Expandable functional tfe copolymer fine powder, the expanded functional products obtained therefrom and reaction of the expanded products.

(54) Title: EXPANDABLE FUNCTIONAL TFE COPOLYMER FINE POWDER, EXPANDED FUNCTIONAL PRODUCTS OBTAINED FROM THE SAME AND REACTION OF THE EXPANDED PRODUCTS.

(54) Title: EXPANDABLE FUNCTIONAL TFE COPOLYMER FINE POWDER, THE EXPANDED FUNCTIONAL PRODUCTS OBTAINED THEREFROM AND REACTION OFTHE EXPANDED PRODUCTS.

(57) Summary

A fine functional TFE copolymer powder is described, wherein the TFE copolymer is a TFE polymer and at least one functional comonomer, and wherein the TFE copolymer has functional groups that are pendant to the polymer chain. The functional TFE copolymer fine powder ream is extruded and expandable paste. Methods for making the TFE copolymer functional are also described. The expanded functional TFE copolymer material can be post-reacted after expansion.

(57) Abstract

A functional TFE copolymer fine powder is described, where the TFE copolymer is a polymer of TFE and at least one functional comonomer, and where the TFE copolymer has functional groups that are pendant to the polymer Chain. The functional TFE copolymer fine powder resin is paste extrudable and expandable. Methods for making the functional TFE copolymer are also described. The expanded functional TFE copolymer material may be post-reacted after expansion.

EXPANDABLE FUNCTIONAL TFE COPOLYMER FINE POWDER,

EXPANDED FUNCTIONAL PRODUCTS OBTAINED FROM THE SAME AND

REACTION OF EXPANDED PRODUCTS

FIELD OF THE INVENTION

Described herein are functional monomer-containing expandable TFE copolymer fine powder resins, the expanded functional products obtained from these copolymers, and the processes for making them. In addition, post-expansion reactions of expandable functional TFE copolymer materials, and products made therefrom, are described.

BACKGROUND OF THE INVENTION

Polytetrafluoroethylene or PTFE is known to have a unique combination of properties including excellent chemical resistance, high temperature thermal stability, low surface energy, and excellent electrical (dielectric) properties. PTFE is also known to have two deficiencies that limit its use: high flow or cold flow and poor resistance to ionizing radiation.

Extending certain forms of PTFE to make microporous expanded PTFE (ePTFE) can improve strength, decrease cold flow or creep, and improve dielectric properties without changing surface or chemical properties. Chemical resistance or inert quality, as well as low surface energy, of PTFE and ePTFE are beneficial properties for some applications. But for other applications, it would be beneficial to selectively modify these properties without degrading the polymer.

There has been a major search to modify the surface or chemical properties of PTFE and micro-porous ePTFE to improve adhesion and compatibility with other materials. For example, efforts have included attempts to decrease creep by radiation crosslinking, increase or decrease free surface energy (eg increase or decrease hydrophilicity), and provide sites for chemical reactions to improve the usefulness of PTFE and / or or ePTFE in specific applications by means of chemical and plasma treatments.

Recently, plasma treatment of microporous ePTFE in the presence of maleic anhydride is reported to have acidic functionality on the surface of microporous ePTFE. Although the exact mechanism of these surface reactions is not reported, it probably results from the formation of free radicals by bond cleavage. Where the carbon-carbon bond strength is known to be about forty percent lower than carbon-fluorine bonds, a majority of the radicals would result from cleavage of carbon-carbon bonds, or major polymer chain cleavage, from this thereby decreasing the molecular weight of the polymer, and restricting the anhydride or acid functionality to the ends of the degraded polymer chains. Plasma graft polymerization is restricted near the surface of the sample.

(Plasma Surface Modification and Plasma Polymerization; N.

Inagoki, Technomic Publishing, 1996, p.44).

Techniques for dispersion polymerization of both tetrafluoroethylene monomer (TFE) and TFE copolymers have been described. There are some references that define and distinguish TFE copolymers based on the concentration of the comonomer. TFE polymers containing less than 1 weight percent comonomer have been referred to as modified homopolymers, or modified PTFE, while TFE polymers containing more

0 that 1 weight percent comonomer have been referred to as TFE copolymers. (Fluoroplastics - Vol 1: Non-Melt

Processible Fluoroplastics; Williams Andrew, Inc., Norwich, NY, at p. 19 (2000).) However, for use herein, TFE polymers containing one or more comonomers in any concentration will be defined as TFE copolymers.

In some processes, the dispersion polymerization of

TFE produces a resin that comes to be known as fine powder. (eg, US Pat. No. 4,016,345 (Holmes,

1977)). Generally, in such processes, sufficient dispersing agent is introduced into a water carrier such that, under the addition of the TFE monomer in the presence of a suitable polymerization initiator and, under stirring and under pressure, autogenous TFE of 10-40 kg / cm², polymerization proceeds until the desired level of colloidal dispersed polymer particles is reached and the reaction is then stopped. The dispersed polymer particles can subsequently be coagulated by known techniques to obtain the fine powder form of the polymer. Fine powders dry at temperatures of around 100 to

200 ° C.

Powder resins are known to be useful in paste extrusion processes and stretch (expansion) processes in which the extruded paste extrudate, after removal of the extrusion auxiliary lubricant, is stretched to produce various porous strong products cross section shapes such as rods, filaments, sheets, tubes etc. Such a stretching process is described in Pat. US Common Property No. 3,953,566 (566 a Gore). The expansion process as applied to fluorocarbon polymers is described in the above '566 patent. As used herein, articles that can be expanded by the process of the '566 patent are said to be expanded, and the resins used in the expansion process to create such articles are said to be expandable TFE polymers or TFE copolymers. expanded them.

Dispersion processes for making TFE copolymers are taught in, for example, US Patent No.

4,792,594 (Gangal et al.), Pat. USA No. 6,541,589 (Baillie), Sol. Pat. USA 2007/0010642 (Sabol and Baillie) and Sol. Pat. USA 11/906, 877 (Ford; filed Oct. 4,

2007). Dispersion processes for making copolymers are also described. It is taught that the fine powders made by these dispersions can be extruded paste and processed by the processes described in Pat. USA No. 3,953,566 to make expanded micro-porous products. The TFE fine powder polymer processed by extrusion or paste expansion has high crystallinity especially for the portion of polymer formed in the subsequent stage of polymerization. This material is sometimes described as the envelope or refuge of the dispersion particle.

Casting injection molded and extrusion cast TFE copolymers include TFE-HFP (hexafluoropropylene) copolymers known as FEP, TFE vinyl perfluoroalkyl ether copolymers known as PFA and MFA, and ethylene and TFE copolymers known as E-TFE.

These polymers are not fine powders and cannot be extruded or expanded paste in microporous products due to low crystallinity.

TFE copolymers made from fluorovinyl ether comonomers having fluorine sulfonyl groups, ester groups, and cyano groups have been described having the following formulas:

I. CF₂= CF - OR_F SW₂F

II. CF₂= CF - OR_F COOCH₃

III. CF₂= CF - OR_F - CN where R_F it is fluoroalkyl or fluororalkyl ether.

(Fluoroplastics-Vol.2: Melt Processible Fluoropolymers;

Williams Andrew Inc .; Perfluorinated Ionomer Membranes,

American Chemical Society Symposium, Series 180, 1982; Pat.

USA No. 3,692,569 (Grot); Moore, Albert L.

Fluoroelastomers Handbook, William Andrew Publishing, 2006). The monomers in structures I and II are copolymerized with TFE to form subsequently hydrolyzed polymers to form sulfonic acid and carboxylic acid. However, these polymers contain sufficient concentration of comonomer that there is little if any crystallinity in the polymers. The monomers of structure III have been polymerized with TFE and perfluoroalkyl vinyl ethers to make perfluoro elastomers where the monomer with structure

III is the crosslinking site for elastomers. The materials have little or no crystallinity and therefore are not expandable to create microporous materials.

Pat's Sunshine. E.Ü.A. 2006/0270780 (Xu et al.) Teaches a modified PTFE with a cyanovinyl ether crosslinking monomer in a microemulsion process. In this patent application, the modified PTFE is not a fine powder and cannot be an extruded and expanded paste according to the '566 process.

The Pat. No. 7,019,083 (Grootaert) teaches a low molecular weight melt processable TFE perfluoropropyl vinyl ether copolymer (PPVE) containing a non-known cyanovinyl ether. It forms as a fine powder and lacks sufficient crystallinity to be extruded paste and processed into microporous products. The Pat. of

US No. 4,326,046 (Miyaka) teaches how to make modified PTFE by including 0.001 to 10 mol% of a comonomer component that has an acid-type functional group (or precursor for an acid). The acid includes carboxylic, sulfonic, or phosphoric acids. The Pat. No. 4,326,046 teaches that the modified polytetrafluoroethylene particle comprises a core made of tetrafluoroethylene homopolymer and the modifying component is included in the sheath layer. The

Pat. US No. 4,326,046 does not teach the extrusion or expansion paste to the modified polymer. Materials that have the high modifier component polymerized in the subsequent polymerization steps would not have sufficient crystallinity to be processed into microporous products by the '566 process.

The Pat. USA No. 7,342,066 for Dadalas et al. teaches the use of a PTFE dispersion in a coating process. PTFE contains up to 1 weight percent of an ionic comonomer (eg, a monomer having acidic groups such as an ionic group) where at least a portion and preferably all of the comonomer is added in the subsequent stage of polymerization. The Pat. from USA No.

7,342,066 does not teach the formation of an extrudable paste or a fine expanded powder. Materials made with the high comonomer concentration in the later stages of polymerization would have low crystallinity and would not be extrudable or expanded paste by the processes of the '566 patent.

There is a need for TFE copolymer materials that contain functional groups that impart specific chemical properties to a polymer, where the copolymer can expand to provide a microstructure characterized by nodes interconnected by fibrils. There is a further need for expanded TFE copolymer materials containing functional groups that can undergo subsequent controlled reactions to impart other specific properties to the expanded material while maintaining the properties of the expanded TFE copolymer material.

SUMMARY OF THE INVENTION

This invention relates to functional TFE copolymers comprising TFE and at least one comonomer comprising a functional group. The functional TFE copolymer has functional groups that are pendant to the polymer chain. The pendant functional groups emanate from a branch of the polymer chain. The functional TFE copolymer can be expanded (stretched under controlled conditions) to produce microporous expanded TFE copolymer material, having a microstructure characterized by nodes (1) interconnected by fibrils (2) (as exemplified in Figs. 1 and 2) .

A process is described for the polymerization of these monomers to produce functional TFE copolymers, as well as dispersions of the functional TFE copolymer.

Furthermore, it is disclosed that the fine powder of the functional TFE copolymer which is extrudable paste and expanded into microporous functional TFE copolymers. The porous functional products produced by the expansion of the polymers, and the reactions of the porous functional TFE materials are described.

BRIEF DESCRIPTION OF THE FIGURES

Fig. 1 SEM photomicrograph of an expanded sheet of functional TFE copolymer taken at ΙΟ, ΟΟΟΧ of amplification.

Fig. 2 SEM microphotography of an expanded sheet of functional TFE copolymer taken at ΙΟ, ΟΟΟΧ of amplification.

Fig. 3 is a representation of an immobilization of a bioactive species for a functional group;

Fig. 4 is a representation of a group substitution reaction of an initial functional group, wherein the initial functional group is reacted to form a secondary functional group;

Fig. 5 is a representation of an immobilization of a bioactive species for a secondary functional group;

Fig. 6 is a representation of an immobilization of a spacer arm for a functional group.

DETAILED DESCRIPTION OF THE INVENTION

Described herein are functional TFE copolymers made from an aqueous dispersion polymerization process, and processes to form fine powders of functional TFE copolymers that are extrudable and paste expandable. The functional TFE copolymer comprises a TFE polymer and at least one comonomer containing a functional group. TFE copolymers comprise functional groups that are pendant to the polymer chain. A process is provided for making the fine powder and functional TFE copolymer and at least one comonomer containing a functional group. Also described is the microporous expanded TFE copolymer having functional groups obtained from fine powders, and the processes for reacting the microporous expanded TFE copolymer having functional groups.

The term TFE copolymer is defined as a TFE polymer that comprises one or more comonomers in any concentration. As used herein the term functional TFE copolymer is defined as a TFE copolymer which has functional groups that are pendant to the polymer chain where the functional TFE copolymer is formed by copolymerizing TFE with comonomers having a functional group . Functional TFE copolymers can be expanded into microporous materials. The expanded functional TFE copolymers made by the processes described herein have a microstructure characterized by nodes interconnected by fibrils and the copolymers have a functional group pendant to the polymer chain.

As used herein, the term "functional comonomer" is a monomer that copolymerizes with TFE in a dispersion polymerization and · when incorporated into the polymer introduces side groups that comprise functional groups that are pendant to the polymer chain.

Functional comonomers that may be useful in this invention include fluorinated or perfluorinated monomers. Fluorinated monomers contain at least one fluorine atom.

Perfluorinated monomers have at least one fluorine atom, and no carbon-hydrogen bonds and carbon-halogen pin bonds other than carbon-fluorine bonds. Suitable functional monomers have the general formulas given in Table 1 where Z is defined as the functional group, the examples of which are provided in Table 2.

Table 1. General structural formulas for comonomers

<td>cx₂= cxz</td><td>X: H, halogen, alkyl, alkyl</td><td>fluoro</td>

<td>cx₂= cx-rz</td><td>X: H, halogen, alkyl, alkyl</td><td>fluoro</td>

<td>A: alkyl,</td><td>alkyl ether, fluoro alkyl ether,</td><td>alkyl ether</td>

<td>perfluoro</td><td></td><td></td>

<td>CF₂= CF-OR_F-</td><td>ZR_F: fluoroalkyl 0 ether alkyl</td><td>fluoro</td>

Functional groups that can be incorporated into the copolymers as pendant groups include, but are not limited to, the functional groups listed in Table 2.

As used herein, the term functional group specifically excludes ether (COC) groups, and groups consisting of carbon-halogen or carbon-hydrogen bonds.

These links are described as -CX₂- or -CX3 where X is either halogen or hydrogen. For purposes herein, while chemical moieties including ether groups, and chemical moieties formed of carbon-halogen bonds and carbon-hydrogen bonds, are not considered functional groups, there may be part of a functional comonomer that comprises a functional group that is suitable for use herein.

Table 2. Functional groups alcohols —C — OH aldehydes —CHO ketones —C = 0 carboxylic acids —COOH or ester salts —COOR, -OCOR where R is alkyl or aryl cyano group or nitrites _C = N amines —C-NH₂, —C — RNH, - C — R₂NRi,

-C-RiR₂R₃N + where R, Ri, R₂ and R₃ are alkyl or fluoroalkyl amide —C = O, —C = OII

NH₂ Ri — N — r₂ where Ri and R₂ are alkyl or fluoroalkyl halide carbonyl —XC = O where X is F or C1 halide sulfonyl sulfonic acid sulfonamide sulfonimide anhydrides carbamates —SO₂X where X is F or C1 —SO₃H or you go out

-SW₂NH₂

- S0₂—NHN — S0₂-C (O) -O- (O) CO = CONH— sulfides csc disulfides

C-SS-C cyanate phosphonic acid or salts —OC = N

OP (= O) OH₂ triazine

NN

I II /^c\

N —C (= NH) -NH2 amidine isocyanate

Other functional groups include but are not limited to sulfate ester, phosphate ester, thiol, imide, carbodiimide, imidazole, azide, azido, styrene, alkylbenzene, phenol, catechol, and the like.

Another aspect of this invention includes a process for reacting the expanded functional TFE copolymer comprising pendant functional groups where at least some of these pendant functional groups that result from the polymerization process, form secondary functional groups that are different from the initial pendant secondary groups. as depicted in FIG. 4. In one embodiment, as depicted in FIG. 4, a group substitution is represented as Y being replaced by the functional group R. Additional reactions of these secondary functional groups are possible and in some embodiments, for example, tertiary functional groups may form in the expanded TFE copolymer material to in addition to changing the nature of a copolymer material of

Expanded functional TFE, for example to obtain a desired chemical property.

The general formulas for the comonomers of this invention are given in Table 1. The concentration of the comonomer containing a functional group in the resulting functional TFE copolymers may be less than 5 mol%, or less than 3 mol%, or less than 2 mol%, or less than 1 mol% or less than 0.5 mol%. The concentration of comonomer having a functional group in the resulting functional TFE copolymers may be greater than 0.015 mol%, greater than 0.04 mol%, greater than 0.07 mol%, greater than 0.1 mol%, greater than 0.5 Mole%, greater than 1.0 mol%, greater than 2 mol%, or greater than 3 mol%.

The concentration of the comonomer containing a functional group in the resulting functional TFE copolymers can be between 0.01 and 5 mol%, 0.01 and 3 mol%, or 0.01 and 2 mol%, and can be measured according to the methods described here .

At least one functional comonomer can be polymerized with

TFE to provide a copolymer having a multiplicity of pendant functional groups. More than a comonomer. Functional can also be provided. Where more than one functional comonomer is provided, functional comonomers can provide the same or different functional groups that are pendant to the polymer chain.

Additionally, one or more non-functional comonomers can be copolymerized with TFE and at least one functional comonomer to form expandable functional TFE copolymers having pendant functional groups. Non-functional comonomers are defined herein as comonomers that do not result in pendant functional groups on the polymer chain. Non-functional comonomers include but are not limited to fluoro-olefins ie hexafluoroproylene (HFP), fluoroalkyl vinyl ethers; PMVE (vinyl perfluoromethyl ether), PEVE (vinyl perfluoroethyl ether) and PPVE (vinyl perfluoropropyl ether).

In one embodiment, a functional comonomer comprises a fluorovinyl ether of the general formula

CF₂= CF- OR_FZ, where R_F represents a fluoroalkyl group optionally interrupted by one or more oxygen (s) and Z represents a functional group from Table 2. Z can be cyano or nitrile, aldehyde, carboxylic acid or salt, ester, amine, amide, carbonyl halide, sulfonyl halide, sulfonic acid or salts, sulfonamide, sulfonimide, anhydride, sulfide, phosphonic acid or salt, hydroxyl (alcohol) , sulfate esters, phosphate esters, isocyanate, thiol, imide, carbodiimide, imidazole, azide, azido, styrene, benzene alkyl, phenol, catechol, and the like. Fluorovinyl ether monomers can include comonomers listed in Table 3.

Table 3. Fluoro vinyl ether functional comonomers.

Vinyl Cyano Ethers

CF₂= CFOR_F—CN where Rf is a fluorinated alkyl or alkyl ether group. Illustrative examples are:

• CF₂= CF-O (CF₂) _n-CN where n = 2-12, or preferably where n = 2-6;

• CF₂= CF — O [CF₂—CF (CF₃) —O] _n—CF₂—CF (CF₃) —CN where n = 0-4, or preferably where n = 0-2;

• CF₂= CF- [OCF₂CF (CF₃) ]_x-OR- (CF₂) „- CN where x = l-2, and n = l-4; and • CF₂= CF — O— (CF₂) _n—0 — CF (CF₃) CN where n = 2-4. A preferred type of monomer includes perfluorinated polyethers having a nitrile group and a trifluorovinyl ether group, including perfluoro (8-cyano-5-methyl-3,6-dioxa1-octene), CF₂= CFOCF₂CF (CF₃) OCF₂CF₂CN.

Sulfonyl Fluoride Vinyl Ethers

CF₂= CFOR_FSW₂F where R_F it is a fluorinated alkyl or an alkyl ether group. Illustrative examples are:

• CF₂= CFOCF₂CF₂

SW₂F • CF₂= CFOCF₂CFOCF₂CF₂SW₂F

CF₃ • CF₂= CFOCF₂CFC9CF₂CFOCF₂CF₂SW₂F

I

CF

I cf₃

CF₂= CFOCF₂GFOCF₂CF₂SW₂F ¿f₂ ©

I © f₃

A preferred comonomer containing sulfonyl fluoride is perfluoro (3,6-dioxa-4-methyl-7-octane sulfonyl fluoride), j

CF₂= CFOCF₂CFDCF₂CF₂SW₂F

I

CF;

Acid or vinyl ether ester or other acid precursors

CF₂= CF- O- R_F-Chorus

CF₂= CF- [OCF₂CF (CF₃) ] _m-O (CF₂) n- (CH₂) POOR where R_F it is a fluorinated alkyl or alkyl ether group; m = 0-20;

n = 1-10; p = l-4; and R = alkyl. Illustrative examples are:

• CF₂= CF- [OCF₂CF (CF₃)] -O (CF₂)₂-CH₂COOCH₃ • CF₂= CFO (CF₂) ₃ch₂cooch₃ • CF₂= CF-OCF₂CF CF₃) OCF₂CF₂COOCH₃ • CF₂= CFO (CF₂) i-¿COOCH₃

I

I • CF₂= CFO (CF₂) i-¿COOC₂H₅ • CF₂= CFOCF₂CF (c! F₃ ) OCF₂CF₂CF₂COOCH₃ • CF₂= CFO (CF₂) i ^ P (OCH₃) 2 • CF₂= CF- [OCF₂CF (CF₃)] -OCF₂CF₂COOH

CF₂= CF- [OCF₂CF (CF₃)] -OCF₂CF₂CH₂OPO (OH)₂

CF₂= CF [OCF₂CF (CF₃)] -ocf₂cf₂ch₂-oconh₂

Hydroxy vinyl ethers

CF2 = CF (OCF₂CFCF3 where p = 0 or 1; m = 0-10; n when m&gt; 0, then p = l nO_p (CF₂) _mCH₂OH = 1-20; when m = 0, then p = 0 ,; and

Illustrative examples are:

CF₂= CF-O-CF₂CF (CF₃) OCF₂CF₂CH₂OH • CF₂= CFOCF₂CF₂GF₂CH₂Oh

CF₃

I

CH₂= CH — O — CH₂CH₂—OR — CH₂—C — OH

Other ic comonomers of TFE copolymers of comonomers listed in

I

CF₃ Ones for use in the preparation described herein include those in Table 4.

Table 4. Other functional fluoromonomers • cf₂= cfso₂f • CF₂= CFCF₂CF₂SW₂F • CF₂= CFCF₂OCF₂GF₂SW₂F • CF₂= CF (CF₂) o-8COOCH₃

I • CF₂= CFCF₂OCF (CF₃) COOCH₃ • CF₂= CFCF₂OCF (CF₃) cf₂ocf (CF₃) cooch₃ • CF₂= CFCF₂O (CF₂)₄COOCH₃

Polymerization is carried out by means of an aqueous dispersion polymerization process to produce a fine powder resin by modifying known processes (eg, US Pat. 4,016,345 to Holmes). The addition of the functional comonomer or optionally other comonomers to the reaction vessel is controlled. Sufficient dispersing agent is introduced into a carrier

I of water where under the addition of the TFE monomer in the presence of a suitable polymerization initiator, and low!

With stirring and under pressure autogenous TFE of 10-40 kg / cm, the polymerization proceeds until the desired level of colloidal functional TFE copolymer particles is reached!

scattered and the reaction stops. The product of the polymerization reaction is the functional TFE copolymer!

dispersed within an aqueous colloidal dispersion.

¡

In one embodiment, the TFE monomer is pressurized in a fine polymerization guide and initiators to suppress the formation of autoclave containing a along with para clot wax, and an agent; emulsifying. The addition of the comonomer functionally or optionally other comonomers to the

I reaction is controlled. Where the comonomers are liquid, the process involves emulsifying the comonomers prior to i

I add the comonomers to the reaction vessel. The comonomers are emulsified as emulsions in water containing a surfactant, preferably a fluoro surfactant.

Both the added amount of functional comonomer and the starting time of comonomer addition are determined based on the desired concentration of the comonomer in the resulting copolymer and comonomer. The step of polymerization reactivity of adding the comonomer, including the added amount of com'onomer and the time in the eJ polymerization batch cycle. which comonomer is added, is controlled to ensure that the comonomer is essentially completely reacted or consumed in the process of i

polymerization before polymerization is around 80-90% complete. The. polymerization step continues, after essentially reacting completely or consuming the comonomer in the polymerization process, consists of

I TFE polymerization (by the end of 10-20% of the polymerization in the absence of the comonomer.

provides a functional TFE copolymer that has high crystallinity of the material produced in the last 10-20% of it

polymerization. The resulting functional TFE copolymer resin is extrudable paste and expanded into structures

This microporous.

In one modality, comonomer prior to the process includes removing the

80?

90?

termination of the polymerization, for example, by evacuating the comonomer under low pressure or steam-assisted distillation.

Subsequently, the polymerization of TFE is resumed and further comprises complete aqueous dispersion.

After the polymerization is complete, the process ects out the aqueous dispersion of particles comprising the steps of decreasing the ⁵ temperature up to around 20 ° C, removing them from the wax, and removing them from the polymerization container. It is removed from the polymerization vessel, diluted with water and coagulated with fine powder by methods known in the art. Fine powder 10 dries in air or under¹ vacuum at 100 to 200 ° C prior to extrusion and paste expansion processing.

In one embodiment, a mixture of functional expanded TFE copolymer may be comprised of a functional expanded TFE copolymer mixed with another copolymer of ¹⁵ TFE having a different concentration of functional comonomer, or different Jipo of functional comonomer, or with i

i TFE homopolymer or a modified TFE polymer. The expandable polymers suitable for mixing with copolymers of

Expandable TFE works but is not limited to PTFE and polymers as described in Pat. USA No. 5, 708,044 (Branca, 1998), Pat. EU

Pat. USA No. 7,531,611 Pat. USA No. 11/906,

In another modality .A. No. 6,541,589 (Baillie, 2003), (Sabol et al., 2009), Request for

877 (Ford), and the like.

the functional expanded TFE copolymer is mixed with a molten processable fluoropolymer or perfluoropolymer, or any other polymer, or combinations thereof, by any conventional method including those taught in Pat. USA No. 6,127,486 for Burger et al. Other polymers that can be blended with the expandable functional TFE copolymers include but are not limited to FEP, PFA, PVDF, ionomers, fluoroelastomers, and the like.

The polymer blend can be mixed through a co-coagulated process of) in the form of a fine powder.

provide desirable properties. For example, to dispersion, or mixed in resin or

The type and / or concentration of the components of the mixture can be selected for mechanical, functional or process components of a mixture can be selected to provide a material that can be processed into a desired final material that has desired mechanical and functional properties.

The filler material, such as carbon, silica, and the like, can also be combined with the functional expandable TFE copolymer by any conventional method including those taught in Pat. USA No. 3,953,566to Gore, Pat. USA No. 4,187,390 for Gore and Pat. USA No. 4,985,296 for Mortimer. In one embodiment, the filler is reacted with pendant functional groups of the expandable TFE copolymer described herein. The filler material can be reacted prior to or after the TFE copolymer expands.

Known paste forming techniques can be used to convert the paste-like polymer resin into an article that can then expand after removing a lubricant.

The stages in the paste formation process include mixing the resin with a lubricant such as odorless mineral spirits and carrying out the formation steps in which the resin is subject to trimming.

The paste extrudable functional TFE copolymers made herein are expandable to microporous structures characterized by having nodes interconnected by fibrils, for example, by processes taught in

USA 3,953,566 for iacer PTFE expanded microporous.

Other processes for expending the extruded paste resin include but are not limited to those methods described in Pat. USA. No. 4,902,423, common property í

for Bacino, Pat EUa !. No. 5,476, 589 to Bacino, Pat.

USA No. 5, 814,405 pa

7,306,729 for Bacino et ra Branca et al., And Pat. USA No.

to the.

In one embodiment, a composite membrane comprises a copolymeric material of a fibril-expensive microstructure where e

Expanded functional TFE having: terized by interconnected nodes copolymer is a TFE copolymer having functional groups pendant to the polymer chain, and other matter

L at least partially absorbed into it. The absorbed material may be a polymer, such as but not limited to an elastomer, or thermoplastic, or thermoset, or it may include an organic material such as but not limited to a biological material. In one embodiment the compound comprises an ion exchange material embedded in the expanded material, as taught in Pat.

I

USA No. 6,254,978 for Bahar et al. In some modalities the material to¹ Asorbed substantially occludes the pores of the expanded material as determined by the compound having one second, as measured by Gurley time greater than 200 using the method described herein. In another embodiment the absorbed material is embedded

I through the thickness of the expanded TFE copolymer described herein. In yet another embodiment the absorbed material is reacted with the pendant functional groups of the expanded material. The absorbed material can be crosslinked with or covalently linked to pendant functional groups using standard crosslinking chemistries known in the art. For example, a perfluorinated sulfonyl fluoride resin can be reacted with ammonia or other amines to form a sulfonamide group.

Sulfonamide groups can be crosslinked, for example by exposing them to elevated temperatures, to form sulfonimide groups.

Dense articles may be formed from expanded TFE copolymer materials according to the methods described in Common Property US Pub. No.

2008/0061472 for Kennedy et al.

In one embodiment, an expanded functional TFE copolymeric material is formed having a microstructure characterized by nodes interconnected by fibrils where the copolymer is a TFE copolymer, and where the comonomer comprises functional groups that, in the copolymer, are chain pendant polymer. Hanging functional groups can impart different properties to TFE copolymers. Expanded functional TFE copolymers, and articles made therefrom, can undergo reactions such as chemical reactions with chemical reagents or reactants to react or change functional groups to impart different chemistries or physics to the expanded article. The reagents include but are not limited to organic material, bioactive species, spacer arms, embedded materials, fillers, synthetic polymers, perfluoropolymers, fluoropolymers, ion exchange materials, elastomers, copolymers of

Functional TFEs described herein, and the like.

Another aspect of this invention includes a process for reacting the expanded functional TFE copolymer comprising pendant functional groups where at least some of the initial pendant functional groups that result from the polymerization process, form secondary functional groups that are different from pendant functional groups. initials, as represented in Figure 4. Additional reactions of the secondary functional groups are possible and in some embodiments, for example, tertiary functional groups may be formed in the expanded TFE copolymer material to further change the nature of an expanded functional TFE copolymer, for example to obtain a chemical property desired.

Organic and biochemical reactions with pendant functional groups described in Table 2 may include reactions between at least some of the initial pendant functional groups to form secondary functional groups. For example, in one embodiment, a crosslinking reaction comprising the reaction of a copolymer of

Functional expanded TFE comprising three initial pendant nitrile groups (-CN) under heating at a temperature above 250 ° C form a triazine structure resulting in crosslinking of the TFE copolymer material.

In a further embodiment, at least some of the initial pendant functional groups chemically react with another chemical to form secondary functional groups. For example, initial pendant functional groups such as amide functional groups, acid halide functional groups, and nitrile groups are reacted with water to form acids as secondary functional groups, according to the following reactions.

-COOR + H2O -► -COOH where R is alkyl or fluoroalkyl;

-CONH2 + H₂O -► -COOH;

-COX + H₂O -► -COOH where X is halogen;

-SOOF + H₂O -► -SOOOH; and

-CN + H₂O -► -COOH

Additional chemical reactions include the reaction of the initial pendant nitrile functional groups with ammonia to form amidine groups as secondary functional groups, for example by the following reaction.

-CN + NH₃ —► -C (= NH) NH₂

In one example, an expanded functional TFE copolymer having pendant functional groups comprises an initial ester group that can be reacted with other esters to form a secondary functional group in the form of a different ester group, according to the following reaction.

Rx-COOR + R₂-COOR '-► Ri-COOR' + R₂-COOR where Ri is the initial functional TFE copolymer eg TFE-EVE &lt;CF copolymer₂= CF—

OCF2CF (CF3) OCF2CF2COOCH3), R is alkyl or luoroalkyl group and

R₂ is an alkyl or fluoroalkyl group and R 'is a different alkyl or fluoroalkyl group than R.

Furthermore, the monomers listed in Table 2 can react using methods that are well known in the art, including but not limited to transamidation, isocyanurate formation, uret formation, dehydrogenation, and unsaturation formation, hydrolysis, aminolysis, condensation, electrophilic addition , nucleophilic substitution, elimination, hydrogen abstraction, Michael addition, and the like.

Where the expanded functional TFE copolymers comprise pendant ester groups and / or pendant acidic functional groups, the initial functional groups may be reacted with ammonia or other amines to form secondary amide functional groups, according to the following reactions.

-COOR + NH₃ -&gt; -CONH₂

-COOH + NH₃ -► -CONH2 where R is alkyl-or fluoroalkyl.

Furthermore, an expanded functional TFE copolymer comprising pendant nitrile starting functional groups can be reacted to reduce nitrile groups to secondary amine functional groups according to the following reaction.

-CN —► -CH2-NH2

In another embodiment where the expanded functional TFE copolymer comprises pendant sulfonyl fluoride starting functional groups which can react with ammonia or other amines to form an expanded TFE copolymer comprising sulfonamide secondary functional groups, the expanded material may further be reacted to form Sulfonimide tertiary functional groups under heating as follows.

-SOOF + NH₃ -&gt; -SO2NH2 —► -SO2NHNSO2 In another embodiment, the functional TFE copolymer of the present invention can be treated with or exposed to radiation with or without the presence of another reagent to change existing functional groups or create new functional groups. In one embodiment the copolymer material of

Functional TFE is exposed to radiation in the resin form and in another embodiment it is exposed in the expanded form.

The expanded microporous TFE copolymer material containing pendant functional groups provides a good medium for chemical reactions. Since the functional groups are from TFE-polymerized comonomers, the pendant functional groups are integrated and can be distributed through the microstructure of the expanded polymeric material. Hanging functional groups are surprisingly available to bring into contact with each other with additional chemical reagents, reagents, organic material, or bioactive species. In addition, the non-functional part of the expanded microporous structure have fluoride concentration (equal to or greater than 95 mol%

TFE) which results in good chemical resistance (solvent) and stability at high temperatures that make the expanded functional copolymer material a good medium for chemical reactions.

In yet another embodiment, the chemical reagents can include natural and synthetic chemicals that are capable of reacting with pendant functional groups of the expanded functional TFE copolymers. Natural materials include biochemicals and biopolymers that include but are not limited to carbohydrates, carbohydrate or polysaccharide polymers, chitin, glycogen, heparin, heparan sulfate, polypeptides and proteins, collagen, gelatin, enzymes, nucleic acids, DNA, RNA, lipids , spheroids, hormones, pharmaceuticals, and other therapeutic agents.

The reagents can also include synthetic polymers. For both natural or biopolymers and synthetic polymers, the reactive site of the reagent can also be a functional group that is pendant to the reactive polymer chain. The reagent reactive site may alternatively be a non-pendant group. Synthetic polymeric reagents include but are not limited to those listed in Table 5.

Table 5. Representative List of Formulas and Synthetic Polymeric Reagents • TFE-PMVE-8CNVE Copolymer

- (CF2-CF2) - [CF₂-CF (OCF₃)] -CF₂-CFOCF₂CF (CF₃) OCF₂CF₂CN • TFE-VDF-HFP-8CNVE Copolymer

- (CF₂-CF₂) - (CH₂-CF₂) - [CF₂-CF (CF₃)] -cf₂cfocf₂cf (CF₃) ocf₂cf₂cn • Poly (vinyl acetate) - [CH2-CH (OCOCH3)] • Poly (vinyl alcohol) - [CH2CH (OH)] • Poly (ethylene glycol) H0- (CH2-CH2-O)_n^-H • Poly (propylene glycol) H0- (ΟΗ₂-ΟΗ₂-ΟΗ₂-Ο) _n^_H • Poly (imine ethylene) - (ΟΗ₂-ΟΗ₂-ΝΗ) • Poly (ethyl acrylate) - [CH₂-CH (COOC₂H₅)] • Poly (acrylic acid) - [CH₂-CH (COOH)] • Poly (acrylonitrile) - [CH₂-CH (CN)] • Poly (vinyl ethylene acetate) - (CH₂-CH₂) _m^_[CH₂CH (OCOCH₃) ]_n• Poly (vinyl ethylene alcohol) - (CH2-CH2)_m- [CH₂CH (OH)]_nfifteen • Poly (acrylamide) - [CH2-CH (CONH2)] • Poly (n-butyl isocyanate) - [N (C4H9) -CO] • Poly (dimethylsiloxane) - [(CH₃) ₂SiO] • Poly (lactic acid) - [O-CH (CH₃) -CO] • Poly (methacrylonitrile) - [CH₂-C (CH₃) (CN)] • Poly (L-lactide) - (CH2-COO) In one embodiment, where the synthetic polymer comprises a —OH group, as in poly (vinyl alcohol) (PVA), the material can be esterified with u pendant functional -COOH group of the expanded microporous functional TFE copolymeric material to form ester bonds connecting PVA and the expanded microporous material. In another embodiment, the pendant functional -COOH group can be preactivated for example, for an acylimidazole using carbonyldiimidazole, which can then be esterified with PVA to form ether linkages which connect to PVA and the microporous expanded material.

In another embodiment, a -CN group of a terpolymer made of TFE, PMVE and 8-CNVE (i.e. see Table 5) can be reacted with a pendant functional -CN group of the microporous expanded functional TFE copolymer material to form groups triazine that crosslink the terpolymer with the expanded microporous material. In a further embodiment, fluoroelastomers that do not contain cyano functional groups can also be used to react with the pendant functional -CN group of the microporous expanded functional TFE copolymer material by adding triallylisocyanurate (TAIC) and peroxide to form crosslinking to improve interface between the fluoroelastomer and the expanded micropore material.

Furthermore, the expanded functional TFE copolymer can be reacted with biochemical materials such as heparin, a polysaccharide. For example, where the biochemical material comprises hydroxyl-OH functional groups, SOOOH sulfonic acid and -COOH carboxylic acid, the -OH group can be reacted with pendant carboxylic acid in a microporous expanded functional TFE copolymer material to form an ester. -OH groups can also react with an ester group in the microporous material to form a new ester group. The -SOOOH group can be reacted with an amine group on the microporous expanded functional TFE copolymer material to form a sulfonamide or sulfonimide. The -COOH group in heparin can be reacted with a pendant functional -OH group in the expanded microporous functional TFE copolymer material to form ester groups. A -COOH group of a biochemical material can also be reacted with an amino group in the microporous expanded functional TFE copolymer material to form amide groups. A -CHO (aldehyde) group of a biochemical material can also react with amino group on the microporous expanded functional TFE copolymer material to form imine groups. In a heparin embodiment, the resin or expanded polymeric material described herein, and in some cases the pendant functional group, is immobilized by various methods including those taught in the

Pat. USA No. 6,461,665 for Scholander et al.

A wide range of natural and synthetic bioactive species and other ligands such as biochemicals or biopolymers, and pharmaceutically or biologically active molecular compounds, or organic material can be reacted or otherwise immobilized to the functional group of a support member, as depicted in Figure 3.

A backing member, as used herein refers to the fine powder resin of the functional TFE copolymer or expanded polymeric material comprising a functional TFE copolymer material as described herein.

As used herein, the terms immobilize, attach, and derivatives thereof refer to adsorption, such as, fission or chemisorption, ligand / receptor interaction, covalent bond, hydrogen bond, or ionic bond of a polymeric substance or species bioactive for a support member. Bioactive species, as used in

<td>Present,</td><td>include enzymes, organic catalysts,</td>

<td>ribozymes,</td><td>organometallic, proteins, glycoproteins,</td>

<td>peptides,</td><td>polyamino acids, antibodies, nucleic acids,</td>

<td>molecules</td><td>spheroidal, antibiotics, antifungals,</td>

<td>cytokines,</td><td>carbohydrates, oleophobes, lipids,</td>

extracellular matrix and / or its individual components, fluorescent dyes and probes, colloidal, pharmaceutical, and therapeutic metals, for example. Cells such as mammalian cells, reptile cells, amphibian cells, avian cells, insect cells, planktonic cells, non-mammalian vertebrate and marine invertebrate cells, plant cells, microbial cells, protists, genetically engineered cells, and organelles , like mitochondria, are also bioactive species. Furthermore, non-cellular biological entities, such as viruses, veins, and prions are considered bioactive species. Natural and synthetic polymers are also considered bioactive species, and can be attached to the support member to alter surface energetics, hydrophilicity, hydrophobicity, and lubricity; to resist adsorption of protein; to enhance affinity adsorption; and the like; Examples of such polymers include but are not limited to those listed in Table 5, and also include but are not limited to polyethylene glycol, polypropylene glycol, hyaluronic acid, alginic acid, heparin, heparan sulfate, polyacrylamide, polyethyleneimine, dextran sulfate, cyclodextrin, agar, agarose, chitin, chitosan, polyvinylpyrrolidinone, polyvinyl alcohol, cellulose and its derivatives, polyaldehyde starch, polyhydroxyethyl methacrylate, silane and its derivatives, or other functional TFE copolymer as described herein, and the like.

A bioactive species can be immobilized to the functional TFE copolymer fine powder resin or expanded polymeric material comprising a material of; functional TFE copolymer described herein, by any conventional method including those taught in Pat. USA No. 5914182 to Drumheller, Pat. USA

No. 5897955 to Drumheller, Pat. USA No. 5874165 for

Drumheller, Pat. USA No. 5916585 for Cook, et al. Bioactive species can be immobilized to the resin or expanded polymeric material as described herein without reaction for the pendant functional group, thereby leaving the functional group available for other reactions.

In one embodiment the bioactive species is immobilized to the resin or expanded polymeric material of the present invention through direct reaction to the pendant functional group, as depicted in Figure 3. In another embodiment, an initial functional group on the support member is converted to a second functional group different from the initial functional group as depicted in Figure 4, and the bioactive species is immobilized to the second functional group as depicted in Figure 5. In yet another embodiment the bioactive species is immobilized to the resin or expanded polymeric material of the present invention through an intermediate component that is attached to the pendant functional group. The intermediate component may comprise a covalent bond between the species and the support member, or it may comprise a spacer arm. A spacer arm is immobilized on the polymeric substrate in some cases, as depicted in Figure 6, to improve the production of the binding surface, to minimize spherical surface-induced effects, or to enhance receptor-ligand interactions. The spacer arm can be homobifunctional, homopolyfunctional, heterobifunctional, heteropolifunctional, zero length, incision, photolytically labile, and the like. The spacer arm, in one embodiment, may also comprise a polymeric surfactant, or a multifunctional copolymer, comprised of at least one domain having a fisisorbent or chemosorbent affinity for the resin or expanded polymeric material of the present invention to allow for the fisisorption or chemisorption of the multifunctional copolymer on the surface of the resin or expanded polymeric material and at least one other domain which is Chemically reactive to allow covalent immobilization of a bioactive species or to allow crosslinking with a suitable crosslinking agent. The spacer arm may also comprise the functional expandable fluoropolymer having the function group listed in Table 2. The spacer arm may also comprise a first layer attached to the pendant functional group and a second layer attached to the first layer. The spacer arm of the first layer can be the same or different than the spacer arm of the second layer.

A wide range of intermediate components, including spacer arms, could be used as taught in Pat. USA No. 5914182 to Drumheller, Pat. USA

No. 5897955 to Drumheller, Pat. USA No. 5874165 for

Drumheller, Pat. USA No. 5916585 for Cook, et al.

Organic species including enzymes, cells, and proteins. and spacer arms, can also be immobilized to the resin or expanded polymeric material as described herein and in some cases to the pendant functional group, by means of methods including those taught in GT Hermanson, Bioconjugate Techniques, 2^to edition, Academic Press (Amsterdam), 2008, and specifically in chapters 1-8, 13-15, 17-18, 22-27, Methods in

Enzymology, Immobilized Enzymes and Cells, Part B, Vol 125,

K. Mosbach (Ed), Academic Press (Orlando), 1987, and SS Wong,

Chemistry of Protein Conjugation and Cross-Linking, CRC

Press (Boca Ratón), 1993, specifically chapters 2-6 and

12.

The bioactive species in one embodiment is also a spacer arm including but not limited to those listed in Table 5, and including but not limiting to polyol such as polyvinyl alcohol; polyamine such as polyethylene amine; polyether such as polyethylene glycol, polyaldehyde such as polyaldehyde starch; polyester such as polyvinyl acetate, polycarboxylic acid such as polyacrylic acid; polyamide, such as polyvinylpyrrolidone, polyarylsiloxane ketone, polyazide, polythiol, polybutyne, polyvidin, polysilane, polydopamine, polyquinone, polysaccharides such as heparin, heparan sulfate, polyamino acid, polynucleic acid, polyalkane, and the like. The spacer arm can be homofunctional, heterofunctional, zero length, stretched, photolytically labile, and the like. In another embodiment two or more bioactive species are immobilized to the resin or expanded polymeric material of the present invention and in some embodiments one is immobilized to the functional pendant group and the other is not. In another embodiment the polymeric material is a medical device. In another embodiment, the polymeric material is a component of a medical device.

As used herein, the term medical device includes but is not limited to temporarily implantable materials and devices such as catheters, balloons, wound dressings, and the like; permanent implantables such as sutures, vascular grafts, stents, stents-grafts, patches, barriers, vascular and heart valves, tissue growth scaffolds, orthotics, plugs, and the like, and non-implantable such as collection bags, dialysis medium, cell growth scaffolds, and the like. A medical device may also include ex vivo or in vitro materials and devices such as but not limited to tubing, membranes, chromatography medium, adsorption medium, affinity medium, bioseparation and biopurification medium, biofilters, protein substrates, and analysis of DNA, and the like. A medical device may also include fabrics, clothing, and the like to protect against disease or pathogenic transmission and the like. A medical device can also be essentially any type of medical device, or a component of a medical device, that can be made from the copolymers of the present invention.

TEST METHODS

Test for breaking strength of microporous ePTFE

A process is provided to test the breaking strength of the extruded and pearled copolymer paste of

Expanded functional microporous TFE. The breaking strength associated with an extruded and expanded TFE (stretched) polymeric bead produced from a particular resin is clearly related to the suitability for general expansion of the resin, and various methods have been employed to measure the breaking strength. The following procedure was used to produce and test the expanded pearl specimens made from copolymers of this invention, the data is reported herein below.

For a given resin, 113.4 g of fine powder resin are mixed together with 130 cc / lb (24.5 g) of Isopar® K. The mixture matures for about 2 hours at 22 ° C in a constant temperature water bath. A 2.54 cm diameter cylindrical preform is made by applying about 1,860 kPa of preforming pressure for about 20 seconds. The preform is inspected to make sure it is free of cracks. An extruded bead is produced by extruding the preform, the resin lubricated through a 0.254 cm diameter mold that has 30 degrees included in the entry angle. The extruder barrel is 2.54 cm in diameter and the ram's movement speed is 50.8 cm / min. The extruder barrel and mold are at room temperature, held at 'C, plus or minus 1.5 ° C. The K Isopar® is removed from the pearl by drying it for around 25 minutes at 225-230 'C.

Approximately the first and last 2.5m of the extruded bead are discarded to eliminate the final effects. A section

0 5.0 cm of extruded bead expands by stretching it to 290'C to a final length of 127cm (expansion ratio of

25: 1) and at an initial stretch rate of 1000% per second, which is a constant rate of 50.8 cm per second. Approximately a length of 30 cm near the center of the expanded pearl is removed, and the maximum breaking load of the removed sample is maintained at room temperature (23 'C plus or minus 1.5' C) is measured using an Instron strain tester ® using an initial sample length of 5.0 cm and a crosshead speed of 5.0 cm / min.

Duplicate measurements are obtained and reported as the average value for the two samples. This procedure is the same as that described in US Patent 6,177,533B1.

Crystallinity measurements of expanded membranes

Infrared spectra were obtained with a Nicolet 550 Series II spectrometer. The expanded membrane samples were used and scanned for 100 scans. The two peaks (about 2363 cm¹ and 778 cm '¹) of interest were used for crystallinity measurements. The degree of crystallinity was calculated using the following equation,

Crystallinity% = 100 - (H77g / (H2363 x 25)) where {¿779 is the peak height near the wave number '778 cm'¹ and H₂363 near the wave number 2363 cm '¹. The base for the peak about 778 cm¹ was obtained from the line between 754 and

810 cm ”¹. The base for the peak about 2363 cm¹ was obtained from the line between 2200 and 2600 cm '¹.

Determination of functional groups

The Digilab FTS4000 infrared spectrometer was used to determine functional groups. FTIR spectra were obtained in ATR mode using Pike Technologies MIRacle

ATR with a Ge crystal. Wave numbers to identify specific functional groups are given in the examples below.

Determination of the compositions of functional TFE copolymers

NMR was used to quantify functional TFE copolymer compositions. All NMR measurements were carried out on a Bruker BioSpin Advance II spectrometer

300 MHz operating at a resonant frequency of 282.4 MHz for fluoride-19 with a pulse duration of 3 ps. Spectra were collected around 296 K on a Bruker-BioSpin 2.5mm crossover polarization magic angle twist probe (CPMAS) positioned on a standard hole 7.05T Bruker ultrashielded superconducting magnet. The samples were positioned at the magic angle and centrifuged at 32.5 kHz. The sample weight for all experiments was around 10 to 25 mg. The software that was used for data acquisition and data processing was Topspin 1.3. Chemical shifts¹⁹F were externally referenced to the CF signal₂ PTFE at 5 123 ppm.

Thickness measurements

Thickness was measured by placing the material between the two Kafer FZ1000 / 30 thickness gauge plates (Kafer

Messuhrenfabrik GmbH, Villingen-Schwenningen, Germany). The average of these two measurements was used.

Density measurements

The density was used to calculate the percentage porosity of expanded materials using 2.2 g / cc as the complete density of the sample. The mold cut of the samples to form the rectangular sections 2.54 cm by

15.24 cm were measured to determine their mass (using a Mettler-Toledo model AG204 analytical balance) and their thickness (using a Kafer FZ1000 / 30 gauge). Using these data, the density was calculated with the following formula:

m

P = w * / * z

In which: p = density (g / cc); m = mass (g); w = width (cm); 1 = length (cm); and t = thickness (cm). The average of the three measurements was used.

Tensile Breaking Load Measurements and Matrix Tensile Strength (MTS) Calculations

The stress breaking load was measured using an INSTRON 1122 stress testing machine equipped with flat face fasteners and a 0.445 kN load cell.

The gauge length was 5.08 cm and the crosshead speed was 50.8 cm / min. The sample dimensions were 2.54 cm by 15.24 cm. For longitudinal MTS measurements, the largest dimension of the sample was machine oriented, or direction under the screen. For cross-sectional MTS measurements, the largest dimension of the sample was oriented perpendicular to the machine direction, also known as the cross-frame direction. Each sample was weighed using a Mettler scale

Toledo Model AG204, then the thickness of the samples was taken using the Kafer FZ1000 / 30 thickness gauge.

Three samples were then individually tested on the strain tester. The average of the measurements of the three maximum loads (i.e. the peak force) was used. The

Longitudinal and transverse MTS were calculated using the following equation:

MTS = (maximum load / cross-sectional area) * (PTFE density) / sample density),

N where the density of PTFE is taken to be 2.2 g / cc.

Bubble point measurements

The bubble point and the average flow pore size were measured according to the general teachings of ASTM F31

6-03 using a Capillary Flow Porometer (Model CFP 1500

AEXL of Porous Materials Inc., Ithaca, NY). The sample membrane was placed in the sample chamber and wetted with

Silicon SilWick fluid (available from Porous Materials Inc.) with a surface tension of 19.1 dynes / cm. The lower sample chamber clamp had a diameter of 2.54 cm, 3.175 mm thick porous metal disc insert (Mott Metallurgical, Farmington, CT, 40 micron porous metal disc) and the upper sample chamber clamp had a hole with a diameter of 3,175 mm. Using Capwin software version 6.62.1 the following parameters were established as specified in the table below.

The values ​​presented for the bubble point and the mean flow pore size were the 'average of the two measurements.

<td rowspan="2"></td><td rowspan="2">Parameter Point of Max flow (cc / m) Bubble flow (cc / m)</td><td>adjustment</td>

<td> 200000 100</td>

<td></td><td>F / PT (old bubble time)</td><td> 40</td>

<td> 5</td><td>Pres minbp (PSI)</td><td> 0</td>

<td></td><td>Zero time (sec)</td><td> 1</td>

<td></td><td>v2incr (cts)</td><td> 10</td>

<td></td><td>preginc (cts)</td><td> 1</td>

<td></td><td>pulse delay (sec)</td><td> 2</td>

<td> 10</td><td>max pres (PSI)</td><td> 500</td>

<td></td><td>pulse width (sec)</td><td> 0.2</td>

<td></td><td>mineq time (sec)</td><td> 30</td>

<td></td><td>presslew (cts)</td><td> 10</td>

<td></td><td>flowslew (cts)</td><td> 50</td>

<td> 15</td><td>eqiter</td><td> 3</td>

<td></td><td>aveiter</td><td> 20</td>

<td></td><td>maxpdif (PSI)</td><td> 0.1</td>

<td></td><td>maxfdif (cc / m)</td><td> 50</td>

<td></td><td>sartp (PSI)</td><td> 1</td>

<td> 20</td><td>sartf (cc / m)</td><td> 500</td>

Gurley measurements

Gurley Air Flow Test measures insurance time for 100 cm³ of air to flow through a 6.45 cm sample² at 12.4 cm of water pressure. Samples were measured on a Gurley Automatic Densitometer

Model 4340. The average of the three measurements was used.

The following examples are intended to be illustrative of the invention, but should not be construed as limiting the scope of the invention in any way.

Example 1

A fine powder resin comprising the copolymer of

TFE and 8-CNVE were prepared as follows.

1.5 kg of paraffin wax, 28 kg of deionized water (DI), 18 g of perfluorooctanoic ammonium acid (APFO) and 5 g of succinic acid were added to a 50-liter horizontal polymerization reactor equipped with a 3-blade stirrer. dissolved in about 50 g of DI water. The reactor and contents were heated above the melting point of the wax. The reactor was repeatedly emptied and pressurized (to about 1 atmosphere or less) with TFE until the oxygen level dropped to 20 ppm or less.

The contents were briefly stirred at about 60 rpm between the vacuum and purge cycles to ensure that the water was deoxygenated. 35 g of (8-cyano-5-methyl-3,6-dioxa-l-octene) perfluoro (8-CNVE) (CF₂= CFOCF₂CF (CF₃) OCF₂CF₂CN), 5 g of

20% APFO, 250 g of DI water were emulsified by

Omni Mixer Homogenizer. To the reactor under vacuum, the above 8-CNVE emulsion was added as a comonomer precharge, and the reactor was heated to 83 ° C. TFE was then added to the reactor until the pressure reached 2.8 MPa, and

KMnO₄ in DI water solution (0.063 g / L) was injected at 80 ml / min. Up to about 4 kg of TFE have been added.

This was accomplished in around 64 minutes. About 320 ml of 20% APFO solution was added in 40 ml increments, the first increment that is added after about 1 kg of TFE has been added to the reactor, and the subsequent increments added after each subsequent 1 kg of

TFE that has been added, so that the final increment was added after 9 kg of TFE have been loaded. KMnO addition rate₄ decreased to 40 ml / min at the level

4 kg TFE and continued at this rate until around 6 kg TFE were added, at which time KMnO addition₄ He stopped.

The polymerization reaction was then allowed to continue and the reaction stopped after about 16 kg of

TFE have been added to the reactor. The weight of the dispersion produced was 4 9.9 kg, and the solid content of the dispersion was 32.1% by weight. The pure dispersion particle size (RDPS) of the polymer particles was

0.175 microns.

The polymer dispersion was dispersed about 15% by weight with DI water and then coagulated with dilute nitric acid (300 ml 65% nitric acid diluted with 700 ml DI water) at about 16 ° C. The dispersion ratio of the diluted polymer to nitric acid was 20 kg dispersion per 100 ml diluted in nitric acid. The stirring speed for coagulation was around 275 rpm. The clot was dried at 130 ° C for 18 hours under vacuum. NMR¹⁹Solid state F was carried out to characterize the composition of the polymer. This polymer contains 0.017 mol% (0.064 wt%) 8-CNVE. The pearl breaking strength was approximately 42 newtons (N).

Example 2

A fine powder resin comprising the copolymer of

TFE and 8-CNVE was prepared as follows.

The procedures for Example 1 were repeated except that the concentration of the KMnO solution₄ was 0.1 g / L. The KMnO solution₄ it was injected at 80 ml / min. until around

0 4 kg of TFE have been added. This was accomplished in around 38 minutes. Then the rate of addition of

KMnO₄ decreased to 40 ml / min and continued at this rate until around 6 kg of TFE have been added, at which time the addition of KMnO₄ He stopped. Total time addition of KMnO solution₄ it was around 43 minutes.

The polymerization reaction was then allowed to continue and the reaction stopped after about 16 kg of

TFE have been added to the reactor. The weight of the dispersion produced was 49.2 kg, and the solid content of the dispersion was 34.5% by weight. The pure dispersion particle size (RDPS) of the polymer particles was

0.208 micras.

The dispersion was coagulated in the same process as described in Example 1 and dried at 130 ° C for 18 hours under vacuum. NMR¹⁹Solid state F was carried out to characterize the composition of the polymer. This polymer contains 0.019 mol% (0.072) wt% 8-CNVE.

5 Example 3

A fine powder resin comprising the copolymer of

TFE and 8-CNVE was prepared as follows.

The procedures for Example 1 were repeated except that 52g of 8-CNVE was added to 5g of 20% APFO and

0 250 g DI water, emulsified by Mixer Homogenizer

Omni, and added as a preload for the reaction. KMnO solution concentration₄ was 0.1 g / L. The KMnO solution₄ it was injected at 80 ml / min until about kg of TFE have been added. This was accomplished in around 63 minutes. So the KMnO addition rate₄ decreased to 40 ml / min and continued at this rate until about kg of TFE has been added. KMnO addition rate₄ it was again increased to 80 ml / min and continued at this rate 5 until around 6 kg of TFE have been added, at which time the addition of KMnCú stopped. The total addition time for the KMnCL solution was about 86 minutes.

The polymerization reaction was then allowed to continue and the reaction stopped after about 16 kg of 10 TFE had been added to the reactor. The weight of the dispersion produced was 52.2 kg, and the solid content of the dispersion was 32.8% by weight. The pure dispersion particle size (RDPS) of the polymer particles was

0.186 micras.

The dispersion was coagulated in the same process as described in Example 1 and dried at 130 ° C for 18 hours under vacuum. NMR¹⁹Solid state F was carried out to characterize the composition of the polymer. This polymer contains 0.044% mol (0.17% by weight) 8-CNVE. The breaking strength of the pearl was 45 N.

Example 4

A fine powder resin comprising the copolymer of

TFE and 8-CNVE was prepared as follows.

5Ί

The procedures for Example 1 were substantially repeated except that 118g 8-CNVE was added to 5g of

20% APFO and 250 g of DI water, were emulsified by the

Omni Mixer Homogenizer, and added as a preload for the reaction. The concentration of the KMnO solution₄ it was 0.15 g / L. The KMnO solution₄ was injected at 80 ml / min until about 2 kg of TFE have been added, at which time the addition of KMnO₄ He stopped. The total addition time of the KMnO solution₄ It was around 143 minutes. 10.4 kg of KMnO solution₄ were added.

The polymerization reaction was then allowed to continue and the reaction stopped after about 13.4 kg of TFE had been added to the reactor. The weight of the dispersion produced was 52.8 kg, and the solid content of the dispersion was 27.9% by weight. The pure dispersion particle size (RDPS) of the polymer particles was 0.194 microns.

The dispersion was coagulated in the same process as

<td>describes</td><td>in Example 1 and</td><td>dried up</td><td>130 'C by</td><td>18 hours under</td>

<td>20 empty.</td><td>NMR ¹⁹F for status</td><td>solid</td><td>took away</td><td>out for</td>

<td colspan="2">characterize the composition</td><td colspan="2">of the polymer.</td><td>This polymer</td>

<td>contains</td><td>0.13 mol% (0.51% in</td><td>weight)</td><td>8-CNVE. The</td><td>resistance to</td>

pearl breakage was 47 N.

Example 5

A fine powder resin comprising the TFE and PSVE copolymer was prepared as follows.

1.5 kg of paraffin wax, 28 kg of deionized water (DI), 18 g of perfluorooctanoic ammonium acid (APFO) and 5 g of succinic acid dissolved in about 50 g of DI water. The reactor and contents were heated above the melting point of the wax. The reactor was repeatedly emptied and pressurized (to about 1 atmosphere or less) with TFE until the oxygen level dropped to 20 ppm or less.

The contents were briefly stirred at about 60 rpm between the vacuum and purge cycles to ensure that the water was deoxygenated. 1500 g of perfluoro (8-sulfonic acid fluoride-5-methyl-3,6-dioxa-l-octene) (PSVE) (CF₂= CFOCF2CF (CF₃) OCF₂CF₂SOOF), 50 g of 20% APFO, and 1500 g of DI water were emulsified by the Omni Mixer Homogenizer. To the vacuum reactor 688 g of the above PSVE emulsion is

0 they added as a comonomer preload, and the reactor was heated to 83 ° C. TFE was then added to the reactor until the pressure reached 2.8 MPa, and KMnÜ4 in DI water solution (0.063 g / L) were injected at 80 ml / min. Until about kg of TFE have been added. A drop in pressure indicated the start of polymerization. TFE was continuously added to maintain pressure. About 320 ml of 20% APFO solution was mixed with the rest of the solution

PSVE. The mixed solution was added in an increment of 43 ml for 200 g of TFE consumed. The first increment was added after around 200 g of TFE has been added to the reactor, and the subsequent increments were added after every subsequent 200 g of TFE have been added. The final increment was added after kg of TFE has been loaded. KMnO addition rate₄ it was decreased to 40 ml / min at the 4 kg TFE level and continued at this rate until around 10 kg of TFE have been added, at which time the addition of KMnO₄ He stopped. This was accomplished in around 47 minutes.

The polymerization reaction was then allowed to continue and the reaction stopped after about 16 kg of

TFE have been added to the reactor. The weight of the dispersion produced was 50.5 kg, and the solid content of the dispersion was 36.6% by weight. The pure dispersion particle size (RDPS) of the polymer particles was

0.270 micras.

The dispersion was coagulated in the same process as described in Example 1 and dried at 130 ° C for 18 hours under ¹⁹Solid state F was carried out for vacuum.

NMR characterize the composition of the polymer. This polymer contains 1.9 mol% (8.0% by weight) 8-CNVE. The breaking strength of the pearl was 28.5 N.

Example 6

A fine powder resin comprising the copolymer of

TFE and EVE were prepared as follows.

1.5 kg of paraffin wax, 28 kg of DI water, 18 g of APFO and 5 g of oxalic acid dissolved in about 50 g of DI water were added to a 50-liter horizontal polymerization reactor equipped with a 3-blade stirrer. . The reactor and contents were heated above the melting point of the wax. The reactor was repeatedly emptied and pressurized (to about 1 atmosphere or less) with

TFE until the oxygen level dropped to 20 ppm or less. The contents were briefly stirred at about rpm between vacuum and purge cycles to ensure that the water was deoxygenated. 80 g of perfluoro (8-carboxymethyl-5-methyl-3,6-dioxa-l-octene) (EVE) (CF₂= CF—

0 OCF₂CF (CF3) OCF2CF₂COOCH3), 5 g of 20% APFO, and 250 g of DI water were emulsified by the Omni Mixer Homogenizer. The above EVE emulsion was added to the reactor under vacuum as a comonomer preload, and the reactor was heated to

83 ° C. TFE was then added to the reactor until the pressure reaches 2.8 MPa, and KMnO₄ In DI water solution (0.15 g / L) was injected at 80 ml / min until about 1 kg of TFE has been added. A drop in pressure indicates that the polymerization started. TFE was continuously added to maintain pressure. After 1 kg of TFE was added, the KMnO injection rate₄ in DI water solution it was decreased to 40 ml / min until 3 kg of TFE had been added and then the solution was injected at 20 ml / min. Up to about 6 kg of TFE has been added, at which time the addition of KMnO₄ He stopped. This was achieved in about 15 minutes. About 320 ml of 20% APFO solution was added in 40 ml increments, the first increment added after around 2 kg of TFE has been added to the reactor, and the subsequent increments were added after every 1 kg of subsequent TFE has been added, so the final increment was added after 9 kg of TFE has been loaded.

The polymerization reaction was then allowed to continue and the reaction stopped after about kg of TFE have been added to the reactor. The weight of the dispersion produced was 45.6 kg, and the solid content of the dispersion was 35.1% by weight. The size of the crude dispersion particle (RDPS) of the polymer particles was

0.232 micras.

The dispersion was coagulated in the same process as described in Example 1 and dried at 180 ° C for 18 hours under vacuum. It was carried out¹⁹Solid state NMR to characterize the polymer composition. This polymer contains 0.098 mol% (0.41% by weight) of EVE. The resistance to breakage of the pearl was 23.6 N.

Example 7

A fine powder resin comprising the copolymer of

TFE and EVE were prepared as follows.

The procedures for Example 6 were substantially repeated except that the reactor was evacuated after 10 kg of TFE had been added to the reactor and then TFE was recharged into the reactor until the reactor pressure was 2.8 MPa. Then the KMnO solution₄ was injected into

80 ml / min. until about 1 kg of TFE has been added. Then the KMnO addition rate₄ it was decreased to 40 ml / min and then 2 kg of TFE was added, the injection rate KMnO₄ decreased to 20 ml / min until 6 kg of TFE have been added, at which time the addition of KMnO₄ He stopped. The total addition time of the KMnO solution₄ it was around minutes.

The polymerization reaction was then allowed to continue and the reaction was stopped after about 16 kg of TFE had been added to the reactor. The weight of the dispersion produced was 46.2 kg, and the solid content of the dispersion was 35.4% by weight. The crude dispersion particle size (RDPS) of the polymer particles was 0.238 microns.

The dispersion was coagulated in the same process as described in Example 1 and dried at 180 ° C for 18 hours under vacuum. It was carried out¹⁹E NMR in solid state to characterize the composition of the polymer. This polymer contains 0.095 mol% (0.40% by weight) of EVE. The breaking strength of the pearl was 28.0 N.

Example 8

An expanded functional copolymer comprising the TFE and 8-CNVE copolymer was prepared as follows.

The resin of Example 3 was mixed with Isopar® K (Exxon

Mobil Corp., Fairfax, VA) at a concentration of 0.217 g / g resin and formed in a pellet of approximately 10 cm in diameter at a pressure of about 2070 kPa. The pellet was heated to around 50 ° C and the pulp was extruded into a tape having dimensions of around

0.076 cm thick and about 15.25 cm wide through a mold that has a reduction rate of about

100 up to 1, at an average extrusion pressure of about 10,300 kPa. The reduction rate is the rate of the cross sectional area of ​​the extruder barrel for the cross sectional area of ​​the extrusion mold outlet. The resulting tape was calendered at a rate of 50 meters / rainuto at about 45 ° C to about 0.020 cm thick and about 15.25 cm wide. The lubricant was removed by heating at 180 ° C to 210 ° C. The width of the dry tape was around 14.6 cm.

The resulting tape was stretched in the longitudinal direction at about 300 ° C and 4.5 meters / minute at a ratio of 10: 1. The resulting tape was about 8.9 cm wide. The resulting tape was stretched crosswise at 300 ° C at 19.8 meters / minute at a 7.5: 1 ratio and sintered at about 390 ° C for about 20 seconds. The resulting membrane was characterized and the results are given in Table 6. A scanning electron micrograph, at 10,000 amplification, of the membrane is given in Figure 1.

Table 6. Properties of the Membrane Made in Example 8

<td></td><td>Example 8 (fine powder produced in Example 3)</td>

<td>Porosity (%)</td><td> 85</td>

<td>Flow pore size medium (pm)</td><td> 0.16</td>

<td>Thickness (pm)</td><td> 2.5</td>

<td>Density (g / cc)</td><td> 0.39</td>

<td>Crystallinity (%)</td><td> 71</td>

<td>Tensile strength of</td><td> 230</td>

<td>average matrix (MPa)</td><td></td>

Example 9

An expanded functional copolymer comprising the TFE and PSVE copolymer was prepared as follows.

A resin made according to Example 5 containing 0.7 6 mol% (3.3 wt%) PSVE was both extruded on a tape and stretched according to the procedures of Example 8 except that the lubricant was removed by heating to around 250 ° C. The extruded tape has a width of about 13 cm and then the tape was stretched paste on a microporous membrane. The resulting membrane was characterized and the results are given in Table

7. A scanning electron micrograph, at 10,000 magnification, of the membrane is given in Figure 2.

Table 7. Properties of the Membrane Made in Example 9

<td></td><td>Example 9</td>

<td>Mass / area (g / m²⁾</td><td> 4.1</td>

<td>Thickness (pm)</td><td> 2.5</td>

<td>Gurley (sec)</td><td> 9.6</td>

<td>Bubble point (kPa)</td><td> 630</td>

<td>Tensile strength of</td><td> 230</td>

<td>average matrix (MPa)</td><td></td>

Example 10

An expanded functional copolymer comprising the TFE-8-CNVE copolymer was reacted as follows.

An expanded microporous functional TFA copolymer membrane was made according to Example 8, from a fine PTFE powder prepared according to the process described in

Example 3 containing 0.044% mol (0.17% by weight) of 8CNVE. The expansion process is carried out at around 300 ° C and then restricted and heated to around 390 ° C in an oven for around 20 seconds, resulting in an expanded microporous membrane containing triazine (around 1560 cm '¹), a reticulated structure, and the unreacted cyano group (about 2297 cm^-1) determined by FTIR.

Example 11

An expanded functional copolymer comprising the TFE-8-CNVE copolymer was reacted as follows.

Aminopropyltriethoxysilane (Aldrich) was mixed with a 95% by weight ethanol solution (Aldrich) / 5% Di water in

6 wt. To provide a 10 wt.% Silane solution.

About five minutes were allowed for hydrolysis and silanol groups formed. A copolymer membrane of

Expanded functional TFE made according to Example 8 from a fine TFE copolymer powder containing 0.044% mol (0.17% by weight) 8-CNVE was immersed in the solution for 2 minutes. It was then rinsed free of excess silane solution by briefly immersing in ethanol and air-drying.

Membrane curing was carried out at 110 ° C for 30 min. The reacted membrane became transparent in the water, indicating that it was hydrophilic. The unreacted membrane was white in water, indicating that it was hydrophobic. A hydrophilic membrane as described herein will exhibit water penetration into the pores of the expanded membrane after exposure to water, including exposure to the surface for water or immersion in water.

Example 12

An expanded functional copolymer comprising the TFE and 8-CNVE copolymer was reacted as follows.

An expanded functional TFE copolymer membrane made according to Example 8 from a fine TFE copolymer powder containing 0.044 mol% (0.17 wt%) of

8-CNVE prepared in Example 3 was first moistened with isopropanol (IPA) (Aldrich) and then immersed in a 28% by weight aqueous ammonium hydroxide solution (Aldrich) at room temperature for 20 hours. Then it was rinsed with DI water and air dried. The reacted expanded functional TFE copolymer membrane contains a new group, amidine (about 1743 cm '¹) , determined by

FTIR.

0 Example 13

An expanded functional copolymer comprising the TFE-8-CNVE copolymer was crosslinked with a fluoroelastomer.

Viton ™ GF-S (fluoroelastomer) 15 was formed with 4 phr of triallylisocyanurate (Aldrich) and 4 phr of Luperox ™ 101 (Aldrich) in a mill; The composite mixture was dissolved in MEK (methyl ethyl ketone) to form a 20% solids solution. An expanded functional TFE copolymer membrane was made according to

0 Example 8 of a fine TFE copolymer powder made according to the process of Example 3 containing 0.044% mol (0.17% by weight) of 8-CNVE. The membrane was absorbed with the Viton ™ compound and dried at 90 ° C. Blocks (Compound A) having a thickness of about 0.5 to 0.76 mm were made by stacking the Viton ™ absorbed expanded functional TFE copolymer membrane. The Viton ™ Composite / Expanded Functional TFE Copolymer was formed by casting at 180 ° C for 10 min followed by post-curing in a convection oven at 233 ° C for 24 hours. Comparative blocks (compound B) were made by a similar process, except that the ePTFE membrane was used in place of the expanded functional TFE copolymer membrane and therefore does not contain 8-CNVE. The Peel Tester

IMASS was used for peel tests that were carried out in peel mode T with a 5 Ib load cell at a rate of 6 in / min. Breakout forces were 2.2 and 1.5 lb / in for Compound A and Compound B, respectively.

Example 14

An expanded functional copolymer comprising the TFE and PSVE copolymer was reacted as follows.

An expanded functional TFE copolymer membrane made by the processing conditions of Example 9, was made of a fine functional TFE copolymer powder containing 1.9 mol% (8.0% by weight) PSVE made according to the process of Example 5 The membrane was first moistened with

IPA and then immersed in a 20% by weight KOH solution (Aldrich) at 100 ° C for 24 hours. It was then rinsed with DI water and immersed in 15% by weight nitric acid (Aldrich) at 60 C for 24 hours. The reacted membrane was rinsed with DI water and dried at 100 ° C for 1 hour. The conversion of the sulfonyl fluoride group (about

1469 cm '¹) in the sulfonic acid group (about 1059 cm '¹) was confirmed by FTIR. '

Example 15

An expanded functional copolymer comprising the TFE and PSVE copolymer was reacted as follows.

An expanded functional TFE copolymer membrane made by the processing conditions of Example 9, was made of a functional TFE fine powder containing 1.9 mol% (8.0% by weight) PSVE made according to the process of the

Example 5. The membrane was first moistened with IPA and then immersed in a 28 wt% aqueous ammonium hydroxide solution at about 5 ° C for 3 hours. The reacted membrane was rinsed with DI water and air dried. The expanded functional TFE copolymer membrane was cured by heating at 200 ° C for 1 hour. The sulfonimide group (about 1740 cm^-1), the crosslinked structure, was determined by FTIR.

Example 16

An expanded functional copolymer comprising the TFE and EVE copolymer was reacted as follows.

The expanded functional TFE copolymer membrane was made of fine powder made according to the process of Example 6.

This fine powder contains 0.098% mol (0.41% by weight) of EVE.

The resin of Example 6 was mixed with Isopar® K (Exxon

Mobil Corp., Fairfax, VA) at a concentration of 0.207 g / g resin and formed in a pellet approximately 10 cm in diameter at a pressure of about 2070 kPa. The pellet was heated to around 50 ° C and the pulp was extruded into a tape having dimensions of around

0.076 cm thick and about 15.25 cm wide through a mold that has a reduction ratio of around

<td colspan="2">15 from 100 to</td><td>1, to</td><td>a</td><td>average extrusion pressure</td><td>of</td>

<td>around</td><td>of</td><td> 15,000</td><td>kPa.</td><td>The reduction ratio is</td><td>the</td>

<td>relationship</td><td>of the</td><td>area</td><td>in</td><td colspan="2">cylinder cross section</td>

<td>extruder</td><td>for</td><td>the area</td><td>in</td><td>cross section of outlet</td><td>of the</td>

<td>mold</td><td colspan="2">extrusion.</td><td>The</td><td>resulting tape was calendered to</td><td>a</td>

around 45 ° C to around

The lubricant was removed by

210 ° C. The width of the dry tape was stretched in the direction rate of 8.2 meters / minute to 0.015 cm thick.

heating at 180 ° C until it was around 15.8 cm.

The resulting longitudinal tape at around 250 ° C and 15.24 meters / minute at a ratio of 2: 1. The resulting tape was about 13.5 cm wide. The resulting tape was stretched crosswise at 300 ° C at 100% per second at a ratio of 6: 1 in the cross direction.

<td>The membrane</td><td>I know</td><td>moistened</td><td>first with</td><td>alcohol</td>

<td>isopropyl and then</td><td>I know</td><td>dipped into</td><td>a solution of</td><td>hydroxide</td>

<td>from aqueous amino to</td><td> 28%</td><td>by weight</td><td>around 5 °</td><td>C during</td>

three hours. The reacted membrane was rinsed with DI water and air dried at room temperature. The reacted membrane became semi-transparent in water indicating that it was hydrophilic. The unreacted membrane was white in water, indicating that it was hydrophobic.

5 Example 17

An expanded functional copolymer comprising the TFE and EVE copolymer was reacted as follows.

The expanded functional TFE copolymer was made according to Example 6. This fine powder contains 0.098% mol (0.41% by weight) EVE. The fine powder was processed to a membrane according to the procedures of Example 16.

The membrane was first moistened with isopropyl alcohol. The pre-wet expanded TFE copolymer membrane was dipped in 50% by weight aqueous sulfuric acid and held at 60 ° C for 24 hours. The membrane was then rinsed with DI water and dried at 60 ° C for 2 hours. FTIR spectra show the presence of carboxylic acid functionality (about 3300 cm¹), showing at least some of the ester functional group was hydrolyzed to carboxylic acid.

Example 18

An absorbed compound was prepared as follows.

An expanded functional TFE copolymer membrane made according to the process as described in Example 9 was made from a fine functional TFE copolymer powder containing 1.8 mol% (7.7% by weight) PSVE made according to Example 5. The expanded material has a mass per area of ​​5.2 g / m². A TFE-PSVE ionomer solution, having approximately 18 mol% PSVE, was prepared according to the teachings of Wu et. to the. [US 2008/007036] in the paragraphs

113-114 and then diluted with ethanol and DI water to solids at

<td> 13.2%</td><td>in</td><td>weight</td><td>in a</td><td>solution of</td><td>13.2% water / ethanol al</td>

<td> 73.8%</td><td>in</td><td>weight.</td><td>This</td><td colspan="2">exchange material solution</td>

<td>ions</td><td>I know</td><td colspan="2">coated in</td><td>a movie</td><td>FLUOROJU (TM) (Mitsubishi</td>

<td colspan="2">Plastics,</td><td>Inc)</td><td colspan="2">placed in a</td><td>Glass plate. The</td>

Coating was done using a decrease blade with a coating space of 7 thousandths (178 microns). The composite membrane was then stretched over the wet coating and allowed for infiltration. After infiltration, it was dried for 20-60 seconds with a hair dryer. Then, a second coating of the same ion exchange material solution was made using a 1.5 mil (38 micron) gap. The second coating was then also dried with a hair dryer for 2060 seconds. This composite membrane absorbed into the FLUOROJU (TM) film on the glass plate was placed in an air oven at 160 ° C for 3 minutes and then stirred to cool. The absorbed composite membrane was then removed from the FLUOROJU (TM) film sponsor. The final measured thickness of this absorbed composite membrane was 12 ± 2 microns. This material was subsequently tested as a solid polymer electrolyte in a fuel cell by first forming a Membrane Electrode Assembly (MEA) using standard processes such as those described in US 2007/007206, paragraph 121. This MEA was subsequently tested using standard fuel cell test protocols such as those described in US

2007/007206. A polarization curve was successfully obtained indicating that the absorbed composite membrane was acting as a solid polymer electrolyte.

Example 19

An inventive solid polymer electrolyte membrane was prepared using the process described in Example 18 using a starting expanded membrane with a mass area 5 per unit of 5.2 g / m², except that in this example the initial decrease space of coating was 5 thousand (125 microns) and the second decrease space was 3 thousand (75 microns). The final measured thickness of this absorbed composite membrane was 12 ± 2 microns. The measured Gurley of this sample was greater than 200 seconds. Further testing shows that the Gurley was greater than 1000 seconds, and greater than 5000 seconds, and greater than 10,000 seconds.

Example 20

The procedures of Example 18 were repeated except that the starting expanded material made according to Example 9 was made from a functional resin containing 1.4 mol% (6.1% by weight) PSVE made according to Example 5. This membrane it has a mass per area of ​​1.6 g / m². The initial decrease space of coating was 6 thousand (150 micras) and the second decrease space was 3 thousand (75 micras). The final measured thickness of this absorbed composite membrane was 12 ± 2 microns. The absorbed composite material produced in this example is also successfully performed as a solid polymer electrolyte as indicated by the polarization curve obtained from the prepared MEA of the material.

Example 21

The procedures of Example 18 were repeated except that the -SOOF pendant groups in the starting expanded material containing 1.7 mol% (7.7% by weight) PSVE were converted to the acidic form, -SO3H. The starting membrane was first moistened with IPA and then immersed in a 20% by weight KOH solution (Aldrich) at 100 ° C for 72 hours.

It was then rinsed with DI water and immersed in 15% by weight nitric acid (Aldrich) at 80 ° C for 24 hours. The converted membrane was further boiled in DI water at 1.0545 15 cm²/ kg (15 psig) for 60 hours and then air-dried at room temperature. The starting membrane has a mass per area of ​​5.2 g / m². The absorbed composite membrane is 12 ± 2 microns thick. The absorbed composite material produced in this example is also successfully performed as a solid polymer electrolyte as indicated by the polarization curve obtained from the prepared MEA of the material.

Example 22

The procedures of Example 21 were repeated except that the starting expanded material containing 1.4 mol% (6.1% by weight) PSVE has a mass per area of ​​1.6 g / m².

The -SOOF pendant groups on the membrane were converted to the acidic form, -SO₃H. The membrane was converted and then boiled in DI water according to Example 21. The final measured thickness of this absorbed composite membrane was 12 ± 2 microns. The absorbed composite material produced in this example also acts successfully as a solid polymer electrolyte as indicated by the polarization curve obtained from the prepared MEA of the material.

Example 23

Three beads were prepared by extruding the paste from three different polymers as described below:

Polymer A) A fine powder resin comprising the copolymer of TFE and PSVE having 1.1% mol of PSVE. The breaking strength of the pearl was 28.5 N.

0 Polymer B) A fine powder resin comprising a copolymer of TFE and PSVE having 1.0% mol of PSVE was composed of a blend of 30% by weight of TFE and PSVE having 3.6% mol of PSVE, and 7 0% by weight of modified TFE made in accordance with the teachings of US Patent No. 6,541,589.

Polymer C) A fine powder resin comprising a copolymer of TFE and PSVE having 1.1% mol of PSVE was composed of a mixture of copolymer of 80% by weight of TFE and

PSVE that has 0.7% mol of PSVE, and 20% by weight copolymer of TFE and PSVE that has 2.7% mol of PSVE.

A 113.4 g sample of each polymer resin was mixed together with Isopar® K at a ratio of approximately 0.250 g / g resin. The mixture was conditioned at 49 ° C for

10-12 hours. A 2.54 cm diameter cylindrical preform was made by applying about 1,860 kPa of preformed pressure for about 20 seconds. The extruder cylinder was 2.54 cm in diameter and the ram movement speed was approximately 1.5 cm / min. Isopar® K was removed from the bead by drying the bead in a moderate manner at 49 ° C for about 24 hours.

Pearl break resistance was measured using an Instron® stress tester using an initial sample length of 2.54 cm and a 2.54 crosshead shape

0 cm / min. The results for the matrix tensile strength reported in Table 8 are the average of 3 or more tests.

Table 8: Tensile Strength of Pearlizing Matrix

<td colspan="3">Tensile strength</td>

<td colspan="2"></td><td>(kPa)</td>

<td>Polymer</td><td>TO</td><td> 7,612</td>

<td>Polymer</td><td>B</td><td> 7,302</td>

<td>Polymer</td><td>C</td><td> 6,343</td>

Approximately the first and last 2.5m of the extruded bead were discarded to eliminate final effects. A 1.9 cm section of the extruded bead expanded to a ratio of approximately 35: 1, by stretching at 250 ° C for a constant real strain rate of 1 s¹ (the engineering rate at the beginning of the expansion at 100% / s). Approximately a length of 30 cm was removed from near the center of the expanded pearl, and the maximum breaking load of the removed sample maintained at room temperature (23 ° C plus or minus 1.5 ° C) is measured using an Instron strain tester. ® using an initial sample length of 2.54 cm and a crosshead speed of 2.54 cm / min. The matrix tensile strength was calculated from the maximum breaking load and the mass of the sample tested.

Table 9: Tensile strength of expanded pearl matrix

<td>Polymer</td><td>TO</td><td>Resistance (kPa) 171,096</td>

<td>Polymer</td><td>B</td><td> 194,156</td>

<td>Polymer</td><td>C</td><td> 126, 607</td>

to the matrix stress

The expanded pearl was then wetted with IPA and dipped in

20% by weight KOH in water at 175 ° C for 4 hours. The expanded pearl was then removed, rinsed with deionized water, and immersed in 15% by weight nitric acid in water at a temperature of 175 ° C for 4 hours. The expanded pearl was then removed, rinsed, and air dried.

The samples were then immersed in water and only the expanded pearl made with the mixture of two copolymers of

Functional TFE, Polymer C, was hydrophilic as it became translucent,

NOVELTY OF ΙΑ INVENTION

Having described the present invention, it is considered as a novelty, and therefore the content of the following is claimed as property: