National Research Council of Canada

Canadian Patents & Development Ltd.

Michael D Guiver

Gilles P Robertson

Oleh Kutowy

Naiying Du

John W Apsimon

Yan Gao

Jianfu Ding

Jingshe Song

Andre Y Tremblay

Jacques Roovers

Yinghua Qi

Tyler B Norsten

Hoai Nam Le Thi

Xigao Jian

Chung M Tam

Fei Wang

Baijun Liu

A polymer of formula (I): where: n is an integer from 10 to 5,000; m is an integer from 10 to 5,000; Ar1 and Ar3 are the same or different and are residues derived from a tetra-hydroxy aromatic monomer, the tetra-hydroxy aromatic monomer being wherein R is the same or different and is H or a C-Calkyl, C-Calkenyl or C-Ccycloalkyl group; and, Ar2 and Ar4 are the same or different and are residues derived from a tetra-halogenated aromatic monomer, the tetra-halogenated aromatic monomer being wherein X is F, Cl or Br, and R1 and R2 are the same or different and are wherein y is an integer from 1 to 8; with the proviso that when Ar1 is the same as Ar3 and Ar2 is the same as Ar4, R1 and R2 are not both &#x2014;CN is useful as a material for gas separation, vapor separation, adsorbents or catalysis.

Ladder polymers with intrinsic microporosity and process for production thereof

A film of a carboxylated polymer of formula (I): wherein the sum of x, y and z is an integer from 10 to 10,000 and degree of hydrolysis is 0.05 or greater provides gas separation materials in which the degree of hydrolysis may be used to tune the selectivity of the gases to an optimal required range. Such films may be prepared by casting a film of a polymer of formula (II): wherein n is an integer from 10 to 10,000, and hydrolyzing all or a portion of the &#x2014;CN groups to form &#x2014;COOH groups.

Carboxylated polymers of intrinsic microporosity (PIMs) with tunable gas transport properties

A polymer of formula (I): where: n is an integer from 10 to 5,000; m is an integer from 10 to 5,000; Ar1 and Ar3 are the same or different and are residues derived from a tetra-hydroxy aromatic monomer, the tetra-hydroxy aromatic monomer being wherein R is the same or different and is H or a C-Calkyl, C2-C8 alkenyl or C-Ccycloalkyl group; and, Ar2 and Ar4 are the same or different and are residues derived from a tetra-halogenated aromatic monomer, the tetra-halogenated aromatic monomer being wherein X is F, Cl or Br, and R1 and R2 are the same or different and are wherein y is an integer from 1 to 8; with the proviso that when Ar1 is the same as Ar3 and Ar2 is the same as Ar4, R1 and R2 are not both &#x2014;CN is useful as a material for gas separation, vapor separation, adsorbents or catalysis. 

Ladder polymers with instrinsic microporosity and process for production thereof

The invention provides a tetrazole-containing polymer of intrinsic microporosity comprising (10) or more subunits, wherein one or more of the subunits comprise one or more tetrazolyl moieties. In one embodiment, a polymer of intrinsic microporosity (PIM-1) was modified using a 'click chemistry' [2+3] cycloaddition reaction with sodium azide and zinc chloride to yield new PIMs containing tetrazole units. Polymers of the present invention are useful as high-performance materials for membrane-based gas separation, materials for ion exchange resins, materials for chelating resins, materials for superabsorbents, materials for ion conductive matrixes, materials for catalyst supports or materials for nanoparticle stabilizers.

Polymers of intrinsic microporosity containing tetrazole groups

A sulfonated poly(aryl ether) (SPAE) having a poly(aryl ether) (PAE) main chain and a sulfonated phenyl group pendent from the main chain are useful in proton exchange membranes (PEMs), particularly for fuel cells. The pendent phenyl group can provide an easily sulfonable site that may be sulfonated under mild conditions, providing the ability to precisely control the sulfonic acid content of the SPAE.

Poly(aryl ether) with pendent sulfonic acid phenyl groups

Ether nitrile co-polymers containing sulfonic acid groups, including wholly aromatic poly(aryl ether ether nitrile)s containing sulfonic acid groups (SPAEEN)s, and poly(phthalazinone ether ketone nitrile) co-polymers containing sulfonic acid groups (SPPEKN)s, intended for fuel cells applications as proton conducting membrane materials, were prepared.

Ether nitrile co-polymers containing sulfonic acid groups for PEM application

A new series of wholly aromatic poly(arylene ether ether ketone ketone)s containing pendant sulfonic acid groups (SPAEEKK) were conveniently prepared by potassium carbonate mediated nucleophilic polycondensation reactions of inexpensive commercially available monomers: 1,3-bis(4-fluorobenzoyl)benzene (BFBB), sodium 6,7-dihydroxy-2-naphthalenesulfonate (DHNS), and 4,4'-biphenol or hydroquinone in N-methyl-2-pyrrolidone (NMP) at 170&#xb0; C. FT-IR and NMR were used to characterize the structures and the sulfonate or sulfonic acid contents (SC) of the polymers. Flexible membrane films were obtained by casting N,N-dimethylacetamide (DMAc) solutions of copolymers. Membrane films in acid form were then obtained by treating the sodium form membrane films in 2 N sulfuric acid at room temperature. Glass transition temperatures (Ts) and decomposition temperatures (Ts) of SPAEEKKs in both sodium and acid forms were determined. Water uptake and swelling ratio values increased with SCs and temperatures. The proton conductivities of acid form membrane films increased with SC value and temperature and reached 5.6&#xd7;10S/cm at 100&#xb0; C. for SPAEEKK-100.

Synthesis of poly(arylene)s copolymers containing pendant sulfonic acid groups bonded to naphthalene as proton exchange membrane materials

Fluorinated comb co-polymers have a main chain including a semi-rigid hydrophobic fluorinated poly(ether) backbone and comb segments in the form of flexible and monodisperse side chains that are more hydrophilic than the backbone. The side chains may be hydrophilic polymeric chains obtained from 'living-type' polymerization, for example polymethacrylates, polyethylene oxides, polystyrenes. Hydrophilic functionality, for example, ionic groups may be selectively introduced onto the side chain post polymerization. The side chain may be sulfonated &#x3b1;-methyl polystyrene. Such polymers are useful in proton exchange membranes.

Fluorinated comb-shaped polymers

A polysulfone-zeolite composite membrane can be used to separate gas pairs such as hydrogen/carbon dioxide. Zeolite, preferably zeolite 3A particles are covalently bonded to the polymer using an aminofunctional methoxysilane as a coupling agent to bind the zeolite particles to an aldehyde modified polysulfone matrix.

Composite gas separation membranes

The invention disclosed relates to a process for producing azide-substituted aromatic polymers such as polysulfones, and to certain novel azide-substituted polysulfones so produced. The process involves attaching azide groups onto the aromatic rings of the polymers by first activating the attachment site by direct lithiation or bromination, followed by lithiation. The lithiated intermediates are converted substantially qantitatively to azides by reacting with a suitable azide, preferably tosyl azide, under substantially anhydrous conditions. Novel azide-substituted polysulfones containing from one to about three azide groups per repeat polymer unit were obtained, the degree of azide substitution being determined by the degree of lithiation. The azides may also be converted to other functional derivatives such as primary amines and cross-linked membranes.

Process for producing azide-substituted aromatic polymers and the

Bromomethyl derivatives of polyaryl ether ketones are obtained by brominating methyl derivatives of the ketones preferably with elemental bromine, optionally under UV light. The bromomethyl derivatives are useful as intermediates for further functionalization of the aromatic polyether ketones. The functionalized derivatives, depending on the substituent, exhibit different properties than the basic polymer, for example increased hydrophilicity and solubility.

Functionalized polyaryletherketones

This invention relates to aromatic polysulfone compounds and their manufacture. More particularly, this invention relates to functional group containing aromatic polysulfones, and their manufacture by metalation with organo-lithium compounds, of halogenated (e.g. brominated or chloromethylated) aromatic polysulfone compounds. The degree of halogenation of the starting material determines the sites that may be metalated, and the degree of metalation determines how many of these sites will be metalated. At least one of the metalated sites may be treated with an electrophile so that the lithium at that site is replaced by a residuum of the electrophile.

Aromatic polysulfone compounds and their manufacture

Halogenation of Udel (trademark) and Radel (trademark) polysulfone occurs adily by electrophilic substitution. The reactive substitution position is situated ortho- to the aryl ether linkage in the Bisphenol-A portion of the repeat units. Halogenated polysulfones are obtained by reaction of the polymer with elemental halogen. Thus, a solution of Udel polysulfone in chloroform, treated with excess bromine at room temperature, gives dibrominated polysulfone III in high yield. The degree of substitution after 18-24 hours is typically 1.80 to 2.05 by bromine analysis. Similar results are obtained by reaction of the polymer with elemental chlorine. Lower degrees of substitution are obtained with shorter reaction times or using lesser amounts of halogen.

Method of manufacturing halogenated aromatic polysulfone compounds and

Reverse osmosis membranes are manufactured by casting a polysulfone casting composition comprising:

Method of manufacturing a reverse osmosis membrane and the membrane so

A process is provided for producing aromatic polysulfones which contain repeating units of the formula: ##STR1## wherein each R is ortho to the sulfone, at least one R per polymer chain is an aliphatic or aromatic substituent, a heteroatom or heteroatom-containing group or a metal or metal-containing group, with any remainder thereof being hydrogen, R.sub.1 and R.sub.2 each represents alkyl or aryl, each R.sub.s is hydrogen, and n is zero or one. The process comprises:

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Ottawa, Canada

Michael D Guiver