JPH06263867A - Hydroxyl-terminated prepolymer and perfluoroalkoxyoxetane monomer - Google Patents

Abstract

PURPOSE: To obtain the subject prepolymer useful in the preparation of resins and coatings having hydrophobicity, low permittivity and low refractive index by polymerizing a specified oxetane monomer.

CONSTITUTION: An oxetane monomer of formula I (wherein (n) is 1-5; (m) is 1 or 2; R is H or a 1-4C alkyl; and R₁ is a 1-20C linear or branched perfluoroalkyl, isoalkyl, haloalkyl or haloisoalkyl or a 4-60C oxaperfluoropolyether) is polymerized in the presence of a Lewis acid catalyst to obtain a hydroxyl-terminated prepolymer of formula II (wherein (n), (m), R and R₁ are as defined above; and (x) is 2 to about 250). A compound of formula I can be obtained by reacting a sulfonic acid derivative of a hydroxyalkyloxetane with a fluoroalkoxide. A hydroxyl-terminated prepolymer of formula II has a polyether skeleton and is useful in the preparation of resins and coatings having hydrophobicity, low permittivity and low refractive index.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION

[0002]

FIELD OF THE INVENTION This invention relates to pendant oxetane monomers with perfluoroalkoxy groups, a method of their preparation and a method of their polymerization, and hydroxy-terminated prepolymers so prepared. Prepolymers have a polyether backbone and are useful for preparing resins and coatings that have hydrophobic properties, low dielectric constants and low refractive indices.

[0003]

Brief Description of the Prior Art Oxetanes can be substituted in the 3-position with methyl groups containing activated functional groups such as nitrato, azide, nitro and difluoroamino. Polymerization of these substituted oxetanes in the presence of polyhydroxyaliphatic compounds produces hydroxy-terminated prepolymers with a polyether backbone with pendant active groups. These polymers are then cured with isocyanates to give U.S. Pat. Nos. 4,393,199 and 4,483,97.
High molecular weight polymers can be formed that are useful as binders in propellant applications such as those described in Nos. 8, 4,707,540, and 4,764,586.

It is desirable to incorporate fluorine into the polyether polymer, however, incorporation of a high proportion of fluorine into the polymer's ether backbone causes thermal and chemical instability, resulting in fluoride ion or hydrogen fluoride. As a result. When fluorine is incorporated into the polymer without ether linkages, the resulting material has a high glass transition temperature, which limits the utility and application of the resulting polymer.

[0005]

BRIEF DESCRIPTION OF THE INVENTION The present invention is directed to an oxetane monomer having an alkoxy side chain in which the ω carbon is fully fluorinated, which is preferably a perfluoroalkoxy side chain, its preparation method, its polymerization method and as a result thereof. And the resulting prepolymer. The monomer is prepared by reaction of the corresponding fluorinated alkoxide with a halogenated derivative of 3-hydroxyalkyloxetane or an aryl sulfonate. An example of the latter is 3-hydroxymethyl-3-
A p-toluenesulfonate derivative of methyloxetane,
Alternatively, it is a derivative of 3,3-bis (hydroxymethyl) -oxetane. A high yield of oxetane with pendent perfluoroalkoxy side chains is obtained.

The fluorinated alkoxyoxetane monomers of the present invention can be readily polymerized in the presence of Lewis acid catalysts, and high yields of hydroxy-terminated prepolymers having molecular weights of 1,000 to about 30,000. , And the polyether skeleton formed by opening the oxetane ring. These prepolymers are useful as hydrophobic, non-stick coatings and as precursors for binders for propellants.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention includes the following oxetane derivatives, their method of preparation, their method of polymerization, and the resulting prepolymer.

[0008]

[Chemical 3]

Where n is 1 to 5 m is 1 or 2 R is hydrogen or alkyl having 1 to 4 carbons,
And R _f is a straight or branched chain perfluoroalkyl, isoalkyl, haloalkyl, or haloisoalkyl having 1 to 20 carbons, or 4 to about 60
Is an oxaperfluoropolyether having carbons.

The present invention also includes the polymerization of the monomers and the resulting hydroxy-terminated prepolymer having the structure:

[0011]

[Chemical 4]

Where n is 1 to 5, m is 1 or 2,
R is hydrogen or alkyl having 1 to 4 carbons,
R ₁ is an alkylene or isoalkylene having 2 to about 5 carbons, R _f is a straight or branched chain perfluoroalkyl, isoalkyl, haloalkyl, or haloisoalkyl having 1 to 20 carbons, or 4 to about Oxaperfluoropolyethers having 60 carbons, and x is 2 to about 250.

The oxetane derivative is obtained by reacting an aryl sulfonate derivative of a hydroxyalkyl oxetane with a fluorinated alkoxide. The aryl sulfonate derivative of hydroxyalkyl oxetane has the general formula:

[0014]

[Chemical 5]

Wherein m is 1 or 2, R is hydrogen or alkyl having 1 to 4 carbons, and R ₃ is C ₆
To monocyclic aryls having from C ₁₀ carbons, such as benzyl, tolyl, xylyl, mesityl. A preferred sulfonic acid is toluene sulfonate, for example the p-toluene sulfonate derivative of oxetane.

The fluorinated alkoxide is obtained by reacting a fluorinated alcohol with sodium hydride in a suitable solvent such as dimethylformamide. Fluorinated alcohols that can be used have the general formula:

R _f (CH ₂ ) _n OH where n is 1 to 5 and R _f is a straight or branched chain perfluoroalkyl, isoalkyl, haloalkyl or haloisoalkyl having from 1 to 20 carbons,
Or an oxaperfluoropolyether having 4 to about 60 carbons. Examples of suitable fluorinated alcohols are trifluoroethanol, heptafluorobutanol, pentadecafluorooctanol, tridecafluorooctanol and the like. Other useful alcohols include fluoroalcohols having other halogens in the omega position, such as omega-haloperfluorinated alcohols of the formula:

[0018]

[Chemical 6]

The fluorinated alkoxyoxetane monomer is easily polymerized in the presence of a Lewis acid catalyst and a polyhydroxyaliphatic compound as a polymerization initiator. In the presence of Lewis acid catalysts, the alcohol releases a proton that initiates the ring-opening polymerization of oxetane propagating through the formation of the following intermediates.

[0020]

[Chemical 7]

Suitable catalysts are Lewis acids, ie compounds which can accept a pair of electrons, examples being boron trifluoride complexes, phosphorus pentafluoride, antimony pentafluoride, zinc chloride, aluminum bromide. Including etc.

Suitable initiators are, for example, ethylene glycol, butane-1,4-diol, propylene glycol, isobutane-1,3-diol, pentane-1,5.
Polyhydroxyaliphatic compounds, such as alkyl and isoalkyl polyols, having 2 to about 5 carbons and 2 to 4 hydroxyls, such as diols, pentaerythritol and the like.

Polymerization can be carried out, for example, with methylene chloride or methyl bromide.
Len, ethylene dichloride, ethylene dibromide, dichloroprop
Preferably halogen such as len, freon, fluorinated solvent, etc.
Chemical C ₁-C_FiveWith a suitable inert solvent that is a hydrocarbon
Performed around the time.

The catalyst and initiator are preferably mixed in the solvent prior to adding the oxetane monomer. An example of a preferred catalyst, initiator and solvent combination is boron trifluoride etherate or boron trifluoride tetrahydrofuranate and butane-1,4-diol in methylene chloride.

Monomers are added to this mixture and solution polymerization is carried out at a solution concentration of 5 to 75% by weight. In the polymerization, the concentration of the catalyst and the proportion of the initiator, eg butane-1,4-diol, can be varied to control the molecular weight of the polymer, the higher the proportion of the initiator, the lower the molecular weight of the prepolymer product. . A useful ratio of boron trifluoride catalyst to initiator is about 100: 1 to about 1: 2.

Polymerization ends with the formation of a hydroxy-terminated polymer according to the following mechanism.

[0027]

[Chemical 8]

Polymerization is homopolymerization or copolymerization, in which a mixture of two or more of the above-mentioned oxetane monomers is added to the polymerization zone. A particularly useful copolymerization is block polymerization, in which comonomers are continuously added in selected proportions to obtain block copolymers of controlled block size and properties.

In order to prepare the prepolymer with the best coating properties, the oxetane monomer should have a 3-substituent in which the R _f group is fully fluorinated at its ω carbon. One of the major applications of the hydroxy-terminated prepolymers of the present invention is the development of hydrophobic, non-stick coatings. The most important criterion in the development of these coatings is the minimization of the surface free energy of the coating, which is a measure of the wettability of the coating and defines important properties such as hydrophobicity and adhesive properties. Hydrogen, for example, terminal carbon containing -CF ₂ H or -CFH ₂ or -CH ₃ is significantly than the surface energy of the fully halogenated groups -CF ₃ group or the like having a surface energy of about 6dyn / cm Large (15-39dy
n / cm) surface energy.

Most preferably, the 3-substituent (R _f ) is perfluoroalkyl. Perfluoroalkyl groups are extremely strong electron withdrawing groups, and their presence alters the electronic and steric properties of oxetane monomers. This affects its ease and functionality of polymerization, molecular weight, and the structure of the polymer, either cyclic or linear.
The most useful hydroxy-terminated prepolymers with fluorinated side chains are those that are well-defined and have a functionality of at least 2. The presence of non-functional or monofunctional materials in the prepolymer results in coatings with poor mechanical and surface properties.

Cyclic groups in the polymer, primarily cyclic tetramers and trimers, are non-functional and reduce the usefulness of the prepolymer. Other non-functional groups can be formed by counterion termination reactions such as diethyl ether and fluoride ion termination. In addition to the role of the fluoroalkyl substituent on its reactivity towards oxetane, other factors such as monomer / initiator ratio, alcohol to Lewis acid ratio, Lewis acid type, reaction temperature, solvent, and concentration are non- and The formation of monofunctional substances is thus controlled.

It is also preferred to use mono-3-substituted oxetanes, ie those in which the value of "m" in the empirical formula is preferably 1. These are preferred because homopolymerization of di-3-substituted oxetane monomers produces crystalline polymers. As an example, the polymerization of 3,3-bis- (chloromethyl) oxetane yields a crystalline polymer that dissolves near 220 ° C.

Hydroxy-terminated prepolymers prepared from the preferred mono-3-substituted oxetane monomers are amorphous low viscosity oils that are easy to process. The prepolymers are relatively pure, while those derived from di-3-substituted oxetane monomers contain large amounts of non-functional cyclic oligomers. Also, the desired surface properties of the prepolymer can be achieved with only one fluorinated substituent at the 3-position of the oxetane monomer, and the second fluorinated substituent does not contribute significantly to the surface properties.

In the following example, the polymerization was butane-1,4
-Performed with boron trifluoride etherate or boron trifluoride tetrahydrofuranate in diol.
The initiator was prepared from commercial grade boron trifluoride etherate that had been distilled prior to use. Butane
The 1,4-diol was distilled from calcium hydride and stored with 4Å molecular sieves prior to use.

The polymerization was carried out in a 100 ml glass flask covered with a jacket and equipped with a mechanical stirrer. NMR analysis of the product was carried out on a Bruker MSL-300 spectrometer at 300 MHZ in deuterated chloroform solution with proton and carbon shifts in ppm for tetramethylsilane and fluorine for fluorotrichloromethane. .
Infrared analysis on Nicor SX- on KBr
Performed by diffuse reflectance on a 5 spectrometer. Thermal analysis was performed on a Dupont DSC9100 analyzer.
Weight average molecular weight is 4 columns (100Å, 500Å,
10 ⁻³ Å and 10 ⁴ Å), determined using Waters gel permeation chromatography fitted with a differential refractive index detector and a Data Module 730. Example 1 3- (2,2,2-trifluoroethoxymethyl) -3
-Preparation of methyl oxetane 50% by weight in mineral oil (2.8 grams, 58.3 mmo
l) The sodium hydride dispersion was washed twice with hexane and suspended in 35 ml of dimethylformamide. Then 5.2 grams (52 mmol) of trifluoroethanol was added and the mixture was stirred for 45 minutes. A solution of 10.0 grams (39 mmol) of 3-hydroxymethyl-3-methyloxetane p-toluenesulfonate in 15 ml of dimethylformamide was added and the mixture was heated at 75-85 ° C for 20 hours, then aliquoted sample. ¹ H NMR analysis of the starting material showed that the starting sulfonic acid had been consumed.

The mixture was poured into 100 ml of ice water and extracted with 2 volumes of methylene chloride. The combined organic extracts were washed twice with water, twice with 2% by weight aqueous hydrochloric acid solution, brine, dried over magnesium sulphate and evaporated to give 6.5 g of 3- (2,2. 2, 2
-Trifluoroethoxymethyl) -3-methyloxetane is produced as an oil containing less than 1% by weight of dimethylformamide. The yield of this product was 90%.
The oil was distilled at 30 ° C. and 0.2 millimeters of mercury to make 4.3 grams of analytically pure product, which corresponds to a yield of 60%. The analysis of the product was as follows: IR (KBr) 2960-2880, 1360-.
1080, 990, 840 cm ^-1 ; ¹ H NMR1.3
3 (s, 2H), 3.86 (q, J = 8.8Hz, 2
H), 4.35 (d, J = 5.6 Hz, 2H), 4.5
1 (d, J = 5.6 Hz, 2H); ¹³ C NMR20.
72, 39.74, 68.38 (q, J = 40 Hz),
77.63, 79.41, 124 (q, J = 272H
z). The calculated values of elemental analysis for C ₇ H ₁₁ F ₃ O ₂ are
C = 45.65, H = 6.02, F = 30.95, and experimental values were C = 45.28, H = 5.83, F = 3.
It was 0.59. Example 2 Preparation of 3,3-bis- (2,2,2-trifluoroethoxymethyl) oxetane A 50 wt% dispersion of sodium hydride in 18.4 grams (0.383 mol) mineral oil was diluted with hexane It was washed once and suspended in 200 ml of dimethylformamide. Then 38.3 grams (0.383m
ol) was added dropwise over a period of 45 minutes, during which halogen gas was released. The mixture was stirred for 30 minutes and 30.0 grams (0.073 mol) 3,3-bis (hydroxymethyl) oxetane di-p- in 50 ml dimethylformamide.
A solution of toluene sulfonate was added. The mixture is 7
Heated to 5 ° C for 64 hours, at which time an aliquot of ¹ H
NMR analysis showed that the starting sulfonic acid had been consumed.

The mixture was poured into water and extracted with 2 volumes of methylene chloride. The combined organic extracts were washed with brine, 2% by weight aqueous hydrochloric acid, water, dried over magnesium sulfate and evaporated to give 17.5 grams of 3,3.
-Bis (2,2,2-trifluoroethoxymethyl) oxetane was produced as an oil containing less than 1% by weight of dimethylformamide. Oil is 42-48 ° C and 1
Purified by bulb-to-bulb distillation at 0.1 millimeters of mercury to make 15.6 grams of analytically pure ether, which corresponds to a yield of 79%. Analysis of the product was as follows: IR (KB
r) 2960-2880, 1360-1080, 99
5,840 cm ⁻¹ ; ¹ H NMR 3.87 (s, 4
H), 3.87 (q, J = 8.8Hz, 4H), 4.4
6 (s, 4H); ¹³ C NMR 43.69, 68.6.
2, (q, J = 35 Hz), 73.15, 75.59,
123.87 (q, J = 275 Hz); ¹⁹ F-74.6.
(S). Calculated values for elemental analysis for C ₉ H ₁₂ F ₆ O ₃ are C = 38.31, H = 4.29, and F = 40.
40, the experimental values are C = 38.30 and H = 4.3.
0 and F = 40.19. Example 3 Preparation of 3- (2,2,3,3,4,4,4-heptafluorobutoxymethyl) -3-methyloxetane 50% by weight dispersed sodium hydride in mineral oil 6.1
Gram (127 mmol) was washed twice with hexane,
Suspended in 60 milliliters of dimethylformamide. Then 24.0 grams (120 mmol) of 2,
2,3,3,4,4,4-heptafluorobutane-1-
All was added and the mixture was stirred for 45 minutes. 15
A solution of 25.0 grams (97.5 mmol) 3-hydroxymethyl p-toluenesulfonate in milliliter dimethylformamide was added and the mixture was 75-
Heated at 85 ° C for 30 hours, at which time an aliquot of ¹ H
NMR analysis showed that the starting sulfonic acid had been consumed.

The mixture was poured into 100 ml of ice water.
It was separated and extracted with 2 volumes of methylene chloride. Mixed
The organic extract was washed twice with water and a 2% by weight aqueous solution of hydrochloric acid was added.
Liquid, washed twice with brine and dried over magnesium sulfate
27.5 grams of 3- (2,2,2
3,3,4,4,4-heptafluorobutoxyethyl)
Produced -3-methyl oxetane as an oil. 33 for oil
Analytically distilled at ℃ and 0.2 millimeters of mercury
Make 12.2 grams of pure ether, which is 44%
Corresponding to the yield of The analysis of the experiment was as follows:
IR (KBr) 2960-2880, 1280-103
0,995,840 cm^-1;¹H NMR 1.31
(S, 3H), 3.67 (s 2H), 3.99 (t,
J = 13.3 Hz 2H) 4.34 (d.J = 5.7 Hz
2H) 4.50 (5.7 Hz, 2H); ¹³C NMR2
0.242 (q, J = 125 Hz) 39.627 (s)
67.778 (3 × 3.J = 145.1 Hz, J = 2)
6.1 Hz), 77.730 (tJ = 142 Hz),
79.110 (t, J = 150 Hz), 108.72
(3 × 4, J = 264 Hz. J = 36 Hz), 114.
7 (3 × 3, J = 256 Hz, J = 30 Hz), 11
7.58 (4x3, J = 286.9 Hz, J = 33.7
Hz);¹⁹F = 81.4, -120.6, -128.
1. C₉H₁₁F₇O₂The calculated value of elemental analysis for
= 38.04, H = 3.90, and F = 46.80.
The experimental values are C = 38.03, H = 3.65, and
F = 46.59.Example 4 3- (2,2,2-trifluoroethoxymethyl) -3
-Methyloxetane Polymerization 34.3 mg (0.
38 mmol) butane-1,4-diol and 10
9.7 mg (0.77 mmol) of boron trifluoride
A solution of elementary etherate was placed in a dry polymerization flask under nitrogen.
For 15 minutes at ambient temperature. Solution to 1.5 ℃
1.20 g in 1.3 g methylene chloride cooled
Rum (6.52 mmol) of 3- (2,2,2-trif
Luoroesoxymethyl) -3-methyloxetane solution
Was added. The resulting solution was 1-2 ° C at 5 o'clock
Stir for a while and then aliquot¹H NMR analysis
The starting oxetane was shown to be consumed. Solution is at ambient temperature
It was warmed up and quenched with water. The organic layer is brine, 2
Washed with a solution of hydrochloric acid in water (% by weight) and evaporated to
Rum's poly-3- (2,2,2-trifluoroethoxy)
Methyl) -3-methyl oxetane as an oil,
Corresponds to a yield of 88%. Polymer analysis is as follows
Was: DSC Tg-45 ° C., decomposition temperature 200 ° C.
Higher than; GPC (THF) molecular weight Mn 737
6, Mw7951, polydispersity 1.08, intrinsic viscosity 0.0
08;¹Molecular weight by H NMR 6300;¹H NM
R0.95 (s, 3H), 3.26 (m, 4H), 3.
52 (2,2H) 3.84 (q.2H);¹³C NMR
17.57, 42.09, 69.30 (q, J = 33H
z), 74.42, 75.90, 125.18 (q, J
= 280 Hz).Example 5 Poly-bis- [3- (2,2,2-trifluoroethoxy)
Preparation of dimethyl) oxetane] 33.9 mg in 3.8 g methylene chloride
(0.378 mmol) of butane-1,4-diol
And 106.3 milligrams (0.75 mmol)
Boron fluoride etherate solution in a dry polymerization flask
Stirred in nitrogen for 15 minutes at ambient temperature. The solution is
Cooled to 1.5 ° C., in 2.3 grams of methylene chloride
1.88 grams (6.67 mmol) of bis- [3-
2,2,2-trifluoroethoxy-methyl)] oxe
A solution of tongue was added. The resulting solution is 1-
Stir for 16 hours at 2 ° C, at which time aliquots of¹H
NMR analysis showed that the starting oxetane was consumed.

The solution was warmed to ambient temperature and quenched with water. The organic layer is washed with brine, 2% aqueous hydrochloric acid,
And evaporated to give 1.62 grams of polybis- [3- (2,
2,2-trifluoroethoxymethyl) -oxetane was prepared, which corresponds to a yield of 85%. The prepolymer was a waxy solid. Polymer analysis was as follows: DSC Tg 54.88 ° C, mp 80.96 ° C.
(26.35 J / g), decomposition temperature was higher than 210 ° C; GPC (THF) molecular weight Mn 5321, Mw 78
04, polydispersity 1.47, intrinsic viscosity 0.008; ¹ H
NMR 1.60 (m), 2.46 (s), 3.36
(S.4H), 3.58 (s, 4H), 3.79 (q,
4H); ¹³ C NMR 45.49, 68.25 (q.J.
= 33 Hz), 69.20.70.97.123.81.
(Q, J = 280 Hz). Example 6 Preparation of poly-3- (2,2,3,3,4,4,4-heptafluorobutoxymethyl) -3-methyloxetane 34.7 mg (0.38 mmol) in 3.4 g methylene chloride. ) Of butane 1,4-diol and 109.7 milligrams (0.77 mmol) of boron trifluoride etherate were stirred under nitrogen in a dry polymerization flask for 15 minutes at ambient temperature. The solution is 1.5
Cooled to 3.3 ° C and 2.0 g in 3.3 grams of methylene chloride.
0 grams (7.08 mmol) of 3- (2,2,3,
3,4,4,4-hepta-fluorobutoxymethyl)-
A solution of 3-methyloxetane was added. The resulting solution was stirred at 1.2 ° C. for 4 hours, at which time ¹ H NMR analysis of an aliquot showed that the starting oxetane had been consumed.

The solution is warmed to ambient temperature and quenched with water.
Was done. The organic layer is washed with brine, 2% aqueous hydrochloric acid,
And evaporated to give 1.65 grams of poly-3- (2,2,3,
3,4,4,4-heptafluorobutoxymethyl) -3
-Methyl oxetane made, which corresponds to a yield of 83%
To do. The prepolymer is an oil and has the following analytical results
GPC (THF) molecular weight Mn 4066, Mw 543
9, polydispersity of 1.34, intrinsic viscosity of 0.054. This oil
1.46 grams extracted with methanol and dried
Of a polymer, which corresponds to a yield of 72%, and
It has the following analytical results: DSC Tg-45 ° C; GPC
(THF) molecular weight Mn 4417, Mw 5658, polydisperse
Degree 1.28, intrinsic viscosity 0.056. Molecular weight¹1 H NMR
8718, ¹1 H NMR 0.93 (s, 3H), 3.2
0 (m, 4H), 3.48 (s, 2H), 3.92
(Q, J = 13.6 Hz, 2H);¹³C NMR16.
14, 40.57, 67.37 (t, J = Hz), 7
2.89, 74.76.Example 7 3- (2,2,3,3,4,4,5,5,6,6,7,
7,8,8,8-Pentadecafluorooctyl oxime
H) -3-methyloxetane A dispersion of 50% by weight sodium hydride in mineral oil (4.
0 g, 83 mmol) was washed with hexane and 20
Suspended in 0 ml of dimethylformamide
It was 30 in 50 ml dimethylformamide
Grams 2,2,3,3,4,4,5,5,6,6,6
7,7,8,8,8-pentadecafluorooctane-1
A solution of all (75 mmol) for a time period of 3 hours
And the resulting mixture was added over 1
Stirred at room temperature for a period of time. Next, 20 ml
9.3 grams (77 mmo in dimethylformamide
l) A solution of 3-chloromethyl-3-methyloxetane
Was added and the resulting mixture was at 75 ° C. for 16:00
Was heated for a while. The mixture is cooled to room temperature and 1 liter
Pour slowly into ice water and use 2 volumes of Freon 113
Was extracted. The combined organic extract is twice with water, 2 wt.
% Aqueous hydrochloric acid solution and washed once with brine, sulfuric acid
Dried over magnesium, filtered and evaporated
To produce 32 grams of crude product. The crude product is steamed under reduced pressure.
26.5 grams (73%) of analytically pure 3-
(2,2,3,3,4,4,5,5,6,6,7,7,
8,8,8-Pentadecafluorooctoxymethyl)-
3-methyloxetane, boiling point 68 to 70 ° C / 1.6m
Make m-Hg oil. The analysis of the experiment is as follows
Was:¹HNMR (CDCL₃/ Freon 113) δ4.
49 and 4.37 (AB, J = 5.5 Hz, 4H),
4.00 (triplet, J = 13.2 Hz, 2H), 3.7
0 (singlet, 2H), and 1.32 (singlet, 2
H);¹³C NMR δ21.02, 40.33, 68.
77 (triplet, J = 146.2 Hz), 78.60,
And 79.87;¹⁹F NMR δ-81.3 (3
F), -119.9 (2F), -122.6 (2F),
-123.3 (2F), -123.5 (2F), -12
3.9 (2F) and -126.8 (2F). C₁₃H₁₁
F₁₅O₂In contrast, the calculated value of elemental analysis is C, 32.2,
It was H, 2.3, F, 58.9, but the experimental value was C, 3
It was 2.2, H, 2.2, F, 58.3.Example 8 3- (3,3,4,4,5,5,6,6,7,7,8,
8,8-Tridecafluorooctyloxymethyl) -3
-Preparation of Methyloxetane In the same manner as above, at 85 ° C for 24 hours in mineral oil
3.9 grams of 50 wt% sodium hydride (81 m
mol) dispersion liquid, where 300 milliliters
12.0 g of 3-in tol dimethylformamide
Bromomethyl-3-methyloxetane (73 mmol)
Is 26.5 grams of 3,3,4,4,5,5,6,6
7,7,8,8,8-Tridecafluorooctane-1-
Reacted with all (72.7 mmol), 21.
5 grams (70% yield) of 3- (3,3,4,4,5,5
5,6,6,7,7,8,8,8-tridecafluoroo
Make cytyloxymethyl) -3-methyloxetane,
This is a colorless oil with a boiling point of 66-68 ° C / 2-2.
5 mm-Hg;¹1 H NMR (CDCL₃) Δ4.50
And 4.36 (AB, J = 5.5 Hz, 4H),
3.78 (t, J = 6.6 Hz, 2H), 3.53
(S, 2H), 2.42 (triplet-triplet, J = 6.6
And 18 Hz, 2H), and 1.31 (s, 3
H);¹³c NMR (CDCL₃) Δ 79.89, 6
3.31, 39.9, 31.64 (t), and 21.
1 (the signal by carbon with fluorine is a complex division of the signal
Not included due to patterns and overlaps);¹⁹F N
MR δ-81.4 (3F), -113.8 (2F),-
118.2 (2F), -122.3 (2F), -12
3.3 (2F), -124.1 (2F), and -12
6.7 (2F). C₁₃H₁₃F₁₃O₂Elemental analysis for
Calculated values are C, 34.8, H, 2.9, F, 55.1
However, the experimental values were C, 35.1, H, 3.0, F, 5
It was 4.7.Example 9 Purification of commercially available fluoroalcohol Zonyl BA-L is a product of DuPont Chemicals
available as a pilot plant product from pont Chemicals)
However, the distribution of fluoroalcohol whose distribution is limited
It is a Gomeric mixture. Zonyl BA-L is a yellow liquid
And is a mixture of the following oligomers by GLC:
: 3,3,4,4,5,5,6,6,7,7,8,
8,8-Tridecafluorooctane 1-ol (C8,
60%); 3,3,4,4,5,5,6,6,7,7,
8,8,9,9,10,10,10-Heptadeca fluo
Rodecan-1-ol (C10, 26%); 3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,11,11,12,12,12-heneico
Safurododecanol (C12, 6%); and various
Unidentified high boiling compounds (8%). Zonyl BA-L is the same
10% by volume of sodium thiosulfate aqueous solution, 10-fold
% Sodium bicarbonate solution (to remove HF
), Water, and brine, dried and filtered
And under reduced pressure (3 mm-Hg) at 50-100 ° C.
69% C8, 26% C1 distilled 83% yield
Make a mixture of 0 and 5% C12.Example 10 3,3,4,4,5,5,6,6,7,7,8,8,8
-Tridecafluorooctyloxymethyl-, 3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,10-Heptadecafluorodecyloxymethy
And 3, 3, 4, 4, 5, 5, 6, 6, 7,
7,8,8,9,9,10,10,11,11,12,
12,12-Heneicosafluorododecyloxymethyi
Preparation of a mixture of ru-3-methyloxetane In a manner similar to that described above, 69% C8, 26% C10 and 26% C10.
And a mixture of 5% C12 fluoroalcohol (51.
6 grams, 129 mmol) at 85 ° C. for 18 hours, 5
27 grams in 00 ml dimethylformamide
3-iodomethyl-3-methyloxetane (127
mmol) to give 60 g of crude product.
create. Crude product is 6 inch Vigerux
Fractionated through the column to produce the following fractions:
Laction # 1 (4.8g) is 3.5-2.9mm
-Hg collected between 25 ° C and 45 ° C, unreacted flux
It was a mixture of Luoro alcohols. Fraction # 2
(2.8 grams) is 45-71 ° C / 0.7-3.0mm
-Hg collected and unreacted fluoroalcohol and fluorine
It was a mixture with a modified oxetane monomer. Last fractal
(49 grams, 80%) is 70-85 ° C / 0.7
Boiling at -0.9 mm-Hg, 73% 3,3,4
4,5,5,6,6,7,7,8,8-Tridecafluo
Rooctyloxymethyl-3-methyloxetane (C8
-Oxetane), 24% 3,3,4,4,5,5,5
6,6,7,7,8,8,9,9,10,10,10-
Heptadecafluorodecyloxymethyl-3-methyl ester
Xetane (C10-oxetane), and 3% 3,
3,4,4,5,5,6,6,7,7,8,8,9,
9,10,10,11,11,12,12,12-hen
Icosafluorododecyl-oxymethyl-3-methyl ester
A mixture of xetane (C12-oxetane), comprising:
It is a colorless oil with a boiling point of 70-85 ° C / 0.7-
0.9 mm-Hg;¹1 H NMR (CDCL₃δ 4.
50 and 4.35 (AB, J = 5.9 Hz, 4H),
3.78 (t, J = 6.6 Hz, 2H), 3.53
(S, 2H), 2.42 (tt, J = 6.6 and 1
7.6 Hz, 2H), and 1.31 (s, 3H); ¹³
c NMR δ 21.3, 31.86 (t, T = 13
0.1 Hz), 40.2, 63.6, 76.8, and
80.2 (the signal for carbon with fluorine is
Not included due to coarse division patterns and overlaps);
¹⁹F NMR δ-81.5, -113.8, -12
2.3, -123.3, -124.1, 124.5,-
125.8, and -126.7.

Example 11 Preparation of 3,3-bis (2,2,3,3,4,4,4-heptafluorobutoxymethyl) oxetane In a manner similar to that described above, 155 grams of 3,3, -bis ( Chloromethyl) oxetane (1 mol) was added to 402 grams of 2 grams in 2 liters of dimethylformamide in the presence of 100 grams of 50 wt% sodium hydride dispersion in mineral oil (2.3 moles) at 85 ° C for 16 hours. ，
Reacted with 2,3,3,4,4-heptafluorobutan-1-ol (2.01 mol), 340 grams (70% yield) of 3,3-bis (2,2,3,3). , 4,
This gives 4,4-heptafluorobutoxymethyl) oxetane, which is a clear colorless liquid. According to Glc analysis, this substance has a purity of 99% or more and a boiling point of 70-
72 ° C./1.0-1.3 mm-Hg; ¹ H NMR (C
DCL ₃ ) δ 4.44 (S, 4H), 3.97 (t,
J = 13.2 Hz, 4H), 3.86 (s, 4H); ¹³
C NMR δ 43.9, 68.1 (t), 73.
5 and 75.6 (signal from carbon with fluorine is not included due to the complex splitting pattern and overlap of signals); ¹⁹ F NMR δ-81.6 (3F), -12
1.0 (2F) and -128.3 (2F). C ₁₃ H
The calculated values of elemental analysis for ₁₂ F ₁₄ O ₃ are C, 32.
4, H, 2.5, and the experimental values are C, 32.3,
H, 2.3.

Example 12 3,3, -bis (2,2,3,3,4,4,5,5,5)
Preparation of 6,6,7,7,8,8,8-pentadecafluorooctyloxymethyl) oxetane In the same manner as above, 15.5 grams of 3,3, -bis- (chloromethyl) oxetane (0 0.1 mol) is 8
1 in mineral oil (0.23 mol) for 32 hours at 5 ° C
84 grams of 2,2,3,3,4,4,5,5, in 300 milliliters of dimethylformamide in the presence of 0.0 grams of 50 wt% sodium hydride dispersion.
Reacted with 6,6,7,7,8,8,8-pentadecafluorooctan-1-ol (0.21 mol), 58 grams (66% yield) of 3,3, -bis (2 ，
Make 2,3,3,4,4,4-heptadecafluorooctyl-oxymethyl) oxetane, which is a clear colorless liquid. A sample for analysis was prepared by chromatographic separation of the products on a silica gel column using methylene chloride as the eluent. The boiling point of the liquid was 130-35 ° C / 1.0-1.2 mm-Hg.
The analysis is: ¹ H NMR (CDC1 ₃ ) δ 4.44
(S, 4H), 3.96 (t, J = 13.4Hz, 4
H), 3.88 (s, 4H); ¹³ c NMR δ 4.
4.2, 68.7 (t), 73.9, and 76.5
(The signal from carbon with fluorine is not included due to the complex splitting pattern and overlap of the signal); ¹⁹ F NM
R δ-81.5 (6F), -119.7 (4F),
-121.5 (4F), -122.6 (8F), -12
3.3 (4F), and -126.8 (4F). C ₂₁ H
Calculated values for elemental analysis for ₁₂ F ₃₀ O ₃ are C, 28.
6, H, 1.4, F, 64.6, but the experimental values were C, 28.2, H, 1.5.

[0043]Example 13 3- (2,2,3,3,4,4,5,5,6,6,7,
7,8,8,8-Pentadecafluorooctyl oxime
Cyl) -3-methyloxetane and 3- (2,2,2-
Trifluoroethoxymethyl) -3-methyloxetane
Copolymerization with 1 liter 3-neck round bottom mechanical stirrer, nitrogen in and out
Tube, reflux concentrator, thermometer and fixed dropping funnel attached
Was given. This equipment is dried with a heat gun and under nitrogen.
Cooled to room temperature with 0.914 grams of trimethylol
Propane (6.52 mmol), 3.1 grams of three
Boron fluoride tetrahydrofuranate (22mmo
l), 160 ml of 1,1,2-trichloroto
Lifluoroethane and 30 ml of anhydrous methyl chloride
Filled with a mixture of Tiren. Mix for 30 minutes at room temperature
Stir and cool to 10 ° C, then 40 millilitres
1 in 1,1,2-trichlorotrifluoroethane
06 grams of 3- (2,2,2-trifluoroethoxy
Methyl) -3-methyloxetane (576 mmol)
And 94 grams of 3- (2,2,3,3,4,4,5,
5,6,6,7,7,8,8,8-pentadecafluoro
Octyloxymethy) -3-methyloxetane (19
(5.2 mmol) solution was treated drop by drop. Monomer
A weak exotherm was observed with the addition of. Add reaction temperature
The temperature is maintained at 18 ° C throughout the reaction, and the reaction progress is NM.
Monitored by R analysis. Mix for 2 hours at 18 ° C
, Then stirred at 25 ° C for 4 hours, at which time
NMR analysis of an aliquot showed that 98% of the oxetane monomer
It has been consumed. 50 ml of reaction mixture
Methylene chloride and 50 milliliters of 1,1,2-to
Diluted with Lichlorotrifluoroethane, 50 milliliters
Quenched with tol water. The organic layers are separated and equal
Washed with 2 volumes of water and at room temperature drop by drop 10 times
Was added to methanol. The precipitated oil is separated and
Methylene chloride and 1,1,2-trichlorotrifluoroe
Redissolve in a 50:50 mixture with tongue and
Transferred to a lilter round bottom flask. The solvent is evaporated under reduced pressure
The resulting oil was 1 at 85 ° C / 2mm-Hg.
170 grams of clear colorless, dried for 6 hours
Of a viscous oil, which corresponds to a yield of 85%. this
NMR analysis of the material shows that it is 74:
It was shown to be a random copolymer at a ratio of 24. Poly
Meter analysis: DSC, T_g= -40 ° C; GPC (TH
F, polystyrene standard) number average molecular weight is 6,1
78, weight average molecular weight 7,286, polydispersity 1.1
8;¹Number average molecular weight by H NMR is 7,040;
Performance is 3; Intrinsic viscosity is 0.065;¹1 H NMR (CD
CL₃) Δ 0.94 (s, -CH ₃) 3.23
(M, skeleton-CH ₂'S), 3.47 (s, -C)
H ₂), 3.75 (q, J = 8.6 Hz, -C)H ₂CF
₃) And 3.85 (t, J = 31.5 Hz, -C)H ₂
C₃F₇);¹1 H NMR (CDC1₃/ Trifluoro
Acetic anhydride) δ 1.00 (s, -CH ₃) 3.37
(M, skeleton-CH ₂'S), 3.49 (s, -CH
₂O), 3.78 (q, J = 8.6 Hz, -C)H ₂CF
₃), 3.96 (t, J = 13.5 Hz, -C)H ₂C₃
F₇), And 4.30 (s, CH ₂OCOCF₃);
¹³c NMR (CDC13) δ 17.1, 41.
2, 41.3, 68.5 (t), 68.9 (q), 7
3.7, 75.3 and 75.5.

In the same manner as described above, 50:50, 33:
Random copolymers of the above monomers in ratios of 67, 25:75 and 10:90 were also prepared. These copolymers were clear, colorless oils soluble in a solvent mixture of methylene chloride and 1,1,2-trichlorotrifluoroethane.

Example 14 3- (2,2,2-trifluoroethoxymethyl) -3
-Methyl oxetane and 3- (2,2,3,3,4
Copolymerization with 4,4-heptafluorobutoxymethyl) -3-methyloxetane In a manner similar to that described in Example 13, 3 ml in 50 ml of 1,1,2-trichlorotri-fluoroethane.
5 grams of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane (190 mmol) and 1
A solution of 83 grams of 3- (2,2,3,3,4,4,4-heptafluorobutoxymethyl) -3-methyloxetane (644 mmol) was added to 0.390 grams of 1,4-butanediol ( 4.33 mmol), 1.5
5 grams of boron trifluoride tetrahydrofuranate (1
1.1 mmol), and 100 ml of methylene chloride to the mixture at 18 ° C. The mixture is 18 ℃
After stirring at room temperature for 3 hours, quenching with water, and precipitating into methanol and drying at 85 ° C./2 mm-Hg for 16 hours, 186 grams of a clear colorless, corresponding to a yield of 85%. Make oil. NMR analysis showed that this material was a 22:78 random copolymer of the above two monomers.

The polymer analysis was as follows: DS
C, T _g = -42 ° C; GPC (THF, polystyrene standard) number average molecular weight 15,660; weight average molecular weight 30,640; polydispersity 1.96; ¹ H NM
The number average molecular weight by R is 18,400; the functionality is 2; the intrinsic viscosity is 0.071; ¹ H NMR (CDC1 ₃ / Freon 113) δ 0.91 (s, C H ₃ ),
3.22 (m, skeletal _{-C H 2 'S), 3.44} (s, -
C H ₂ O), 3.79 (q, J = 8.8 Hz, -C H ₂
CF ₃ ) and 3.86 (t, J = 13.5 Hz, -C
H ₂ C ₃ F ₇ ); ¹ H NMR CDC ¹ ₃ / Freon 113 / trifluoroacetic anhydride) δ 0.95 (s,
_{-C H 3), 3.23 (m} , skeletal -C H ₂ 'S),
_{3.46 (s, -C H 2 O} ), 3.77 (q, J = 8.
6 Hz, C H ₂ CF ₃ ) 3.87 (t, J = 13.5
_{Hz, -C H 2 C 3 F} 7), and 4.31 (s, C H
^{_{2 OCOCF 3); 13 C NMR}} (CDC1 3 / Freon 113) δ 17.3,41.6,41.8,6
8.6 (t), 69.3 (q), 74.2, 75.6,
And 75.9 (not including signal from carbon with fluorine).

In a similar manner, 50:50 and 75: 2.
A random copolymer of the above monomers in a ratio of 5 was also prepared. The copolymer was a clear colorless oil soluble in tetrahydrofuran, methylene chloride and 1,1,2-trichlorotrifluoroethane (Freon 113).

Example 15 3- (3,3,4,4,5,5,6,6,7,7,8,
8,8-Tridecafluorooctyloxymethyl) -3
Preparation of Methyloxetane In a manner similar to that described in Example VII, 10 grams of 3- (3,3,4,4,5,5,6,6,7,7,8,
8,8-Tridecafluorooctyloxymethyl) -3
A solution of methyl oxetane (22.3 mmol) in 3 ml of Freon 113 was added to 1 part in methylene chloride.
09 mg of boron trifluoride tetrahydrofuranate (0.78 mmol) and 35 mg of 1,4
10 to a mixture of butanediol (0.39 mmol)
It was added drop by drop at ° C. The mixture was stirred at room temperature for 24 hours, quenched with water and precipitated in methanol and dried at 80 ° C./2 mmHg for 16 hours, then
8.3 grams of poly 3- (3,3,4,4,5,5,5
Make 6,6,7,7,8,8,8-tridecafluorooctyl-oxymethyl) -3-methyloxetane, which is a clear colorless oil. Polymer analysis was as follows: Intrinsic viscosity (THF / 30 ° C.) 0.067d
L / g; GPC: M _n = 5,340, M _w = 6,62
0, polydispersity = 1.24; DSC, Tg = -38 ° C;
¹ H NMR (CDCl ₃ / Freon 113) δ 3.
67 (t, 5.9 Hz, 2H), 3.31 (s, 2)
H), 3.21 (m, 4H), 2.35 (m, 2H),
And 0.93 (s, 3H); ¹ H NMR (CDCl
₃ / Freon 113) δ 0.95 (s, 3H), 2.
37 (brt, J = 18.3 Hz, 2H), 3.25
(M, 4H), 3.35 (s, 2H), 3.71 (t,
6.0 Hz, 2H), and 4.30 (AB, -C H ₂
OCOCF ₃ ); number average molecular weight based on ¹ H NMR is 4,756; ¹³ C NMR (CDCl ₃ / Freon 11
3) δ17.35, 31.75 (t), 41.5, 6
3.4, 74.1 and 74.3.

Example 16 3,3,4,4,5,5,6,6,7,7,8,8,8
-Tridecafluorooctyloxymethyl-, 3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,10-heptadecafluorodecyloxymethyl-, and 3,3,4,4,5,5,6,6,7,
7,8,8,9,9,10,10,11,11,12,
Copolymerization of a mixture of 12,12-henicosafluorododecyloxymethyl-3-methyloxetane In the same manner as described in Example 13, 30 grams of C8- (73%) in 10 milliliters of Freon 113,
A solution of C10- (24%), and C12 (3%) oxetane monomer (62 mmol) was added to 300 milligrams of boron trifluoride tetrahydrofuranate (2.14 mmol) and 95 in 30 milliliters of methylene chloride.
Milligram of 1,4-butanediol (1.05mmo
It was added dropwise to the mixture of l) at 10 ° C. The mixture was stirred at room temperature for 24 hours, quenched with water, and precipitated in methanol at 16 ° C./2 mm-Hg.
After drying for a period of time, 24 grams of the title copolymer was produced, corresponding to a yield of 80%. The copolymer was a colorless viscous oil. The copolymer was analyzed as follows: Intrinsic viscosity = 0.075 dL / g; GPC: M _n = 6,63
9, M _w = 9,368, polydispersity = 1.41; ¹ H
NMR (CDC1 ₃ / Freon 113) δ 0.95
(S, 3H), 2.37 (br t, J = 18.3H)
z, 2H), 3.25 (m, 4H), 3.35 (s, 2)
H), 3.71 (t, 6.0 Hz, 2H), and 4.
_{30 (AB, -C H 2 OCOCF} 3); 1 H number average molecular weight based on NMR is 5,021; ¹³ C NMR (CD
CL ₃ / Freon 113) δ 17.35, 31.75
(T), 41.1, 41.5, 63.4, 74.1 and 74.3.

Example 17 Polymerization of 3,3-bis (2,2,3,3,4,4,4-heptafluorobutoxymethyl) oxetane In the same manner as described in Example 13, 75 ml of Freon 113 was used. A solution of 252 grams of 3,3, -bis (2,2,3,3,4,4,4-heptafluorobutoxymethyl) oxetane (523 mmol) in 1
1.05 g of boron trifluoride tetrahydrofuranate (7.5 mmo in 78 ml of methylene chloride)
1) and 0.265 grams of 1,4-butanediol (2.93 mmol) was added at 10 ° C.
The mixture was stirred at room temperature for 48 hours, at which time NMR analysis of an aliquot showed 96% conversion. The reaction was quenched with water and the polymer precipitated into methanol at 80 ° C.
After drying at ½ mm-Hg for 16 hours, 211 grams of poly 3,3-bis (2,2,3,3,4,4,4-
Heptafluorobutoxymethyl) oxetane was made, which was a colorless oil in 84% yield. GPC analysis of this oil showed that it was a mixture of 68% linear material and 32% cyclic material. The cyclic product was isolated and identified as the cyclic tetramer, which is a white waxy solid with a melting point of 80 ° C .; ¹ HNMR δ 3.87.
(T, J = 13.5 Hz, 4H), 3.54 (s, 4
H), and 3.32 (S, 4H) (no end groups were observed with the addition of trifluoroacetic anhydride); ¹³
C NMR δ 71.2, 68.6, 68.4 (t), and 46.2 (signal not due to carbon with fluorine included).

The above oil is the substance methylene chloride / Freon 1
It was first dissolved in 13 (75:25 mixture), the polymer was precipitated in a 10-fold excess of methanol, the precipitated oil was stirred with tetrahydrofuran for 2 days at room temperature and finally 85
It was further purified by separating the inactive fractions and drying for 16 hours at 2 mm-Hg at 0 ° C. This produced 128 grams of a clear viscous oil, which represented 51% of the overall yield. The oil by GPC analysis is 9
It was determined to be a mixture of 1% linear polymer and 9% cyclic tetramer. Polymer analysis was as follows: DSC, Tg = -43 [deg.] C; gpc: _Mn = 5,52.
6, M _w = 7,336, PD = 1.32; ¹ H NM
R (CDCl ₃ / Freon 113 / TFAA) δ
3.39 (s, 4H), 3.59 (s, 4H), 3.8
7 (t, J = 13.5 Hz, 4H) and 4.40
(S, -CH ₂ OCOCF ₃ ); number average molecular weight based on ¹ H NMR = 5,200; ¹³ C NMR (CDCl ₃
/ Freon 113) δ46.4, 68.5 (t), 7
0.1 and 72.1 (not including signal from carbon with fluorine).

The present invention has been described with reference to the presently preferred embodiments illustrated. The present invention is not intended to be limited by the present disclosure of the presently preferred embodiments. Instead, it is intended to be defined by the compounds, products and equivalents thereof, and method steps and equivalents set forth in the claims below.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Gerald E. Mansart, United States, 95630 El Dorado Hills, Claydon Place, 1386 (72) Inventor Thomas The Archibald United States, 95825 California , Sacramento, American River Drive, Number A, 2356

Claims (43)

[Claims] 1. A hydroxy-terminated prepolymer having the following structure: Where n is 1 to 5, m is 1 or 2, R is hydrogen or alkyl having 1 to 4 carbons, R ₁ is alkylene having 2 to about 5 carbons or iso Alkylene, R _f is a straight or branched chain perfluoroalkyl having 1 to 20 carbons, isoalkyl, haloalkyl, or haloisoalkyl, or oxaperfluoropolyether having 4 to about 60 carbons, and x
Is a hydroxy-terminated prepolymer of from 2 to about 250. 2. A hydroxy-terminated prepolymer according to claim 1, wherein m is 2 and n is 1. 3. R _f is trifluoromethyl,
A hydroxy-terminated prepolymer according to claim 2. 4. The hydroxy-terminated prepolymer of claim 2, wherein R _f is heptafluoropropyl. 5. The hydroxy-terminated prepolymer of claim 2, wherein R _f is pentadecafluoroheptyl. 6. The hydroxy-terminated prepolymer of claim 1, wherein m is 1 and n is 1. 7. R _f is trifluoromethyl,
A hydroxy-terminated prepolymer according to claim 6. 8. The hydroxymethyl-terminated prepolymer of claim 6, wherein R _f is heptafluoropropyl. 9. The hydroxy-terminated prepolymer of claim 6, wherein R _f is pentadecafluoroheptyl. 10. The hydroxy-terminated prepolymer of claim 1, wherein m is 1 and n is 2. 11. The hydroxy-terminated prepolymer of claim 10, wherein R _f is tridecafluorohexyl. 12. The hydroxy-terminated prepolymer of claim 10, wherein R _f is heptadecafluorooctyl. 13. The hydroxy-terminated prepolymer of claim 10, wherein R _f is henicosafluorodecyl. 14. A hydroxy-terminated prepolymer having a molecular weight of 1,000 to about 30,000 and one to two perfluoroalkoxides of the formula CH ₂ O (CH ₂ ) _n R _f Having a polymer skeleton formed by opening an oxetane ring of an oxetane monomer that is substituted at the 3-carbon position with a group, where n is 1 or 2 and R _f is a straight chain having 1 to 20 carbons. A hydroxy-terminated prepolymer that is a chain or branched perfluoroalkyl, isoalkyl, haloalkyl, or haloisoalkyl, or an oxaperfluoropolyether having from 4 to about 60 carbons. 15. The hydroxy-terminated prepolymer of claim 14, wherein n is 2. 16. The hydroxy-terminated prepolymer of claim 15, wherein R _f is tridecafluorohexyl. 17. The hydroxy-terminated prepolymer of claim 15, wherein R _f is heptadecafluorooctyl. 18. The hydroxy-terminated prepolymer of claim 17, wherein the polymer backbone is a copolymer of two or three oxetane monomers having different R _f groups. 19. The hydroxy-terminated prepolymer of claim 15, wherein R _f is henicosafluorodecyl. 20. The hydroxy-terminated prepolymer of claim 19, wherein the polymer backbone is a copolymer of two or three oxetane monomers having different R _f groups. 21. The hydroxy-terminated prepolymer of claim 14, wherein n is 1. 22. The hydroxy-terminated prepolymer of claim 21, wherein R _f is trifluoromethyl. 23. The hydroxy-terminated prepolymer of claim 22, wherein the polymer backbone is a copolymer of two or three oxetane monomers having different R _f groups. 24. The hydroxy-terminated prepolymer of claim 22, wherein the oxetane monomer has two of the alkoxy groups on the 3-position carbon. 25. The hydroxy-terminated prepolymer of claim 21, wherein R _f is heptafluoropropyl. 26. The hydroxy-terminated prepolymer of claim 25, wherein the polymer backbone is a copolymer of 2 or 3 oxetane monomers having different R _f groups. 27. The hydroxy-terminated prepolymer of claim 25, wherein the oxetane monomer has two of the alkoxy groups on the carbon at the 3-position. 28. The hydroxy-terminated prepolymer of claim 21, wherein R _f is pentadecafluoroheptyl. 29. The hydroxy-terminated prepolymer of claim 25, wherein the polymer backbone is a copolymer of two or three oxetane monomers having different R _f groups. 30. A perfluoroalkoxy oxetane monomer having the formula: Where n is 1 to 5, m is 1 or 2, R is hydrogen or alkyl having 1 to 4 carbons, and R _f is a straight chain having 1 to 20 carbons or A perfluoroalkoxy oxetane monomer that is a branched chain perfluoroalkyl, isoalkyl, haloalkyl, or haloisoalkyl, or an oxaperfluoropolyether having from 4 to about 60 carbons. 31. R _f is perfluoroalkyl,
The perfluoroalkoxy oxetane monomer according to claim 30. 32. The perfluoroalkoxy oxetane monomer according to claim 31, wherein m is 2 and n is 1. 33. The perfluoroalkoxy oxetane monomer of claim 31, wherein R _f is trifluoromethyl. 34. The perfluoroalkoxy oxetane monomer according to claim 31, wherein R _f is heptafluoropropyl. 35. The perfluoroalkoxy oxetane monomer of claim 31, wherein R _f is pentadecafluoroheptyl. 36. The perfluoroalkoxy oxetane monomer according to claim 31, wherein m is 1 and n is 1. 37. The perfluoroalkoxy oxetane monomer of claim 35, wherein R _f is trifluoromethyl. 38. The perfluoroalkoxy oxetane monomer of claim 35, wherein R _f is heptafluoropropyl. 39. The perfluoroalkoxy oxetane monomer of claim 35, wherein R _f is pentadecafluoroheptyl. 40. The perfluoroalkoxy oxetane monomer according to claim 31, wherein m is 1 and n is 2. 41. The perfluoroalkoxy oxetane monomer according to claim 39, wherein R _f is tridecafluorohexyl. 42. The perfluoroalkoxy oxetane monomer according to claim 39, wherein R _f is heptadecafluorooctyl. 43. The perfluoroalkoxy oxetane monomer according to claim 39, wherein R _f is henicosafluorodecyl.