of tetrafluoroethylene and heated 4 hours at 60-~5C. After separation of the insoluble product and drying, 2.4 g of a~ite solid polymer ~as ob~ned. Differential Scanning Calorimetry shawed a major cryst~ll;n~ melting point at 310C and a ~unor one at 297C. F-l9 ~ysis sh~ed the copolymer to contain 1.4 m~le ~ of the ~;~xnle (3~). Both the infrared and F-l9 ~ s ectra agreed with the copolym~r ~u~L~
This application is a division of copending application Serial;~o. 427 320, filed 1983~av 03.
*denotes trade mark
Claims (10)
1. A fluorodioxole having the following formula:
wherein Y is hydrogen or chlorine; Z is hydrogen, fluorine, or chlorine; and R is fluorine or the tri-fluoromethyl group; with the proviso that when R is trifluoromethyl, only one of Y and Z can be hydrogen or chlorine; and for either type of R substituent,when one of Y and Z is hydrogen, the other of Y and Z is other than chlorine.
wherein Y is hydrogen or chlorine; Z is hydrogen, fluorine, or chlorine; and R is fluorine or the tri-fluoromethyl group; with the proviso that when R is trifluoromethyl, only one of Y and Z can be hydrogen or chlorine; and for either type of R substituent,when one of Y and Z is hydrogen, the other of Y and Z is other than chlorine.
2. A fluorodioxole of Claim 1 where Y is hydrogen.
3. A fluorodioxole of Claim 2 wherein Z is hydrogen or fluorine.
4. A fluorodioxole of Claim 2 wherein R is fluorine.
5. A fluorodioxole of Claim 2 wherein R is trifluoromethyl.
6. A fluorodioxole of Claim 1 wherein Y is chlorine.
7. A fluorodioxole of Claim 6 wherein Z is fluorine.
8. A fluorodioxole of Claim 6 wherein R is fluorine.
9. A fluorodioxole of Claim 6 wherein R is trifluoromethyl.
10. A process for making a fluorodioxole of Claim 1 wherein a dioxolane having the following formula:
in which Y is hydrogen or chlorine; Z is hydrogen, fluorine, or chlorine; and R is fluorine or trifluoro-methyl is contacted in a tetrahydrofuran solution with magnesium in the presence of catalytic amounts of iodine and of a water-soluble mercury salt or metallic mercury.
in which Y is hydrogen or chlorine; Z is hydrogen, fluorine, or chlorine; and R is fluorine or trifluoro-methyl is contacted in a tetrahydrofuran solution with magnesium in the presence of catalytic amounts of iodine and of a water-soluble mercury salt or metallic mercury.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000451912A CA1199645A (en) | 1982-05-06 | 1984-04-12 | Fluorodioxoles and fluorodioxole polymers |
| CA000469344A CA1203808A (en) | 1982-05-06 | 1984-12-04 | 4,5-dichloro-1,3-dioxolane derivatives |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US375,468 | 1982-05-06 | ||
| US06/375,468 US4431786A (en) | 1982-05-06 | 1982-05-06 | Novel fluorodioxoles and fluorodioxole polymers |
| CA000427320A CA1188848A (en) | 1982-05-06 | 1983-05-03 | Fluorodioxoles and fluorodioxole polymers |
| CA000451912A CA1199645A (en) | 1982-05-06 | 1984-04-12 | Fluorodioxoles and fluorodioxole polymers |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000427320A Division CA1188848A (en) | 1982-05-06 | 1983-05-03 | Fluorodioxoles and fluorodioxole polymers |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000469344A Division CA1203808A (en) | 1982-05-06 | 1984-12-04 | 4,5-dichloro-1,3-dioxolane derivatives |
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| Publication Number | Publication Date |
|---|---|
| CA1199645A true CA1199645A (en) | 1986-01-21 |
Family
ID=25670021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000451912A Expired CA1199645A (en) | 1982-05-06 | 1984-04-12 | Fluorodioxoles and fluorodioxole polymers |
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| Country | Link |
|---|---|
| CA (1) | CA1199645A (en) |
-
1984
- 1984-04-12 CA CA000451912A patent/CA1199645A/en not_active Expired
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