巴西专利BR112012021569A2 polymer composition, membrane, process for preparing a membrane, use of the polymer composition, and

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POLYMER COMPOSITION, MEMBRANE, PROCESS FOR THE PREPARATION OF A MEMBRANE, USE OF POLYMER COMPOSITION, AND, OLIGO- OR POLYURETHANE COMPOUND. Compound of oligo- or polyurethane of the formula (I) where k are independently numbers from 1 to 100, m is in the range 1 -100, (X) is a block of the formula (II) and (Y) is a block of the formula (III), (A) is a residue of an aliphatic or aromatic diisocyanate binder, (B) is a residue of a linear oligo- or polysiloxane containing final alkanol groups, and optionally still containing one or more aliphatic ether fractions, and ( C) is an aromatic oligo- or polysulfone block, can be advantageously used as anti-adhesion additives in polymer compositions for example, for membranes; related oligo- or polyurethanes where m is 0 are especially suitable for the preparation of antimicrobial water separating membranes.
公开号:BR112012021569A2
申请号:R112012021569-8
申请日:2011-03-01
公开日:2020-08-25
发明作者:Thomas Weiss；Jaleh Mansouri
申请人:Polymers Crc Ltd；
IPC主号:

专利说明:

“POLYMER COMPOSITION, MEMBRANE, PROCESS FOR THE PREPARATION OF A MEMBRANE, USE OF THE COMPOSITION OF - POLYMER, AND, OLIGO- OR POLYURETHANE COMPOUND” i The present invention concerns unprecedented% 5 - polyurethane block copolymers based on poly siloxane (surfactants) with anchoring units, their use as anti-adhesion additives especially in membrane preparation, and polymer membranes, especially for purposes of microfiltration, ultrafiltration or gas separation or purification, containing the unpublished copolymers.
The bioencryption problem is pronounced in semipermeable membranes used for separation purposes such as microfiltration, ultrafiltration or reverse osmosis. Membranes can be classified according to their pore size in most application profiles. For example, in ultrafiltration water filtration membrane applications (approximate pore diameter: 100 - 1000 nm) they are used for wastewater treatment retaining organic and bio-organic material. Much smaller diameters are required in desalination applications (reverse osmosis; approximate pore diameter 1 nm) to retain ions. In these applications, the environment is an aqueous phase, where potential blockage can occur due to the adhesion of microorganisms and the formation of biofilms. As a result, a membrane with anti-adhesion properties is desired, which can reduce the formation of biofilm and thus requires less cleaning cycles.
US-5102547 proposes several methods for the incorporation of oligodynamic materials including silver powders and silver colloids in —membranes. US-6652751 compares various bacteriostatic membranes obtained after bringing polymer solutions containing a metal salt into contact with a coagulation bath containing a reducing agent. Membranes containing certain modified polymers have also been proposed to improve the resistance to encryption; WO 09/098161 describes certain polysulfones functionalized with alkoxyamine as additives for the purpose. WO 07/053163 recommends the incorporation of certain copolymers - from a graft based on a polysiloxane backbone in polymeric materials, such as coatings to confer anti-crust properties, Hydrophobic properties of polysiloxanes have already been explored to confer “encryption-release properties ”To surfaces coated with these polymers or certain copolymers containing polysiloxane blocks (see S. Krish-nan, J. Mater. Chem. 2008, 18, 3405, and references cited therein).
Certain block copolymers with urethane bonding are now found, which show especially advantageous anti-crust properties. Due to their good compatibility, the present block copolymers can be completely incorporated into other matrix polymers, or rigidly anchored in these matrices and enriched on the surface.
Thus, the present block copolymers can conveniently be used as an additive that imparts antimicrobial and anti-adhesion properties to polymeric articles and their surfaces, for example, when incorporated into a membrane, especially a membrane for water filtration purposes. The present block copolymers contain one or more polysiloxane blocks as a diol component (B), the final alkanol groups of which are optionally extended by one or more ether fractions. Still conveniently contained are aromatic polysulfone blocks (C) as the second diol component. Bonding between the diol blocks is carried out by urethane (A) binders derived from aromatic or aliphatic diisocyanates.
In a first general aspect, the present invention thus belongs to the oligo- and polyurethane molecules giving rise to said components (A), (B) and (C) of the rodei formula. (O) 'where k are independently numbers from 1 to 100, í m is in the range 1-50, where (X) is a block of the formula ——O — CO —- N— (A) —3N — CO— O— (B) -—-— HHO) (II) and (V) is a block of the formula —O — CO-N— (A) N — CO-O— (C) —— HH (1), ( A) is a residue of an aliphatic or aromatic diisocyanate binder, (B) is a residue of a linear oligo- or polysiloxane containing final alkanol groups, and optionally still containing one or more aliphatic ether fractions, and (OC) is a block of oligo or aromatic polysulfone.
Blocks (X) and (1) in formula I can be in statistical order or, again, in blocks; the usual procedure (see the present examples) yields blocks (X) and (Y) in statistical order. Fractions (A), (B) and (C) can also comprise minor amounts of tri- or polyvalent residues, for example, including a minor amount of a trilsocyanate and / or tetraisocyanate in the preparation of the present oligo- or polyurethane. The resulting branched species share the advantageous properties of the present linear oligo- and polyurethanes, and are included by the present invention.
Preferred oligo- and polyurethane molecules of the invention contain at least one block (X) and at least one block (Y); preferred n in the range of 2 to 50, and preferred k ranging from 1 to 20. The molecular weight (Mn) is preferably in the range 1500 to 100000, more preferably in the range 4000 a. 25000, Above all preferred compounds show a polydispersity] ranging from 1.5 to 3.0,. 5 Preferred (A) is a divalent residue selected from CyCi7 alkylene and Ar. Preferred (B) is a divalent residue of an oligo- or polysiloxane of the formula “[Ak-O] -AK-Si (R2) - [0-Si (R2)] .- O-Si (R2) -Ak- [0-Ak] a- (IV) where Ak represents alkylene Cy-Cy, R represents alkyl —CyCa, each dep, qeq 'is independently a number selected in the range 0-50, In most preferred fractions (B) of the formula (IV), p ranges from 1 to 50, especially from 2 to 50, Preferred (C) is a diphenyl sulfone monomer or linear oligomer or polymer block containing 1 -50 fractions phenyl-SO, z-phenyl, and optionally still 1 -50 additional fractions Ar, whose fractions are, in the case of the oligomer or polymer, linked by selected means of direct bonds and Sp spacers; Air is selected from -Ph-Ph- and -Ph-Sp-Ph-; Ph is phenyl or phenyl substituted by Cy-Cs alkyl; where Sp spacers independently are -O- or Cy-C alkylene; 3.
Final groups in the oligomer or polymer (accented by asterisks * in formula D) are mainly mono-reacted constituents of polyurethane (eg, OH free from the diol component, or mono-reacted diisocyanate [-CO-NH-UM-NCO], attached to (B) or (C) on the right side of formula 1, or mono- reacted diol component HO- (B) - or HO- (C) attached on the left side of formula 1). Chain termination can also be carried out by including a certain amount (for example, up to 20 mol%) of monofunctional constituents, for example, monoalcohols R '- (B) -OH or R'- - (C) -OH where R' is alkyl (such as Cy-C4 alkyl), Ar or especially H; R '] (appropriately attached to (B) or (C)) thus forming one or both groups: final 5 In this way, the present oligo- and polyurethanes are essentially free from typical silane final groups such as SI (R ”) 3, where R ”is either H, alkyl, alkoxy.
The invention also relates to a membrane, especially a semipermeable membrane, comprising the above polymer composition. The membrane of the invention generally shows an enrichment of at least 8 times of silicon, especially an enrichment of 8 to 25 times of silicon, in the section 2-10 nm of the membrane surface over the average silicon content of the membrane. The invention includes the use of this membrane as a filter membrane in a process of water treatment, water separation or gas separation.
Still, it has been surprisingly observed that polysulfone fractions are not necessarily required in copolymers used as additives in water filtration membranes, yet providing good silicone enrichment on the membrane surface, and good - properties that operate the membrane, such as anti-adhesion and flow recovery effect in the aqueous environment. The invention thus also concerns, in a second aspect, a water filtration membrane comprising an oligo- and polyurethane comprising the components mentioned above (A) and (B), but not (C) or any other sulfone fraction, of the -COn-emquen formula varies from to 100, especially from 2 to 50, where (X) is a block of the formula ——O — CO-N— (A) —rN — TYCO — O— (B) -——-—— H H o)
(A) is a residue of an aliphatic or aromatic diisocyanate binder, - (B) is a residue of a linear oligo- or polysiloxane, especially containing 3 or more Si atoms, and containing final groups “5 —alkanol, and optionally still containing one or more fractions of aliphatic ether.
Constituents - additional to the membrane generally comprise (as component b) one or more additional organic polymers selected from the group consisting of polyvinyl pyrrolidone, vinyl polyacetates, cellulose acetates, polyacrylonitriles, polyamides, polyolefins, polyesters, polysulfones, polyethersulfones, polycarbonates, polyether ketones, polyether sulfonated ketones, polyamide sulfones, polyvinylidene fluorides, polyvinyl chlorides, polystyrenes and polytetrafluoroethylenes, copolymers thereof, and mixtures thereof; preferably selected from the group consisting of polysulfones, polyethersulfones, polyvinylidene fluorides, polyamides, cellulose acetate and mixtures thereof.
Final groups in oligo- or polyurethane without sulfone are mainly mono-reacted constituents of polyurethane (for example, OH free from the diol component, or mono-reacted diisocyanate [-CO-NH-A-NCO]. In this way, the present oligo- and polyurethanes are essentially free of typical silane end groups such as SIi (R ”) 3, where R” is any one of H, alkyl, alkoxy.
Preferred meanings for (A) and (B) are as defined for copolymers of formula I above; especially, the molecular weight (Mn) of the polyurethane is preferably in the range 1500 to 100000; (A) is preferably a divalent residue selected from Cx-Cp7 alkylene and Ar; (B) is preferably a divalent residue of an oligo- or polysiloxane of the formula
- [AK-O], - AK-Si (R2) - [O-Si (R2)], - O-Si (R2) -Ak- [0-Ak] 4- (IV) where Ak represents Cy alkylene -C, a, R represents% Cy-Cy alkyl, and each of qeq 'independently is a number selected in. range 0-50, and p ranges from 1 to 50, especially from 2 to 50; 'Aré -Ph-Sp-Ph-; Ph is phenyl or phenyl substituted by Cr-Ca alkyl; and Sp is independently selected from the direct bond, -O-, C alkylene; -C ;. The water filtration membrane (semipermeable membrane) preferably consists essentially of a polymer composition - comprising the oligo- or polyurethane previously in an amount of 0.1 to 25% by weight of the total polymer composition, especially in a homogeneous or at the same stage enriched on the surface. It can also comprise one or more antimicrobial or bacteriostatic agents, especially silver in ionic and / or metallic form, such as silver colloid, silver glass, silver zeolite, silver salts, elemental silver in powder form, microparticle, nanoparticle or clustering, and often shows an enrichment of at least 8 times silicon, especially an enrichment of at least 8 to 25 times silicon, in the 2-10 nm section of the membrane surface over the average silicon content of the membrane.
The process for preparing the semipermeable water treatment membrane of the invention generally comprises incorporating the foregoing oligo- or polyurethane, an additional polymer as noted in component (b), and optionally additional additives in the membrane material.
The following samples represent examples with average analytical data for a variety of polyurethanes for use especially in water filtration membranes according to the invention (see examples below for abbreviations / identification of block or monomer components; reasons given are in mol) : Poly (polydimethylsiloxane-block-co-polyethylene oxide) urethane one. polyurethane containing IM22 and HDI as a binder characterized by: i Gel permeation chromatography for molecular weight. 5 (kDa): Mn 135; Mw31 +15; Mp22 + 7; PD2.4 + 0.5 NMR spectroscopy "H: (SiMes0) / (CHL0): 0.71 Elemental analysis [4%]: C: 44.7; H: 8.7; Si: 15, 7 Poly (polydimethylsiloxane-block-co-polyether) urethane a polyurethane containing IM15-PEG 2000 (1: 1) and HDI as a binder characterized by Gel permeation chromatography for molecular mass (kDa): Mn 15 + 7; Mw 30 + 16; Mp 22 + 10; PD 2.0 + 0.6 H NMR spectroscopy: (SiMez0) / (CEL0): 0.27-1.07 Elementary analysis [4%]: C: 40.06 - 47, 2; H: 8.1 - 8.5; Si: 10.5- 22.0 Poly (polydimethylsiloxane-block-co-polyethersulfonyl) Juran a polyurethane containing PSU1 -IMI5 (2: 1) and HDI as a binder characterized by: Gel permeation chromatography for molecular mass (kDa): Mn8 + 2; Mw18 + 3; Mp 16 + 2; PD2,2 + 0,3 H NMR spectroscopy: (SiMez0) / (CMe>): 0,58 Analysis elemental [4%]: C: 56.8; H: 6.3; Si: 10.0 Poly (polydimethylsiloxane-block-co-polyethylene oxide-block-co-polyethersulfonyl) urethane containing PSUI -IM22 (2: 1) and HDI as a binder characterized by: Gel permeation chromatography for mo mass lecular (kDa): Mn 5 + 2; Mw 14 + 4; Mp 14 + 5; PD 2.7 + 0.2 'NMR spectroscopy: (SiMez0) / (CMe>): 1.45 Elemental analysis [4%]: C: 62.6; H: 6.2; Si: 10.6
Poly (polydimethylsiloxane-block-co-polyethylene oxide-block-polydimethylsiloxane) - urethane containing IMI5-IM 22 (1: 1) and HDI as. ligand characterized by: Gel permeation chromatography for molecular weight E 5 (kDa): Mn18 + 3; Mw36 + 17; Mp31 +11; PD1,90,6 H-NMR spectroscopy: (SiMe, 0) / (C3H410): 0.91 Elemental analysis [%]: C: 40.2; H: 8.5; Si: 24.6 Poly (polydimethylsiloxane-block-co-polyethylenoxid-block-polydimethylsiloxane) - urethane or containing IM11 -IM22 (2: 1) and HDI as a binder characterized by: Gel permeation chromatography for molecular mass (kDa): Mn 15 5; Mw 34 + 7; Mp 28 + 17; PD 2.3 + 0.4 The polyurethane reaction for the preparation of the present copolymers is analogous to one commonly used to constitute a wide variety of polymers, such as soft and hard polyurethanes in multiple applications and uses.
Typically, the reaction is carried out in the presence of non-polar or less polar aprotic solvents and with the use of catalysts, such as amines (imidazoles), organic tin compounds and others.
Typical diols used are polyethylene glycols with various molecular weights, polyesterols or OH-terminated oligomers or polymers.
Thus, a wide variety of copolymers are accessible with respect to the use of technically available diisocyanates, such as aliphatic diisocyanates (especially = HDI hexamethylenediisocyanate), diisocyanate isophorone, aromatic methylendi-phenyldiisocyanate (MDI) or 2,4-toluenediisocyanate (TDI).
The product variety is much more expandable, if mixtures of different diols are taken into account, resulting in thin polymer structures with statistically linked diol block sequences.
In this way, the present block copolymers linked to the XnYm urethane can be produced in a rational manner with high variability to achieve application requirements. As the subject of the present invention, OH-terminated silicon-based surfactants are used as. diol components in combination with diisocyanates. Typical monomers for the preparation of gifts: 5 - polyurethanes: A) Diisocyanates o N o
EGGS .oo 9 (81) O = C * NON = C: -O (A2) oe: Y-eÃ S-necso 2 (As) B) Diols H — Fo — cH — o (81) Ho A UU SiMe; lo-SiMez | -O-siMe, A OH (82) Y ee OH god mol A sivero sivezto serie, A ToNAe (B3) CO) Di6is
DIOLF-OFO-O + O-L O + OL-OFO-OTOL:: oDDE-DIOOD-Oj. (C2) 2 q 2 OFO-DHO-Otod oos with n, m each ranging from 1 to 100. Polymer compositions, fabrication and processing of the membrane The present copolymers are preferably used as anti-adhesion additives in polymer compositions, such as membrane compositions, especially water processing or gas separation membranes.
Fabrication of ultrafiltration membranes often includes solvent-induced phase separation (SIPS). The present - polymers are preferably used as additives in this process.
In the SIPS process, educt polymers (for example, selected from polyvinyl pyrrolidone, vinyl acetates, cellulose acetates, polyacrylonitriles, polyamides, “polyolefins, polyesters, - polysulfones, polyethersulfones, polycarbonates, polyether ketones, sulfonated polyether ketones, polyamide polyvinylidene fluorides, polyvinyl chlorides, polystyrenes and polytetrafluoroethylenes, copolymers thereof, and mixtures thereof; preferably selected from the group consisting of polysulfones, polyethersulfones, polyvinylidene fluorides, polyamides, cellulose acetate and mixtures thereof, especially including polyether sulfone) dissolved in a suitable solvent (eg, N-methylpyrrolidone, .dimethylacetamide or dimethylsulfoxide) together with the additives. In a next step, a porous polymeric membrane is formed under conditions, 5 - controlled in a coagulation bath. In most cases, the coagulation bath contains water as a coagulant, or the coagulation bath is an aqueous medium, in which the matrix-forming polymer is not soluble. The cloud point of the polymer is defined in the ideal ternary phase diagram. In a bimodal phase separation, a microscopic porous architecture is then obtained and water-soluble components (including polymeric additives) are finally found in the aqueous phase.
In the case that the polymeric additive is simultaneously compatible with the coagulant and the matrix polymers, it results in segregation on the surface. With segregation on the surface, enrichment of the additive is observed. The membrane surface thus offers new (hydrophilic) properties compared mainly to the polymer that forms the matrix, the enrichment induced by the phase separation of the additive of the invention leading to non-adhesive surface structures.
An important property of the additive that modifies the unprecedented surface is the formation of a dense covering combined with a strong anchoring effect to the polymeric matrix.
In many cases, a surface structure is achieved by microstructured self-settling monolayers (SAM), which prevent the adhesion of microbes.
The present copolymers combine structural elements, which encourage detachment from encryption. These copolymers are especially used as a mixing additive, since they contain an antifouling segment and an anchor, the combination of which is especially used for membrane applications; the silicone fraction is still a good “thickening polymer” for polysulfone, thus providing | structural stability and contributing to the low properties of. leaching. : The present copolymers combine low energy segments and hydrophilic segments.
Phenomenally, these segments go back to form nanoscale structures in the topography of the membrane surface.
In the case of simultaneous self-assembly of the copolymers during the SIPS process, the membrane surfaces are covered by substructures that lead to lower membrane encrusting properties both by added topographic fractions (area release and / or dimension) and surface energy structure ( electrostatic interaction with the environment). Anti-encryption properties of the present polymer compositions, especially of membranes, can be improved by the additional incorporation of one or more antimicrobial or bacteriostatic agents in the composition.
A preferred agent is an oligodynamic metal, especially silver in ionic and / or metallic form.
Optionally, the silver component can be accompanied by Zinc oxide as a component.
Silver components used include silver colloids, silver glass, silver zeolite, silver salts, elemental silver in the form of powder or microparticles or nanoparticles or clusters.
An advantageous method of preparing an antimicrobial membrane includes formation of elementary silver particles in situ in the melting solution containing one or more (co) polymers of the present polymer composition in dissolved form. - Particles of elemental silver, especially those embedded in semipermeable membranes and / or polymer matrices close to the surface of the final article, can be transformed into silver halide particles, such as AgCl, AgBr, Agl, for example, by treatment with a hypo halide solution (eg NaOCl).
A typical process for preparing a solution for preparing membranes is characterized by the following steps: “1. Dissolve matrix polymers for a membrane dope in a suitable solvent, typically NMP, DMA, DMSO or mixtures thereof.
% 5 2. Add pore-forming additives, such as sulfonated PVP, PEG, PES or mixtures thereof.
3. Heat the mixtures until a viscous solution is obtained; typically temperatures at 5-250 ° C, preferred 25-150 ° C, more preferred 60-90 ° C.
4. Add the anti-adhesion silicone-polyurethane additive to the dope at 5-250 ºC, preferred 25-150 ºC, and more preferred 60-90 º C. Optionally other additives, for example, compounds containing silver can be added in the same step.
5. Stir the solution / suspension until a mixture is formed - 1 to 11h, typically homogenization is completed in 2 h.
6. Fuse the membrane dope into a coagulation bath to obtain a membrane structure. Optionally, the fusion can be enhanced using a polymeric (non-woven) support to mechanically stabilize the membrane structure. To test the bioactivity for the application a standard procedure in the manufacture of straight membrane is used.
7, Analyze the membrane for additive content.
The following examples illustrate the invention. Unless otherwise stated, room temperature denotes a temperature of 20-25 ° C; molecular weight data (such as Mw, Mn) are as - determined by gel permeation chromatography; and water contact angle (WCA) measurements are performed according to the static drop method.
Abbreviations used in the examples and elsewhere: L liter
NMP N-methylpyrrolidone PD Polydispersity PEG Polyethylene Glycol PES Polyethersulfone PVP Polyvinylpyrrolidone thf Tetrahydrofuran% by weight, wt% percentage by weight Components used in the examples: A) HDI diisocyanates: 1,6-Hexamethylene diisocyanate (Desmodur H &, commercial product) TDI: 2,4-Toluenediisocyanate (commercial product from Aldrich, Germany) MDI: Diphenylmethane-4,4 "-diisocyanate (Desmodur 44 MC, commercial product from Bayer, Germany) B) Diol 1 H — ForcHA-on (PEG) PEG 2000 (Fluka; m = 45) HO A Simez [-O-SiMez | -O-SiMe, YEAR Polydimethylsiloxane; m = 10 available as IM 118 (IM11) m = 50 available as 1 M 158 (IMI5) each from Wacker , Germany. ”Jr ol + siverto-sivest-o-sive, APT A no (1 (IM22) Poly dimethylsiloxane-b-polyethylene oxide: IM 220, available from Wacker, Germany.
OC) Dio] 2
SJ 16 2 and DTOLOTO - O + OL Mn = 4 kDa, Mw = 6-7 kDa (PSU) oOO 0 o (PSU) ooo (PSU3Z) o too: (PSU4) Ultrason & M 2020 PSR (commercial product of BASF, Germany) (PSUS) D) Additional polymers and solvents: Tetrahydrofuran: commercial product from Aldrich, Germany.
N-methylpyrrolidone (NMP): commercial product from Aldrich, - Germany.
Polyvinylpyrrolidone (PVP): Luvitec & PVP 40 K commercial product from BASF, Germany.
Example 1: Preparation of siloxane-block-polyurethane: Instruments: 250 ml Erlenmeyer glass tube, magnetic stirrer, thermal plate, condenser, internal thermometer Diol components are mixed in 120 ml of tetrahydrofuran (thf) at 25 ºC.
According to the sum of the OH numbers of the diol components, the diisocyanate component is added to a | dosage.
Solid diisocyanate components are added as a | 15 solution in 30 mL of thf.
After stirring the mixture for 5 minutes, catalysts (1,8-diazabicyclo [5.4.0] - undec-7-ene (DBU): 0.1 g; and dibutyltin dilaurate: 0.1 g) are added.
The highly observable 2325 cm NCO absorption vibration is used to monitor the progress of the reaction.
The reaction mixture is stirred for 15 h at 25 ºC; subsequently, all volatile components are evaporated using a rotary evaporator and strong vacuum pump.
The crude polymeric compounds are characterized. by elemental analysis, 1 H NMR and gel permeation chromatography.
The following table 1 shows the quantities of reagents used and the characterization 7 5 - dospolymers obtained.
Table 1: Composition of copolymers (quantities [g] refer to the component in the left column) sample fDiot 1 TJ biol2 Ta Disc, el —— NCoor Ao kMSs bh5 hM hs Ho o ho | AL Ms hs mM bs or gg ho À) azo pu ho hM 6 to jog kh | at Pur jo = E ko og ho | ao —esur jo is Ro ho ao ps jo 2 65 Mor hp ho | A5o sur fo ie o ho Ao sus ho and ER Mor so ho | to the MT 5 mM bh kB 639 ha | asso is so good hs | no imo is Mr ba ho | Characterizations of polyurethane block copolymers: Gel permeation chromatography (GPC) in tetrahydrofuran — polystyrene as a reference; elemental analysis (EA) and NMR "H spectroscopy in d; -dimethylsulfoxide as solvent.
Results are shown in Table 2. Table 2: Copolymer characteristics Sample | GPC (Da) Elementary analysis CH; Si CHLO (cH3) Si mo dm mw ae mm fc mo xs year pests Pros Passa RI Ii ui [al J19440 [31743 [25567 | 163 | 402 | 85 Poa nn og2 [| azo Jogz 23039 123796 | aaa o II [ant 6193 [16933 [16116 | 261 | 626 | 62 | 106 | 145 | 194 | 075 | [aso | sma J149o [15144 | 261 | 567 | 64 | 100 os | Paso powder Jo 10404 fozor | a PC o shallo as a as ss Cv o ao as are aaa sa Ano res ao faoss aaa O [| aso 16596 | 3102% [27402 | 235 | 447 | 87 Los o [Year 11365 J22002 [18933 Pa pg II on Polyurethane (surfactant) silicon shows typical molecular mass distributions with Mn: 5-18 kDa; Mw 14-36 and a —polidispersity of 1.9-2.9.
Example 2: Membranes The following procedure is carried out in the preparation of. membranes:: Place N-methylpyrrolidone (NMP) (70 mL) in a flask of 7 5 - three necks with a shaker.
Add polyvinylpyrrolidone Luvitec & PVP 40 K (6 8) to the NMP and increase the temperature to 60 ºC and stir until a clear homogeneous solution is obtained, Mix to the required amount of the inventive polyurethane (example 1 additive; 5% by weight with respect to polyether sulfone, 0.9 g) to 6 g of NMP and sonicated for 20 minutes and add the solution to the PVP solution and stir until the solution is homogeneous.
Add Ultrasson & 2020 PSR polyethersulfone (PES, 18 g) to the solution and stir until a viscous solution is obtained.
Degass the solution overnight at room temperature (30-40 ºC). Reheat the membrane solution to 70 ºC.
Fuse the membrane into the glass with a melting knife (200 µm) at room temperature and allow to dry for 30 seconds before immersion.
Membrane fused in a 25 ºC water bath.
After 10 minutes of immersion, rinse the membrane with hot water (65-75 ºC, 30 minutes). Membrane preparation must form a continuous film having microstructural characteristics of UF membranes; a - continuous film (at least 10 X 15 in size) with a layer of thin skin on the top (1 -2 microns) and a porous layer (thickness: 100-150 microns) is obtained characterized by: Width of the void at the top : 2.0 um; skin layer: 1.2 pn; thickness: 120 um; pore size in the skin layer: 1-3 um.
Physical-chemical performance of the membrane:
Analysis of silicone-polyurethane additives on the membrane surface is performed using a variety of surface characterization techniques, electron scanning microscope / energy dispersive X-ray spectroscopy (SEM / EDX) to view morphology and obtain information qualitative distribution of silicon and, thus, additive distribution on the surface, X-ray photoelectron spectroscopy (XPS) for. obtain quantitative information on the silicon content on the surface (1 -4: monolayers = 2-10 nm). This information allows the determination of a 1 5 - enrichment factor of the polymeric additive on the membrane surface) and matrix-assisted laser desorption ionization as a mass spectrometry imaging technique (MALDI-MS) in which the sample , often a section of thin tissue, is moved in two dimensions, while the mass spectrum is recorded. Here, qualitative information on the nature of the additive (fragments of dimethylsiloxane- and polyethylene glycol) and its surface distribution are available. Topographic microdomains of bilateral additive phase separation in the roof must be observed in a resolution of 420x420 nm.
Characterization of membranes by SEM / EDX and XPS: The membranes are characterized by XPS (X-ray photoelectron spectroscopy). The concentration obtained from silicon atoms at a depth of 2-10 nm of the surface indicates a high enrichment based on theoretical silicon in bulk material at 5% by weight of initial additive carrying the polyethersulfone (enrichment factor EF =% by weight of Si on the surface /% by weight of Si calculated).
Results are compiled in the following table 3; Si [Si] concentrations are given in% by weight, as sampled for 3 points of 0.5 mm each, by mass (calculated) or on the surface (2-10 nm).
—Table3: Characteristics of the membrane in THESE [the aaa [the membrane weight [Si] calculated Si] surface | EF MB Jasobr 8 - las 15 Mo a and Bo 8 Me from DD to O)
EC EVT RR RC o Paid CJ O) o ss) Mr none o XPS measurements indicate the enrichment of polymeric additives on the membrane surface (2-10 nm deep) depending on the type of additive with a factor of 10-18 ( calculated from an average of 5% by weight of additives with respect to PES).
An SEM / EDX analysis is performed for the M1 membrane containing the additive A110O on the surface. Is the homogeneous distribution of the additive also recognized at a resolution of 420x420 nm of an area 100x100 um by MALDI-ToF SIMS, mapping silicon to the surface of the MI membrane. The characteristic fragments for silicon and PEG (mass fragment m / z245) are observed. The Si / PEG ratio suggests a homogeneous distribution of the additive on the surface.
Characterization of membranes by water contact angle and water flow: Water flow is performed in a dead-end filtration cell (110 mL capacity, membrane area 1.59x10 M ) Connected to a supply reservoir with a nitrogen cylinder as a pressure source. The filtration cell consists of a cylindrical vessel, equipped with a porous support in which the membrane is placed. A stirrer is installed in the cell and a speed of 400 rpm is maintained during —test, Experiments are operated at constant pressure (100 kPa) and permeate is collected in a beaker placed on an electronic scale. A pressure transducer is connected to the upstream side of the membrane to measure the pressure in the cell. Both scales and pressure transducers are connected to a computer to record data. Membranes are humidified with ethanol — before flow measurement. Results for M6 to M11 and M12 membranes (comparison) are average values obtained from 5 measurements [WCA] or 3
"21: measurements [water flow. Membranes of the invention show a wide angle of contact with water of more than 68º and a good flow of water. Example 3: Anti-adhesion performance: Two tests are applied to estimate the properties' 5 - anti-adhesion of membrane surfaces.
a) protein adhesion; the recovery of the flow of the membranes of the invention is determined with respect to a membrane without additive: Surfaces are brought into contact with BSA (bovine serum albumin) as a model protein. BSA adhesion reduces water flow; the flow can be recovered by washing with water (Jw) or by additional chemical treatment (Jc) with sodium hydroxide. Flow recovery (normalized to the initial water flow) indicates the membrane's ability to self-clean and reduce fouling.
Instruments: X-flow membrane cell, UV-wis spectrometer Procedure: Water flow and BSA filtration are performed using a non-commercial experimental prototype of Perspex cross flow module with 3 mm high, 25 mm wide channel dimensions and 110 mm in length. A supply pressure of 100 kPa is obtained using a peristaltic supply pump (Cole Parmer Master flow Model 7529-00) and adjusted by a ball valve located at the module outlet. With the dimension of the channel given, a cross flow velocity of 0.2 m / s is maintained for all experiments. A pressure transducer (Labom Diff.
- Pressure transmitter CP1310) connected to both the power supply and the permeate sides of the membrane is used to measure TMP (transmembrane pressure); a scale is used to monitor the permeate flow.
The experiment consists of four main stages: initial water flow, encrustation, washing with water and chemical cleaning. It is
”22: sequence is repeated 3 times for each membrane. In a typical run, a strip of membrane sized. appropriate is cut from a straight blade and mounted on the flow cell: cross; polypropylene is used as a support. The membrane is pre-compacted: 5 to 25kPa until a constant flow is obtained. Then the pressure is reduced to 100 kPa and the initial water flow (Ji) is measured (for about 1 hour). Then the ultrafiltration experiments are performed with 0.5% by weight of BSA solution (pH is adjusted to 4.9-5.1 by adding in drops of 0.1 M HCl) at a constant pressure of 50 kPa and a constant flow of about 41 + 3 L / m'h for 90 minutes. Constant flow is achieved using a Gilson pump in the permeate line. Then the membrane is washed with water for 15 minutes (1 L / min) and pure water flow is measured (Jwl). Chemical cleaning is done by washing the membrane with 0.2% by weight of NaOH solution for 15 minutes and after buffering the cell, water flow is measured again (JC).
The cycle is repeated 3 times. Flow recovery and resistance removal for different membranes are estimated. Permeate samples are taken for analysis by UV spectrometer to estimate rejection. Samples of the inventive membranes are taken from the permeate / retentate to examine the release of the active component.
The following table 4 shows the flow of membranes of the invention in relation to the flow observed with a membrane (M12) that does not contain the copolymer of the invention (recovery after 3 cycles).
Table 4: Flow recovery after 3 cycles using water washing and adding chemical cleaner (Jc) | The present membranes show good flow recovery. |
"23: b) Anti-adhesion of bacteria: Relative adhesion effects are quantified using antibody-antigen reactions to monitor bacteria. Adhered to the surface. Escherichia coli and Staphylococcus aureus test is: conducted according to DIN EN ISO / EC 17025.
: 5 The samples are incubated with a test cell system. Loose cellular material is removed in defined washing steps. Cells adhered to the sample surface are detected in an immune assay using antigen-antibody reactions. Adherence is monitored by a relative semiquantitative cell unit count. In this way, a first reaction - with antibody occurs in the adhered test cell system; coupling in this first level antibody, a specific enzyme is fixed by a secondary antibody. After adding a staining substrate, an enzyme-catalyzed staining reaction occurs; staining is proportional to the amount of cells adhered to. Compared to white (membrane without polyurethane additive) the relative adhesion is evaluated. Each sample is independently measured nine times. The test result for the sample is normalized for | mean of the blank sample (comparative). The relative membership results as a data quotient | samples and the comparative blank. Multiplication by | 20 - 100 results regarding adherence in percentage units. Samples with a relative adhesion> 100% demonstrate greater adhesion of bacteria from | test. Materials with a relative adhesion of <100% demonstrate decreased adhesion (reduced adhesion). Results are compiled in the following table 5. Table 5: E. coli (Ec) or S. aureus (Sa) adhesion with respect to —comparative membrane Membranes of the invention effectively inhibit adhesion | bacterial. Example 4: Copolymers used in straight blade membranes. Block siloxane-urethane copolymers are prepared accordingly. with example 1. The ratio between the different diols and the type of isocyanates Í: 5 —usersereported in the table below: Es bNBIC ARA g g E E g CoB 2 TT aodr 7 | 40 | [op In | 71 to sos | Table 6: copolymer composition These copolymers were characterized by GPC and elementary analysis: Copolymer Mw Elemental analysis Da D C: 63%; H: 6.58%; N: 9033 | 3811 | 7286 | 2.37 1.37%; O: 16.8%; S:
3.54%; Si: 5.3% C: 66.3% :; H: 5.64%; N: [10161 | 3454 | 9112 | 2.94 1.38%; 0: 15.6%; 8:
4.15%; Si: 3.3% C: 68.6%; H: 6.50%; N: 9527 | 3129 | 7470 | 3.04 1.41%; 0 15.5%; S: 4.1%; Si: 2.8% C: 64.9%; H: 6.8; N: 1.48; E 18633 | 4467 | 13372 | 4.17 O: 15.4%; S: 3.7%; Si: 4.3% Table 7: GPC (PS calibration) and elementary analysis of —copolymers These additives were used at 5% by weight to prepare straight blade membranes according to the procedure described in example 2. The membranes are characterized by XPS (X-ray photoelectron spectroscopy). Great enrichment based on theoretical silicon in bulk material at 5% by weight of initial additive carrying polyethersulfone (enrichment factor EF =% by weight of Si on the surface
% by weight of Si calculated). Results are reported in the following table; concentrations of. Si [Si] are given in% by weight, as sampled at 3 points of 0.5. mm each, by mass (calculated) or on the surface (2-10 nm). : surface mass: 121%; S: 34% No. MA 0.25% 3.8% 15.2 D.0%; 0: 18.7%; Si p.8%: T2.9%; S: 3.1% No.: MA3 and 0.15% 3.7% 24.7 D2%; 0: 18.0%; Si. T%: 714%; S: 3.0% No.: MA4 D 0.10% 3.9% 39 16%; 0: 19.4%; Si B.9%: 710.1%; S: 2.9% MAS No. E 0.19% 4.4% 23.2 b4%; 0: 20.1%; Si A% Table 8: Si concentration in mass of straight blade and surface membranes. Enrichment factor as a ratio between Si on the surface and in the mass.
XPS measurements show that the enrichment of polymeric additives on the membrane surface changes based on the composition and chemical structure of the additive. In general, an additive with a lower Si content shows greater enrichment on the surface (EF). Membranes are then characterized by contact angle, flow recovery after cleaning with water or chemistry and water flow. The procedure for testing the water and chemical flow is described on page 13-14 (CasePF70441). water luxury angle of [| W 3 JL / m H ontact (º) Ma | on | 09 19040 MA3 | 06 | 085 p2060 MA £ | 084 | LO 20040 Mas | o63 | 085 18040 'ontrole Table 9: Flow recovery after 3 cleaning cycles with water (JW) or chemical (JC). Contact angle (º) and water flow.
Membranes functionalized with siloxane - urethane block copolymers of the invention show better flow recovery after cleaning with both water and chemical (compared to standard non-straight blade PES membrane).
) Water flow is in the same range as the standard membrane which means that these additives do not significantly impact the membrane pore structure. Contact angle for functionalized membranes is greater compared to standard PES (membrane surface is more hydrophobic), this is a reflection of this behavior of the additives for —auto enrichment on the membrane surface as can be detected by and a greater amount of Si on the surface if compared to the dough.

权利要求:
Claims (17)
[1]
1. Polymer composition, characterized by the fact that 7 comprises: an oligo- or polyurethane of the formula I Lotiel O) in which ken are independently numbers from 1 to 100, m is in the range 1 -100, (X) is a block of the formula —O —- CO-N— (A) —N — CO —- O— (B) —— HH) and (Y) is a block of the formula —O — CO-N —- (A) —N —-CO-OAC) - n H [UDA A) is a residue of an aliphatic or aromatic diisocyanate binder, (B) is a residue of a linear oligo- or polysiloxane containing alkanol end groups, and optionally containing one or more fractions aliphatic ether, and OC) is a block of aromatic oligo or polysulfone; a mixture of such oligo- or polyurethanes; and b) one or more additional organic polymers selected from the group consisting of polyvinyl pyrrolidone, vinyl polyacetates, cellulose acetates, polyacrylonitriles, polyamides, polyolefins, polyesters, polysulfones, polyethersulfones, —polycarbonates, polyether ketones, polyether sulfonated ketones, sulfonated polyols. , polyvinylidene fluorides, polyvinyl chlorides, polystyrenes and polytetrafluoroethylenes, copolymers thereof, and mixtures thereof; preferably selected from the group consisting of polysulfones, polyethersulfones, polyvinylidene fluorides, polyamides, cellulose acetate and mixtures thereof. s
[2]
Polymer composition according to claim 1:! characterized by the fact that the molecular weight (Mn) of the compound of the formula ITénafaixal.500 to 100.000, in which not each are in the range 1 to 50, and ké na | range 1 to 20,
[3]
Polymer composition according to either of claims 1 or 2, characterized in that in the oligo- or polyurethane of formula I (A) is a divalent residue selected from C37-C7 alkylene and Ar; (B) is a divalent residue of an oligo- or polysiloxane of the formula TAK-O) -AK-Si (R2) - [0-Si (R2)] - O-Si (R2) -Ak- [0-Ak] y- (IV) where Ak represents Cx-Ca alkylene, R represents —CyC alkyl, and each dep, q and q independently is a number selected in the range 0-50; (C) is a diphenyl sulfone monomer or linear oligomer or polymer block containing 1 -50 phenyl-SOz-phenyl fractions, and optionally still 1 -50 additional Ar fractions, whose fractions are, in the case of the oligomer or - polymer, bonded joined by Sp spacers; Ar is -Ph-Sp-Ph-; Ph is phenyl or phenyl substituted by Cy-Cs alkyl; and Sp independently is selected from direct bond, -O-, Cy-C alkylene; 3.
[4]
Polymer composition according to any one of claims 1 to 3, characterized in that it comprises the oligo- or polyurethane of formula I in an amount of 0.1 to 25% by weight of | total polymer composition, especially in a homogeneous phase or in the same phase enriched on the surface.
[5]
Polymer composition according to any one of claims 1 to 4, characterized in that it comprises j: additionally one or more antimicrobial or bacteriostatic agents, 7 - especially silver in ionic and / or metallic form, such as colloid silver, silver glass, silver zeolite, silver salts, elemental silver in the form of powder, microparticle, nanoparticle or grouping.
[6]
6. Membrane, especially semipermeable membrane, characterized in that it comprises a polymer composition, as defined in any one of claims 1 to 5.
[7]
7. Membrane according to claim 6, characterized by the fact that it shows an enrichment of at least 8 times of silicon, especially an enrichment of at least 8 to 25 times of silicon, in the section 2-10 nm of the membrane surface on the average silicon content of the membrane,
[8]
8. Process for the preparation of a membrane, especially a semipermeable membrane for purposes of water treatment and / or gas separation, characterized in that the process comprises incorporating a polymer composition as defined in - any one of claims 1 to 5 in the membrane material.
[9]
9, Use of the polymer composition as defined in any of claims 1 to 5, characterized by the fact that it is for the preparation of an antimicrobial membrane, especially for purposes of water separation or gas separation.
[10]
10. Oligo- or polyurethane compound of the formula T A + ott + otA- (O) characterized by the fact that k and n are independently numbers from 1 to 100, m is in the range 1 -100,. (X) is a block of the formula ——O — CO-N— (A) —y3N — CO —- O— (B) -——: HH 0) and (Y) is a block of the formula —O —- CO-NH (A) - N —CO-O C) HH 0), (A) is a residue of an aliphatic or aromatic diisocyanate binder, (B) is a residue of a linear oligo- or polysiloxane containing final alkanol groups, and optionally still containing one or more fractions aliphatic ether, and (C) is a block of aromatic oligo or polysulfone; especially for use as an antimicrobial or antibioadhesive additive.
[11]
11. Compound according to claim 10, characterized by the fact that the molecular weight (Mn) of the compound of formula 1 is in the range
1,500 to 100,000, especially in the 4,000 to 25,000 range, where n and m are in the range 1 to 50, and k is in the range 1 to 20.
[12]
12. Use of an oligo- or polyurethane according to formula 1, as defined in any one of claims 1 to 5 or 10 to 11, characterized by the fact that it is like an additive that confers properties - anti-adhesive or bacteriostatic to a composition polymer, especially to a polymer membrane.
[13]
13. Water filtration membrane, characterized by the fact that it comprises an oligo- and polyurethane of the formula where n ranges from 2 to 100, especially from 2 to 50, where (X) is a block of the formula |
| | ——O — CO-N— (A) —rYN — CO-O— (B) —— HH 0) '(A) is a residue of an aliphatic diisocyanate binder or - aromatic, S (B) is a residue of a linear oligo- or polysiloxane, especially containing 3 or more Si atoms, and containing final groups - alkanol, and optionally still containing one or more aliphatic ether fractions.
[14]
14. Water filtration membrane according to claim 13, characterized in that it additionally comprises one or more organic polymers selected from the group consisting of polyvinyl pyrrolidone, vinyl polyacetates, cellulose acetates, polyacrylonitriles, polyamides, —poliolefins, polyesters, polysulfones, polyethersulfones, polycarbonates, polyether ketones, sulfonated polyether ketones, polyamide sulfones, polyvinylidene fluorides, polyvinyl chlorides, polystyrenes and polytetrafluoroethylenes, copolymers thereof, and mixtures thereof; preferably selected from the group consisting of polysulfones, polyethersulfones, polyvinylidene fluorides, polyamides, cellulose acetate and mixtures thereof.
[15]
15. Water filtration membrane according to claim 13 or 14, characterized in that (A) is a divalent residue selected from C3-C7 alkylene and Ar (B) is a divalent residue of an oligo- or polysiloxane from formula - [AK-OJ-Ak-Si (Ra) - [O-Si (R2)]; - O-Si (R2) -AK- [0-Ak] lg- (IV) where Ak represents Cx- alkylene Ca, R represents Ci-Ca alkyl, and each of qeq 'independently is a number selected in the “range 0-50, epvariade 1 to 50, especially from 2 to 50; Ar is -Ph-Sp-Ph-;
[16]
Ph is phenyl or phenyl substituted by Cy-C4 alkyl; and Sp is independently selected from direct link, -O-,. C-C3 alkylene. . 16. Use of an oligo- or polyurethane of the formula - (X) n- as Í 5 - defined in any one of claims 13 to 15, characterized by the fact that it imparts anti-adhesive or bacteriostatic properties to a water filtration membrane.
[17]
A compound according to any one of claims or 11, characterized in that it is selected from 10 a) poly (polydimethylsiloxane-block-co-polyethylene oxide) urethane derived from; ee H to Aro] smefo siverlo site, ToN AO where n is in the range 0-100 (especially 5 to 80) and is in the range 1 -100 (especially in the range 5 to 80), and 1,6-hexamethylene diisocyanate as binder; b) poly (polydimethylsiloxane-block-co-polyether) urethane derived from polyethylene glycol] of the formula H — Ho — eH = -on and polydimethylsiloxane of the formula HO A SiMe; [- O-SiMez | -O-SiMe, A OH in one molar ratio ranging from 1: 2 to 2: 1, where m in both formulas is in the range 5 to 80, and 1,6-hexamethylene diisocyanate as a binder; c) poly (polydimethylsiloxane-block-co-polyethersulfonyl) urethane derived from ethersulfone of the formula o and DHOF-OT + O-O FO and polydimethylsiloxane of the formula Ho.
SiMe; -o-siMez | -O-SiMe, OH is in a molar ratio ranging from 3: 1 to 1: 1, where m in both º formulas is in the range 5 to 80, and 1,6-hexamethylene diisocyanate as a binder; d) poly (polydimethylsiloxane-block-co-polyethyleneoxid-block-co- - polyethersulfonyl) urethane derived from a polyethersulfone of the formula DH + OPF-O FO-O + OL and polydimethylsiloxane derived from the formula Ho Jr ol simezo-simezfo-Sime , It's from"
in a molar ratio ranging from 3: 1 to 1: 1, where n and m are in the range 5 to 80, and hexamethylene diisocyanate as a binder;
e) poly (polydimethylsiloxane-block-co-polyethylene oxide-block-
—Polidimethylsiloxane) -urethane derived from HO A Series; o-SiMez | -0-SiMe, A OH e. 1 -S PP H to ol seo siverl-o Sive, AT, o Ao in a molar ratio ranging from 1: 2 to 2: 1, where neither formulas are in the range 5 to 80, and 1,6-hexamethylene diisocyanate as a binder.

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法律状态:
2020-09-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2020-10-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2020-10-27| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 9A ANUIDADE. |

2021-01-19| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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EP10155922|2010-03-09|

EP10155922.7|2010-03-09|

EP10166455|2010-06-18|

EP10166455.5|2010-06-18|

PCT/EP2011/052956|WO2011110441A2|2010-03-09|2011-03-01|Polyurethane block copolymer based on poly siloxane tenside for membranes|

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