KR20070017191A - Fluorinated aromatic polymers - Google Patents

Abstract

Fluorinated polymers of interest have aromatic groups in their repeat units and at least about 25% of the available aromatic ring positions are fluorinated. Aromatic rings may be present along the side chain of the polymer backbone and / or polymer. In particular, at least about 55% of the aromatic ring position is fluorinated for polymers having aromatic groups along the polymer backbone. Approaches to fluorinating aromatic polymers may include polymer melts in contact with appropriate fluorination reagents. In another approach, fluorination is carried out in a polymer solution. The fluorination reaction can be carried out in a batch operation mode or in a continuous operation mode.

Description

Fluorinated aromatic polymers {FLUORINATED AROMATIC POLYMERS}

The present invention relates generally to fluorinated aromatic polymer compositions with high levels of fluorination. The invention further relates to a process comprising a polymer melt of an aromatic polymer for fluorinating the aromatic group of the polymer. The present invention also relates to a solution based on the method of fluorinating aromatic polymers.

Fluorinated polymers have been found for commercial use. In particular, Teflon ^® and other commercially available polytetrafluoroethylene (PTFE) have been found to be used in a wide range as coatings, binders, lubricants and other products. PTFE has been found to have desirable properties for certain applications such as resistance to corrosion and durability. Other commercially important fluorinated polymers include, for example, poly (vinyl fluoride) and poly (vinylidene fluoride) useful in protective coatings.

Aromatic polymers, on the other hand, have been found for use as plastics, which can have a high degree of mechanical strength. In particular, aromatic polycarbonates can have a high impact strength. Some aromatic polymers can be crystalline or semi-crystalline, which can cause desirable mechanical properties. In addition, some aromatic polymers can be treated using the preferred process approach. For example, some preferred polymers can be treated as melts in extrusion or molding processes to form a wide variety of desirable shapes, shapes, and the like.

Summary of the invention

In a first aspect, the invention relates to a composition comprising an aromatic polymer having an aromatic side chain group wherein at least about 25% of the side chain aromatic ring positions are substituted with fluorinated substituents.

In a further aspect, the invention relates to a composition comprising an aromatic polymer having an aromatic backbone group wherein at least about 55% of the backbone aromatic ring position is substituted with a fluorinated substituent.

In another aspect, the present invention relates to a method of fluorinating an aromatic polymer based on a polymer melt. In some embodiments, the method includes reacting a fluorinating agent with a melt of an aromatic polymer to fluorinate the polymer at a position along the aromatic ring.

In a further aspect, the present invention relates to a method of fluorinating an aromatic polymer based on an aromatic polymer solution. In some embodiments, the method comprises reacting a fluorinating agent with an aromatic polymer solution to fluorinate the polymer at a position along the aromatic ring.

Detailed description of the invention

It has been found that advantageous properties of fluorinated polymers can be achieved through fluorinated aromatic polymers. In particular, as described herein, the aromatic polymer has an aromatic group in the repeating unit of the polymer. The fluorinated polymer produced by placing fluorinated substituents on the aromatic ring position of the aromatic polymer is more resistant to chemical degradation and can be more inert and more water repellant with respect to contact with other articles. . The aromatic nature of the polymer may be responsible for the desirable properties of the fluorinated polymer. In particular, aromatic polymers can have high mechanical strength and wear resistance values. In some embodiments, it may be desirable to conduct the polymerization after fluorination of the polymer. A wide range of preferred and commercially available aromatic polymers can be selected as the starting material for fluorination by fluorination of the polymer. Preferred properties of the fluorinated polymer can be selected through the selection of starting polymers and the selection of fluorination conditions during the polymer processing step for the formation of the fluorinated product.

In selected embodiments, the fluorination reaction is carried out using the polymer melt as the shear can be applied in the polymer melt to mix the fluorination reagent through the polymer to obtain the desired degree of fluorination. In further or alternative embodiments, the fluorination reaction is carried out in a solution comprising a solvent capable of dissolving the aromatic polymer. The article can be formed from a fluorinated aromatic polymer. Suitable articles include, for example, carriers for sensitive articles, such as electrical components, fluid handling devices and parts thereof, and components for electrochemical cells.

As used herein, an aromatic polymer has an aromatic group in the repeating unit of the polymer. Aromatic groups have a ring structure with resonance stabilization energy with respect to many unsaturated chemical bonds. The aromatic group includes a carbon ring and a heterocyclic ring, which may include, for example, a nitrogen atom or a sulfur atom. In addition, the aromatic group may be a single ring structure or a polycyclic structure having one or more rings in a conjugated structure such as bicyclic, tricyclic or the like. Examples of hydrocarbon aromatic groups include phenyl, naphthyl, benzyl groups. Examples of heterocyclic aromatic groups include furanyl, thiophenyl, pyrrolyl groups. In aromatic polymers, aromatic groups may be present along the polymer backbone and / or aromatic groups may be present along the polymer side chain. If an aromatic group is present in the polymer backbone, the polymer backbone may further comprise linear or branched groups. In general, aromatic groups may be substituted to replace hydrogen atoms with other chemical groups, and in this case are fluorinated. In particular, the aromatic group may be substituted as long as the aromatic nature of the cyclic group is not impaired.

In general, polymers have a distribution of polymer sizes / molecular weights. The polymer size is the average chain size, i.e.,-[X] _n- (where X is the polymer repeat unit, which can be represented by the appropriate formula, and n is the average value of integers for the distribution characterizing the polymer chain length It can be characterized by). Alternatively, the average chain length can be expressed by the average molecular weight of the polymer. Thus, as used herein, X comprises aromatic ring groups along the polymer chain, ie along the polymer backbone, and / or on the side chains extending from the polymer backbone. In general, the polymer properties depend on both the average chain size / average molecular weight and the distribution of chain size / molecular weight. Distribution and average chain size generally depend on the conditions used to form the polymer. Identifying the distribution and the average polymer chain size can be difficult and can only be predicted based on the polymer's properties such as polymer flow in the melt or solution. In addition, commercial polymers can only be characterized schematically, unless the producer discloses all available information. In addition, the polymer may be crosslinked. Crosslinking includes chemical bonds between polymer chains and correspondingly increases in molecular weight. As used herein, to distinguish small oligomers, the term polymer is expected to have at least five average repeat numbers (n above).

Particularly of interest polymer compositions have at least some aromatic ring positions substituted with fluorinated substituent groups. The fluorinated group may simply be a fluorine atom bonded to an aromatic ring, or the fluorinated group may be a more complex structure with fluorine atoms in the structure, such as, for example, trifluoromethyl groups. In some embodiments, at least about 25% of the available ring positions are bonded to the fluorinated group. Available ring positions are those along the aromatic group that make the bond available that are not involved in the bonding or crosslinking of the aromatic bond or polymer backbone. Thus, for example, the naphthalene molecule C ₁₀ H ₈ has eight available positions. One position is required to bond the group to the polymer to form the side chain, as the naphthalene group bound to the polymer in the side chain has seven available positions. Two positions are required to bond the group along the polymer backbone, with the naphthalene groups bonded along the polymer backbone having six available positions. If the aromatic group is involved in chemical crosslinking, this also removes the available aromatic ring position. The basic polymer structure, i.e., any aromatic sites involved in the bonding of the polymer backbone, or chemical crosslinking, is considered unavailable.

In general, the fluorinated aromatic polymers described herein can be formed by any approach. For example, the fluorinated monomer can be used to form the polymer in the formation of the polymer. However, in some embodiments, it may be desirable to fluorinate the polymer after the polymerization process. Thus, after polymerization, fluorination can be carried out to select a wide range of commercial polymers as starting materials for the fluorination reaction. The fluorination process may then focus on obtaining the desired fluorination properties of the product polymer. When crosslinking is carried out, this may be carried out before, at or after the fluorination reaction.

The fluorination process can be carried out in a polymer melt or polymer solution. The fluorination reagent can be combined with the polymer melt. It is confirmed that the desired degree of fluorination can be achieved by supplying shear to the polymer melt at the time of reaction or part thereof to distribute the fluorinated reactant through the polymer. For example, shear may be fed to a highly commercial shear mixer or extruder. The fluorination reaction may not be combined or may be combined with a method for forming the final product in one continuous process. For example, the extruder can inject the fluorinated product formed in the extruder into a mold or the like for product formation.

In some embodiments, the fluorination is in a polymer solution. In particular, the polymer is dissolved in a suitable solvent and a fluorinated reactant is added to the solution under appropriate conditions to effect the fluorination reaction. After completion of the fluorination reaction, the fluorinated polymer can be removed from the solvent or further treated with the final product.

The chemical composition of the fluorinated reactant determines the fluorinated nature of the aromatic compound. In general, fluorinated reactants can be selected based on, for example, reactivity, fluorinated product composition, handling problems, the nature of the fluorination process (melt based or solvent based) and cost. By way of example, some fluorinated reactants replace aromatic cyclic hydrogen atoms, halogen atoms and / or hydroxyl hydrogen atoms with fluorine atoms. Other reactants replace aromatic cyclic hydrogen atoms with fluorinated hydrocarbon groups and the like. The fluorinated hydrocarbon group may be a linear or branched alkyl group, which may or may not include other functional groups, such as oxygen, sulfur, or nitrogen atoms. Similarly, the group may contain other halogen atoms in addition to fluorine atoms.

The degree of fluorination generally depends on, for example, the amount of reactants, the reaction conditions and the reaction time. Any desired degree of fluorination can be carried out using the process approach described herein. In some embodiments, the polymer is essentially completely fluorinated at the available aromatic ring position.

Fluorination of polymers generally results in polymer products having greater resistance to chemical degradation and improved mechanical, physical and optical properties. Thus, products formed from fluorinated products may last longer for reuse and / or provide greater protection to components associated with the product along with the polymer. In addition, the product polymer may be more transmissive to visible light, which may be desirable for some applications. In some embodiments, the article can be reused due to improved performance. Similarly, fluorinated polymers are generally waterproof / moisture resistant. Fluorinated polymers may be useful for product formation where moisture resistance is desirable. In addition, fluorinated polymers are generally more inert to most other materials, such that sensitive polymers and corresponding articles can be contacted with fluorinated polymers without causing side effects with the sensitive articles.

Various articles may be formed from the fluorinated polymers described herein. Some articles are of particular interest and performance may be improved due to properties attributed to aromatic fluoropolymers. For example, fluoropolymers can advantageously be incorporated into carriers for semiconductor wafers. The carrier is designed to protect the wafer from various physical and chemical attacks. Wafer carriers are further described in US Pat. No. 6,520,338, entitled "Wafer Carrier Having A Low Tolerance Build-Up," by Bores et al., Which is also incorporated herein by reference. Described in the heading. In addition, some fluid handling systems are designed to handle corrosive polymers. It may be desirable to use inert fluorinated aromatic polymers for such systems. For example, a quick connect fill system for corrosive liquids is a U.S. patent, entitled "Quick Connect Fill System," by Hennan et al., Which is further incorporated herein by reference. 6,497,260. Similarly, some components of electrochemical cells such as cells, electrolyzers and fuel cells may be formed from polymeric materials. Some of these components, for example, are water resistant in fuel cells, or are water resistant, so water management can be an important factor for polymeric materials. The components of the electrochemical cell may or may not be electrically conductive. Conductive fillers such as metal powders or conductive carbon powders such as graphite or carbon black may be used to introduce electrical conductivity into the polymer. Suitable electrochemical cell components include, for example, electrodes or fuel cell anode plates. Fuel cell components are further described in US Pat. No. 6,555,262, entitled "Wicking Strands For A Polymer Electrolyte Membrane," by Kaiser et al., Which is further incorporated herein by reference. Described.

Fluoropolymer  Composition

Aromatic fluoropolymers described herein have aromatic groups in polymer repeat units. The properties of the polymer can be selected to provide the desired properties to the particular product. Similarly, the degree of fluorination can be selected to balance various factors, such as polymer properties and process considerations. Due to limitations on the polymer structure with respect to aromaticity and fluorination, a wide range of polymers can be formed by fluorination as described herein.

The base polymer structure can match any range of base polymer structure. Suitable polymers in connection with suitable polymers having aromatic side chains include, for example, polystyrene, which is a vinyl polymer comprising side chain phenyl groups. Suitable polymers comprising aromatic polymer backbones are, for example, polyimides, polysulfones, polyethersulfones, polyarylsulfones, polysulfides, polyetheretherketones, polyetherketones, polyetherketone ketones, poly (phenylene oxides) , Poly (phenylene sulfide), polyetherimide, aromatic polyesters such as polycarbonate and poly (ethylene terephthalate), copolymers thereof and mixtures thereof. A wide range of these polymers and other suitable polymers are commercially available. For suitable embodiments, these polymers can be used as starting materials for the fluorination process.

In general, the properties of the fluorinated polymers are related to the properties of the polymer starting material as well as to the fluorination process. The properties of the fluorinated polymers are generally selected based on the nature of the final product. For structural products, polymers are generally chosen to have an average molecular weight sufficient to provide adequate mechanical strength, while for other products, lower molecular weight polymers with lower molecular weight may be appropriate. Thus, in some embodiments, the polymer has a molecular weight of at least about 200 Daltons, in other embodiments, at least about 500, and in further embodiments, a molecular weight of at least about 750 Daltons. On the other hand, in some embodiments, the average molecular weight is generally at least about 10,000 Daltons, in further embodiments at least about 25,000 Daltons, in further embodiments, at least about 50,000 Daltons, and in other embodiments about 75,000 Daltons to about 5,000,000 daltons. In addition, the degree of aromaticity in the polymer affects the polymer properties. Some aromatic polymers can form crystalline structures. In general, the polymer of particular interest has an aromatic ring in the repeating unit corresponding to at least about 10% by weight of the repeating unit, and in some embodiments, at least about 20% by weight, and in further embodiments, the aromatic ring Have a corresponding at least about 40% by weight of repeat units. Those skilled in the art will appreciate that other molecular weight ranges and weight% ranges within the apparent range are contemplated and are within the specification.

As mentioned above, aromatic polymers can be fluorinated in aromatic rings in several possible ways. For example, hydrogen atoms bonded to aromatic carbon atoms can be replaced with fluorinated sites. The nature of the fluorinated substituents depends on the nature of the fluorinated reactants. In some embodiments, the hydrogen atom may be replaced with a fluorine atom bonded directly to the aromatic atom. In other embodiments, the ring substituents can be replaced or modified with fluorine containing substituents, such as fluorinated carbon containing groups.

In general, the degree of fluorination depends on the fluorination reaction. The degree of fluorination can be expressed as a percentage of aromatic ring position with fluorine containing substituents. As described above, the available aromatic ring positions are considered as aromatic carbon atoms that do not participate in bonding with the polymer structure in the polymer backbone, along chemical crosslinking, or in bonds to another aromatic group. In some embodiments, essentially all of the available aromatic ring positions are combined with fluorinated substituents, suggesting that at least about 95% of the available ring positions are fluorinated. In some embodiments, at least about 25% of the available ring positions are fluorinated, while in further embodiments, at least about 35%, in further embodiments, at least about 50%, in some embodiments, at least about 55% At least about 60%, and in further embodiments at least about 75% of the available ring positions are fluorinated. Those skilled in the art will appreciate that additional ranges of fluorination within the apparent scope are contemplated and are within the specification.

Fluorination Reagent

The chemical composition of the fluorination reaction determines the substituents placed on the aromatic ring. In particular, some fluorination reagents can replace cyclic hydrogen atoms with fluorine atoms. Other reagents may replace hydrogen atoms with fluorine containing substituents attached to aromatic carbon atoms. Another reagent is reactive with respect to other aromatic substituents such as halogen or hydroxyl groups.

HF and F ₂ are compounds which are effective for fluorinating aromatic rings with fluorine atoms in connection with fluorinating agents for placing aromatic fluorine atoms. Fluorine F ₂ is an extremely reactive gas as an oxidant. Due to the strong reaction nature of the fluorine gas, the reaction must be carefully relaxed in order to fluorinate the aromatic ring without disrupting the polymer molecules. HF is a highly strong acid that is water soluble. HF is a gas in its pure state.

Another reagent adds a fluorine containing group to the aromatic ring. For example, fluorocarbon iodides can be added to the aromatic ring to substitute sites for fluorocarbons. The carbon chain bonded to the aromatic ring may be saturated or unsaturated, and may be linear, branched or cyclic. The fluorocarbon iodide may not be perfluorinated or may be perfluorinated to contain no hydrogen atoms. For example, trifluoromethyl iodide (CF ₃ I), perfluoroethyl iodide (CF ₅ I), perfluoroisopropyl iodide (C ₃ F ₇ I) and perfluoroprop Neodymide (C ₃ F ₇ I), and many other suitable compounds, are available from Aldrich Chemical, Milwaukee, Wisconsin. Other suitable alkylating agents include, for example, fluorinated peroxides such as bisperfluoroalkylperoxides.

Other fluorocarbon reactants may add fluorine containing groups to the appropriate aromatic polymer. For example, poly-phenols having a phenol ring along the backbone or in the side chain where the ring is fluorinated via hydroxyloxygen. Suitable fluorination reagents include, for example, chlorodifluoromethane (DuPont) fluoro-olefins such as tetrafluoroethylene and hexafluoropropylene (both available from DuPont) or perfluorovinylether . Perfluoromethylvinylether, perfluoroethylvinylether and perfluoropropylvinylether are available from DuPont. In the case of polyaryl halides, the aromatic cyclic halide group is reacted with methyl 2- (fluorosulfonyl) difluoroacetate (DuPont) to introduce a -CF ₃ group into the aromatic cyclic.

Melt -Based process approach

The melt based process approach may generally be based on polymer melts carried out in a heated apparatus while applying shear. In general, the fluorinating agent may be added initially or after the polymer has melted, and the fluorinating agent may be added slowly at one time or over time. However, it may be desirable to slowly add the fluorinating agent to the molten polymer. The reaction can be carried out in a suitable commercial process apparatus. The amount of reactants, reaction time and reaction conditions can be selected to achieve the desired level of fluorination.

Suitable apparatus includes, for example, heated mixers and extruders. In particular, suitable mixers are, for example, Buss Kneader K 600 CP (Davy Process Technoloty AG, Switzerland), Century Inc. (Michigan) Ring Extruder from Transverse City, Banbury Mixer (Farrel Corp., Ansonia, CT), or Thermo Hakke Twin Blade Mixer (Para, NJ) Hakes Instruments, Moose. Single spiral extruders or multi-helical extruders can be used, such as twin spiral extruders. Multi-helical extruders may have the advantage of better mixing in the extruder. Similarly, suitable commercial extruders include, for example, the Berstorff model ZE or KE extruder (Hannover, Germany), the Leistritz model ZSE or ESE extruder (Smallville, NJ) and the Davis-Standard Mark series. Extruder (Pawcatuck, Connecticut). Fluorination reagents can be added to the polymer melt through ports in the reactor / extruder, and shearing may be applied to mix the fluorinating agent through the polymer melt to achieve relatively uniform fluorination through the bulk of the polymer. In the extruder, the polymer can be introduced from the hopper into the extruder. The fluorinating agent can be added to the molten polymer traveling through the extruder through the pot. For example, HF can be introduced into the extruder as a gas, while perfluoroalkyl iodides or bisperfluoroalkylperoxides are generally added into the extruder as a liquid or solution. The location of the pot, the rate of movement of the polymer through the extruder, the temperature of the extruder and the rate of addition of the fluorinating agent can be selected to obtain the desired results of the fluorination reaction.

The fluorinated polymer is dispensed through the extruder outlet. A die may be placed at the exit of the extruder to shape the shape of the extruded polymer. The molded polymer may be further polished or molded to form an article, or any polymer conversion process, such as some, may be designated to form a raw material for forming the article using compression molding, transfer molding, and injection molding. Can be. For example, the polymer is polished with a thin sheet to form a coating and then laminated in another structure, for example in the form of a polymer. Similarly, when fluorination is carried out in a high shear mixer, the polymer can be transferred to another process apparatus to form the polymer in the desired form.

Solution-Based Process Approach

In a solution based process, the polymer is dissolved into a solution. The fluorinating agent can then be added to the solution as a gas or a liquid / solution. For example, HF gas can be buffled in solution or dissolved in a suitable solvent. Perfluoroalkyl iodides or bisperfluoroalkylperoxides can generally be added as liquids or solutions. The reaction can be carried out using a commercial reactor. In some embodiments, it is desirable to mix the solution in the reaction.

The fluorination reaction in solution can be carried out in a batch or continuous process. Suitable equipment is available depending on the process type. For example, in a continuous solution based process, the polymer solution is conveyed from the reservoir through the reactor to the outlet. The fluorinated reactant may be combined with the polymer solution as it is added to the reactor, or may be added to the flowing polymer solution through an appropriate port. Suitable instruments for the continuous fluorination process include, for example, booth kneader K 600 CP (David Process Technologies AG, Switzerland), or a ring extruder (Century Inc., Transverse City, Michigan). do. For batch operation all reactants may be formulated in solution or fluorinated reactants may be added slowly over time. Some suitable reactors adjust the temperature to control the reaction in the appropriate temperature range for the reaction. In some embodiments, proper bench scale synthesis can be performed using flasks and heating / cooling mantles.

Generally, the polymer is dissolved in a suitable concentration of solution where the polymer can be well dispersed. The choice of solvent depends on the nature of the polymer and the fluorinated reactant. In general, aromatic polymers may be soluble in suitable organic solvents, such as aromatic solvents. The supplier generally provides the appropriate information about the solvent to process the particular polymer. Solvent mixtures may be used to facilitate incorporation of both polymers and fluorination reagents.

The amount of reactants as well as the reaction time and reaction conditions can be used to control the degree of fluorination. Assuming that termination of the reaction is acceptable and that the materials are properly mixed, the degree of fluorination can only be adjusted based on the amount of reactants. The degree of mixing can be adjusted to achieve the desired amount of fluorination of the uniform aromatic ring.

Some fluorination reactions are exothermic. The reaction rate generally increases with increasing temperature. If more heat is generated, it may be desirable to cool the reactants to control the reaction rate. On the other hand, if the reaction proceeds very slowly, it may be desirable to heat the reactants. In general, those skilled in the art can adjust the amount of reactants, reaction time and reaction conditions to achieve the desired results.

After fluorination of the polymer, the polymer may be further processed to the final product. In particular, the polymer may be further processed in solution, or the solvent may be removed, for example by evaporation, to obtain a polymer and further processed into a melt. Concentration of the polymer solution may provide the desired amount of viscosity for further processing by molding, gloss, extrusion, and the like. After the final product is formed, the remaining solvent can be removed.

Fluorination of aliphatic and silicone based polymers for comparison with the approaches described herein is described in the article "Synthesis of fluorinated polymer by chemical modification," by Reisinger and Hillmyer, Progress in Polymer Science. , 27 (2002) 971-1005.

The embodiments described herein are intended to be illustrative and not limiting. Further embodiments are included in the claims. While the present invention has been described in connection with specific embodiments, those skilled in the art will recognize that modifications may be made in detail in form without departing from the spirit and scope of the art.

Claims (44)

At least about 55% of the backbone aromatic ring position comprises an aromatic polymer having an aromatic backbone group substituted with a fluorinated substituent. The group according to claim 1, wherein the polymer is composed of polycarbonate, polyimide, polyetherether ketone, polyetherimide, polyethersulfone, polyphenylene sulfide, polyetherketone, polyetherketone ketone, copolymers thereof and mixtures thereof A polymer composition selected from. The polymer composition of claim 1, wherein the polymer further comprises aromatic groups in the polymer side chain. The polymer composition of claim 1, wherein at least about 60% of the aromatic ring positions are substituted with fluorinated substituents. The polymer composition of claim 1, wherein at least about 75% of the aromatic ring positions are substituted with fluorinated substituents. The polymer composition of claim 1 wherein essentially all of the aromatic ring positions are fluorinated. The polymer composition of claim 1, wherein the fluorinated substituent comprises a fluorine atom substituent. The polymer composition of claim 1, wherein the fluorinated substituent comprises a fluorinated alkyl group. The polymer composition of claim 1, wherein the fluorinated substituent comprises a trifluoromethyl group. The polymer composition of claim 1, wherein the fluorinated substituent comprises a pentafluoroethyl group. The polymer composition of claim 1, wherein the aromatic group comprises at least about 10% by weight of the polymer repeating unit. A composition comprising an aromatic polymer having an aromatic side chain wherein at least about 25% of the side chain aromatic ring positions are substituted with fluorinated substituents. 13. The composition of claim 12, wherein the polymer comprises polystyrene. 13. The polymer composition of claim 12, wherein at least about 55% of the aromatic ring positions are substituted with fluorinated substituents. 13. The polymer composition of claim 12, wherein the polymer further comprises aromatic groups along the polymer backbone. 13. The polymer composition of claim 12, wherein essentially all of the aromatic ring positions are fluorinated. 13. The polymer composition of claim 12, wherein the fluorinated substituent comprises a fluorine atom substituent. 13. The polymer composition of claim 12, wherein the fluorinated substituent comprises a fluorinated alkyl group. A method of fluorinating an aromatic polymer comprising reacting a fluorinating agent with a melt of the aromatic polymer to fluorinate the polymer at a position along the aromatic ring. 20. The method of claim 19, wherein shear is applied during at least some of the reaction processes. The method of claim 20, wherein shear is applied using an extruder. 22. The method of claim 21, wherein the fluorinating agent is added via a port in the extruder away from the extruder die. The method of claim 20 comprising applying a shear to the mixer and further injection molding the fluorinated polymer. The method of claim 19, wherein the polymer has aromatic groups along the polymer backbone. The process of claim 19 wherein the polymer is a polycarbonate, polyimide, polyetherether ketone, polyetherimide, polyethersulfone, polyphenylene sulfide, polystyrene, polyetherketone, polyetherketone ketone, copolymers thereof and mixtures thereof Method selected from the group consisting of: The method of claim 19, wherein the fluorinating agent comprises HF. The method of claim 19 wherein the fluorinating agent comprises perfluoroalkyl iodide. 20. The method of claim 19, wherein the fluorinating agent comprises bisperfluoroalkylperoxides. 20. The method of claim 19, wherein the fluorinated polymer is at least about 25% of the aromatic cyclic positions substituted with fluorinated substituents. The method of claim 19, wherein the reaction process is carried out in batch mode. The method of claim 19, wherein the reaction process is conducted in continuous mode. A method of fluorinating an aromatic polymer, comprising reacting a fluorinating agent with an aromatic polymer in solution to fluorinate the aromatic polymer at a position along the aromatic ring. 33. The method of claim 32, wherein the solution comprises an organic liquid. The method of claim 33, wherein the organic liquid comprises an aromatic solvent. 33. The method of claim 32, wherein the fluorinating agent is slowly added to the solution while mixing the solution. 33. The method of claim 32, wherein the temperature of the solution is controlled within a selected range. 33. The method of claim 32, wherein the fluorinating agent comprises HF. 33. The method of claim 32, wherein the fluorinating agent comprises perfluoroalkyl iodide. 33. The method of claim 32, wherein the fluorinating agent comprises bisperfluoroalkylperoxide. 33. The method of claim 32, wherein the aromatic polymer has aromatic groups along the polymer backbone. 33. The process of claim 32 wherein the polymer is a polycarbonate, polyimide, polyetherether ketone, polyetherimide, polyethersulfone, polyphenylene sulfide, polystyrene, polyetherketone, polyetherketone ketone, copolymers thereof and mixtures thereof Method selected from the group consisting of: 33. The method of claim 32, wherein the fluorinated polymer is substituted with at least about 25% of the aromatic ring positions with fluorinated substituents. 33. The method of claim 32, wherein the reaction process is carried out in a batch operation. 33. The method of claim 32, wherein the reaction process is carried out in a continuous operation.