Partially fluorinated polyesters from ketene acetals and fluorinated vinyl monomers

Partially fluorinated polyesters are disclosed having increased biodegradability and water repellancy. The incorporation of an ester group into the backbone of the partially fluorinated compound permits modification of the compound's physical properties.

FIELD OF THE INVENTION 
This invention concerns partially fluorinated polyesters derived from the 
free radical initiated reaction of fluorinated olefins with cyclic ketene 
acetals. The incorporation of an ester group into the backbone of the 
partially fluorinated polymer permits the modification of physical 
properties of the resulting polymer to provide such characteristics as 
increased biodegradability and enhanced water repellancy. The copolymers 
of this invention are useful as films and fibers and as intermediates in 
the preparation fluorinated diols. 
BACKGROUND OF THE INVENTION 
Bailey, et al., J. Polymer Science: Polymer Chemistry Edition, Vol. 20, 
3021-3030 (1982), disclose the free radical ring-opening polymerization of 
2-methylene-1,3-dioxepane to form poly-.epsilon.-caprolactone. Under the 
same conditions, 2-methylene-1,3-dioxolane and 2-methylene-1,3-dioxane 
generated polymers with mixed ring-opened and non-ring-opened structures. 
Copolymerization of the dioxepane with vinyl monomers (styrene, 
4-vinylanisole, methyl methacrylate or vinyl acetate) in a 1:1 molar ratio 
gave copolymers which contained less than 50 mol % dioxepane. 
Bailey, et al., Makromol. Chem., Vol. 183, 1913-1920 (1982), disclose the 
free radical ring-opening polymerization of 
2-methylene-4-phenyl-1,3-dioxolane to produce 
poly[.gamma.(.beta.-phenyl)butyrolactone]. Copolymerization of this 
dioxolane with vinyl monomers (styrene, methyl methacrylate, vinylacetate 
or 4-vinylpyridine) in a 1:1 molar ratio gave copolymers which contained 
less than 41 mol % dioxolane. 
Bailey, et al., Macromolecules, Vol. 15, 711-714 (1982), disclose the free 
radical polymerization of cis- and 
trans-4,7-dimethyl-2-methylene-1,3-dioxepane and 
5,6-benzo-2-methylene-1,3-dioxepane to produce the corresponding 
polyesters. The cis-/transmonomer copolymerizes with 1:1 mixtures of 
styrene or methyl methacrylate to give copolymers which contain less than 
30 mol % dioxepane. The benzo-dioxepane copolymerizes with stryrene, 
4-vinylanisole or methyl methacrylate to give copolymers which contain 
less than 33 mol % dioxepane. 
Bailey et al., J. Macromol. Sci. Chem., A21(8 and 9), 979-995 (1984), 
disclose the hydrolysis of a copolymer of 2-methylene-1,3-dioxepane and 
styrene (r.sub.1 =0.021 and r.sub.2 =22.6) to give an oligomer terminated 
with a hydroxyl group and a carboxylic acid group. Similarly, hydrolysis 
of an ethylente/2-methylene-1,3-dioxepane copolymer gave a series of 
ethylene oligomers with 9 to 47 ethylene units which were terminated with 
a hydroxyl group and a carboxylic acid group. The copolymerization of the 
dioxepane with vinyl chloride is also disclosed. 
The polymers of the present invention can be distinguished from those of 
the prior art by the alternating structure of the fluoro-olefin/cyclic 
ketene acetal copolymer. Further, the copolymers of the present invention 
permit a one step reduction process for the formation of highly 
fluorinated diols. Conventional syntheses for the fluorinated diols 
require a tedious multiple step process. 
SUMMARY OF THE INVENTION 
This invention provides a partially fluorinated polyester of general 
structure I 
##STR1## 
wherein the polyester consists essentially of an alternating copolymer of 
a fluorinated olefin and the cyclic ketene acetal monomer 
X=F, CF.sub.3, Cl, Br, I, OCF.sub.3, OCF.sub.2 CF.sub.3, OCF.sub.2 CF.sub.2 
CF.sub.3, OCF.sub.2 CF(CF.sub.3)O(CF.sub.2).sub.2 CF.sub.3 ; 
R=--CHR.sup.1 --(CH.sub.2).sub.n --CHR.sup.2 --(where n=0-2) or 
##STR2## 
R.sup.1 and R.sup.2 are independently H, C.sub.1 -C.sub.4 alkyl or phenyl; 
said partially fluorinated polyester is derived from the free-radical 
initiated copolymerization of a fluorinated olefin, A, CF.sub.2 =CFX (X 
defined as above), and a cyclic ketene acetal, B, having the general 
structure 
##STR3## 
This invention also provides partially fluorinated polyester terpolymers, 
of general structure II, below, from the free radical initiated 
copolymerization of a fluorinated olefin, A, a cyclic ketene acetal, B, 
and an olefin, C 
##STR4## 
R.sup.3 =H, C.sub.1 -C.sub.4 alkyl R.sup.4=H, C.sub.1 -C.sub.4 alkyl, 
C.sub.1 -C.sub.4 alkoxy 
The terpolymer, II, has the general structure 
##STR5## 
wherein 0.1.ltoreq.i.ltoreq.1.9 and i+=2 when the olefin, C, tends to 
alternate with the fluoroolefin and has little or no tendency to 
copolymerize with B. 
This invention also provides partially fluorinated diols of the general 
structure III by the reduction of the corresponding copolymer, I, 
##STR6## 
where R and X are as defined above. 
This invention also provides diols of the general form IV 
##STR7## 
by the reduction of the corresponding terpolymer, II, where R, R.sup.3 and 
R.sup.4 are as defined above. 
The present invention differs from the prior art by providing a one step 
process for producing the partially fluorinated structure I from available 
monomers. Further, an essentially alternating structure with a=b is 
possible, depending upon the concentration of monomers in the polymer. 
DETAILED DESCRIPTION OF THE INVENTION 
The copolymers of this invention are partially fluorinated polyesters 
formed by the free radical initiated reaction of a fluorinated olefin with 
a cyclic ketene acetal and an optional hydrocarbon olefin. 
Suitable fluorinated olefins include tetrafluoroethylene (TFE) and 
derivatives of TFE in which one fluorine has been replaced by chlorine, 
bromine, iodine, a perfluoroalkyl or a perfluoroether group. Preferred 
fluorinated olefins include TFE, chlorotrifluoroethylene (CTFE), 
hexafluoropropylene (HFP), perfluoromethylvinvylether (PMVE) and 
perfluoropropylvinylether (PPVE). 
Suitable cyclic ketene acetals are 5-7 membered ring heterocyclic 
bisethers, in which the ether oxygens are part of a 2-methylene-1,3-dioxo 
group. The heterocycle may contain aromatic or lower alkyl substitutents. 
Examples of suitable cyclic ketene acetals include 
2-methylene-1,3-dioxolane, 2-methylene-4-phenyl-1,3-dioxolane, 
2-methylene-1,3-dioxane, 2-methylene-1,3-dioxepane (MDO), 
4,7-dimethyl-2-methylene-1,3-dioxepane and 
5,6-benzo-2-methylene-1,3-dioxepane. Preferred acetals include MDO and the 
above dimethyl and benzo derivatives of MDO, most preferably MDO. 
The ratio of comonomers in the resultant copolymer or terpolymer will 
depend on the concentration of monomers in the polymerization medium. This 
concentration, in turn, will be determined by the amount of monomer 
charged and the relative solubilities of the monomers in the 
polymerization medium. Relative solubilities of the monomers may change as 
the polymerization proceeds. 
Copolymerization of approximately equimolar amounts of a suitable 
fluorinated olefin and a suitable cyclic ketene acetal give an essentially 
1:1 alternating copolymer in which the acetal is present predominantly in 
the ring-opened form. Some acetal-derived dyads may also be present in the 
polymer. The amount of acetal-derived dyads can be minimized by increasing 
the fluorinated olefin:acetal ratio. However, large excesses of TFE and 
CTFE may result in the formation of mixtures of polyfluoroolefin and the 
1:1 alternating copolymer. Conversely, excess acetal increases the number 
of acetal dyads and triads in the copolymer. 
Terpolymers can be made by using a third monomer in the polymerization 
reaction which tends to alternate with the fluoroolefin, but which 
copolymerizes poorly, if at all, with the ketene acetals. Suitable 
monomers include an unsubstituted olefin (ethylene) and terminal, alkyl- 
or alkoxy-substituted olefins such as propylene, isobutylene and ethyl 
vinyl ether. The terpolymers of this invention vary in character from 
soft, sticky glasses to clear, brittle glasses. 
The copolymers and terpolymers of this invention are useful as films and 
fibers and as intermediates in the preparation of novel fluorinated diols, 
which in turn can be used to prepare a variety of fluorinated condensation 
polymers, such as polyesters and polyurethanes. 
All of the monomers used to prepare the copolymers and terpolymers of this 
invention are known in the art. 
Suitable initiators for the free radical polymerization include 
azobisnitriles and diacyl or dialkyl peroxides. Preferred initiators 
include 2,2'-azobis(isobutyronitrile), lauroyl peroxide and di-t-butyl 
peroxide. 
The copolymers of this invention can be made by free radical-initiated 
polymerization in solution. Suitable solvents include alcohols, 
halogenated hydrocarbons and aromatic solvents. Preferred solvents include 
t-butyl alcohol, F-113, FC-75 and benzene. When a volatile fluoro-olefin 
or termonomer is used, the reaction is typically conducted in a sealed 
vessel at elevated pressures. The pressure is not critical, but should not 
exceed the safe operating limits of the reaction vessel. The 
polymerization can be run at 25.degree. C. to 150.degree. C. Above 
150.degree. C., dimerization of some of the fluoroolefin monomers, such as 
TFE and CTFE, may occur. Preferably, the temperature is 50.degree. C. to 
130.degree. C. The reaction time is from 0.5 to 16 h; preferably, the 
reaction time is 4 to 12 h. The product is isolated by filtration or 
precipitation in a non-solvent. Further purification can be accomplished 
by redissolving the polymer in a polar solvent, filtering the polymer 
solution and reprecipitating the polymer in a non-solvent. 
The copolymer can be characterized by conventional analytical techniques. 
.sup.19 F, .sup.13 C and .sup.1 H nmr are particularly useful for 
determining the monomer sequence. 
The copolymers of this invention can be reduced to the corresponding diols 
by reaction with an appropriate reducing agent, preferably lithium 
aluminum hydride. 
The diols derived from the copolymers of this invention can be reacted with 
dimethylterephthalate to make polyterephthalates as shown in the following 
equation: 
##STR8## 
X=F, Cl, Br, I, CF.sub.3, OCF.sub.3, OC.sub.2 F.sub.5, O(CF.sub.2).sub.2 
CF.sub.3, OCF.sub.2 CF(CF.sub.3)O(CF.sub.2).sub.2 CF.sub.3 The procedure 
used for this reaction is substantially that disclosed by Sorenson et al., 
[Preparataive Methods of Polymer Chemistry, 2nd Edition, 1968, pages 
132-33, Interscience Publishers (John Wiley & Sons)], for the formation of 
poly (1,4-cyclohexanedicarbinyl terephthalate) from 
1,4-cyclohexanedicarbinol and dimethyl terephthalate.

EXAMPLE 1 
Copolymerization of Tetrafluoroethylene (TFE) and 2-Methylene-1,3-Dioxepane 
(MDO) 
A 240 mL pressure vessel (Hastelloy-Shaker tube) was charged sequentially 
with MDO (18.2 g, 0.16 mole) dissolved in nitrogen-saturated t-cutyl 
alcohol (40 mL) and 2,2'-asobis (isobutyronitrile) (0.06 g, 
3.6.times.10.sup.-4 mole, Vaso.TM.64, DuPont) dissolved in 
nitrogen-saturated t-butyl alcohol (40 mL). The vessel was closed, cooled 
in dry ice/acetone bath and evacuated with a mechanical oil pump. The 
evacuated vessel was placed in a shaking apparatus and TFE (16.0 g, 0.16 
mole) added. The vessel was shaken and heated slowly to 76.degree. C. at 
which time the autogenous pressure was 1524 kPa. After 20 min. at 
74.degree.-46.degree. C., the pressure had dropped to to 372 kPa and 
slowly decreased to 186 kPa over 12 h. The vessel was cooled to 26.degree. 
C. and the pressure (62 kPa) was bled off. The vessel contained a hard 
white rubbery solid suspended in t-butyl alcohol. The solid polymer was 
blended in an Osterizer with ice and water (5.times.) and then with 
methanol (2.times.). The macerated solid was dried under oil pump vacuum 
for 1 h at room temperature to remove most of the methanol. The solid was 
then dissolved in 300 mL of hot (ca. 60.degree. C.) tetrahydrofuran (THF) 
and the hot solution filtered. The filtrate was added slowly to 900 mL of 
methanol to precipitate the polymer which was then blended with a 
methanol-dry ice mixture (3.times.) to homogenize the solid. The solid 
polymer weighed 27.27 g after drying in a vacuum oven overnight 
(45.degree. C., 0.1 mm). 
Anal. calcd. for [(CF.sub.2 CF.sub.2)(CH.sub.2 C(O)O (CH.sub.2).sub.4)]: C 
44.86; H 4.71; F 35.44; O 14.94. Found: C 45.75; H 4.74; F 37.49; O 15.20 
(by difference). This corresponds to a TFE/MDO copolymer which contains 
52.3 mol % MDO, based on C. 
IR and NMR (.sup.19 F, .sup.1 H) spectra are also consistent with a 
substantially 1:1 alternating TFE/MDO copolymer. Comparison of relative 
NMR peak areas suggests that the copolymer contains 52-53 mol % MDO, 
including 5.5-7.3 mol % MDO dyads. 
This synthesis of TFE/MDO was repeated to give a TFE/MDO copolymer which 
contained 51.6 mol % MDO. A sample of the copolymer was molded at 
150.degree. C. and 2000 psi to give opaque film 30 mils thick. Tensile 
yield: 2,200 psi. Tensile max: 4,700 psi. Tensile break: 4,600 psi. 
Elongation max: 468%. Tensile modulus: 42,400 psi. 
Molecular weight analysis: M.sub.n =19,800; M.sub.w =144,000; M.sub.w 
/M.sub.n =7.27. The density of the copolymer is 1.4378 (as determined by 
density gradient). Inherent viscosity=0.25 g/DL in o-xylene at 90.degree. 
C. .eta.=0.509. 
Thermal analysis (differential scanning calorimetry, DSC): T.sub.m 
=95.degree. C., first heating; 78.1.degree. C., second heating; T.sub.g 
=-28.4.degree. C., second heating. 
EXAMPLE 2 
Copolymerization of TFE and MDO 
The pressure vessel used in Example 1 was charged with Vazo.TM.64 (0.075 g, 
4.6.times.10.sup.-4 mole) and MDO (25.0 g, 0.22 mole) dissolved in 100 mL 
of nitrogen saturated t-butyl alcohol. The vessel was closed, cooled and 
evacuated as in Example 1 and charged with TFE (26 g, 0.26 mole). The 
vessel was shaken and warmed slowly to 65.degree. C. at which time the 
autogenous pressure was 2124 kPa. The vessel was shaken at 
62.4.degree.-71.3.degree. C. for 11.75 h, at which time the pressure was 
359 kPa (64.4.degree. C.). The vessel was cooled to room temperature and 
vented. The vessel contained a white solid polymer contaminated with dark 
specks of thread lubricant from the vessel closure. The product was 
blended with cold methanol (3.times.) and weighed 40.17 g after drying. 
Analysis of the .sup.1 H MNR spectrum indicates that the copolymer contains 
52.6 mol % MDO. 
EXAMPLE 3 
Copolymerization of TFE and MDO 
The procedure described in Example 1 was repeated using 0.075 g of 
Vazo.TM.64, 19.0 g of MDO (0.17 mole), 100 mL of t-butyl alcohol and 15 g 
of TFE (0.15 mole). The vessel was shaken at 75.degree. C. for 12 h. The 
precipitated polymer weighed 24.6 g after maceration and drying. 
Anal. calcd. for [(CF.sub.2 CF.sub.2)(CH.sub.2 C(O)O (CH.sub.2).sub.4)] C 
44.86; H 4.71; F 35.44; O 14.94. Found: C 45.58; H 4.98; F 34.23. This 
corresponds to a TFE/MDO copolymer which contains 51.8 mol % MDO, based on 
C. 
A sample of the copolymer was molded at 150.degree. C. and 2000 psi to give 
opaque film 30 mils thick. Tensile yield: 2,200 psi. Tensile max: 4,000 
psi. Tensile break: 3,900 psi. Elongation max: 399%. Tensile modulus: 
42,700 psi. 
Molecular weight analysis: M.sub.n =16,000; M.sub.w =133,000. M.sub.w 
/M.sub.n =8.31. The density of the copolymer is 1.4288 (as determined by 
density gradient). .eta.=0.457. 
Thermal analysis (differential scanning calorimetry, DSC): T.sub.m 
=94.5.degree. C., first heating; 74.31.degree. C., second heating; T.sub.g 
=-28.7.degree. C., second heating. 
EXAMPLE 4 
Copolymerization of TFE and MDO 
The procedure described in Example 1 was repeated using 0.075 g of 
Vazo.TM.64, 100 mL of nitrogen-saturated Freon.TM.113 (Dupont), 11.4 g of 
MDO (0.10 mole) and 11 g of TFE (0.11 mole). The vessel was shaken at 
75.degree. C. for 12 h. The dried polymer weighed 18.60 g. 
Anal. calcd. for [(CF.sub.2 CF.sub.2)(CH.sub.2 C(O)O (CH.sub.2).sub.4)]: C 
44.87; H 4.71; F 35.48; O 14.94. Found: C 44.80; H 4.82; F 32.42. This 
corresponds to a TFE/MDO copolymer which contains 49.8 mol % MDO, based on 
C. 
A sample of the copolymer was molded at 150.degree. C. and 2000 psi to give 
opaque film 30 mils thick. Tensile yield: 2,200 psi. Tensile max: 4,800 
psi. Tensile break; 4,800 psi. Elongation max: 411%. Tensile modulus: 
44,100 psi. Molecular weight analysis: M.sub.n =23,100; M.sub.w =128,200. 
M.sub.w /M.sub.n =5.55. The density of the copolymer is 1.4487 (as 
determined by density gradient). .eta.=0.481. 
Thermal analysis (differential scanning calorimetry, DSC): T.sub.m 
=99.9.degree. C., first heating; 80.9.degree. C, second heating; T.sub.g 
=-28.9.degree. C., second heating. 
EXAMPLE 5 
Copolymerization of TFE and MDO 
The procedure described in Example 1 was repeated using 0.05 g of 
Vazo.TM.64, 100 mL of Freon.TM.113, 5.7 g of MDO (0.05 mole) and 30 g of 
TFE (0.30 mole). The vessel was heated under autogenous pressure at 
65.degree. C. for 1 h and at 75.degree. C. for 12 h. The product was 
isolated as described in Example 3 and weighed 23.67 g. 
Extraction of the product with hot THF (200 mL), followed by precipitation 
of the polymer in methanol gave a polymer which weighed 4.17 g after 
drying. 
Anal. calcd. for [(CF.sub.2 CF.sub.2)(CH.sub.2 C (O)O(CH.sub.2).sub.4)]: C 
44.86; H 4.71; F 35.44; O 14.94. Found: C 44.70; H 4.50; F 37.20. This 
corresponds to a TFE/MDO copolymer which contains 47.96 mol % MDO, based 
of C. 
The THF-insoluble residue weighed 7.73 g after drying. Elemental analysis 
confirmed that this residue is essentially pure polytetrafluoroethylene. 
EXAMPLE 6 
Copolymerization of MDO and TFE 
The procedure described in Example 1 was repeated using Vazo.TM.64 (0.070 
g), benzene (100 mL), MDO (19.0 g, 0.017 mol) and TFE (20.0 g, 0.20 mol). 
The polymerization was conducted under autogenous pressure at 65.degree. 
C. for 6 h. The product separated into two layers. The upper layer (105.2 
g) contained benzene (94.05%) and MDO (5.13%), as analyzed by GC. The 
lower layer was added to methanol (500 mL) to give a solid polymer which 
weighed 4.32 g after drying. 
EXAMPLE 7 
Copolymerization of MDO and TFE 
The procedure described in Example 1 was repeated using Vazo.TM.64 (0.05 
g), FC 75.TM. (100 mL, fluorinated solvent commercially available from the 
3M Company), MDO (11.4 g, 0.10 mol), TFE (12 g, 0.12 mol). The 
polymerization was conducted under autogenous pressure at 65.degree. C. 
for 15 h. The dry solid polymer weighed 5.25 g. 
EXAMPLE 8 
Copolymerization of MDO and TFE 
The procedure described in Example 1 was repeated using lauroyl peroxide 
(0.05 g, Lucidol.TM., Pennwalt), t-butyl alcohol (100 mL), MDO (19 g, 0.17 
mol) and TFE (20.0 g, 0.20 mol). The polymerization was conducted under 
autogenous pressure at 65.degree. C. for 3 h. the dry solid polymer 
weighed 17.9 g. 
EXAMPLE 9 
Copolymerization of MDO and TFE 
The procedure described in Example 1 was repeated using di-t-butyl peroxide 
(0.10 g), t-butyl alcohol (100 mL), MDO (11.4 g, 0.10 mol) and TFE (12.0 
g, 0.12 mol). The reaction mixture was heated under autogenous pressure at 
120.degree. C. for 14 h. The solid polymer weighed 15.77 g after drying. 
EXAMPLE 10 
Copolymerization of MDO and Hexafluoropropylene (HFP) 
The vessel described in Example 1 was charged as described above with 0.075 
of Vazo.TM.64, 11.4 g MDO, 100 mL of nitrogen-saturated t-butyl alcohol 
and 15.0 g of HFP. The vessel was shaken and heated to 75.degree. C. at 
which time the autogenous pressure was 696 kPa. After the vessel was 
shaken at 73.degree.-75.degree. C. for 12 h, the pressure had dropped to 
359 kPa. The vessel was cooled to room temperature and vented. The 
resulting liquid and white solid were blended with dry ice and methanol 
(3.times.). On warming, the solid was very sticky. The solid was dissolved 
in methylene chloride and slowly poured into dry ice/methanol. The cold 
solid was put in a jar and dried for 2 days. The resultant polymer was a 
clear tough gum which weighed 15.61 g. 
Anal. calcd. for [(CF.sub.2 C(CF.sub.3)F)(CH.sub.2 C 
(O)O(CH.sub.2).sub.4)]: C 40.92; H 3.82; F 43.15; O 12.11. Found: C 43.20; 
H 4.34; F 39.34. This corresponds to a HFP/MDO copolymer which contains 
55.85 mol % MDO, based on C. .sup.1 H NMR analysis is consistent with an 
HFP/MDO copolymer which contains 53.4-54.9 mol % MDO and 13-18% MDO-dyads. 
IR(cm.sup.-1): 2960, 1740, 1200. 
The polymer is amorphour and has a T.sub.g at -24.3.degree. C. Thermal 
gravimetric analysis (TGA) in air: onset of decomposition=377.7.degree. 
C.; Maximum Rate at 399.9.degree. C. 
Molecular weight analysis: M.sub.n =14,000; M.sub.w =53,800. M.sub.w 
/M.sub.n =3.85. .eta.=0.252 DL/g. 
EXAMPLE 11 
Copolymerization of MDO and Chlorotrifluoroethylene (CTFE) 
The procedure described in Example 2 was repeated using 0.075 g of 
Vazo.TM.64, 100 mL of t-butyl alcohol, 11.4 g of MDO (0.10 mole) and 13.0 
g of CTFE (0.11 mole). The vessel was shaken at 75.degree. C. for 12 h 
under autogenous pressure. The dried solid polymer weighed 20.03 g. 
The product presses to a soft, rubbery film at 120.degree.-150.degree. C., 
and is soluble in THF. 
Anal. calcd. for [(CF.sub.2 CFCl)(CH.sub.2 C(O) O(CH.sub.2).sub.4)]: C 
41.66; H 4.37; cl 15.37; F 24.72; O 13.88. Found: C 42.35; H 4.58; Cl 
14.91; F 24.56. This corresponds to a CTFE/MDO copolymer which contains 
53.6 mol % MDO, based on C. .sup.1 H NMR analysis is consistent with a 1:1 
alternating CTFE/MDO copolymer. 
Molecular weight analysis: M.sub.n =30,200; M.sub.w =121,000. M.sub.w 
/M.sub.n =4.01. 
Thermal analysis (differential scanning calorimetry, DSC): T.sub.me 
=70.2.degree. C., first heating; T.sub.g =-14.degree. C., second heating. 
EXAMPLE 12 
Copolymerization of MDO and Perfluoropropylvinyl ether (PPVE) 
The procedure described in Example 2 was repeated using 0.075 g of 
Vazo.TM.64, 100 mL of t-butyl alcohol, 11.4 g of MDO (0.10 mole) and 28 g 
of PPVE (0.105 mole). The vessel was shaken at 75.degree. C. for 12 h 
under autogenous pressure. The isolated polymer is a soft, sticky gum 
which is soluble in THF and methylene chloride. It weighed 10.13 g after 
drying. 
Anal. calcd. for [(CF.sub.2 CF (OCF.sub.2 CF.sub.2 CF.sub.2 
CF.sub.3)(CH.sub.2 C(O)O(CH.sub.2).sub.4)]: C 34.75; H 2.65; F 49.98; O 
12.62. Found: C 35.08; H 2.85; F 48.70. This corresponds to a PPVE/MDO 
copolymer which contains 51.0 mol % MDO, based on C. The .sup.1 H NMR 
spectrum was in accord with an essentially 1:1 alternating PPVE/MDO 
copolymer. 
Molecular weight analysis: M.sub.n =8,830; M.sub.w =14,300. M.sub.w 
/M.sub.n =1.62. 
EXAMPLE 13 
Copolymerization of MDO, TFE and Isobutylene (IB) 
The procedure described in Example 1 was repeated using 0.10 g of 
Vazo.TM.64 (6.times.10.sup.-4 mole), 16.3 g of MDO (0.143 mole), 100 mL of 
t-butyl alcohol, 8.0 g of IB (0.143 mole) and 28.6 g of TFE (0.286 mole). 
The vessel was shaken under autogenous pressure at 70.degree.-78.degree. 
C. for 12 h. (Except for an exotherm at 70.degree. C., the reaction was 
run at 74.degree.-75.degree. C.) The crude reaction product, a soft 
polymer, was blended with ice water and methol. After soaking overnight in 
methanol, the polymer was filtered off. The polymer was dissolved in 
methylene chloride, repreciptated in a large excess of methanol and dried 
in a vacuum oven to give a clear, hard gum (28.2 g). 
Elemental analysis. Found: C 43.00; H 4.86; F 42.28. This corresponds to a 
TFE/MDO/IB copolymer of 1/0.554/0.295 (i.e., TFE=54.1, MDO=29.6, IB=15.95 
mole %). 
.sup.1 H NMR analysis gives a TFE/MDO/IB ratio of 1/0.32/0.37 (i.e., 
TFE=59.1, MDO=19.1, IB=21.9 mole %). The polymer consists primarily of 
TFE/IB units, followed by TFE/MDO units, with appreciable amounts (ca. 
20%) of TFE/IB/IB units. Some MDO dyads (5.7% of the MDO) and IB dyads 
(11.8% of the IB) are also present. 
Molecular weight analysis: M.sub.n =12,000; M.sub.w =35,100. M.sub.w 
/M.sub.n =2.92. 
Thermal analysis, differential scanning calorimetry DSC): T.sub.m 
=41.4.degree. C., first heating; T.sub.g =-13.8.degree. C., second 
heating. TGA in air: Onset of decomposition=380.7.degree. C.; Maximum rate 
of decomposition=407.1.degree. C. 
EXAMPLE 14 
Copolymerization of MDO, TFE and IB 
The procedure described in Example 1 was repeated using 0.10 g of 
Vazo.TM.64 (6.times.10.sup.-4 mole), 7.7 g of MDO (0.067 mole), 100 mL of 
t-butyl alcohol, 13.0 g of IB (0.23 mole) and 30 g of TFE (0.30 mole). The 
vessel was shaken at 73.degree.-76.degree. C. for 12 h. Crude product was 
isolated by blending first with ice water, then methanol and finally 
filtering off the solid. After drying in a vacuum oven, the white, rubbery 
polymer weighed 24.14 g. This solid was dissolved in toluene and the 
solution filtered to remove traces of insoluble material. Evaporation of 
the toluene gave 21.49 g of soft polymer. 
Elemental analysis. Found: C 44.60; H 5.09: F 45.00. This corresponds to a 
TFE/MDO/IB copolymer of 1/0.283/0.681 (i.e., TFE=50.9, MDO=14.4, IB=34.7 
mole %). 
.sup.1 H NMR analysis gives a TFE/MDO/IB ratio of 1/0.23/0.91 (i.e., 
TFE=46.7, MDO=10.7, IB=42.5 mole %). Molecular weight analysis: M.sub.n 
=9,980; M.sub.w =23,100. M.sub.w /M.sub.n =2.31. 
Thermal analysis, differential scanning calorimetry DSC): T.sub.m 
=70.7.degree. C., first heating; T.sub.g =4.1.degree. C., second heating. 
TGA: Onset of decomposition=384.6.degree. C.; Maximum rate of 
decomposition=420.6.degree. C. 
EXAMPLE 15 
Copolymerization of MDO, TFE and IB 
The procedure described in Example 10 was repeated using 0.13 g of 
Vazo.TM.64 (7.8.times.10.sup.-4 mole), 8.6 g of MDO (0.074 mole), 100 mL 
of t-butyl alcohol, 18.0 g of IB (0.32 mole) and 40.0 g of TFE (0.40 
mole). The vessel was shaken at 73.degree.-75.degree. C. for 19 h. After 
work-up, 32.65 g of polymer was isolated. 
Elemental analysis. Found: C 45.94; H 5.33; F 44.62. 
.sup.1 H NMR analysis gives a TFE/MDO/IB ratio of 1/0.66/0.93 (i.e., 
TFE=38.5, MDO=25.6, IB=35.8 mole %). 
Molecular weight analysis: M.sub.n =10,100; M.sub.w =27,900. M.sub.w 
/M.sub.n =2.76. Density: 1.3945. 
Thermal analysis, differential scanning calorimetry DSC): T.sub.m 
=81.1.degree. C., first heating; T.sub.g =8.5.degree. C., second heating. 
TGA in air: Onset of decomposition=381.9.degree. C.; Maximum rate of 
decomposition=429.3.degree. C. 
A sample of the copolymer was pressed at 150.degree. C. to give a clear, 
soft film. Tensile yield: 1,000 psi. Tensile max: 1,200 psi, Tensile 
break: 1,200 psi. Elongationmax: 270%. Tensile modulus: 20,900 psi. 
EXAMPLE 16 
Copolymerization of MDO and Perfluoromethylvinyl Ether (PMVE) 
The procedure described in Example 2 was repeated using Vazo.TM.64 (0.075 
g), t-butyl alcohol (100 mL), MDO (17.1 g, 0.15 mol) and PMVE (37 g, 0.22 
mol). The reaction mixture was heated to 65.degree. C. for 10 h under 
autogenous pressure. The isolated polymer was a soft gum which weighed 
30.65 g after drying. The polymer is soluble in THF and chloroform. 
Elemental Analysis. Calc'd for a 1:1 copolymer, C.sub.9 H.sub.10 F.sub.6 
O.sub.3 : C 38.58; H 3.59; F 40.69. Found: C 39.65, 39.92; H 3.62, 3.92; F 
43.55, 43.74. 
The T.sub.g is between -28.degree. C. and -24.degree. C. 
.sup.1 H nmr (ppm, CDCl.sub.3 solvent, TMS ref.): 4.18 (t, 2, --O--CH.sub.2 
--(CH.sub.2).sub.3 --); 3.08 (d, 2, --CH.sub.2 --C(O)O--); 2.05 (m, 2, 
--CH.sub.2 --CF.sub.2 --); 1.70 (m, 4, --CH.sub.2 --(CH.sub.2).sub.2 
--CH.sub.2 --). 
EXAMPLE 17 
Copolymerization of MDO and Perfluoro-2-methyl-3oxahexylvinyl Ether 
A mixture of Vazo.TM.64 (0.04 g), anhydrous potassium carbonate (0.05 g), 
t-butyl alcohol (25 mL) perfluoro-2-methyl-3-oxahexylvinyl ether (24.64 g, 
0.061 mol) and MDO (4.5 g, 0.039 mol) was stirred and heated at about 
58.degree. C. under autogeneous pressure for about 18 h. The reaction 
mixture became more viscous during this period. The reaction mixture was 
freed of excess perfluoroether, t-butyl alcohol and other volatiles by 
vacuum distillation at 25.degree.-72.degree. C. at 760-1.7 Torr. The 
distillation residue (9.56 g) was extracted with methylene chloride 
(5.times.25 mL). The desired product, a methylene chloride-insoluble clear 
gum, weighed 8.71 g after drying. 
Elemental Analysis: Calc'd for C.sub.14 H.sub.10 F.sub.16 O.sub.4 : C 
30.79; H 1.85; F 55.65. Found: C 31.17, 31.10; H 1.96, 1.89; F 55.64, 
55.60. 
1H nmr (ppm, CDCl.sub.3 /F113, TMS ref.): 4.2 (t, 2, --O--CH.sub.2 
--(CH.sub.2).sub.2 --); 33.2 (m, 2, --(CH.sub.2).sub.2 --CH.sub.2 
--CF.sub.2 --); 2.21 (d, 2, --.fwdarw.CF--CH.sub.1 --O--); 1.6 (m, 
4,--(CH.sub.2).sub.2 --CH.sub.2 --CF.sub.2 --). 
Mw=101,000; Mw/Mn=9.21. (Determined by GPC in hexafluoroisopropanol using 
polyethylene terephthalate standards.) 
EXAMPLE 18 
Reduction of TFE/MDO Copolymer to 3,3,4,4-Tetrafluorooctane-1,8-diol 
A solution of TFE/MDO copolymer, I, (42.8 g), prepared as in Example 2 was 
dissolved in tetrahydrofuran (THF, 435 mL) and added to a mixture of 1M 
lithium aluminum hydride (in THF, 150 mL) and anhydrous THF (150 mL) over 
1.5 h. After stirring overnight at ambient temperature, the cloudy 
reaction mixture was decomposed by sequential addition of water (6.0 mL), 
15% aqueous sodium hydroxide (6.0 mL) and water (18.0 mL). The 
precipitated salts were removed by filtration and washed with THF 
(3.times.50 mL). The combined filtrate solutions were dried with anhydrous 
sodium sulfate (130 g). The solids were removed by filtration and the THF 
distilled off under vacuum to give crude 
3,3,4,4-tetrafluorooctane-1,8-diol (41.8 g). the crude product was 
distilled through a short path distillation apparatus. The fraction 
collected at a bath temperature of about 98.degree.-124.degree. C. at ca. 
0.065 Torr weighed 29.8 g and solidified on standing (m.p. 
52.degree.-55.degree. C.). 
Elemental Analysis. Calcd for C.sub.8 H.sub.14 F.sub.4 O.sub.2 : 44.64, C; 
6.47, H; 34.83, F. Found: 44.53, 44.40, C; 6.84, 6.63, H; 34.57, F. 
IR (cm.sup.-1) : 3338 (OH), about 1200 (CF). No absorption at 1740 (COOR). 
.sup.1 H NMR (ppm rel. to TMS; CDDl.sub.3 solvent): 3.9 (2, HOCH.sub.2 
CH.sub.2 CF.sub.2 --); 3.65 (2, HOCH.sub.2 (CH.sub.2).sub.2 CH.sub.2 
CF.sub.2 --); 2.3 (2, HOCH.sub.2 (CH.sub.2).sub.2--CH.sub.2 CF.sub.2 --); 
ca. 2 (4,HOCH.sub.2 (CH.sub.2).sub.2 CH.sub.2 CF.sub.2 --); ca. 2 (4, --OH 
and HOCH.sub.2 CH.sub.2 CF.sub.2 --). 
.sup.19 F NMR (ppm rel. to F11; CDCl.sub.3 solvent): -114.6 (multi); -116 
(multi). 
EXAMPLE 19 
Reduction of PMVE/MDO Copolymer to 
3,4,4-Trifluoro-3-trifluoromethoxy-1,8-octanediol 
A solution of PMVE/MDO copolymer (63.73 g) in THF (300 mL) was added over a 
2 h period to 170 mL of a 1M solution of LiAlH.sub.4 in THF at 
35.degree.-40 .degree. C. After standing overnight at ambient temperature, 
the reaction mixture was decomposed by sequential addition of water (7 
mL), 15% aqueous sodium hydroxide (7 mL) and water (21 mL). The THF 
solution was filtered and dried with anhydrous sodium sulfate (200 g). The 
THF was removed by distillation and the pale yellow liquid residue (56.1 
g) was distilled through a short path distillation apparatus. A center 
fraction (39.4 g) was collected at a bath temperature of 
75.degree.-78.degree. C. at 0.05 Torr and was the desired diol. 
Elemental Analysis: Calc'd for C.sub.9 H.sub.14 F.sub.6 O.sub.3 : C 38.04; 
H 4.97; F 40.11. Found: C 39.88, 39.76; H 5.38, 5.54; F 39.85. 
IR (cm.sup.-1): 3338 (strong, OH); 1200 (strong, CF). No absorption at 1740 
(CO). 
EXAMPLE 20 
Reduction of PPVE/MDO Copolymer to 
3,4,4-Trifluoro-3-perfluoro-1-propoxyoctane-1,8-diol 
PPVE/MDO copolymer (155.2 g), prepared as in Example 12, was dissolved in 1 
L of anhydrous THF and the resulting solution added over about 3.5 h to 
300 mL of a 1M solution of lithium aluminum hydride in THF at 
21.degree.-40.degree. C. The resultant slightly turbid solution was 
stirred (ca 18 h) at ambient temperature. The reaction mixture was treated 
sequentially water (11.5 ml), 15% aqueous sodium hydroxide (11.5 mL) and 
water (34.5 mL). The salts were removed by filtration and the filtrate 
dried with anhydrous sodium sulfate (200 mL). The mixture was filtered and 
the filtrate concentrated to give 149.9 g of liquid which was then 
distilled through a short path distillation column (Kugelrohr) under 
reduced pressure. A central fraction was collected at an air bath 
temperature of 88.degree.-107.degree. C. at 0.075 Torr and weighed 93.8 g. 
Elemental and spectroscopic analysis was consistent with diol structure 
II. 
Elemental analysis: calcd. for C.sub.11 H.sub.14 F.sub.10 O.sub.3 : 34.39, 
C; 3.67, H; 49.45, F. Found: 35.29, 35.46, C; 4.04, 3.90, H; 47.94, 48.03, 
F. 
IR (cm .sup.-1): 3338 (OH), ca. 1200 (CF). No absorption was observed at 
1740 (COOMe). 
.sup.1 H NMR (ppm rel. to TMS, CDDl.sub.3 solvent): ca. 4 (4, HOCH.sub.2 
CH.sub.2 CF&lt;); 3.9 (2, HOCH.sub.2 CH.sub.2 CF&lt;); 3.65 (2, HOCH.sub.2 
(CH.sub.2).sub.2 CH.sub.2 CF.sub.2--); 2.30 (2, HOCH.sub.2 
(CH.sub.2).sub.2 CH.sub.2 CF.sub.2 --); 1.62 (4, HOCH.sub.2 
(CH.sub.2).sub.2 CH.sub.2 CL.sub.2 -). 
EXAMPLE 21 
Reduction of HFP/MDO copolymer to 
3,4,4-Trifluoro-3-trifluoromethyl-1,8-octanediol 
HFP/MDO copolymer (12.5 g, prepared as in Example 10) was dissolved in 
anhydrous THF (125 mL) and added to a stirred mixture of 30 mL of 1M 
lithium aluminum hydride/THF and 75 mL of anhydrous THF at 
35.degree.-40.degree. C. After the addition was complete the turbid 
reaction mixture was stirred for ca. 16 h at ambient temperature. The 
mixture was treated sequentially with water (1.3 mL), 15% aqueous solium 
hydroxide (1.3 mL) and water (4.0 mL). The THF was removed in vacuo and 
the residue distilled through a short path distillation column under 
reduced pressure. Two fractions were collected at a bath temperature of 
85.degree.-98.degree. C. 0.04-0.05 Torr. 
Elemental Analysis: Calcd. for C.sub.9 H.sub.14 F.sub.6 O.sub.2 ; C 40.31; 
H 5.26; F 42.50. Found: (Cut 1) C 41.35, 41.66; H 5.38, 5.41; F 38.55, 
39.04; (Cut 2) C 40.56, 40.60; H 5.13, 5.32; F 42.47, 42.77. 
IR (cm.sup.-1): 3338 (OH), ca. 1200 (CF). 
.sup.1 H NMR (ppm rel. to TMS, CDCl.sub.3 solvent): 3.9 (2, HOCH.sub.2 
CH.sub.2 --); 3.7 (2, HOCH.sub.2 (CH.sub.2).sub.3 --); 2.35 (2, --CH.sub.2 
CF.sub.2 --); ca. 2.21 (4, HO-- and --CF--CH.sub.2 --); 1.65 (4, 
--CH.sub.2).sub.2 --). 
EXAMPLES 22-27 
Polyterephthalates from 
3,4,4-Trifluoro-3-perfluoro-1-propoxy-octane-1,8-diol 
A mixture of Sb.sub.2 O.sub.3 (0.012 ), Ca(OAc)2.H.sub.2 O (0.050 g), 
octane-1,8-diol (8.45 g, 0.022 mol) and dimethyl terephthalate (3.88 g, 
0.02 mol) was charged into a small round bottomed flask surmounted by a 
short distillation head. The mixture was purged of air by evacuation and 
flushing with argon (3.times.). The mixture was melted by immersion in an 
oil bath at about 150.degree. C. and a capillary was inserted into the 
molten mixture. The temperature was raised to 200.degree. C. with a slow 
stream of argon flowing through the capillary. After 1 h at 200.degree. 
C., the temperature was raised to 250.degree. C. for about 1.2 h, at which 
time the evolution of the methanol had ceased. The capillary was removed. 
The melt was then heated from 250.degree.-276.degree. C. over about 2.3 h 
as the pressure was reduced from 1 atm to about 0.85 Torr. The melt was 
cooled and the reaction flask removed from the short still and attached to 
a short path still. The polymerization was finished at 
272.degree.-305.degree. C. (air bath temperature) under 0.15-0.04 Torr. 
The melt was cooled and removed by breaking the flask. The terephthalate 
polymer was a light brown elastic gum which weighed 7.42 g. 
The polymer is soluble in methylene chloride, 1,1,2-trichloroethane, 
N,N-dimethyl acetamide and chlorobenzene. The polymer is amorphous and has 
a glass transition around 6.degree. C., as measured by differential 
scanning calorimetry. 
Essentially the same procedure was used to prepare polyterephthalates from 
the diols HO--(CH.sub.2).sub.4 --CF.sub.2 --CFX--(CH.sub.2).sub.2 --OH 
(X=F, CF.sub.3) and copolymers of the diols (X=O(CF.sub.2).sub.2 CF.sub.3, 
CF.sub.3) with octane diol. Polyoctylene terephthalate was also made from 
1,8-octane diol. Data on these polymers is summarized in the following 
Table. 
______________________________________ 
##STR9## 
Tm 
Mole Max GPC.sup..sym. 
Ex. X Y % Onset 
.degree.C. 
Tg Product 
Mw Mn 
______________________________________ 
22 H H 100 127.5 
135.8 
* White 22,200 
2.42 
Crystal- 
21,800 
2.61 
line 
Plastic 
23 F F 100 146.5 
155.5 
* Tan 17,700 
3.44 
Crystal- 
17,800 
3.69 
line 
Plastic 
24 F CF.sub.3 
100 + + 6 Tan 10,700 
3.20 
Amor- 11,100 
3.15 
phous 
25 H H 80 104.3 
114.5 
* White 9,500 
2.87 
F CF.sub.3 
20 Crystal- 
10,300 
2.53 
line 
Plastic 
26 F ** 100 + + 6 Tan 14,800 
2.18 
Amor- 14,400 
2.45 
phous 
27 H H 80 + + 36 White 6,700 
2.93 
F ** 20 Crystal- 
6,300 
2.85 
line 
Plastic 
______________________________________ 
Starting Materials 
22. 8.04 g 1,8-octanediol (0.055 m); 9.71 g 
DMT (0.05 m); 
0.015 g (isopropyl).sub.4 Ti catalyst 
23. 11.45 g (HO(CH.sub.2).sub.4CF.sub.2CF.sub.2(CH.sub.2).sub.2 OH 
(0.052 m); 9.71 g DMT (0.005 m); 
0.020 g (isopropyl).sub.4 Ti catalyst 
##STR10## 
(0.077 m); 13.59 g DMT (0.070 m); 
0.020 g (isopropyl).sub.4 Ti catalyst 
##STR11## 
12.63 g DMT (0.065 m); 
7.98 g 1,8-octane diol (0.055 m); 
0.10 g PbO catalyst; 
##STR12## 
3.88 g DMT (0.020 m); 
0.012 Sb.sub.2 O.sub.3 Catalyst 
0.050 Cu(OAc).sub.2.H.sub. 2 O 
##STR13## 
7.98 g 1,8-octanediol (0.055 m) 12.62 DMT 
(0.065 m); 0.025 g (isopropyl).sub.4 Ti catalyst 
______________________________________ 
* No Tg observed in two heats DSC 
+ No Tm observed DSC 
.sup..sym. 0.1% Hexafluoroisopropanol with polyethylene terephthalate 
standards 
** O(CF.sub.2).sub.2 CF.sub.3 
Although preferred embodiments of the invention have been illustrated and 
described in examples 1 through 27, it is to be understood that there is 
no intent to limit the invention to the precise constructions herein 
described. Rather it is to be understood that the right is reserved to all 
modifications and changes coming within the scope of the invention as 
defined by the appended claims.