WO2008141323A1

WO2008141323A1 - Polyoxetane compositions and methods for their production

Info

Publication number: WO2008141323A1
Application number: PCT/US2008/063564
Authority: WO
Inventors: Kenneth J. Wynne; Biao Duan; Ying Zheng
Original assignee: Virginia Commonwealth University
Priority date: 2007-05-14
Filing date: 2008-05-14
Publication date: 2008-11-20

Abstract

Polyoxetanes are made by first combining monomer with butanediol or other initiator, followed by a subsequent adding step in which BF3 or other catalyst is added. There are provided inventive polyoxetanes not previously produced by conventional methods. For example, polyoxetane polyurethanes with favorable surface nano-thicknesses are made. Polyoxetanes with advantageous water-resistance or oil-resistance also are made.

Description

POLYOXETANE COMPOSITIONS AND METHODS FORTHEIRPRODUCTION

Description

Field of the Invention

The present invention generally relates to polymers (especially polyoxetanes) and their production.

BACKGROUND OF THE INVENTION

Various polymers have been made conventionally and have important uses. Certain methods for carrying out polymerization including but not limited to methods for producing polyoxetanes and certain polyoxetanes and other polymers previously have been known.

Herein the following phrases and terms have their ordinary meanings:

"Oxetane" means trimethylene oxide.

"Polyoxetane" means a polymer with a 1,3-propylene oxide main chain, that is, -C-C-C- O-. The term polyoxetane is a general term that encompasses "homo-polyoxetanes" that have one repeating unit derived from one monomer, and "co-polyoxetanes".

"Poly-co-oxetane" or poly(co-oxetane) or co-polyoxetane are synonymous terms that mean a polyoxetane that has more than one repeating unit.

"Diol" has the same meaning as glycol or dihydric alcohol, that is, a compound containing two hydroxyl groups.

"Telechelic" means an oligomer or polymer with functional groups at either end of the main chain.

Although many advantageous polymer materials have been provided previously, it would be desirable if there could be provided higher molecular weight polyoxetane and co-polyoxetane telechelics, for a number of reasons. For example, high molecular weight would be required for improved mechanical properties. Actually being able to make a polymer material so as to have a desired property or improved property is, of course, much more difficult in the chemical arts than wanting or hoping for such an improved property.

SUMMARY OF THE INVENTION

The invention provides a method of making polyoxetanes and poly-co-oxetanes that facilitates making high molecular weight telechelics (such as, e.g., telechelics that are polyoxetanes and have a molecular weight exceeding 8 kDa; telechelics that are poly-co-oxetanes and have a molecular weight exceeding 8 kDa; etc.).

The present inventors sought higher molecular weight polyoxetane and co-polyoxetane telechelics (which through this invention are now provided) for several reasons. For semicrystalline polyoxetanes, e.g., P[Bis-3FOx] (see Fig. 3C), high molecular weight is required for improved mechanical properties. For non-crystalline telechelics P[A] and co-telechelics P[AB] increased molecular weight provides increased "nano-thickness" when used as soft blocks in surface modifiers. Non-crystalline polyoxetanes with increased molecular weights also provide candidates for advanced lubricants and compatibilizers.

The present inventors discovered that the separation of what were previously considered to be co-catalysts provided advantageous results, e.g., that adding a diol (which previously would have been considered a co-catalyst or initiator) to the monomer (or comonomers) before adding this combination to a solution OfBF₃ etherate, resulted in preparation of higher molecular weight polyoxetanes. By using the inventive production methods in which an initiator compound (such as a diol initiator compound, etc.) is first added to the monomer (or the co-monomers) before a subsequent addition of this combination to the Lewis acid catalyst (such as BF₃, etc., a Lewis acid catalyst in solvent; etc.), various polyoxetanes can be produced such as, e.g., high- molecular-weight polyoxetanes. The advantages of higher molecular weight depend on the nature of the A and B oxetane side chains and the purpose for which the resultant polyoxetanes and co-polyoxetanes are prepared.

In one preferred embodiment, the invention provides a method of producing a polyoxetane composition, comprising the steps of: combining a diol initiator compound (such as, e.g., an alkyl or isoalkyl diol, such as, e.g., ethylene glycol; butane- 1,4-diol; propylene glycol; isobutene-l,3-diol; etc., with butane- 1,4-diol being preferred) with at least a first monomer (such as, e.g., a 3-FOx monomer; a 5-FOx monomer; a 7-FOx monomer; a 9-FOx monomer; an ME_nOx monomer where n = O, 1, 2, 3 or 7; a BBOx monomer; etc.) to form a combination (such as, e.g., a combination in solvent); adding the combination of step a) to a Lewis acid catalyst (such as, e.g., boron trifluoride, boron trifluoride etherate, etc.), such as, e.g., inventive methods of producing a polyoxetane composition wherein the combining step a) is performed at ambient temperature, at atmospheric pressure, for a period of time in a range of about 1 minute to 10 minutes; inventive methods of producing a polyoxetane composition wherein the adding step b) is performed with the combination of monomer and initiator being a solution at ambient temperature in a range of about 10 to 30 degrees C, while the catalyst is at a temperature in a range of about -5 to 5 degrees C, at ambient pressure, for a period of time in a range of about 2 to 12 hours; inventive methods of producing a polyoxetane composition in which the at least a first monomer is a solution (such as, e.g., a solution comprising one selected from the group consisting of: a 3-FOx monomer; a 5-FOx monomer; a 7-FOx monomer; a 9-FOx monomer; an ME_nOx monomer where n = O, 1, 2, 3 or 7; and a BBOx monomer; a solution comprising the first monomer and further comprising a second monomer; wherein the second monomer is different from the first monomer; and wherein the second monomer is selected from the group consisting of: a 3-FOx monomer; a 5-FOx monomer; a 7-FOx monomer; a 9-FOx monomer; an ME_nOx monomer where n = O, 1, 2, 3 or 7; and a BBOx monomer; etc.); inventive methods of producing a polyoxetane composition including performing the adding step b) until a polyoxetane composition (such as, e.g., (1) a random A-B copolymer comprising at least two different monomers A and B represented P[AB] where P means the ring opened structure of monomer A and monomer B, respectively; (2) a semicrystalline material comprising an oxetane monomer with two identical side chains represented by P[BiS-A] where P and A have the same meanings as above; (3) a homo-polyoxetane composition represented by P[A] having a 1,3-propylene oxide main chain at which are two different groups at the three position, wherein a first group on the 2- propylene oxide position is a methyl or ethyl group and wherein a second group on the 2- propylene oxide position is a side chain selected from the group consisting of 3FOx, 4FOx, 5FOx, 7FOx, MOx, MeIOx, Me20x, Me30x and Me70x, wherein P and A have the same meanings as above; (4) a block soft block copolymer that is non-crystalline and is represented by P[A][B] or P[A]_m[B]_n, wherein P, A and B have the same meanings as above, and m and n represent molecular weights of the A and B blocks respectively; etc.) is formed; inventive methods of producing a polyoxetane composition consisting essentially of the combining step a) and the adding step b); inventive methods of producing a polyoxetane composition including performing the adding step b) until a co-polyoxetane composition is formed, said co-polyoxetane having an alkylenebromide side chain (such as, e.g., an alkylenebromide side chain that is BBOx) that is reactive with an amine to produce a P[AB] co-polyoxetane having a quaternized side chain (such as, e.g., a formed P[AB] co-polyoxetane having a quatnerized side chain that is processable into a polyurethane comprising a soft block having charge concentrated in the soft block; etc.); inventive methods for producing a polyoxetane composition wherein the formed polyoxetane composition has a surface soft block nano-thickness in a range of 2-4 nm; inventive methods for producing a polyoxetane composition wherein the formed polyoxetane composition has a molecular weight exceeding 8 kDa; inventive methods for producing a polyoxetane composition wherein the formed polyoxetane composition is a semi-crystalline material having a molecular weight exceeding 6kDa; inventive methods for producing a polyoxetane composition wherein the formed polyoxetane composition on a surface thereof has oil-resistance represented by a hexadecane contact angle of greater than 70 degrees and/or water resistance represented by a water contact angle exceeding 104 degrees; inventive methods of producing a polyoxetane composition wherein the formed polyoxetane composition has a water solubility property of at least 5 g/L; inventive methods for producing a polyoxetane composition wherein the formed polyoxetane composition comprises a high-molecular-weight chain with Mn exceeding 8 kDa; inventive methods for producing a polyoxetane composition wherein the formed polyoxetane composition is a coating; and other inventive methods.

In another preferred embodiment, the invention provides a polyoxetane composition, wherein the polyoxetane composition is selected from the group consisting of: (1) a random A-B copolymer comprising at least two different monomers A and B represented P[AB] where P means the ring opened structure of monomer A and monomer B, respectively; (2) a semicrystalline material comprising an oxetane monomer with two identical side chains represented by P[BiS-A] where P and A have the same meanings as above; (3) a homo- polyoxetane composition represented by P[A] having a 2-propylene oxide position at which are two groups, wherein a first group on the 2-propylene oxide position is a methyl or ethyl group and wherein a second group on the 2-propylene oxide position is a side chain selected from the group consisting of 3FOx, 4FOx, 5FOx, 7FOx, MOx, MeIOx, Me20x, Me30x and Me70x, wherein P and A have the same meanings as above; and (4) a block soft block copolymer that is non-crystalline and is represented by P[A][B] or P[A]_m[B]_n, wherein P, A and B have the same meanings as above, and m and n represent molecular weights of the A and B blocks respectively, such as, e.g., an inventive co-polyoxetane composition having an alkylenebromide side chain (such as, e.g., BBOx) that is reactive with an amine to produce a P[AB] co-polyoxetane having a quaternized side chain (such as, e.g., a P[AB] co-polyoxetane having a quaternized side chain that is processable into a polyurethane comprising a soft block having charge concentrated in the soft block); an inventive polyoxetane composition that has a surface soft block nano-thickness in a range of 2-4 nm; an inventive polyoxetane composition that has a molecular weight exceeding 8 kDa; an inventive polyoxetane composition that is a semi-crystalline material having a molecular weight exceeding 6kDa; an inventive polyoxetane composition that on a surface thereof has oil-resistance represented by a hexadecane contact angle of greater than 70 degrees and/or water resistance represented by a water contact angle exceeding 104 degrees; an inventive polyoxetane composition that has a water solubility property of at least 5 mg/L; an inventive polyoxetane composition comprising a high-molecular- weight chain exceeding a value for Mn of 6 kDa; an inventive polyoxetane composition that is a coating; P[(3FOx)(BBOx)-0.75:0.25], P[(ME2Ox)(BBOx)-0.75:0.25], P[(3FOx)(C12)-0.75:0.25]; P[(ME2Ox)(C12)-0.75:0.25], P[3F0x], P[Bis-3F0x], P[3FOx-BBOx-0.875:0.125], P[3FOx-C12-0.875:0.125], HMDI- BD(30)-P[3FOx-C12-0.88:0.12], P[ME2Ox-BBOx-0.75:0.25], P[3FOx-BBOx-0.70:30]; P[ME20x]; and other inventive compositions. The representation P[(3FOx)(BBOx)-0.75:0.25] is identical to P[3FOx:BBOx-0.75:0.25] and to P[3FOx:BBOx]-0.75:0.25. The representation MEnOx is identical to the representation ME_nOx. In a further preferred embodiment, the invention provides a polyoxetane polyurethane composition, comprising a surface soft block having a nano-thickness in a range of 2-4 nm.

The invention in another preferred embodiment provides a polyoxetane composition having a surface which is oil-resistant and/or water-resistant, the surface having oil-resistance represented by a hexadecane contact angle of greater than 70 degrees and/or water resistance represented by a water contact angle exceeding 104 degrees.

BRIEF DESCRIPTION OF THE DRAWINGS -

The foregoing and other objects, aspects and advantages will be better understood from the following detailed description of a preferred embodiment of the invention with reference to the drawings, in which:

Figs. 1 to II show structures for A and B monomers that may be used in the inventive polymerization methods to make P[A] homo-polyoxetanes, P[AB] random co-polyoxetanes, and P[Bis-A] semi-crystalline polyoxetanes.

Figs. 2, 2A depict respective reactions which are ring opening polymerizations leading to inventive homo-polyoxetanes (see Fig. 2) and inventive co-polyoxetanes (see Fig. 2A).

Figs. 3 to 3H depict ring-opened structures of monomers as found in inventive P[A], P[AB], and P[Bis-A] polyoxetanes.

Fig. 4 is a schematic showing the surface concentration of fluorous A groups that are pendant to the polyoxetane chain 4. P[A] in Fig. 4 is made according to Fig. 2, with R¹ = CH₃-; R₂ = A. Fig. 4A is a cross-sectional slice of a coating employing a P[A] polyoxetane polyurethane as a surface modifier and shows the concentration of the P[A] polyoxetane polyurethane, 42, at the surface of a bulk polyurethane 4OC; Figure 4 shows the nano-thickness 41 of the surface concentrated polyoxetane soft blocks 4. Fig. 4B is a general chemical formula corresponding to surface concentrated soft block 4, the compositions of which are shown in Figure 3, 3A, and 3C.

Fig. 5 is a schematic showing the surface concentration of fluorous or other surface concentrating A groups that are pendant to the polyoxetane chain 4 and act to concentrate B groups that otherwise might not be surface concentrated. P[AB] in Fig. 5 is made according to Fig. 2A, R¹ = R³ = CH₃-; R² = A; R⁴ = B. Fig. 5 A is a cross-sectional slice of a coating employing a P[AB] polyoxetane polyurethane as a surface modifier and shows the concentration of the P[AB] polyoxetane polyurethane, 52, at the surface of a bulk polyurethane 4OC; Fig. 5 shows the nano-thickness 51 of the surface concentrated polyoxetane soft blocks 4. Fig. 5B is a general chemical formula corresponding to surface concentrated soft block 4, compositions of which are shown in Figure 3E, 3G, and 3H. Fig. 6 is a graph of number average molecular weight of P[3FOx] as a function of mole percent BF₃ catalyst, relative to 3FOx monomer. DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT OF THE INVENTION

The invention provides a method of producing a polyoxetane composition, comprising the steps of: combining a diol initiator compound with at least a first monomer to form a combination; and adding the combination of step a) to a Lewis acid catalyst (such as, e.g., boron trifhioride or boron trifluoride etherate catalyst).

As examples of the diol initiator compound are, e.g., an alkyl or isoalkyl diols, such as, e.g., ethylene glycol; butane- 1,4-diol; propylene glycol; isobutene- 1,3 -diol; etc. The preferred example of the diol initiator is butane- 1,4-diol.

As examples of the first monomer are, e.g., a 3FOx monomer (see Fig. 1 where n=0); a 5FOx monomer (see Fig. 1 where n=l); a 7FOx monomer (see Fig. 1 where n=2); a MOx monomer (See Figure IE); a MElOx monomer (see Figure IA where m^l); a ME20x monomer (see Fig. IA where m=2); a ME30x monomer (see Fig. IA where m=3); an ME70x monomer (see Fig. IA where m=7); a 4FOx monomer (see Fig. IB where n=l); an 8FOx monomer (see Fig. IB where n=3); a BrOx monomer (see Fig. 1C); a BBOx monomer (see Fig. ID); an Hy40x monomer (see Fig. IF); a Bis-3F0x monomer (see Fig. IG); an HMDI monomer (see Fig. IH); a BD monomer (see Fig. II); etc.

Inventive homo-polyoxetanes may be produced from a monomer 1 (such as, e.g., a monomer shown in Figs. 1-11), by the ring opening polymerization shown in Fig. 2. Inventive co-polyoxetanes may be produced from the monomers 1 and 11 (such as, e.g., the monomers shown in Figs. 1-11) reaction equation by the ring opening polymerization shown in Fig. 2 A. In Figs. 2, 2A, the notation for monomers 1, 11 is an alternate representation of the monomers in Figs. 1-11 appreciated by those in the chemical arts. For example, in Fig. 2, if the monomer 1 is 3FOx, then R¹ is -CH₃ and R² is CF₃CH₂OCH₂-. The ring-opened monomer structure 2 may be produced as shown in Fig. 2, and the ring-opened monomer structure 2 may then be used to produce inventive homo-polyoxetanes. The ring-opened monomer structure 2 A may be produced as shown in Fig. 2A, and the ring-opened monomer structure 2A may then be used to produce inventive co-polyoxetanes.

By forming a ring opening reaction (such as a ring opening reaction according to Fig. 2 or a ring-opening reaction according to Fig. 2A), there are formed ring-opened structures (see Figs. 3-3H) of monomers as found in inventive P[A], P[AB], and P[Bis-A] polyoxetanes, including: P[3F0x] (see Fig. 3 where n=0); P[5F0x] (see Fig. 3 where n=l); P[7F0x] (see Fig. 3 where n=2); P[9F0x] (see Fig. 3 where n=3); P[MOx] (see Fig. 3A where m=0); P[MElOx] (see Fig. 3A where m=l); P[ME20x] (see Fig. 3A where m=2); P[ME30x] (see Fig. 3A where m=3); P[ME7Ox] (see Fig. 3 A where m=7); P[BBOx] (see Fig. 3B); P[Bis-3FOx] (see Fig. 3C); P[BrOx] (see Fig. 3D); P[(3FOx)(BBOx)-m:n] (see Fig. 3E); P[(MEmOx)(BBOx)-m:n] (see Fig. 3F); P[(3FOx)(C12)-m:n] (see Fig. 3G); P[(MEm0x)(C12)-m:n] (see Fig. 3H). "MEmOx" means PEG-like (polyethylene glycol = PEG) side chains with a methylene group "M" and O, 1 , 2, 3, or 7 ethylene oxide groups "E" defined as follows: m=0, MOx, or -CH₂OCH₃; m=l, MElOx, Or -CH₂(CH₂CH₂O)CH₃; m=2, ME20x, or -CH₂(CH₂CH₂O)₂CH₃; and m=7, ME70x, or -CH₂(CH₂CH₂O)₇CH₃. With MEmOx terminology, it is understood that the number of repeat ethylene oxide "E" units may be average values. That is, the alcohols used to make the monomers may be mixtures that contain more than one value for "m". By 3FOx, 5FOx, 7FOx and 9FOx is meant side chains with 3, 5, 7, and 9 fluorine atoms, that is, CF₃CH₂OCH₂-, CF₃CF₂CH₂OCH₂-, CF₃(CF₂)₂CH₂OCH₂-, CF₃(CF₂)₃CH₂OCH₂-, respectively; by 4FOx and 8FOx is meant side chains with 4 and 8 fluorine atoms, that is CF₂HCF₂CH₂OCH₂- and CHF₂(CF₂)₃CH₂OCH₂-, respectively. By BBOx is meant a bromo-butoxymethyl side chain or Br-(CH₂)₄OCH₂- . The term "FOx" is also used herein to refer to all fluorous side chains, that is, 3FOx, 5FOx, 7FOx, 9FOx, 4FOx, and 8FOx.

Various inventive polyoxetanes and inventive co-polyoxetanes may be produced according to a ring-opening reaction as in Fig. 2 or Fig. 2A, and some examples are as follows.

1. Homo-polyoxetane telechelics having Rl ≠ R2. When two different side chains are pendant to the 1,3 -propylene oxide main chain, the polyoxetane does not crystallize but remains as an oil with a low glass transition temperature (Tg). Tg' s depend on the side chains and range down to -70 ⁰C or even lower when the side chain is a PEG-like. The solubility characteristics are determined by the nature of the side chain. For example, if one of the side chains is largely fluorous (e.g., FOx side chains, Fig. 3), the telechelic will be water insoluble but soluble in organic solvents such as THF. If the side chain is largely polyethylene glycol-like (PEG-like, MEnOx, Fig. 3A), the telechelic will be soluble in water or alcohols.

An example of homo-polyoxetane telechelics having R¹ ≠ R² is P[3F0x], Figure 3 where n-0. Using the inventive catalyst addition sequence, P[3FOx] was prepared in molecular weights up to 31 kDa. Access to higher molecular weight homo-telechelics is important for incorporation into polymers such as polyurethanes that are used as surface modifiers. P[3F0x] has reactive end groups which facilitates incorporation into segmented copolymers such as polyurethanes and into block copolymers. When incorporated into segmented polyurethanes the P[FOx] moiety becomes the soft block, while the hard block originates from diisocyanates and diols such as Figs. IH and. II, respectively, etc. Such P[FOx] polyurethanes may be added to conventional polyurethanes wherein surface modification of the majority polyurethane is effected. The conventional polyurethane then acquires the surface property of the minor P[FOx] constituent. This is advantageous as the P[FOx] surface domain is oil and water resistant.

Figure 4 shows a feature of segmented copolymer polyurethane additives such as soft blocks derived from P[A] telechelics, namely, the "nano-thickness" of the soft block is a function of molecular weight. "Nano-thickness" herein means the estimated thickness of the soft block domain at the surface of a solid polymer incorporating a P[A] or P[AB] soft blocks. The nano- thickness may be approximated by using the well known relationship of root-mean-square (rms) end-to-end distance to chain length according to the following equation 1.

- 2 \ /2 r )_fa = V2« / (equation 1)

For equation 1, see, e.g., Chanda, M. Advanced Polymer Chemistry; Marcel Dekker: New York, 2000. hi equation 1, the variables have their usual meanings, namely,

l \r ² V /^A f_{a =} rms end to end distance (fa = valence angle model);

n = number of bonds in the chain, and / (the letter I) = the bond distance for bonds in the chain.

Referring again to Fig. 4, polyurethane P[A]-polyoxetane soft block surface modifiers are shown. The modifier comprises the surface concentrated P[A] soft block 4OA, which comprises the oxetane main chain 4 and side chains A and the associated hard blocks 4OB. In Fig. 4, side chain A can be a fluorous group or a combination of more than one fluorous groups. Thermodynamic surface concentration is achieved from end-group-like side chains. In Fig. 4, a nano-domain generated by soft blocks 4 is shown having a nano-thickness 41. A successful polymer surface modifier introduces a nano-domain 41 at 2 wt% that has a nano- thickness, which can be estimated. Fig. 4A is a cross-sectional slice of a coating employing a P[A] polyoxetane polyurethane as a surface modifier and shows the concentration of the P[A] polyoxetane polyurethane, 42, at the surface of a bulk polyurethane 4OC; Fig. 4B is a general chemical formula corresponding to surface concentrated soft block 4, the compositions of which are shown in Figs. 3, 3A, and 3C.

The calculation of the rms end to end distance for P [3FOx] is shown in the following Table 1. The 3FOx repeat unit has a molecular weight of 172 g/mol.

Table 1 shows representative calculations for two P[3FOx] soft block chains of molecular weight 4 kDa and 16 kDa. The 4 kDa molecular weight is typical of that obtained from combining co-catalysts according to the conventional method such as Comparative Example 1 , while 16 kDa is achieved from the inventive method by combining monomer and co-catalyst (initiator) and adding this combination to a solution OfBF₃ catalyst. From the calculation shown in Table 1, an rms end-to-end distance of 1.6 nm is found for the 4 kDa chain, while an rms end- to-end distance of 3.1 nm is found for the 16 kDa chain. Thus, the nano-thickness of the 4 kDa surface nano-domain is estimated at 1.6 nm, while the value for the 16 kDa P[FOx] nano-domain is about 3.2 nm. Put another way, the nano-thickness of the inventive 16 kDa chain is double that of the conventional 4 kDa chain. Table 1.

It will be appreciated that the above Table 1 is an illustration of calculating molecular weight of nano-thickness of an inventive polyoxetane or co-polyoxetane.

To simplify the estimation of nano-thickness, there may be used the fact that the ratio of rms end to end distance for chain 1 to chain 2 is the ratio of the square root of the number of bonds in the respective polymer chains 1 and 2: For the P[3FOx] example in Table 1,

2 rms \_ _ (93) 1/ rms. (23) 1/2 = 2.0

There are several approximations associated with the above calculations that use the "valence angle" model. The approximations include uncertainties associated with the presence of bulky side chains and the fact that the chain is in a condensed state of matter. In addition, the calculation is for a single chain, while a given telechelic or soft block has chains with a broad distribution of molecular weights. However, the ratios calculated above are significant in estimating nano-thicknesses. For example, uncertainties associated with the presence of bulky side chains may tend to cancel when considering ratios of nano-thicknesses. The valence angle model calculations demonstrate how to calculate "nano-thickness". By calculating respective nano-thicknesses, it will be appreciated that inventive polyoxetanes and co-polyoxetanes provide increased molecular weight of the soft block compared to polyoxetanes and co-polyoxetanes made from the same starting materials but according to a conventional method in which the diol or other initiator and the BF₃ catalyst are used together as co-catalysts (as was conventional) rather than each used in separate steps according to the present invention.

Being able to access and use high molecular weight polyoxetane soft blocks stands in contrast to conventional soft blocks such as PTMO (polytetramethylene oxide) for which the maximum molecular weight is about 2 kDa. Inventive high molecular weight P[A] soft blocks facilitate generation of inventive nano-domains (Fig. 4) with estimated thicknesses of greater than 2 nm. Benefits of increased nano-thickness stemming from higher molecular weights include improved phase separation; that is, the "purer" the soft block nano-domain, the better the soft block can express a designed function when used as a surface modifier (Fig. 4).

2. Co-polyoxetane telechelics having Rl ≠ R2 and R3 ≠ R4. As for P[A] soft blocks, that is homo-polyoxetane telechelics having R¹ ≠ R² (Fig. 2), P[AB] co-polyoxetane soft blocks having R¹ ≠ R² and R³ ≠ R⁴ also benefit from the nano-thickness advantages of high molecular weight discussed above in section 1.

Interesting and often unexpected surface properties result from pairing a fluorous side chain (R¹ = fluorous = A, Fig. 5) with a second side chain (R² = B, Fig. 5). A model for surface composition of P[AB]-co-polyoxetane polyurethanes is shown in Fig. 5.

In Fig. 5 are shown inventive P[AB]-co-polyoxetane soft block surface modifiers. Side- chain A represents a fluorous group or related group that tends to surface-concentrate. Side chain A can be a fluorous chaperone in Fig. 5. Side chain B represents a functional group in Fig. 5. In Fig. 5, complementary A and B side chains produce an inventive surface and an inventive surface property, hi Fig. 5, thermodynamic surface concentration from end-group-like side chains is provided. A successful polymer surface modifier introduces a nano-domain 51 (Fig. 5) at 2 wt%, the nano-domain having nano-thickness 51.

Fig. 5A is a cross-sectional slice of a coating employing a P[AB] polyoxetane polyurethane as a surface modifier and shows the concentration of the P[AB] polyoxetane polyurethane, 52, at the surface of a bulk polyurethane 4OC; Fig. 5B is a general chemical formula corresponding to surface concentrated soft block 4, the compositions of which are shown in Figure 3E, 3G, and 3H. The surface concentration of soft blocks in polyurethanes is well-known, Ratner, B. D.; Cooper, S. L.; Castner, D. G.; Grasel, T. G. J Biomed Mater Res 1990, 24, 605-620; Tingey, K. G.; Andrade, J. D. Langmuir 1991, 7, 2471-2478; Garrett, J. T.; Runt, J.; Lin, J. S. Macromolecules 2000, 33, 6353-6359; Garrett, J. T.; Siedlecki, C. A.; Runt, J. Macromolecules 2001, 34, 7066-7070. In addition to having such a surface concentration, the inventive polymer surfaces also have one or more of the following features or considerations which distinguish the P[AB]-So ft block approach for concentrating a desired functional group B at a polymer surface: a. Multiple P[AB] side chains that act as pseudo-chain ends (see Jalbert, C; Koberstein, J. T.; Hariharan, A.; Kumar, S. K. Macromolecules 1997, 30, 4481-4490). b. Differing solubility parameters for the P[AB]-soft block and other coating constituents that enhance phase separation. c. A low P[AB] soft block T_g that may enhance effectiveness of the B surface function. d. Synergistic, functional A and B repeat units that together produce an inventive surface property. e. Fluorous A (or other surface-concentrating side chain) repeats that act as "chaperones" to surface-concentrate B groups which, in the absence of A, would not be surface concentrated, (see Makal, U; Wood, L.; Ohman, D. E.; Wynne, K. J. Biomaterials 2006, 27, 1316-1326). f. A "green" method for surface concentrating functionality B, as a multiplicity of short, environmentally acceptable Rf side chains A are employed. As to this approach, see the use of mixed fluorous tails (see Ernsting, M. J.; Bonin, G. C; Yang, M.; Labow, R. S.; Santerre, J. P. Biomaterials 2005, 26, 6536-6546) that contain eight-carbon R_f moieties, which are known to be perfluorooctanoic acid (PFOA) precursors (see Ellis, D. A.; Mabury, S. A.; Martin, J. W.; Muir, D. C. G. Nature 2001, 412, 321-324; Giesy, J. P.; Kannan, K. Environmental Science & Technology 2001, 55, 1339-1342; Martin, J. W.; Whittle, D. M.; Muir, D. C. G.; Mabury, S. A. Environmental Science and Technology 2004, 38, 5379-5385); g. Compositional economy by using the P[AB]-soft block polyurethane as a minor surface modifier constituent (< 2 wt%) in a blend such that the polymer modifier defines the surface properties and the matrix polymer defines bulk mechanical properties and adhesion to substrate.

For P[AB]-soft block polyurethanes, considerations a-c provide a combination of thermodynamic driving forces that act to enhance soft block surface concentration. Of considerable interest is d, a feature that has been observed in the majority of inventive P[AB]- soft block polyurethanes. That is, some new surface characteristic, often unexpected, such as morphology or wetting behavior has been found for almost every neat P[AB]-polyurethane composition. These discoveries provide a rich basis for control or tuning polymer surface behavior.

For 2 wt% (or less) P[AB]-soft block polyurethanes, the presence of the fluorous A group (nFOx, Fig. 3) plays an important "chaperone" role in surface concentration of the functional B group (e) (see Makal, U.; Wood, L.; Ohman, D. E.; Wynne, K. J. Biomaterials 2006, 27, 1316- 1326). Compositional economy (f) is only of importance if the fidelity of the neat P[AB]-So ft block polyurethane surface property is maintained at 2 wt% or less P[AB]-soft block polyurethane content (Fig. 5).

3. Semicrystalline polyoxetanes, P[BiS-A], or homo-polyoxetanes where Rl = R2 (Fig. 2). It is well known that molecular weight determines the properties of semicrystalline polymers. Thus low molecular weight polyethylene (PE) is wax-like, while high molecular weight PE is a tough thermoplastic with a myriad of uses. Thus, achieving high molecular weight semicrystalline polyoxetanes via the equation of Fig. 2, where R¹ = R² = R, is of considerable importance in the improvement of mechanical properties including toughness. P[BiS-ROx], where P = polymerized monomer, Bis = 2 and R = identical side chains (R¹ = R² = R, Fig. 2) such as 3FOx have reactive terminal -OH groups. These can be used to incorporate P[BiS-ROx] into a wide variety of segmented and block copolymers through standard reactions, such as the reaction with isocyanates (e.g, Fig. IH) and diols (Fig. II) to produce polyurethanes or with isocyanates and diamines to produce urethane ureas.

As an example of the preparation of high molecular weight P[BiS-ROx], we describe the preparation of P[Bis-3F0x] of molecular weight (Mn) 21 kDa. The structure of P[Bis-3F0x] is shown schematically in Fig. 3C. An objective of this work is to provide non-PFOA alternatives having both hydrophobicity (water repellency) and oleophobicity (oil repellency) and applicability to conventional coatings. By "PFOA" is meant perfluoro-octanoic acid, which is bioacumulative and is a degradation product of fluorous surfactants and surface modifiers with chains such as -CH₂CH₂(CFa)₇CF₃ or -CH₂CH₂(CF₂)C)CF₃.

P(Bis-3F0x) (Fig. 3C) was prepared by cationic ring opening polymerization of 3,3- bis(2,2,2-trifluoroethoxymethyl)oxetane (Bis-3F0x) according to Fig. 2, R¹ = R² = CF₃CH₂OCH₂-. Conventionally, the monomer would be added to co-catalysts in methylene chloride. (See Malik, A. A.; Manser, G. E.; Archibald, T. G., US 5,650,483, 1995.) In the inventive method described herein, the diol co-catalyst was added together with monomer in homogeneous solution (CH₂Cl₂) to BF₃/CH₂C1₂ at -5 ⁰C. A 50:1 monomer to BF₃ ratio was used. Simultaneous addition of diol co-catalyst and monomer was done so that the concentration of any generated HF or H⁺ might be low and relatively constant with time. M_n was determined by ¹H- NMR/end group analysis (see id.). It is noteworthy that this inventive procedure resulted in much higher molecular weight 2IkDa P(Bis-3F0x) compared to that described by Malik (6 kDa) (id.) and Jiang (2 kDa) (see Jiang, W.-C; Huang, Y.; Gu, G.-T.; Meng, W.-D.; Qing, F.-L. Applied Surface Science 2006, 253, 2304-2309). The T_g of P(Bis-3FOx) is -40 to -45 ⁰C for M_n 5 - 21 kDa.

Inventive 2IkDa P(Bis-3FOx) coatings have two particularly interesting features: (1) processing dependent surface morphology and (2) a water contact angle (after melt processing) that increases with time. Surface-confined micro-crater-like structures were formed on as-cast coatings, which were prepared by dip-coating from P(Bis-3FOx)/THF solution. This observed structure is likely due to solvent evaporation. The surface is rough (Rq = 850 nm) but has a mostly continuous contact line (θ_water = 116 ± 5°). Melting the solvent cast coating yielded relatively smooth, transparent (quenched) or translucent (slow cooled) coatings with wetting behavior characteristic of fluorous polymers (see Anton, D. Advanced Materials (Weinheim, Germany) 1998, 10, 1197-1205; Xiang, M. L.; Li, X. F.; Ober, C. K.; Char, K.; Genzer, J.; Sivaniah, E.; Kramer, E. J.; Fischer, D. A. Macromolecules 2000, 33, 6106-6119; Katano, Y.; Tomono, H.; Nakajima, T. Macromolecules 1994, 27, 2342-2344). The water contact angle is 106 ± 4 ° for slow-cooled surfaces. The slow cooled coatings undergo slow crystallization. This results in an increase in AH_1n from 22.7 J/g (slow cooled) to 28.9 J/g for a sample aged 45 days. Remarkably, this further crystallization results in a complex, roughened surface topology characterized by sharp asperities that increases the water contact angle by 20-30 °. The 3D 25^χ25 μm TM-AFM height images reveal a striking increase in R_q from 30 nm (Id) to 140 nm (45d). This increase in roughness is due to the formation of lamellae aggregates that protrude from the surface. Most of the lamellae aggregates appear edge-on to the surface.

The combination of different lamella orientations in the inventive material produces sharply defined asperities over nanometer to micrometer scales. Such surface roughness over multiple length scales is well known to produce the self-cleaning "Lotus effect" described by Barthlott. (Neinhuis, C; Barthlott, W. Annals of Botany 1997, 79, 667-677.) With contact angles as high as 140°, the wetting behavior of the asperity-rich morphology for inventive P(Bis-3FOx) reflects a mostly discontinuous 3 -phase contact line.

Inventive coatings may be formed as follows.

Certain inventive P[BiS-A] polyoxetanes are semicrystalline. P[Bis-3FOx] is an example of an inventive P[Bis-A] polyoxetane that forms coatings on its own.

Certain inventive P[A] and P[AB] polyoxetanes are oils. They may be made into a polyurethane, polyurethane urea or other block copolymer composition to form coatings. Inventive polyoxetanes of the form P[A] and P[AB] maybe processed into coatings by combination with a hard block (as in a polyurethane) or with some other reinforcing phase to create a coating.

The present inventors are the first to provide polyoxetanes with oil-resistance represented by a hexadecane contact angle of greater than 80 degrees (said contact angle also being greater than 70 degrees) and/or water resistance represented by a water contact angle exceeding 108 degrees (said contact angle also being greater than 104 degrees).

It will be appreciated that examples according to the invention have been provided above. The invention also may be appreciated with reference to the following examples, without the invention being limited to the examples.

COMPARATIVE EXAMPLE 1. Oxetane monomers or oxetane comonomers are added to a solution of catalyst (typically BF₃ etherate) and butane diol, according to Malik et al., US 5,703,194, 1995; Malik et al., US Pat. No. 5,650,483, 1995; Malik et al., US Pat. No. 5,637,772, 1997; Malik et al., US Pat. No. 5,807,977, 1998; Malik et al. US Pat. No. 6,037,483, 2000; Malik et al., US Pat. No. 6,479,623, 2002; Malik et al., US Pat. No. 7,148,309, 2006 (with the present inventor Wynne being an inventor on several of these mentioned patents). These now- conventional methods typically provide fluorous polyoxetane homotelechelics (e.g., Fig. 2, R¹ = CF₃CH₂OCH₂-, R² = -CH₃) or "P[3FOx]", see Figure 3) or polyoxetane co-telechelics such as P[(3FOx)(5FOx)-m:n] (Fig. 2A, R¹ = CF₃CH₂OCH₂-, R² = R⁴ = CH₃, R³ = CF₃CF₂CH₂OCH₂-). Molecular weights (Mn) are typically less than 8 kDa using the methods of this comparative example.

COMPARATIVE EXAMPLE IA. The present inventors used a method according to Comparative Example 1, which consisted of mixing BF₃ etherate catalyst with a butane diol co- catalyst followed by addition of a mixture of comonomers, to prepare several co-polyoxetane compositions, including: P[(ME2Ox)(BBOx)-m:n], P[(3FOx) (BB0x)-m:n], P[(ME2Ox)(C12)- m:n], P[(3FOx) (C12)-m:n] and others. The molecular weights were in the 2.5 - 8 kDa range depending on the co-monomers employed.

COMPARATIVE EXAMPLE 2 (Hoy U.S. Patent 3,417,034). In Hoy Example II, 1000 grams of 5-oxatetracyclo-[6,2,l,0²'⁷,0^4>6]undecan-9(10)-ol (6.02 moles) was combined with 1860 grams of dichloroethyl ether and 37 grams of butanol (0.5 mole) as a chain modifier. The amount of butanol was indicated to be approximately that theoretically required to produce a polymer having 12 repeating units. The stirred mixture was cooled to 10 degrees C. and maintained at a temperature of from about 10 to 22 degrees C while 20 grams of boron trifluoride ethyl etherate catalyst dissolved in 170 grams of dichloroethyl ether was added slowly over a period of 90 minutes. After drying overnight there reportedly was obtained 903 grams of a white powdered polymerization product having a hydroxyl equivalent weight of 178.

Butanol is mono-functional (-OH) and acts as a chain terminator. Thus, low molecular weight polymers are prepared via Hoy Example II.

INVENTIVE EXAMPLES

For the Inventive Examples below, monomers were purified by distillation using a spinning band column. This gave monomers with 99.5+ purity, as checked by GC-MS. Lower purity monomers gave lower molecular weight polyoxetane telechelics and co-telechelics.

EXAMPLE 1

P[AB]-co-polyoxetanes. This Example 1 describes the preparation of an inventive P[AB] -co-polyoxetane where A is the fluorous 3FOx repeat and B is BBOx (see Fig. 3E). Here, the feed ratio of comonomers defined the mole fraction of co-repeats, viz., 0.75 3FOx and 0.25 BBOx. The combining of the comonomers with the co-catalyst (initiator) butane diol gave a high molecular weight P[AB]-co-telechelic (M_n = 13 kDa).

Preparation of PIY3FOx)fBBOxV0.75:0.251 (Fig. 3E, m = 0.75, n= 0.25) BBOx oxetane monomer was prepared according to Kawakami, Y.; Takahashi, K.; Hibino, H. Macromolecules 1991, 24, 4531-4537. To a 50 mL addition funnel were added 3FOx (14.95 g, 81 mmol), BBOx (6.4 g, 27mmol), 1 ,4-butanediol (90μL, lmmol) and 2OmL anhydrous CH₂Cl₂. This mixture solution was added drop wise to a two-necked 100 ml flask with 0.25 mL BF₃ OEt₂ in 25mL anhydrous CH₂Cl₂ at 0 ⁰C within 3 hour. The reaction system was stirred and maintained at 0 ⁰C for another 15 hours. 5 mL H₂O was added in and stirred at room temperature for 0.5 hour to stop the reaction. The CH₂Cl₂ solution was washed by H₂O (40 mL x 3) and the solvent was evaporated and the residue was dried at 80⁰C under vacuum for 48 hours to afford 19.54 g copolymer P[3FOx:BBOx]-0.75:0.25, where R = CF₃CH₂-. ¹H NMR (CDCl₃): δ 0.91 ppm (-CH₃, 3H,s), 1.68 ppm (-CH₂-for BBOx, 2H), 1.92 ppm (-CH₂- for BBOx, 2H), 3.19 ppm (backbone -CH₂-, 4H,m), 3.4 ppm (-CH₂Br-, 2H),3.45 ppm (-OCH₂-, 2H,s), 3.75 ppm (-CH₂CF₃-, 2H,m). M_n=13,000g/mole, that is, 13 kDa.

INVENTIVE EXAMPLE 2

This Inventive Example 2 describes the preparation of a P[AB]-co-polyoxetane where A is the hydrophilic ME20x repeat and B is BBOx (see Fig. 3F). Here, the feed ratio of comonomers defined the mole fraction of co-repeats, viz., 0.75 ME2Ox and 0.25 BBOx. The combining of the comonomers with the co-catalyst (initiator) butane diol gave a high molecular weight PfABJ-co-telechelic (M_n = 8 kDa).

Preparation of PΓ(ME2OX)(BBOX)-0.75:0.251 (Figure 3, CH₃(OCH₂CH₂)₂- gives a "ME20x" side chain). BBOx oxetane monomer was prepared according to Kawakami, supra. The ME2Ox oxetane monomer was synthesized as follows: A mixture of 2-(2-methoxyethoxy) ethanol (2Og, 0.17mol ) and NaH (4g, 0.17 mol ) in 50 mL anhydrous tetrahydrofuran (THF) was stirred vigorously at room temperature until no more H₂ released from the system. The system was cooled to 0 ⁰C by ice-water bath and 3-bromomethyl-3-methyloxetane (BrOx) ( 27g, 0.17 mol ) was added drop wisely within 2 hours. The reaction mixture was brought to room temperature and stirred over night. After filtration 100 mL H₂O was added in and the product was extracted by CH₂Cl₂ and distilled with CaH₂. (60 ⁰C / 0. lmmHg). ¹H NMR (CDCl₃) δl .32 (- CH₃, 3H, s), 63.39 (-OCH₃3H, s), 53.55 (-OCH₂CH₂O-, 4H, m), 53.67 (-OCH₂CH₂O-, 4H, and - CH₂, 2H, m), 54.35 (ring CH₂, 2H, d), 54.52 (ring CH₂, 2H, d).

To prepare P[(ME2Ox)(BBOx)-0.75:0.25], using an additional funnel and under a nitrogen purge, a mixture of BBOx (4.23g, 18mmol), ME20x (12.Og, 54mmol), 1,4-Butanediol (59μL, 0.66mmol) and 5OmL anhydrous CH₂Cl₂ was added to the two-necked 100 ml flask containing BF₃-OEt₂ and 25mL anhydrous CH₂Cl₂ over 3 hours. The reaction system was stirred for 15hours at 0 ⁰C. The reaction was quenched with addition and stirring of H₂O for 0.5 hour. Organic solution was washed by water H₂O (40 mL x 3). The solvent was evaporated and the residue was dried at 8O⁰C under vacuum for 48 hours to obtain 15.77g copolymer P[(ME2Ox)(BBOx)-0.75:0.25]. ¹H NMR (CDCl₃): δ 0.91 ppm (-CH₃, 3H,s), 1.68 ppm (-CH₂- for BBOx, 2H), 1.92 ppm (-CH₂-for BBOx, 2H), 3.19 ppm (backbone -CH₂-, 4H,m), 53.30 ppm (-CH₂, 2H, s), 3.38 ppm (-OCH₃ 3H, s), 3.4 ppm (-CH₂Br-, 2H), 3.55 ppm (-OCH₂CH₂O-, 4H, m). M_n= 8,000g/mole.

The following Examples 3-4 describe quantitative quaternization of BBOx to C12 to give a new P[AB] telechelic. This P[AB] telechelic is novel in that it incorporates quaternary charge on a side chain. Quarternization is accomplished by the reaction of the BBOx telechelic with N, N-dimethyldodecylamine.

INVENTIVE EXAMPLE 3

Preparation of P[(3FOx)fC12V0.75:0.251 (Fig. 3G);

[-N(CH₃)₂(C₁₂H₂₅ )]⁺ (Br)^" = C12 = [CH₃(CH₂)_n(CH₃)₂N]Br). 4.4g P[(3FOx)(BBOx)-0.75:0.25] telechelic (M_n= 13,000g/mole) and N, N-dimethyldodecylamine ( 2.03 g, 6.6 mmol ) were dissolved in 20 mL acetonitrile. The mixture was heated to reflux and stirred for 15 hours under nitrogen. The solvent and excess N, N-dimethyldodecylamine was evaporated under vacuum to give a highly viscous product P[(3FOxϊC12V0.75:0.251 (Fig. 3G). By ¹H NMR, the bromomethyl group was converted to the alkylammonium bromide, quantitatively.

INVENTIVE EXAMPLE 4

Preparation of P[(ME2OxVC12V0.75:0.251 (Fig. 3H); [-N(CH₃)₂(C₁₂H₂₅)]⁺ (Br)^" = C12 = [CH₃(CH₂)_n(CH₃)₂N]Br). 5.22g P[(ME2Ox)(BBOx)-0.75:0.25] telechelic (M_n= 8,000g/mole) was dissolved in 4.5 mL acetonitrile. The solution was heated to reflux. N, N-dimethyldodecylamine (2.27 g , 7.38 mmol ) was added slowly. The mixture was stirred for 15 hours under nitrogen. The solvent and excess N, N- dimethyldodecylamine was evaporated under vacuum to give a highly viscous product P[(ME2Ox)(BBOx)-0.75:0.25]. By ¹H NMR, the bromomethyl group was converted to the alkylammonium bromide, quantitatively.

INVENTIVE EXAMPLE 4A

Water solubility. Quaternization of the BBOx side chain markedly increases water solubility. For example, the water solubility was tested for a P[ME2Ox-C12-75:25] cotelechelic. A solubility of 50 g/L was observed in making up a stock solution. The solubility limit was judged to be significantly higher than this value.

INVENTIVE EXAMPLE 4B

Solubility is composition dependent. Five milligrams of P[ME2Ox-C 12-90: 10], which has only 10 mole percent alkylammonium side chains in the co-telechelic, was mixed with 1 milliliter of Nanopure water. Not all of the co-telechelic dissolved as evidenced by the presence of an opaque solution. P[A]-homo-polyoxetanes

3FOx telechelics, that is poly(3-trifluoroethoxymethyl-3-methyl)oxetane (Fig. 3) were prepared by using different catalyst to monomer ratios. The results of six reactions (Table 2, Fig. 6) demonstrated that the monomer to catalyst ratio had only a modest effect on the P[3FOx] molecular weight (Table 2). Thus, this method is fairly insensitive to this variable. An example of one of the preparations is given below. This example corresponds to run 3 (see Table 2, line 3).

INVENTIVE EXAMPLE 5

PBFOxI with Mn = 32 kDa. 3FOx monomer (2Og, 108.7mmol) and O.lg (l.lmmole) butane diol (BD) in 26.5 Ig anhydrous CH₂Cl₂ was added slowly to 2OmL anhydrous CH₂Cl₂ solution containing 0.3 Ig (2.2mmole, 2% catalyst) BF₃-OEt₂ at 0⁰C within 4 hours. The ratio of monomer to solvent was 0.38 by weight. The reaction system was stirred and maintained at 0 ⁰C. After 18 hours it was warmed to room temperature and quenched with 90 ml deionized water. The organic phase was washed first with 2 wt% HCl, then with 3 wt% NaCl solution and precipitated in methanol/water (3:1) mixture to yield telechelic P[3FOx] with 32,055 g/mole (32.0 kDa) molecular weight. Table 2. The effect of monomer to catalyst ratio on degree of cationic ring opening polymerization of 3FOx monomer to P[3FOx].

P[Bis-A]-homo-polyoxetanes.

INVENTIVE EXAMPLE 6

Preparation of Pp3is-3FOx]. 3,3-Bis(2,2,2-trifluoro-ethoxymethyl)oxetane (Bis-3FOx) was synthesized according to Malik, A. A.; Archibald, T. G.; Carlson, R. P.; Wynne, K. J.; Kresge, E. N., US 6479623, 2002 and Jiang, W.-C; Huang, Y.; Gu, G.-T.; Meng, W.-D.; Qing, F.-L. Applied Surface Science 2006, 253, 2304-2309. Monomer was distilled before use using a spinning band distillation column: 90-94 ⁰C Il mmHg. BF₃OEt₂ and dichloromethane (CH₂Cl₂, anhydrous) were purchased from Aldrich. 1 ,4-butanediol (BD) was purchased from Acros Chemicals and used as received. Tetrahydrofuran (THF) was bought from Fisher, used as received.

Synthesis of telechelic polyoxetane (P(Bis-3FOx)). Cationic ring-opening polymerization was employed using BF₃OEt₂ and butane diol as catalyst and co-catalyst, respectively. A stock solution of BF₃ OEt₂ /CH₂Cl₂ was first prepared by mixing 0.5g BF₃ OEt₂ with 5 mL anhydrous CH₂Cl₂. To a N₂ purged three-neck round bottom flask, 1 rnL BF₃ OEt₂ /CH₂Cl₂ solution containing 0.71 mmol BF₃ OEt₂ was added with 8 mL CH₂Cl₂ The reaction mixture was stirred at 0 ⁰C. Monomer (Bis-3FOx) (11.28g, 40 mmol) and 0.032g butanediol (0.35 mmol) were mixed with 1OmL anhydrous CH₂Cl₂, and added drop by drop to the flask. The reaction mixture was stirred at -5 to 0 ⁰C for 15 h. The solution was then warmed up to room temperature and quenched with 20 mL water. The water layer was carefully decanted and the organic phase was washed with 3 wt% aq. HCl followed by 3 wt% aq. NaCl solution. The mixture was precipitated into MeOH/H₂O mixture (1 : l/v:v). After filtration, the precipitated telechelic polyoxetane was dried in a vacuum oven at 60 ⁰C for overnight. The product (P(Bis- 3FOx)) was obtained as a white solid (9 g, 80% yield). ¹H-NMR: δ = 3.74 (q, 4H, CH₂CF₃), δ = 3.53 (s, 4H, C-CH₂-O), δ=3.31 (s, br, 4H, CH₂-C-CH₂-O-) ppm. ¹³C-NMR δ = 45.8, 68.7 (q), 71.3, 71.8, 124 (q) ppm. The molecular weight (M_n) by 'H-NMR/end-group analysis was 21 kDa. Characterization. Telechelic molecular weight (M_n) was determined by ^lH-NMR/end- group analysis.² Trifluoroacetic acid (TFAA) was added to the polymer/CDCl₃ solution, and was stirred at 40 ⁰C for at least Ih before ¹H-NMR measurement. The ratio of methylene peaks adjacent to the fluoroacetyl group (~4.4ppm) compared to methylene next to CF₃ in the repeat unit (~3.8 ppm) was used for calculation of D_v for the telechelic.

¹H-NMR spectra were recorded using a Varian spectrometer (Inova 400 MHz). A TA Q series™ (TA instrument) was used for temperature modulated differential scanning calorimetry (MDSC). MDSC was used for measuring melting temperature (T_m) and glass transition temperature (T_g) of telechelics with modulation amplitude of ± 0.5 ⁰C, modulation period of 60 s, and heating rate of 5 °C.

Coating preparatioa Samples were prepared by dip-coating polymers from THF solutions (20-25 wt %) onto glass cover slips (Corning, 24 x 40 x 0.5mm). The samples were placed in an upright position at room temperature and covered by a beaker for slow solvent evaporation for 12 h. Coatings were further dried in vacuum for 4h. These films are "as-cast" films. For melt processing, coatings were heated at 1 atm to 85-90 °C, held for 15 min and cooled to ambient temperature at a rate of ~ 0.5 °C/min.

Crystallization, hi studies of polymer crystallization, two paths have been designated, namely, melt-crystallization and cold-crystallization. The difference between these two paths is the initial state prior to crystallization (Wunderlich, B. Journal of Chemical Physics 1958, 29, 1395-1404; Cai, J. L.; Li, T.; Han, Y.; Zhuang, Y. Q.; Zhang, X. Q. Journal of Applied Polymer Science 2006, 100, 1479-1491). A paper particularly relevant to P(Bis-3FOx) describes cold and melt crystallization, respectively, for syndiotactic polypropylene, which has a T_g below ambient (-6 ⁰C) and two melting endotherms (95-120 °C)( Supaphol, P.; Spruiell, J. E. Polymer 2000, 42, 699-712). The experimental section of this paper by Supaphol and Spruiell clearly defines isothermal melt and isothermal cold crystallization.

The path for isothermal crystallization from the melt state (melt crystallization) involves cooling from the melt to a specified temperature below T_m and above T_% and holding the sample at that temperature until crystallization is complete. The path for cold crystallization involves cooling from the melt to the glassy state (below T_g) followed by heating to a specified temperature above T_g but below T_m, at which temperature crystallization occurs isothermally.

In this inventive Example, the polymer coating was melted and slow-cooled to room temperature. Crystallization during slow cooling is non-isothermal melt-crystallization. Ambient temperature is above T_g (-39 ⁰C) for P(Bis-3FOx); crystallization occurring over 6-8 weeks (which resulted in the unprecedented asperity / ridge formation) is a crystallization / crystal perfection process (isothermal crystallization). Wetting Behavior. The static contact angles and image profiles were obtained using a Rame-Hart goniometer equipped with a camera. The contact angles were either calculated using Drop Image software or were estimated by printing out images, assigning a three phase contact line, and measuring angles with a protractor. DCA measurement uses Wilhelmy plate method. The interrogation liquid was deionized water (Milli Q, 18 MΩ cm). The water surface tension was checked before each experiment by using a flamed glass cover slip, and was usually 72.6 ± 0.4 dyne/cm, hi a typical experiment, a coated slide was attached to the electrical balance and a beaker of water was placed on the stage. The stage was automatically raised and lowered, usually at the speed of 100 μm/s to allow water to impinge upon the slides. And the dwell time between advancing and receding test segment was 10s. By analyzing the resulting force distance curves (fdc's), the advancing (θ _adv) and receding (θ _rec) contact angles were obtained.

Atomic Force Microscopy (AFM). Surface morphology of the inventive crystalline telechelic was obtained by tapping mode atomic force microscopy (TM-AFM) using either a Veeco instrument Nanoscope IIIA or V. Topographic and phase contrast images were acquired with a standard silicon tip. The setpoint ratio (A_exp/A_o) was in the range of 0.8-0.9. P[AB] telechelics and P[AB]-cotelechelic polyurethanes.

INVENTIVE EXAMPLE 7

Preparation of the P[3FOx:BBOx-0.875:0.1251 telechelic. BBOx oxetane monomer was prepared according to Kawakami, supra. To a 50 mL addition funnel were added 3FOx (14.95 g, 81 mmol), BBOx (2.85g, 12mmol), 1,4-butanediol (90 μL, 1 mmol) and 20 mL anhydrous CH₂Cl₂. This mixture solution was added drop wise to a two-necked 100 ml flask with 0.25 mL

BF₃-OEt₂ in 25mL anhydrous CH₂Cl₂ at 0⁰C within 3 hour. The reaction system was stirred and maintained at 0 ⁰C for another 15 hours. 5 mL H₂O was added in and stirred at room temperature for 0.5 hour to stop the reaction. The CH₂Cl₂ solution was washed by H₂O ( 40 mL x 3) and the solvent was evaporated and the residue was dried at 80⁰C under vacuum for 48 hours to afford 19.54 g copolymer P[3FOx:BBOx-0.875:0.125] telechelic. ¹HNMR (CDCl₃): δ 0.91 ppm (-CH₃, 3H,s), 1.68 ppm (-CH₂-for BBOx, 2H), 1.92 ppm (-CH₂- for BBOx, 2H), 3.19 ppm (backbone -CH₂-, 4H,m), 3.4 ppm (-CH₂Br-, 2H),3.45 ppm (-OCH₂-, 2H,s), 3.75 ppm (-CH₂CF₃-, 2H,m). M_n-17,000g/mole or M_n = 17 kDa.

INVENTIVE EXAMPLE 8

Alkylammonium Substitution of PIY3FOx)(BBOx)-0.875:0.1251 telechelic to yield PΓ(3FOX)(C12)-0.875:0.1251 alkylammonium co-telechelic. P[3FOx-BBOx]-0.875:0.125 telechelic (3.38 g) and N, N-dimethyldodecylamine (C12) ( 1.5 mL , 8.8mmol ) were dissolved in The solvent and excess N, N-dimethylhexylamine was evaporated under vacuum. ¹H-NMR spectra showed δ 0.91 ppm (-CH₃, 3H,s), 1.35 ppm (-CH₂-,18H,broad), 1.68- 1.92 ppm (-CH₂-, 6H,broad), 3.19 ppm (backbone -CH₂-, 4H,m), 3.4 ppm (-CH₂N-, 2H, CH₃-N-CH₃,6H), 3.45 ppm (-OCH₂-, 2H,s), 3.75 ppm (-CH₂CF₃-, 2H,m). The ¹H-NMR spectrum confirmed the preparation of P[(3Fox)(C12)-0.875:0.125] alkylammonium co-telechelic. By ¹H NMR, the bromobutoxymethyl group was converted to the alkylammonium bromide, quantitatively.

INVENTIVE EXAMPLE 9

P[AB1-cotelechelic polvurethane synthesis: HMDI-BD(30)-P|^'3FOx-C12-0.88:0.121. HMDI-BD(30)-P[3FOx:C12-0.88:0.12] was synthesized using a two step polymerization. In a 25OmL round bottom flask under nitrogen P[3FOx:C12-0.88:0.12] telechelic (3.Og) and 0.97g is dissolved in 2OmL of n-methylpyrrolidinone (NMP). 5 drops of 10 vol% dibutyltin dilaurate (T- 12) in tetrahydrofuran (THF) were added to the mixture which was heated to 65⁰C. The preparation of diisocyanate-terminated prepolymer was confirmed by FT-IR spectroscopy (urethane carbonyl, 1724 cm^"1, and N-H, 3346 cm^"1, absorbances). hi the second stage, BD was added and heating was continued (65⁰C) until all isocyanate groups were consumed (ca. 5h). The course of the chain extension reaction was monitored with FT-IR by following the disappearance of the sharp isocyanate band at 2267cm^"1. As the viscosity increased during the chain extension reaction, NMP was added to dilute the reaction mixture. The final solids content of the polymer solution was 50-60%. The product, HMDI-BD(30)-P[(3FOx)(C12)-0.88:0.12], was precipitated into saturated NaBr solution for purification and then dried in a vacuum oven for 24hrs.

INVENTIVE EXAMPLE 10

Preparation of PΓME2OX-BBOX-0.75:0.25] telechelic. Through an addition funnel, a mixture of BBOx (4.23g, 18mmol), ME20x (12.Og, 54mmol), 1 ,4-Butanediol (59μL, 0.66mmol) and 5OmL anhydrous CH₂Cl₂ was added to the two-necked 100 ml flask containing BF₃-OEt₂ and 25mL anhydrous CH₂Cl₂ under nitrogen purge within 3 hours. The reaction system was stirred for 15hours at 0 ⁰C. The reaction was quenched with addition and stirring of H₂O for 0.5 hour. Organic solution was washed by water H₂O ( 40 niL x 3). The solvent was evaporated and the residue was dried at 8O⁰C under vacuum for 48 hours to obtain 15.77g copolymer. ¹HNMR (CDCl₃): δ 0.91 ppm (-CH₃, 3H,s), 1.68 ppm (-CH₂-for BBOx, 2H), 1.92 ppm (-CH₂-for BBOx, 2H), 3.19 ppm (backbone -CH₂-, 4H,m), δ3.3O ppm (-CH₂, 2H, s), 3.38 ppm (-OCH₃ 3H, s), 3.4 ppm (-CH₂Br-, 2H), 3.55 ppm (-OCH₂CH₂O-, 4H, m), 3.64 ppm (-OCH₂CH₂O-, 4H, m). The ¹H- NMR spectrum indicated quantitative conversion to P[ME2Ox-BBOx-0.75:0.25] telechelic. M_n=6000g/mol

INVENTIVE EXAMPLE 11 Preparation of the P[3FOx-BBOx-0.70:301 telechelic. BBOx oxetane monomer was prepared according to Kawakami, supra. To a 50 mL addition funnel were added 3FOx (7.475 g, 40 mmol), BBOx (5.45 g, 23 mmol), 1,4-butanediol (0.057 g, 0.63 mmol) and 20 mL anhydrous CH₂Cl₂. This mixture solution was added drop wise to a two-necked 100 ml flask with 0.178 g

BF₃OEt₂ (1.26 mmoles BF₃) in 25mL anhydrous CH₂Cl₂ at 0 ⁰C within 3 hour. The reaction system was stirred and maintained at 0 ⁰C for another 15 hours. 5 mL H₂O was added in and stirred at room temperature for 0.5 hour to stop the reaction. The CH₂Cl₂ solution was washed by H₂O ( 40 mL x 3) and the solvent was evaporated and the residue was dried at 80⁰C under vacuum for 48 hours to afford 11.5 g P[3FOx-BBOx]-0.70:30 telechelic. M_n=12,000g/mole or M_n = 12 kDa. In this case the target composition from the monomer addition stoichiometry was P[3FOx-BBOx-0.63:37], but by ¹H-NMR spectroscopy, the ratio of repeat units in the prepared telechelic was P[3FOx-BBOx-0.70:30].

INVENTIVE EXAMPLE 12

Referring to Fig. 6, there is shown the results of experimentation for number average molecular weight of P[3FOx] as a function of mole percent BF₃ catalyst, relative to 3FOx monomer. The ratio of butane diol to BF₃ was constant (0.5).

INVENTIVE EXAMPLE 13

Preparation of P[ME20x] homo-telechelic series

ME20x monomer was synthesized as described above for preparation of P[(ME20x) (BBOx)-0.75:0.25]. The ME20x telechelic polymer [poly(3-methoxyethoxyethoxy-methyl, 3- methyl)oxetane] (see Fig. 3A, m=2) was synthesized as follows: ME20x monomer (5.65g, 27.7mmol) and butane diol (0.024g, 0.266mmole) in 1OmL anhydrous CH₂Cl₂ was added over a period of 12 hours to a stirred 1OmL solution of anhydrous CH₂Cl₂ containing 0.076g (0.535mmole) BF₃-OEt₂ held at -5⁰C under a dry N₂ purge. The reaction system was stirred and maintained at -5⁰C under N₂ purge a further 8 hours then warmed to room temperature and quenched with 15ml DI water. The mixture was transferred to a separatory funnel and the organic phase was rinsed 3 times with 15mL of DI water allowing 24hours for settling between rinses. CH₂Cl₂ was removed from the organic layer by rotary evaporator at 65⁰C and full vacuum. The product was then transferred to a vacuum drying oven and maintained at 0 torr and 65 ⁰C for 24 hours. NMR end group analysis of the P[ME2Ox] product gave an M_n of 17,975g/mole or 18 kDa.

While the invention has been described in terms of its preferred embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the appended claims.

Claims

CLAIMSWhat we claim as our invention is:

1. A method of producing a polyoxetane composition, comprising the steps of: a) combining a diol initiator compound with at least a first monomer to form a combination; b) adding the combination of step a) to a Lewis acid catalyst.

2. The method of claim 1, wherein the Lewis acid catalyst is selected from the group consisting of: boron trifluoride and boron trifluoride etherate.

3. The method of claim 1, wherein the first monomer is selected from the group consisting of: a 3FOx monomer; a 5FOx monomer; a 7FOx monomer; a 9FOx monomer; an ME_nOx monomer where n = O, 1, 2, 3 or 7; and a BBOx monomer.

4. The method of claim 1 , wherein the at least a first monomer is a solution comprising one selected from the group consisting of: a 3FOx monomer; a 5FOx monomer; a 7FOx monomer; a 9FOx monomer; an ME_nOx monomer where n = O, 1, 2, 3 or 7; and a BBOx monomer.

5. The method of claim 1, wherein the diol initiator compound is an alkyl or isoalkyl diol.

6. The method of claim 5, wherein the alkyl or isoalkyl diol is selected from the group consisting of: ethylene glycol; butane- 1,4-diol; propylene glycol; isobutene-l,3-diol.

7. The method of claim 1, wherein the diol initiator is butane- 1,4-diol.

8. The method of claim 1, wherein the at least a first monomer is a solution comprising the first monomer and further comprising a second monomer; wherein the second monomer is different from the first monomer; and wherein the second monomer is selected from the group consisting of: a 3FOx monomer; a 5FOx monomer; a 7FOx monomer; a 9FOx monomer; an ME_nOx monomer where n = O, 1, 2, 3 or 7; and a BBOx monomer.

9. The method of claim 1 , wherein the combination of step a) is in solvent.

10. The method of claim 1, wherein the Lewis acid catalyst is in solvent.

11. The method of claim 1, wherein the combining step a) is performed at ambient temperature, at atmospheric pressure, for a period of time in a range of about 1 minute to 10 minutes.

12. The method of claim 1, wherein the adding step b) is performed with the combination of monomer and initiator being a solution at ambient temperature in a range of about 10 to 30 degrees C, while the catalyst is at a temperature in a range of about -5 to 5 degrees C, at ambient pressure, for a period of time in a range of about 2 to 12 hours.

13. The method of claim 1, including performing the adding step b) until a polyoxetane composition is formed.

14. The method of claim 1, consisting essentially of the combining step a) and the adding step b).

15. The method of claim 13, wherein the formed polyoxetane composition is selected from the group consisting of: (1) a random A-B copolymer comprising at least two different monomers A and B represented P[AB] where P means the ring opened structure of monomer A and monomer B, respectively; (2) a semicrystalline material comprising an oxetane monomer with two identical side chains represented by P[Bis- A] where P and A have the same meanings as above; (3) a homo-polyoxetane composition represented by P[A] having a 1,3-propylene oxide main chain at which are two different groups at the three position, wherein a first group on the 2-propylene oxide position is a methyl or ethyl group and wherein a second group on the 2- propylene oxide position is a side chain selected from the group consisting of 3FOx, 4FOx, 5FOx, 7FOx, MOx, MeIOx, Me20x, Me30x and Me70x, wherein P and A have the same meanings as above; and (4) a block soft block copolymer that is noncrystalline and is represented by P[A][B] or P[A]_m[B]_n, wherein P, A and B have the same meanings as above, and m and n represent molecular weights of the A and B blocks respectively.

16. The method of claim 1, including performing the adding step b) until a co- polyoxetane composition is formed, said co-polyoxetane having an alkylenebromide side chain that is reactive with an amine to produce a P[AB] co-polyoxetane having a quaternized side chain.

17. The method of claim 16, wherein the alkylenebromide side chain is BBOx.

18. The method of claim 16, wherein the formed P[AB] co-polyoxetane having a quaternized side chain is processable into a polyurethane comprising a soft block having charge concentrated in the soft block.

19. The method of claim 15, wherein the formed polyoxetane composition has a surface soft block nano-thickness in a range of 2-4 nm.

20. The method of claim 15, wherein the formed polyoxetane composition has a molecular weight exceeding 8 kDa.

21. The method of claim 15, wherein the formed polyoxetane composition is a semi- crystalline material having a molecular weight exceeding 6kDa.

22. The method of claim 15, wherein the formed polyoxetane composition on a surface thereof has oil-resistance represented by a hexadecane contact angle of greater than 70 degrees and/or water resistance represented by a water contact angle exceeding 104 degrees.

23. The method of claim 15, wherein the formed polyoxetane composition has a water solubility property of at least 5 g/L.

24. The method of claim 15, wherein the formed polyoxetane composition comprises a high-molecular-weight chain with Mn exceeding 8 kDa.

25. The method of claim 15, wherein the formed polyoxetane composition is a coating.

26. A polyoxetane composition, wherein the polyoxetane composition is selected from the group consisting of: (1) a random A-B copolymer comprising at least two different monomers A and B represented P[AB] where P means the ring opened structure of monomer A and monomer B, respectively; (2) a semicrystalline material comprising an oxetane monomer with two identical side chains represented by P[Bis- A] where P and A have the same meanings as above; (3) a homo-polyoxetane composition represented by P[A] having a 2-propylene oxide position at which are two groups, wherein a first group on the 2-propylene oxide position is a methyl or ethyl group and wherein a second group on the 2-propylene oxide position is a side chain selected from the group consisting of 3FOx, 4FOx, 5FOx, 7FOx, MOx, MeIOx, Me20x, Me30x and Me70x, wherein P and A have the same meanings as above; and (4) a block soft block copolymer that is non-crystalline and is represented by P[A][B] or P[A]_m[B]_n, wherein P, A and B have the same meanings as above, and m and n represent molecular weights of the A and B blocks respectively.

27. The composition of claim 26 which is a co-polyoxetane composition, said co- polyoxetane having an alkylenebromide side chain that is reactive with an amine to produce a P[AB] co-polyoxetane having a quaternized side chain.

28. The composition of claim 27, wherein the alkylenebromide side chain is BBOx.

29. The composition of claim 26, wherein the P[AB] co-polyoxetane having a quaternized side chain is processable into a polyurethane comprising a soft block having charge concentrated in the soft block.

30. The composition of claim 26 wherein the polyoxetane composition has a surface soft block nano-thickness in a range of 2-4 nm.

31. A polyoxetane polyurethane composition, comprising a surface soft block having a nano-thickness in a range of 2-4 nm.

32. The composition of claim 26, wherein the polyoxetane composition has a molecular weight exceeding 8 kDa.

33. The composition of claim 26, wherein the polyoxetane composition is a semi- crystalline material having a molecular weight exceeding 6kDa.

34. The composition of claim 26, wherein the polyoxetane composition on a surface thereof has oil-resistance represented by a hexadecane contact angle of greater than 70 degrees and/or water resistance represented by a water contact angle exceeding 104 degrees.

35. A polyoxetane composition having a surface which is oil-resistant and/or water- resistant, the surface having oil-resistance represented by a hexadecane contact angle of greater than 70 degrees and/or water resistance represented by a water contact angle exceeding 104 degrees.

36. The composition of claim 26, wherein the polyoxetane composition has a water solubility property of at least 5 mg/L.

37. The composition of claim 26, wherein the polyoxetane composition comprises a high- molecular-weight chain exceeding a value for Mn of 6 kDa.

38. The composition of claim 26, wherein the polyoxetane composition is a coating.

39. The composition of claim 26, wherein the polyoxetane composition is selected from the group consisting of: P[(3FOx)(BBOx)-0.75:0.25], P[(ME2Ox)(BBOx)-0.75:0.25], P[(3FOx)(C12)-0.75:0.25]; P[(ME2Ox)(C12)-0.75:0.25], P[3FOx], P[Bis-3FOx], P[(3FOx)(BBOx)-0.875:0.125], P[(3FOx)(C12)-0.875:0.125], HMDI-BD(30)- P[(3FOx)(C12)-0.88:0.12], P[(ME2Ox)(BBOx)-0.75:0.25], P[(3FOx)(BBOx)- 0.70:30]; and P[ME2Ox].