NEW POLYMER COMPOSITIONS

Abstract

Polymer composition comprising a) an oligo- or polyurethane U of the formula (I) wherein k and n independently are numbers from 1 to 100, m is from the range 1-100, (X) is a block of formula (II) and (Y) is a block of the formula (III), (A) is a residue of an aliphatic or aromatic diisocyanate linker, (B) is a residue of a linear oligo- or polysiloxane containing alkanol end groups, and optionally further containing one or more aliphatic ether moieties, and (C) is an aromatic oligo- or polyarylene ether block that is at least partly etherified at its terminal positions with one alkylene glycol unit; or a mixture of such oligo- or polyurethanes; and b) one or more further organic polymers P selected from the group consisting of polyvinyl pyrrolidone, polyvinyl acetates, cellulose acetates, polyacrylonitriles, polyamides, polyolefines, polyesters, polyarylene ethers, polysulfones, polyethersulfones, polyphenylenesulfones, polycarbonates, polyether ketones, sulfonated polyether ketones, polyamide sulfones, polyvinylidene fluorides, polyvinylchlorides, polystyrenes and polytetrafluorethylenes, copolymers thereof, and mixtures thereof; preferably selected from the group consisting of polysulfones, polyphenylenes, polyethersulfones, polyvinylidene fluorides, polyamides, cellulose acetate and mixtures thereof.

##STR00001##

Claims

1: A polymer composition, comprising: a) an oligo- or polyurethane U of the formula I ##STR00025## wherein k and n independently are numbers from 1 to 100, m is from the range 1-100, (X) is a block of formula ##STR00026## and (Y) is a block of the formula ##STR00027## (A) is a residue of an aliphatic or aromatic diisocyanate linker, (B) is a residue of a linear oligo- or polysiloxane comprising alkanol end groups, and optionally further comprising one or more aliphatic ether moieties, and (C) is an aromatic oligo- or polyarylene ether block that is at least partly etherified at its terminal positions with one alkylene glycol unit; or a mixture of such oligo- or polyurethanes; and b) one or more further organic polymers P selected from the group consisting of polyvinyl pyrrolidone, polyvinyl acetates, cellulose acetates, polyacrylonitriles, polyamides, polyolefines, polyesters, polyarylene ethers, polysulfones, polyethersulfones, polyphenylenesulfones, polycarbonates, polyether ketones, sulfonated polyether ketones, polyamide sulfones, polyvinylidene fluorides, polyvinylchlorides, polystyrenes and polytetrafluorethylenes, copolymers thereof, and mixtures thereof; preferably selected from the group consisting of polysulfones, polyethersulfones, polyvinylidene fluorides, polyamides, cellulose acetate and mixtures thereof.

2: The polymer composition according to claim 1, wherein at least 70% of the terminal positions of said aromatic oligo- or polyarylene ether blocks (C) are etherified with one unit of ethylene glycol unit.

3: The polymer composition according to claim 1, wherein the molecular weight (Mn) of the compound of formula I is from the range 1500 to 500000, wherein n and m each are from the range 1 to 50, and k is from range 1 to 20.

4: The polymer composition according to claim 1, where in the oligo- or polyurethane U of the formula I (A) is a divalent residue selected from C.sub.2-C.sub.12-alkylene and methyl-2,4-phenylene, methyl-2,6-phenylene, 3,3,5-trimethyl-5-methylen-3-cyclohexylen, and methylene-4,4-diphenylen; (B) is a divalent residue of an oligo- or polysiloxane of the formula
-[Ak-O].sub.q-Ak-Si(R.sub.2)[OSi(R.sub.2)].sub.pOSi(R.sub.2)-Ak-[O-Ak].sub.q.-(IV) wherein Ak represents C.sub.2-C.sub.4-alkylene, R stands for C.sub.1-C.sub.4-alkyl, and each of p, q and q independently is a number selected from the range 0-80; (C) is a polyarylene ether block according to formula (V) ##STR00028## that is at least partly etherified at its terminal positions with one alkylene glycol unit.

5: The polymer composition according to claim 1, wherein polyurethane U comprises at least one copolymer selected from: a) poly(polydimethylsiloxane-block-co-polysulfonyl)urethane derived from a polysulfone of formula ##STR00029## and polydimethylsiloxane of formula ##STR00030## in a molar ratio ranging from 3:1 to 1:3, where e and fin both formulas is from the range 5 to 80, and 1,6-hexamethylene diisocyanate as linker; b) poly(polydimethylsiloxane-block-co-polysulfonyl)urethane derived from a polysulfone of formula ##STR00031## and polydimethylsiloxane of formula ##STR00032## in a molar ratio ranging from 3:1 to 1:3, where e and fin both formulas is from the range 5 to 80, and 4,4-methylenediphenyldiisocyanate as linker; c) poly(polydimethyl siloxane-block-co-polyethylenoxid-block-co-polysulfonyl)urethane derived from a polysulfone of formula ##STR00033## and polydimethylsiloxane of formula ##STR00034## in a molar ratio ranging from 3:1 to 1:3, wherein e, f and g are from the range 5 to 80, and hexamethylene diisocyanate as linker; d) poly(polydimethyl siloxane-block-co-polyethylenoxid-block-co-polysulfonyl)urethane derived from a polysulfone of formula ##STR00035## and polydimethylsiloxane of formula ##STR00036## in a molar ratio ranging from 3:1 to 1:3, wherein e, f and g are from the range 5 to 80, and 4,4-methylenediphenyldiisocyanate as linker.

6: The polymer composition according to claim 1, comprising the oligo- or polyurethane U of formula I in an amount of 0.1 to 25% by weight of the total polymer composition.

7: The polymer composition according to claim 1, further comprising one or more antimicrobial or bacteriostatic agent.

8: A membrane, comprising a polymer composition of claim 1.

9: The membrane of claim 8, having an at least 4-fold enrichment of silicon, in the section 2-10 nm from the membrane surface over the membrane's average silicon content.

10: The membrane according to claim 8, wherein said membrane is a UF, MF, RO, FO or NF membrane.

11: A method for water treatment applications, treatment of industrial or municipal waste water, desalination of sea or brackish water, dialysis, plasmolysis, or food processing, comprising applying the membrane according to claim 8.

12: A membrane element, comprising at least one membrane according to claim 8.

13: A membrane module, comprising at least one membrane according to claim 8.

14: A filtration system, comprising at least one membrane module according to claim 11.

15: A process for the preparation of a membrane, the process comprising incorporating a polymer composition according to claim 1 into a membrane material.

16: A process for preparation of an antimicrobial membrane, the process comprising incorporating a polymer composition according to claim 1 into a membrane material.

17: An oligo- or polyurethane compound of the formula I ##STR00037## wherein k and n independently are numbers from 1 to 100, m is from the range 1-100, (X) is a block of formula ##STR00038## and (Y) is a block of the formula ##STR00039## (A) is a residue of an aliphatic or aromatic diisocyanate linker, (B) is a residue of a linear oligo- or polysiloxane containing alkanol end groups, and optionally further containing one or more aliphatic ether moieties, and (C) is an aromatic oligo- or polyarylene ether block that is at least partly etherified at its terminal positions with one alkylene glycol unit.

18: The compound according to claim 17, the molecular weight (Mn) of the compound of formula I being from the range 1500 to 500000, wherein n and m are from the range 1 to 50, and k is from range 1 to 20.

19: A process for preparing a compound according to formula (I) according to claim 17, comprising: a) reacting aromatic bishalogeno compounds and aromatic biphenols or salts thereof in the presence of at least one suitable base, wherein an excess of aromatic biphenols is used to obtain an OH-terminated polyarylene ethers; b) reacting the OH-terminated polyarylene ether obtained in a) with ethylene carbonate; c) reacting the compound obtained in b) with an aliphatic or aromatic diisocyanate linker; d) reacting the compound obtained in c) with a linear oligo- or polysiloxane containing alkanol end groups, and optionally further containing one or more aliphatic ether moieties; wherein d) is carried after c) and/or at least partly simultaneously with c).

20: The compound according to claim 17, which is selected from the group consisting of: a) poly(polydimethylsiloxane-block-co-polysulfonyl)urethane derived from a polysulfone of formula ##STR00040## and polydimethylsiloxane of formula ##STR00041## in a molar ratio ranging from 3:1 to 1:3, where e and fin both formulas is from the range 5 to 80, and 1,6-hexamethylene diisocyanate as linker; b) poly(polydimethylsiloxane-block-co-polysulfonyl)urethane derived from a polysulfone of formula ##STR00042## and polydimethylsiloxane of formula ##STR00043## in a molar ratio ranging from 3:1 to 1:3, where e and fin both formulas is from the range 5 to 80, and 4,4-methylenediphenyldiisocyanate as linker; c) poly(polydimethyl siloxane-block-co-polyethylenoxid-block-co-polysulfonyl)urethane derived from a polyulfone of formula ##STR00044## and polydimethylsiloxane of formula ##STR00045## in a molar ratio ranging from 3:1 to 1:3, wherein e, f and g are from the range 5 to 80, and hexamethylene diisocyanate as linker; d) poly(polydimethyl siloxane-block-co-polyethylenoxid-block-co-polysulfonyl)urethane derived from a polysulfone of formula ##STR00046## and polydimethylsiloxane of formula ##STR00047## in a molar ratio ranging from 3:1 to 1:3, wherein e, f and g are from the range 5 to 80, and 4,4-methylenediphenyldiisocyanate as linker.

21: A method for imparting antiadhesive or bacteriostatic properties to a polymer composition, comprising adding an oligo- or polyurethane according of formula I according to claim 17 as an additive to a polymer composition.

Description

EXAMPLES

[0288] Abbreviations used in the examples and elsewhere: [0289] DCDPS 4,4-Dichlorodiphenylsulfone [0290] DHDPS 4,4-Dihydroxydiphenylsulfone [0291] NMP N-methylpyrrolidone [0292] DMAc Dimethylacetamide [0293] PWP pure water permeation [0294] MWCO molecular weight cut-off [0295] DMF dimethylformamide [0296] THF tetrahydrofurane [0297] PESU polyethersulfone

[0298] The viscosity of copolymers was measured as a 1% by weight solution of the copolymer in NMP at 25? C. according to DIN EN ISO 1628-1.

[0299] Copolymers prepared were isolated from their solution by precipitation of solutions of the copolymers in water at room temperature (height of spray reactor 0.5 m, flux: 2.5 I/h). The so obtained beads were then filtered and washed with water/ethanol 1:1 (by volume) at room temperature. The beads were then dried to a water content of less than 0.1% by weight at 80 to 120? C. at 0.1 bar.

[0300] The molecular weight distribution and the average molecular weight of the polyarylene ether blocks and of the copolymers obtained were determined by GPC measurements.

[0301] GPC-measurements of PESU-based blocks were done using DMAc as solvent. After filtration (pore size 0.2 ?m), 100 ?l of this solution (4 mg/ml) was injected in the GPC system. For the separation 4 different columns (heated to 85? C.) were used (GRAM pre-column, GRAM 30A, GRAM 1000A, GRAM 1000A, separation material: polyester copolymers). The system was operated with a flow rate of 1 ml/min. As detection system an RI-detector was used (DRI Agilent 1100).

[0302] The calibration was done with PMMA samples of defined molecular weight and narrow molecular weight distribution.

[0303] GPC-measurements of PSU-based blocks were done using THF as solvent. After filtration (pore size 0.2 ?m), 100 ?l of this solution (2 mg/ml) was injected in the GPC system. For the separation 3 different columns (heated to 35? C.) were used (PLgel pre-column, 2 PLgel Mixed B, separation material: crosslinked PS/DVB). The system was operated with a flow rate of 2 ml/min. As detection system an RI-detector was used (DRI HP 1100).

[0304] The calibration was done with polystyrene samples of defined molecular weight and narrow molecular weight distribution.

[0305] The composition of the copolymers obtained with respect to the content of siloxane groups, ethylene groups and polyarylene ether units were determined by comparing the signal intensities in .sup.1H-NMR in CDCl.sub.3.

[0306] The results of the evaluations are shown in tables 1 and 2.

[0307] Synthesis of Polyurethanes U

[0308] 1. Synthesis of Polyarylene Ether Blocks

Example 1.1

[0309] In a 4 liter glass reactor fitted with a thermometer, a gas inlet tube and a Dean-Stark-trap, 574.34 g of DCDPS, 510.00 g of Bisphenol A and 329.78 g of potassium carbonate with a volume average particle size of 32.4 ?m were suspended in 950 ml NMP in a nitrogen atmosphere. The mixture was heated to 190? C. within one hour. In the following, the reaction time shall be understood to be the time during which the reaction mixture was maintained at 190? C.

[0310] The water that was formed in the reaction was continuously removed by distillation. The solvent level inside the reactor was maintained at a constant level by addition of further NMP. After a reaction time of six hours, a sample of 25 ml was taken from the flask and the reaction mixture was cooled to 120? C. 44.93 g of ethylene carbonate were added and the reaction mixture was stirred at 120? C. for two hours. 250 ml of cold (room temperature) NMP were added and the reaction mixture was let to cool to room temperature. The potassium chloride formed in the reaction was removed by filtration and the copolymer obtained was isolated as described above.

Example 1.2

[0311] In a 4 liter glass reactor fitted with a thermometer, a gas inlet tube and a Dean-Stark-trap, 459.78 g of DCDPS, 456.56 g of Bisphenol A and 297.15 g of potassium carbonate with a volume average particle size of 32.4 ?m were suspended in 950 ml NMP in a nitrogen atmosphere. The mixture was heated to 190? C. within one hour. In the following, the reaction time shall be understood to be the time during which the reaction mixture was maintained at 190? C.

[0312] The water that was formed in the reaction was continuously removed by distillation. The solvent level inside the reactor was maintained at a constant level by addition of further NMP. After a reaction time of six hours, a sample of 25 ml was taken from the flask and the reaction mixture was cooled to 120? C. 89.8 g of ethylene carbonate were added and the reaction mixture was stirred at 120? C. for two hours. 250 ml of cold (room temperature) NMP were added and the reaction mixture was let to cool to room temperature. The potassium chloride formed in the reaction was removed by filtration and the copolymer obtained was isolated as described above.

Example 1.3

[0313] In a 4 liter glass reactor fitted with a thermometer, a gas inlet tube and a Dean-Stark-trap, 574.34 g of DCDPS, 510 g of Bisphenol A and 329.78 g of potassium carbonate with a volume average particle size of 32.4 ?m were suspended in 950 ml NMP in a nitrogen atmosphere. The mixture was heated to 190? C. within one hour. In the following, the reaction time shall be understood to be the time during which the reaction mixture was maintained at 190? C.

[0314] The water that was formed in the reaction was continuously removed by distillation. The solvent level inside the reactor was maintained at a constant level by addition of further NMP. After a reaction time of six hours, 250 ml of cold (room temperature) NMP were added and the reaction mixture was let to cool to room temperature. The potassium chloride formed in the reaction was removed by filtration and the copolymer obtained was isolated as described above.

TABLE-US-00001 TABLE 1 Properties of copolymers obtained in examples 1.1 to 1.3. Terminal Terminal Mw/Mn OH-groups EO-groups Example [g/mol] [wt-%] [wt-%] 1.1 (intermediate sample) 8500/4100 0.83 1.1 (final product) 8800/4200 <0.1 2.0 1.2 (intermediate sample 4900/2600 1.67 1.2 (final product) 5100/2650 <0.1 3.1 1.3 9200/4380 0.82

Example 2: Preparation of Polyurethanes

[0315] The products obtained in example 1.1 to 1.3 were used as starting materials for making polyurethanes using the procedure described in WO 2014/170391 p. 14, In 24 to p. 15, In 22 using polydimethylsiloxane-b-polyethyleneoxide (Wacker? IM22, Wacker Chemie, OH number 60.3 mg KOH/g according to DIN 53240) and 4,4-MDI. The starting materials used and the properties of the copolymers obtained are given in table 2.

TABLE-US-00002 TABLE 2 Properties of copolymers 2.1 to 2.3. polyarylene amount of poly- ether used dimethylsiloxane- amount (example no.) b-Polyethylenoxid of MDI Mw/Mn Example amount used (IM 22) used used [kD] 2.1 1.1, 250 g 62.5 g 23.5 g 44.1/14.2 2.2 1.2, 250 g 62.5 36.0 42.1/13.7 2.3 1.3, 250 g 62.5 23.9 21.2/8.4

[0316] The copolymers according to the invention show much higher molecular weight than those known from the art.

Example 3: Preparation of Flat Sheet Membranes

[0317] Into a three neck flask equipped with a magnetic stirrer there were added 80 ml of N-methylpyrrolidone (NMP), 5 g of polyvinylpyrrolidone (PVP, Luvitec? K40) and 15 g of polyethersulfone or mixtures of polyethersulfone (Ultrason? E 6020P, viscosity number (ISO 307, 1157, 1628; in 0.01 g/mol phenol/1,2 orthodichlorobenzene 1:1 solution): 82; glass transition temperature (DSC, 10? C./min; according to ISO 11357-1/-2): 225? C.; molecular weight Mw (GPC in DMAc, PMMA standard): 75000 g/mol) and copolymers according to examples 2.1, 2.2 and 2.3. The composition of membranes prepared are given in table 3. The mixture was heated under gentle stirring at 60? C. until a homogeneous clear viscous solution was obtained. The solution was degassed overnight at room temperature. After that the membrane solution was reheated at 60? C. for 2 hours and casted onto a glass plate with a casting knife (300 microns) at 60? C. using an Erichsen Coating machine operating at a speed of 5 mm/min. The membrane film was allowed to rest for 30 seconds before immersion in a water bath at 25? C. for 10 minutes.

[0318] After the membrane had detached from the glass plate, the membrane was carefully transferred into a water bath for 12 h. Afterwards the membrane was transferred into a bath containing 2500 ppm NaOCl at 50? C. for 4.5 h to remove PVP. The membrane was then washed with water at 60? C. and one time with a 0.5 wt.-% solution of sodium bisulfite to remove active chlorine. After several washing steps with water the membrane was stored wet until characterization started.

[0319] Flat sheet continuous film with micro structural characteristics of UF membranes having dimension of at least 10?15 cm size were obtained. The membrane showed a top thin skin layer (1-3 microns) and a porous layer underneath (thickness: 100-150 microns).

[0320] Membrane Characterization:

[0321] Using a pressure cell with a diameter of 60 mm, the pure water permeation of the membranes was tested using ultrapure water (salt-free water, filtered by a Millipore UF-system). In a subsequent test, a solution of different PEG-Standards was filtered at a pressure of 0.15 bar. After filtration (pore size 0.2 ?m), 100 ?l of this solution (1.5 mg/ml) was injected in the GPC system. For the separation 2 columns (heated to 23? C.) were used (TSKgel GMPWXL, separation material: hydroxylated PMMA). The system was operated with a flow rate of 0.8 ml/min. As detection system an RI-detector was used (DRI Agilent 1200).

[0322] The calibration was done with PEG/PEO samples of defined molecular weight and narrow molecular weight distribution.

[0323] For mechanical testing dumbbell-shaped probes 7.5 cm long and 1.3/0.5 cm wide are cut out and used to evaluate the mechanical properties of the membranes according to ISO 527-1, Probe-Type 5A, speed: 50 mm/min, average values of 5 samples are given.

[0324] The obtained data are summarized in table 3

TABLE-US-00003 TABLE 3 Compositions and properties of membranes 3.1 to 3.8 Experiment No. 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 PESU [wt.-%] 15 14.25 14.25 14.25 17 16.15 16.15 16.15 polymer 2.1 0 0.75 0 0 0 0.85 0 0 [wt.-%] polymer 2.2 0 0 0.75 0 0 0 0.85 0 polymer 2.3 0 0 0 0.75 0 0 0 0.85 [wt.-%] PVP [wt.-%] 5 5 5 5 5 5 5 5 NMP [wt.-%] 80 80 80 80 78 78 78 78 PWP 870 980 1020 670 720 820 870 590 [kg/m2*h*bar] MWCO [kg/mol] 90 78 73 95 75 64 65 78 Tensile Strength 2.8 2.7 2.7 2.35 3.1 3.0 3.0 2.5 [MPa] Elongation at 23 45 47 24 24 52 55 25 Break [%]

[0325] Membranes comprising polyurethane according to the invention as additives show improved mechanical properties over membranes known from the art. Membranes comprising polyurethane according to the invention as additives further show significantly improved permeabilities and MWCO.